Note: Descriptions are shown in the official language in which they were submitted.
. . . . . . . . .... . _.. . .. .... .:. r ,.,,. , .. . . .. ... . . , :. ...,
. ..... . , ., . . . . ... . . .. . .. .. .. .
CA 02299754 2000-02-23
A-21979/A/22031 /CGC 2020
HYDROXY-SUBSTITUTED N-ALKOXY HINDERED AMINES
The instant invention pertains to hindered amine compounds which are
substituted on
the N-atom by N-alkoxy moieties containing one to three hydroxyl groups. These
materials are
particularly effective in stabilizing polyolefins, especially thermoplastic
polyolefins, against the
deleterious effects of oxidative, thermal and actinic radiation. The compounds
are also effective
in stabilizing acid catalyzed and ambient cured coatings systems.
Background of the Invention
4-Hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine and 4-oxo-1-oxyl-2,2,6,6-
tetramethyl-
piperidine are reported to have been used to trap carbon centered radicals
formed from
methanol, ethanol, isopropanol and sec-butanol by S. Nigam et al., J. Chem.
Soc., Trans.
Faraday Soc. 1, 1976, 72, 2324 and by K.-D. Asmus et al., Int. J. Radiat.
Biol., 1976, 29, 211.
United States Patent No. 5,627,248 and European Patent Application No. 135,280
A2
describe, respectively, difunctional and monofunctional living free radical
polymerization
initiators, some of which contain hindered amine ethers substituted by hydroxy
groups. These
compounds differ substantially in structure and performance from the instant
compounds.
European Patent Application No. 427,672 Al and United States Patent No.
4,972,009
mention, but do not exemplify, respectively, hydroxylamine and nitrone
structures, some of
which contain C1-C4 hydroxyalkoxy substituted 2,2,6,6-tetramethylpiperidine
derivatives. Such
structures are outside the scope of the instant invention.
United States Patent No. 5,204,473 describes N-hydrocarbyloxy hindered amine
derivatives that are prepared exclusively from organic compounds containing
only carbon and
hydrogen atoms. Such compounds are structurally quite different from the
instant compounds.
United States Patent No. 5,004,770 describes hindered amine compounds which
are
substituted on the N-atom by alkoxy moieties which alkoxy groups are
themselves
õ,..
CA 02299754 2000-02-23
=2-
unsubstituted. These compounds are especially useful in polymers including
polybutadiene,
polystyrene, ABS, polyacetal, polyamide, polyester, polyurethane and
polycarbonate.
United States Patent No. 5,096,950 also describes hindered amine compounds
which
are substituted on the N-atom by alkoxy moieties which alkoxy groups are
themselves
unsubstituted. These compounds are found to be useful in polyolefins.
The instant compounds are N-alkoxy substituted derivatives of 2,2,6,6-
tetraalkyl-
piperidines where the alkoxy group is substituted by one to three hydroxy
moieties. The instant
compounds also comprise N-alkoxy bridged derivatives of the 2,2,6,6-
tetraalkylpiperidines
where the alkoxy moiety, which is substituted by one to three hydroxy groups,
is shared by two
hindered amine molecules. The free hydroxy moieties of these compounds may be
reacted with
carboxylic acids, acid chlorides or esters to form simple esters or
polyesters, or with
isocyanates to form urethanes or polyurethanes.
The instant compounds, because of their low bascity which is shared by the
simple
unsubstituted N-alkoxy compounds cited in the two patents mentioned above, are
of particular
value in the stabilization of polyolefins and automotive coating compositions
where the activity
of the more basic hindered amine stabilizes is significantly reduced because
of interaction with
the polymer substrate or acid catalytic system needed for curing such
substrate.
Examples of polyolefin compositions in which the instant compounds are
effective
include flame retardant polyolefins where acidic residues from the
decomposition of the
halogenated flame retardants deactivate hindered amines not having the N-OR
group,
greenhouse films and agricultural mulch films where acidic residues from
pesticides interfere
with the activity of "normal" hindered amine stabilizers, and in thermoplastic
polyolefins where
pigment interactions with basic hindered amine stabilizers interfere with
painting the substrate
surfaces. Examples of coating compositions in which the instant compounds are
effective
include melamine crosslinked thermoset acrylic resins, which are cured using
strong acids that
interact with basic hindered amine stabilizers. The instant compounds are also
effective in
acrylic alkyd or polyester resins with isocyanate crosslinking agents, and in
epoxy resins with
carboxylic acid, anhydride, or amine crosslinking agents.
CA 02299754 2000-02-23
-3-
Thus, current compounds are advantageously used in compositions also
containing
costabilizers, flame retardants (e.g. tris(3-bromo-2,2-
bis(bromomethyl)propyl)phosphate,
decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), or ethylene bis-
(dibromo-
norbornanedicarboximide)), catalysts (e.g. acids like toluene sulfonic acid,
metal driers or
amines), fillers, or in agricultural applications wherein pesticides come in
contact with the
stabilized polymer. Preferred is a composition wherein component (a) is
polypropylene,
polyethylene, thermoplastic polyolefin (TPO), ABS or high impact polystyrene
(HIPS), and
component (b) is an effective synergistic mixture of
(i) a compound of formula (1) to (30); and
(ii) a flame retardant selected from the group consisting of the halogenated,
phosphorus,
boron, silicon and antimony compounds, metal hydroxides, metal hydrates, metal
oxides and
mixtures thereof.
While the unsubstituted N-OR compounds described in U.S. Patent Nos. 5,004,770
and
5,096,950 also perform well in the compositions described in the paragraph
above, the instant
compounds differ significantly in both structure and in performance from the
prior art
compounds by virtue of the presence of the one to three free hydroxy groups
present on the N-
alkoxy moiety. These hydroxyl groups in the instant compounds provide said
compounds with
superior antistatic properties, compatibility in more polar environments such
as polyurethane
based and in water-borne automotive coating systems, and in stabilizing
painted automotive
thermoplastic olefin structures.
The instant compounds are particularly suited for
(a) providing superior compatibility in polycarbonates and polycarbonate/ABS
blends
compared to the N-OE prior art compounds; and
(b) providing superior compatibility in polyesters and polyamides compared to
the prior
art N-OE compounds.
Qbiects of the Invention
There are two objects to the instant invention which are:
CA 02299754 2000-02-23
-4-
1. Novel compounds having on the 1-position of the hindered amine a moiety -O-
E-OH
where the OH group provides important properties;
2. compositions stabilized by the novel compounds described above; and
3. a process for the synthesis of the novel compounds.
Detailed Disclosure
The instant invention pertains to novel compounds having 1-alkoxy substituted
hindered
amine derivatives where the alkoxy moiety is substituted by one to three
hydroxy groups as
described in formulas (1) to (15); or to novel compounds having 1 -alkoxy
bridged hindered
amine derivatives where the alkoxy moiety, substituted by one to three hydroxy
groups, is
shared by two hindered amine molecules as described in formulas (16) to (28);
or to oligomeric
or polymeric hindered amine molecules made from the reaction of dialkyl esters
or isocyanates
with hydroxy substituted N-alkoxy derivatives of 4-hydroxy-2,2,6,6-
tetraalkylpiperidine as
described in formula (29); or to simple diester or urethane derivatives of
hydroxy substituted N-
alkoxy derivatives of 4-hydroxy-2,2,6,6-tetramethylpiperidine as described in
formula (30)
G4f G2
O N-OlE- (OH)b
G1 z
G1 Gz
HO
N-'O-E" ( OH ) b
H
G1 Gs
(2)
CA 02299754 2000-02-23
-5-
G1 G3
R1 O
N-O-E- (OH)
Rz >C:o b
m
Gi Gs
(3)
Gl Gz Gl Gz
O O
(HO) E-O-N DCN-O-E- (OH) b
O O
Gl Gz Gl G2
(4)
O G1 G2
N N-O-E- (OH)b
Rz --l
O G1 Gs
(5)
G1 Gz
R O
3
N-O-E- (OH) b
H
G1 Gz n
(6)
CA 02299754 2000-02-23
-6-
~ 4 Gi G2
RS N
N-O-E- (OH) b
H
G1 G D
(7)
O Gi Os
.. ~~ =
R6 C N-O-E- ( OH ) b
Gl Gs n
(8)
R 7 Gl G2
N
N N-O-E- (OH)b
~--N
Re G1 Gz
(9)
Rio ` /Rio
Gl Gz N- (CH2 )Q N G1 G2
( HO ) -E-O'-N -
~ -E- OH
b Ry~ N N >'-Ry N~O ( ) b
N
G Gz Ri R G1 G2
(10)
CA 02299754 2000-02-23
-7-
H\ H
Gl G2 N (CH2)n N-(CHz)p N-(CHz )n N
N < ~ /1~. \ ( HO ) b E-0-N N N
N Ril Ris
I
I ~\
C' ~ N N N Ra
Gs \N_R2 G
1
Gl Gl IGI
Gl Gl Gz N Gz N G2
G2 N Gs O 2 O"
I E- (OH)
O" E_ (OH) E_ (OH) b b
b
{11)
i13
ii- (O
( CHz ) k ,
H R
9
G1
G1
2 N G;
O,
E- (OH)
x
(12)
CA 02299754 2000-02-23
-8-
i13
R14 ( CH3 )h - (0) a i i - ( O )d ( CHz )h Ria
(CHz
I
H Ry
1
Ga
z N Gs
L
O"
E- (OH) b
y
(13)
rRio
( CHzCHz )m
O
H Rs
G1 G1
2
s N G2
O"
E- ( OH ) b
z
(14)
CA 02299754 2000-02-23
-9-
R16 N ( CHz )Q N~~ RiT
NN
G G1 G G1 R 4 a2 N Gz 'z N Gz is
O~ O~
E- (OH) b E- (OH)b
Y
(15)
G1 Gz
0 NO L- (OH)b
C" G2
~ 2
(16)
G1 G2
R1 O
N-O L-' (OH) b
O
Rz m
G1 Gz
2
(17)
G
Gi 2 Gl Gz
OL- (OH)b
O O
Gl Gz Gl Gz 2
(18)
CA 02299754 2000-02-23
.10=
O G1 G2
R2
N N-'O L- (OH) b
O G'1 G2
2
(19)
Gl GT
R19 O
N-O L-- ( OH )
H b
G1 G2
(20)
l G2 G1 GZ
0O
[OHEO_:<-
Rz N-O L- (OH)b
H H
G Gz G1 Ga
(21)
R G
121 l [R2G2 2 N
N-O L- ( OH )
H b
Gi G= 2
(22)
CA 02299754 2000-02-23
-~~-
Gl C2 i 23 i 23 Gl G2
(HO) -E-O-N N- R24N N-O L- (OH)
b H H b
G1 Gz G1 Gz
(23)
Q Gi [R2:_O L- (OH) b
G Gz 2
(24)
i G2 O O Gi G2
[(Ho)E_o_:_ R26 C N-O L- (OH)b
G1 G2 G1 G2 2
(25)
R7 Gi G2
N
N ~-R 9 N-O L- ( OH )
ll:-- N
R8 G1 G2
(26)
CA 02299754 2000-02-23
-12-
= Rio\ /Rio
G2
G G2 N- (CH~ )q N G G
i
(RO) R-O-N R ~N N~ ~_R9 N-O L- (OH)
b 9 b
N=< N
G1 G2 R7 R G1 Gs
(27)
1t13
R14 (CHa)h (O)a i i-(O)a (CH2)h R1a
(CHz)
I
H Ry
G G1
2 N G2
0 L- (OH) b
2
(28)
Gi Gz
T` O
O O
N-0-G-0 R27 ORze
H
G1 Gz z
(29)
CA 02299754 2000-02-23
-13-
G
i G
O 2 O
II II
R29 C-O N-O-G-O-C-R29
G G2
(30)
G, and G2 are independently alkyl of 1 to 4 carbon atoms, or G, and G2
together are
pentamethylene; preferably G, and G2 are each methyl;
E is a straight or branched chain alkylene of 1 to 18 carbon atoms,
cycloalkylene of 5 to
18 carbon atoms, cycloalkenylene of 5 to 18 carbon atoms, a straight or
branched chain
alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted
by one or two
alkyl groups of 1 to 4 carbon atoms;
b is 1, 2 or 3 with the proviso that b cannot exceed the number of carbon
atoms in E or
L, and when b is 2 or 3, each hydroxyl group is attached to a different carbon
atom of E or L; the
two hindered amine groups are generally, but not always, attached to two
different carbon
atoms of L;
in each of the formulas (1) to (15)
mis0or1;
R, is hydrogen, hydroxyl or hydroxymethyl;
R2 is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon
atoms;
n is 1 to 4;
when n is 1,
CA 02299754 2000-02-23
29276-830
- 14 -
R3 is alkyl of 1 to 18 carbon atoms, alkoxycarbonyl-
alkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to 18
carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2-
(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which
alkyl is interrupted by oxygen, an acyl radical of an aliphatic
or unsaturated aliphatic carboxylic or carbamic acid containing
2 to 18 carbon atoms, an acyl radical of a cycloaliphatic
carboxylic or carbamic acid containing 7 to 12 carbon atoms, or
acyl radical of an aromatic acid containing 7 to 15 carbon
atoms;
when n is 2,
R3 is alkylene of 2 to 18 carbon atoms, a divalent
acyl radical of an aliphatic or unsaturated aliphatic
dicarboxylic or dicarbamic acid containing 2 to 18 carbon
atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic
or dicarbamic acid containing 7 to 12 carbon atoms, or a
divalent acyl radical of an aromatic dicarboxylic acid contain-
ing 8 to 15 carbon atoms;
when n is 3,
R3 is a trivalent acyl radical of an aliphatic,
unsaturated aliphatic, or cycloaliphatic tricarboxylic acid or
tricarbamic acid containing 6-18 carbon atoms, or a trivalent
acyl radical of an aromatic tricarboxylic or tricarbamic acid
containing 9-18 carbon atoms, or R3 is a trivalent acyl radical
of a tris(alkylcarbamic acid) derivative of cyanuric acid
containing 12-24 carbon atoms, such as 1,3,5-tris[6-carboxy-
aminohexyl]-2,4,6-trioxo-s-triazine;
when n is 4,
R3 is a tetravalent acyl radical of an aliphatic or
unsaturated aliphatic tetracarboxylic acid, especially 1,2,3,4-
butanetetracarboxylic acid, 1,2,3,4-but-2-enetetracarboxylic
acid, 1,2,3,5-pentanetetracarboxylic acid and 1,2,4,5-pentane-
tetracarboxylic acid, or R3 is a tetravalent acyl radical of
an aromatic tetracarboxylic acid containing 10 to 18 carbon
atoms;
p is 1 to 3,
CA 02299754 2000-02-23
29276-830
- 14a -
R4 is hydrogen, alkyl of 1 to 18 carbon atoms or
acyl of 2 to 6 carbon atoms;
when p is 1,
CA 02299754 2000-02-23
-15-
R5 is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of an aliphatic
or
unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon
atoms, an acyl
radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12
carbon atoms, an acyl
radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R4
and R5 together
are -(CH2)SCO-, phthaloyl or a divalent acyl radical of maleic acid;
when p is 2,
Rg is alkylene of 2 to 12 carbon atoms, a divalent acyl radical of an
aliphatic or
unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18
carbon atoms, a divalent
acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7
to 12 carbon atoms,
or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15
carbon atoms;
when p is 3,
R5 is a trivalent acyl radical of an aliphatic or unsaturated aliphatic
tricarboxylic acid
containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic
tricarboxylic acid
containing 9 to 15 carbon atoms;
when n is 1,
Rg is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -
NHalkyl of 1
to 18 carbon atoms or -N(alkyl)2 of 2 to 36 carbon atoms,
when n is 2,
RB is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18 carbon
atoms,
-NH-alkylene-NH- of 2 to 18 carbon atoms or -N(alkyl)-alkylene-N(alkyl)- of 2
to 18 carbon
atoms, or Rfi is 4-methyl-1,3-phenylenediamino,
when n is 3,
CA 02299754 2000-02-23
-16-
Rg is a trivalent alkoxy radical of a saturated or unsaturated aliphatic triol
containing 3 to
18 carbon atoms,
when n is 4,
Rs is a tetravalent alkoxy radical of a saturated or unsaturated aliphatic
tetraol containing
4 to 18 carbon atoms,
R7 and R8 are independently chlorine, alkoxy of 1 to 18 carbon atoms, -O-Ti,
amino
substituted by 2-hydroxyethyl, -NH(alkyl) of 1 to 18 carbon atoms, -N(alkyl)T,
with alkyl of 1 to
18 carbon atoms, or -N(alkyl)2 of 2 to 36 carbon atoms,
Ra is a divalent oxygen atom, or R9 is a divalent nitrogen atom substituted by
either
hydrogen, alkyl of 1 to 12 carbon atoms or T,
GiGZ
Ti N-O--g- (OH) b
G1 Gz
R,o is hydrogen or methyl,
q is 2 to 8,
R;; and R12 are independently hydrogen or the group T2
CA 02299754 2000-02-23
-17-
Tz
R 2
N N N'RZ
G1
G1 G1 G1
G2 N Gs G2 N G2
O O~
E- (OH)b
E- (oH)b
R13 is hydrogen, phenyl, straight or branched alkyl of 1 to 12 carbon atoms,
alkoxy of 1
to 12 carbon atoms, straight or branched alkyl of 1 to 4 carbon atoms
substituted by phenyl,
cycloalkyl of 5 to 8 carbon atoms, cycloalkenyl of 5 to 8 carbon atoms,
alkenyl of 2 to 12 carbon
atoms, glycidyl, allyloxy, straight or branched hydroxyalkyl of 1 to 4 carbon
atoms, or silyl or
silyloxy substituted three times independently by hydrogen, by phenyl, by
alkyl of 1 to 4 carbon
atoms or by alkoxy of 1 to 4 carbon atoms;
814 is hydrogen or silyl substituted three times independently by hydrogen, by
phenyl, by
alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms;
d is 0 or 1;
hisOto4;
k is 0 to 5;
xis3to6;
y is 1 to 10;
z is an integer such that the compound has a molecular weight of 1000 to 4000
g/mol
(=atomic units, amu),
CA 02299754 2000-02-23
-18-
R15 is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8 carbon
atoms, especially
branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, -
N(alkyi)T, with alkyl of 1
to 8 carbon atoms, or -N(alkyl)2 of 2 to 16 carbon atoms,
R,g is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl
of 1 to 4
carbon atoms, s-triazinyl substituted once by chlorine and once by R15, or s-
triazinyl substituted
twice by R15 with the condition that the two R15 substituents may be
different;
,
R17 is chlorine, amino substituted by alkyl of 1 to 8 carbon atoms or by Ti, -
N(alkyl)T,
with alkyl of 1 to 8 carbon atoms, -N(alkyl)2 of 2 to 16 carbon atoms, or the
group T3
Ts = N ( CH= )Q N-'Rle
i i
G G
z N Gs 2 N Gs
1 1
O\ O\
E- (OH) b E- (OH) b
R18 is hydrogen, acyl of 2 to 4 carbon atoms4 carbamoyl substituted by alkyl
of 1 to 4
carbon atoms, s-triazinyl substituted twice by -N(alkyl)2 of 2 to 16 carbon
atoms or s-triazinyl
substituted twice by -N(alkyl)T, with alkyl of 1 to 8 carbon atoms;
L is straight or branched chain alkylene of 1 to 18 carbon atoms,
cycloalkylene of 5 to 8
carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18
carbon atoms, a
straight or branched chain alkylene of 1 to 4 carbon atoms substituted by
phenyl or by phenyl
substituted by one or two alkyl of 1 to 4 carbon atoms,
in formulas (16) to (28), R,, R2i R7, R8, R9, R,o, R13, R,a, d,h, k, m, q, and
T, have the
same meanings as in formulas (1) to (15);
Rt9 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbon
atoms, glycidyl,
2,3-dihydroxypropyl, 2-hydroxy or 2-(hydroxymethyl) substituted alkyl of 3 to
12 carbon atoms
CA 02299754 2000-02-23
-19-
which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or
unsaturated aliphatic
carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical
of a cycloaliphatic
carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl radical
of an aromatic acid
containing 7 to 15 carbon atoms;
R20 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an
aliphatic or
unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18
carbon atoms, a divalent
acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7
to 12 carbon atoms,
or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15
carbon atoms;
R2, is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms;
R22 is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of an
aliphatic or
unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon
atoms, an acyl
radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12
carbon atoms, an acyl
radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R4
and Rg together
are -(CH2)5CO-, phthaloyl or a divalent acyl radical of maleic acid;
R23 is hydrogen, alkyl of 1 to 4 carbon atoms or acyl of 2 to 6 carbon atoms;
R24 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an
aliphatic or
unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18
carbon atoms, a divalent
acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7
to 12 carbon atoms,
or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15
carbon atoms;
R2S is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -
NHalkyl of 1
to 18 carbon atoms or -N(alkyl)2 of 2 to 36 carbon atoms,
R2e is alkylenedioxy of 2 to 18 carbon atoms, alkenyienedioxy of 2 to 18
carbon atoms, -
NH-alkylene-NH- of 2 to 18 carbon atoms or -N(alkyl)-alkylene-N(alkyl)- of 3
to 18 carbon
atoms,
CA 02299754 2000-02-23
-20-
in formulas (29) and (30), G is a carbon centered diradical derived from a
primary,
secondary or tertiary alcohol G-OH, where
z is as defined above, and
G is straight or branched chain alkylene of 1 to 18 carbon atoms,
cycloalkylene of 5 to 8
carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18
carbon atoms, a
straight or branched chain alkylene of 1 to 4 carbon atoms substituted by
phenyl or by phenyl
substituted by one or two alkyl of 1 to 4 carbon atoms, with the proviso that
in formula (29)
successive hindered amine moieties can be oriented in either a head to head or
head to tail
fashion;
T4 is hydrogen or
0 0
T4 is _11 ~
R27 O-R28
R27 is a straight or branched chain alkylene of 1 to 18 carbon atoms,
cycloalkylene or
cycloalkenylene of 5 to 8 carbon atoms, phenylene or -NH-alkylene-NH- of 2 to
18 carbon
atoms including 5-amino-l-aminomethyl-1,3,3-trimethylcyclohexane and -NH-
xylylene-NH-;
Gy G2 G, G2
R28 is alkyl of 1 to 4 carbon atoms; N-O-G-OH ; or HO N-O-G-
G, G2 G, G2
Rn is a straight or branched chain alkyl or -NH-alkyl of 1 to 18 carbon atoms
or -NH-
cycloalkyl of 5 to 8 carbon atoms; and
with the further proviso that in formulas (1) and (2), when b is 1, E is not
methyl, ethyl, 2-
propyl or 2-methyl-2-propyl.
Preferably, G, and G2 are each methyl.
CA 02299754 2000-02-23
-21-
'Preferably, in formulas (1) to (28), b is 1 or 2, most preferably 1.
Of special technical importance are compounds of formula (1) and (2) when b is
1 and E
is methylene, ethylene, 2-propylene or 2-methyl-2-propylene.
When b is 1, E-OH and L-OH are respectively a carbon-centered radical or
diradical
formed preferably from 2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-l-
propanol, 2-methyl-2-
butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-
decanol, 1-
dodecanol, 1 -octadecanol, 2-butanol, 2-pentanol, 2-ethyl- 1 -hexanol, cyclo
hexanol, cyclooctanol,
allyl alcohol, phenethyl alcohol or 1-phenyl-1 -ethanol; most preferably E-OH
and L-OH are
formed from 2-methyl-2-propanol or cyclohexanol.
When b is 2, E-OH and L-OH are respectively a carbon-centered radical or
diradical
formed preferably from 1,2-ethanediol, 1,2-propanedial, 1,3-propanediol, 1,2-
butanediol, 1,3-
butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol,
1,3-
cyclohexanediol or 1,4-cyclohexanediol; most preferably E-OH and L-OH are
formed from 1,4-
butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-
cyclohexanediol or 1,4-
cyclohexanediol.
When b is 3, E-OH and L-OH are respectively a carbon-centered radical or
diradical
formed from glycerol, 1,1,1-tris(hydroxymethyl)methane, 2-ethyl-2-
(hydroxymethyl-1,3-
propanediol, 1,2,4-butanetriol or 1,2,6-hexanetriol; most preferably E-OH and
L-OH are formed
from glycerol, 1,1,1-tris(hydroxymethyl)methane, 2-ethyl-2-(hydroxymethyl-1,3-
propanediol.
Preferably in formulas (29) and (30), -G-O- is formed from ethanol, phenethyl
alcohol,
cyclohexanol or 2-methyl-2-propanol (= tert-butyl alcohol).
Preferably in formula (3), m is 0, R, is hydrogen or hydroxymethyl, and R2 is
hydrogen;
or m is 1, R, is hydroxy or hydroxymethyl, and R2 is hydrogen, methyl or
ethyl.
Preferably in formula (5), R2 is hydrogen or dodecyl.
CA 02299754 2000-02-23
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Preferably in formula (6), n is 1-3, and when n is 1, R3 is allyl, glycidyl,
acryloyl,
methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl,
methoxycarbonylpropionyl, methoxy-
carbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when
n is 2, R3 is
succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, cis- or trans-5-
carbamoyl-1-
(carbamoylmethyl)-1,3,3-trimethylcyclohexane or toluene-2,4-dicarbamoyl; or
when n is 3, R3 is
1,3,5-tris(6-carbamoylhexyl)-2,4,6-trioxo-s-triazine.
Preferably in formula (7), p is 1 or 2, and when p is 1, R4 is hydrogen and R5
is butyl; or
R4 and RS together are the divalent acyl radical of maleic acid; or when p is
2, R4 is hydrogen or
acetyl, and R5 is 1,6-hexanediyl.
Preferably in formula (8), n is 1 or 2, and when n is 1, RB is ethoxy, 6-
methyl-l-heptyloxy,
ethylamino, butylamino or octylamino; or when n is 2, R6 is 1,2-ethanedioxy,
1,4-butanedioxy,
ethylenediamino, hexamethylenediamino, or 4-methyl-1,3-phenylenediamino.
Preferably in formula (9), R7 and Ra are independently chlorine, octylamino,
tert-octyl-
amino or amino substituted by T, and ethyl, butyl or dodecyl; and R9 is a
divalent nitrogen atom
substituted by ethyl, butyl or dodecyl.
Preferably in formula (10), q is 2, 4 or 6, R7 is chlorine, octylamino,
octadecylamino or
amino substituted by T, and ethyl, butyl or dodecyl; and R,o is hydrogen.
Preferably in formula (11), n is 3, p is 2, R2 is ethyl, butyl or dodecyl; and
one of Rõ or
R12 is T2, and the other is hydrogen.
Preferably in formula (12), k is 3, R9 is a divalent oxygen atom or is a
divalent nitrogen
atom substituted by ethyl, butyl or dodecyl, R13 is hydrogen or methyl, and
when d is 0, x is 5 or
6, and when d is 1, x is 3 or 4.
Preferably in formula (13), d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8, Rs
is a divalent
oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or
dodecyl, R13 is hydrogen,
methyl, ethyl, methoxy or ethoxy, and R14 is hydrogen or trimethylsilyl.
CA 02299754 2000-02-23
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Preferably in formula (14), R9 is a divalent oxygen atom, R,o is hydrogen or
methyl, m is
0 and z is an integer such that the molecular weight of the compound is 1500-
3000 amu.
Preferably in formula (15) q is 6, y is 1-7, R15 is tert-octylamino,
morpholino, amino
substituted by T, and butyl, which may also be designated as Ti-butylamino,
R16 is hydrogen,
acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-
bis(diethylamino)-s-triazinyl, s-
triazinyl substituted twice by T1-butylamino or s-triazinyl substituted once
by diethylamino or
dibutylamino and once by T,-butylamino, R17 is dibutylarrmino, diethylamino,
T,-butylamino or Rõ
is T3 where R18 is acetyl or ethylcarbamoyl.
Preferably in formula (17), m is 0, R, is hydrogen or hydroxymethyl, and R2 is
hydrogen;
or m is 1, R, is hydroxy or hydroxymethyl, and R2 is hydrogen or methyl.
Preferably in formula (19), R2 is hydrogen or dodecyl.
Preferably in formula (20), R,9 is hydrogen, allyl, acryloyl, methacryloyl,
octadecanoyl or
hexadecanoyl.
Preferably in formula (21), R20 is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-
hexane-
dicarbamoyi, or cis- or trans-5-carbamoyl-1-(carbamoyimethyl)-1,3,3-
trimethylcyclohexane.
Preferably in formula (22), R2, is hydrogen and R22 is hydrogen or butyl; or
R21 and R22
together are the divalent acyl radical of maleic acid.
Preferably in formula (23), R23 is hydrogen or acetyl, and R24 is ethylene or
hexamethylene.
Preferably in formula (24), R25 is ethoxy, 6-methyi-l-heptyloxy, ethylamino,
butylamino or
octylamino.
Preferably in formula (25), R26 is 1,2-ethanedioxy, 1-4-butanedioxy,
ethylenediamino or
hexamethylenediamino.
CA 02299754 2000-02-23
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Preferably in formula (26), R7 and RB are independently chlorine, octylamino,
tert-octyl-
amino, octadecylamino, T,-ethylamino, T,-butylamino or T,-dodecylamino, and Rg
is a divalent
nitrogen atom substituted by ethyl, butyl or dodecyl.
Preferably in formula (27), q is 2, 4 or 6, R7, is chlorine, octylamino,
octadecylamino, T,-
ethylamino, T,-butylamino or T,-dodecylamino, and R,a is hydrogen.
Preferably in formula (28), d is 0 or 1, h is 0-2, k is 0 or 3, R9 is a
divalent oxygen atom
or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R13 is
hydrogen, methyl, ethyl,
methoxy or ethoxy, and R14 is hydrogen or trlmethylsilyl.
Preferably in formula (29), R27 is ethylene, trimethylene, tetramethylene,
octamethylene,
1,6-diaminohexane or 5-amino-l-arninomethyl-1,3,3-trimethylcyclohexane; z is
an integer such
that the molecular weight of the compound is 1500-3000 amu, R28 is methyl or
ethyl, and G is
ethylene, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl,
-CH(C6HS)CH2- or -CHzC(CH3)2-.
Preferably in formula (30), R29 is pentadecyl, heptadecyl, butylamino or
cyclohexylamino.
Still more preferred embodiments of the instant invention are the compounds of
formulas
(1) to (30) where E-OH, L-OH and G-O- are formed from 2-methyl-2-propanol (=
tert-butyl
alcohol) or cyclohexanol.
Most preferably in formula (6), when n is 1, R3 is acryloyl, methacrloyl,
glycidyl,
octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl,
methoxy-
carbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R3 is succinyl,
glutaryl, adipoyl,
sebacoyl, 1,6-hexanedicarbamoyl or cis- or trans-5-carbamoyl-1-
(carbamoylmethyl)-1,3,3-
trimethylcyclohexane or toluene-2,4-dicarbamoyl; or when n is 3, R3 is 1,3,5-
tris(6-
carbamoylhexyl)-2,4,6-trioxo-s-triazine.
Most preferably in formula (7), p is 1 or 2, and when p is 1, R4 is hydrogen
and R5 is
hydrogen or butyl; or when p is 2, R4 is hydrogen, and R5 is 1,6-hexanediyl.
CA 02299754 2000-02-23
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Most preferably in formula (9), R7 is chlorine, octylamino or T,-butylamino,
Re is chlorine
or T,-butylarnino, and R9 is a divalent nitrogen atom substituted by butyl.
Most preferably in formula (10), q is 6, R7 is Tj-butylamino; and R,o is
hydrogen.
Most preferably in formula (11), n is 3, p is 2, and one of Rõ or R12 is T2,
and the other
is hydrogen.
Most preferably in formula (12), k is 3, R9 is a divalent oxygen atom, R13 is
hydrogen or
methyl, and d is 0, x is 5 or 6, and when d is 1, x is 3 or 4.
Most preferably in formula (13), d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8,
R9 is a divalent
oxygen atom, R13 is hydrogen, methyl, ethyl, methoxy or ethoxy, and R14 is
hydrogen or
trimethylsilyl.
Most preferably in formula (15) q is 6, y is 1-7, R,g is T,-butylamino, R,e is
hydrogen,
acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-
bis(diethylamino)-s-triazinyl, s-
triazinyl substituted twice by T,-butylamino or s-triazinyl substituted once
by diethylamino or
dibutylamino and once by T,-butylamino, R17 is dibutylamino, diethylamino, T,-
butylamino or Rõ
is T3 where R,8 is acetyl or ethylcarbamoyl.
Most preferably in formula (20), R,9 is hydrogen, octadecanoyl or
hexadecanoyl.
Most preferably in formula (22), R2, is hydrogen and R22 is hydrogen or butyl.
Most preferably in formula (23), R23 is hydrogen, and Ra; is hexamQthylene.
Most preferably in formula (26), R, is chlorine, octylamino or T,-butylamino,
R8 is
chlorine or T,-butylamino, and R9 is a divalent nitrogen atom substituted by
butyl.
Most preferably in formula (27), q is 6, R7 is Ti-butylamino, and Rs is a
divalent nitrogen
atom substituted by butyl.
CA 02299754 2000-02-23
29276-830
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Most preferably in formula (29), R2, is ethylene, trimethylene, tetramethylene
or
octamethylene, z is an integer such that the molecular weight of the compound
is 1500 to 2000
amu, and R28 is methyl.
Most preferably in formula (30), R29 is pentadecyl or heptadecyl.
Still more preferred embodiments of the instant invention are the compounds of
formulas
(1) to (30) where E-OH, L-OH and -G-O- are formed from 2-methyl-2-propanol (=
tert-butyl
alcohol).
Especially preferred compounds of formula (6) are those where n is 1, R3 is
acryloyl,
methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl
or methaxy-
carbonylbutyryl or methoxycarbcmylpentanoyl, and where n is 2, R3 is succinyl,
glutaryl, adipoyl or sebaooyl.
Especially preferred compounds of formula (7) are those where R4 is hydrogen,
and
when p is 1, R5 is hydrogen or butyl, or when p is 2, RS is hexamethylene.
Especially preferred compounds of formula (9) are those where R, is chlorine,
octylamino or T,-butylamino, R8 is T,-butylamino, and R9 is a divalent
nitrogen atom substituted
by butyl.
Especially preferred compounds of formula (10) are those where q is 6, R, is
T,-
butylamino and R,o is hydrogen.
Especially preferred compounds of formula (11) are those where n is 3, p is 2,
one of Rõ
or R,Z is T2 and the other is hydrogen.
Especially preferred compounds of formula (12) are those where d is 1, k is 3,
x is 3 or 4,
R9 is divalent oxygen atom, and R13 is methyl.
Especially preferred compounds of formula (13) are those where k is 3, y is 4-
8. R9 is a
divalent oxygen atom, R13 is hydrogen or methyl, d and h are 0, R14 is
hydrogen, or d is 1 and h
is 0, and R14 is trimethylsilyl.
CA 02299754 2000-02-23
27 -
'Especially preferred compounds of formula (14) are those where m is 0, R9 is
a divalent
oxygen atom, R,o is hydrogen or methyl, and z is an integer such that the
molecular weight of
the compound is 1500-3000 amu.
Especially preferred compounds of formula (15) are those where q is 6, y is 1-
7, R15 is
T,-butylamino, R,e is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)-
s-triazinyl, 2,4-
bis(diethylamino)-s-triazinyl, s-triazinyl substituted twice by T,-butylamino
or s-triazinyl
substituted once by diethylamino or dibutylamino and once by Ti-butylamino, R
is dibutyl-
amino, diethylamino, or T3 where R,8 is acetyl or ethylcarbamoyl.
Especially preferred compounds of formula (20) are those where R,9 is
hydrogen,
octadecanoyl or hexadecanoyl.
Especially preferred compounds of formula (21) are those where R20 is
succinyl, glutaryl,
adipoyl or sebacoyl.
Especially preferred compound of formula (30) is that where R29 is heptadecyl.
The instant invention also pertains to a polymer composition or a recording
material (a)
containing an effective stabilizing amount of one or more compounds selected
from the
compounds of formula (1) to formula (30) as described above (b), including
compounds of
formulae (1) and (2) when b is 1 and E is methyl, ethyl, 2-propyl or 2-methyl-
2-propyl. In
general, effective stabilizing amounts of a compound of the invention are from
0.01 to 10 %,
especially from 0.05 to 5% by weight, based on component (a), of the
stabilizer of component
(b).
Preferably, the organic material to be stabilized is a natural, semi-synthetic
or synthetic
polymer or a color photographic material, especially a thermoplastic polymer
or a coating
composition.
Most preferably, the polymer is a polyolefin, especially a thermoplastic
polyolefin useful
in automotive coatings and applications or a urethane based automotive
coating.
CA 02299754 2000-02-23
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'The compounds of this invention exhibit superior hydrolytic stability,
handling and
storage stability as well as good resistance to extractability when present in
a stabilized
composition.
In general, organic materials which can be stabilized include
1. Polymers of monoolefins and diolefins, for example polypropylene,
polyisobutylene, polybut-
1-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene, as well as
polymers of
cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which
optionally can be
crosslinked), for example high density polyethylene (HDPE), high density and
high molecular
weight polyethylgne (HDPE-HMW), high density and ultrahigh molecular weight
polyethylene
(HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene
(LDPE), linear
low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding
paragraph, preferably
polyethylene and polypropylene, can be prepared by differe4.and especially by
the following,
methods:
a) radical polymerisation (normally under high pressure and at elevated
temperature).
b) catalytic polymerisation using a catalyst that normally contains one or
more than one
metal of groups lVb, Vb, VIb or VIII of the Periodic Table. These metals
usually have
one or more than one ligand, typically oxides, halides, alcoholates, esters,
ethers,
amines, alkyls, alkenyls and/or aryls that may be either 7t- or a-coordinated.
These
metal complexes may be in the free form or fixed on substrates, typically on
activated
magnesium chloride, titanium(Ill) chloride, alumina or silicon oxide. These
catalysts
may be soluble or insoluble in the polymerisation medium. The catalysts can be
used
by themselves in the polymerisation or further activators may be used,
typically metal
alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said
metals being elements of groups la, Ila and/or Illa of the Periodic Table. The
activators
may be modified conveniently with further ester, ether, amine or silyl ether
groups.
These catalyst systems are usually termed Phillips, Standard Oil Indiana,
Ziegler (-
Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
CA 02299754 2000-02-23
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2. Miztures of the polymers mentioned under 1), for example mixtures of
polypropylene with
polyisobutylene, polypropylene with polyethylene (for example PP/HDPE,
PP/LDPE) and
mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl
monomers, for
example ethylene/propylene copolymers, linear low density polyethylene (LLDPE)
and mixtures
thereof with low density polyethylene (LDPE), propylene/but-l-ene copolymers,
propylene/isobutylene copolymers, ethylene/but-l-ene copolymers,
ethylene/hexene copo-
lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers,
ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylenersoprene copolymers,
ethylene/alkyl
acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl
acetate copolymers
and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers
and their salts
(ionomers) as well as terpolymers of ethylene with propylene and a diene such
as hexadiene,
dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers
with one another
and with polymers mentioned in 1) above, for example polypropylene/ethylene-
propylene
copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-
acrylic acid
copolymers (EAA), LLDPE/EVA, LLDPE/EAA and altemating or random
polyalkylene/carbon
monoxide copolymers and mixtures thereof with other polymers, for example
polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications
thereof (e.g.
tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).
6. Copolymers of styrene or a-methylstyrene with dienes or acrylic
derivatives, for example
styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate,
styrene/butadiene/alkyl
acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,
styrene/acryloni-
trile/methyl acrylate; mixtures of high impact strength of styrene copolymers
and another
polymer, for example a polyacrylate, a diene polymer or an
ethylene/propylene/diene terpo-
lymer; and block copolymers of styrene such as styrene/butadiene/styrene,
styrenerso-
prene/styrene, styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/ styrene.
CA 02299754 2000-02-23
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7. Graft copolymers of styrene or a-methylstyrene, for example styrene on
polybutadiene,
styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers;
styrene and
acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile
and methyl meth-
acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene;
styrene, acrylonitrile
and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on
polybutadiene;
styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and
acrylonitrile on
ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl
acrylates or
polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene
copolymers, as well as
mixtures thereof with the copolymers listed under 6), for example the
copolymer mixtures known
as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers,
chlorinated and
brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated
or sulfochlorinated
polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin
homo- and
copolymers, especially polymers of halogen-containing vinyl compounds, for
example polyvinyl
chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene
fluoride, as well as
copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl
chloride/vinyl acetate or
vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from a,R-unsaturated acids and de(vatives thereof such as
polyacrylates
and polymethacrylates; polymethyl methacrylates, polyacrylamides and
polyacrylonitriles,
impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with
other unsaturated
monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl
acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide
copolymers or acry-
lonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers de(ved from unsaturated alcohols and amines or the acyl
derivatives or acetals
thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate,
polyvinyl benzoate,
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl
melamine; as well as their
copotymers with olefins mentioned in 1) above.
CA 02299754 2000-02-23
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12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols,
polyethylene
oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which
contain
ethylene oxide as a comonomer; polyacetals modified with thermoplastic
polyurethanes,
acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides
with styrene
polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or
polybutadienes
on the one hand and aliphatic or aromatic polyisocyanates on the other, as
well as precursors
thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids
and/or from
aminocarboxylic acids or the corresponding lactams, for example polyamide 4,
polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12,
aromatic polyamides
starting from m-xylene diamine and adipic acid; polyamides prepared from
hexamethylenediamine and isophthalic or/and terephthalic acid and with or
without an ela-
stomer as modifier, for example poly-2,4,4,-trimethylhexamethyiene
terephthalamide or poly-m-
phenylene isophthalamide; and also block copolymers of the aforementioned
polyamides with
polyolefins, olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with
polyethers, e.g. with polyethylene glycol, polypropylene glycol or
polytetramethylene glycol; as
well as polyamides or copolyamides modified with EPDM or ABS; and polyamides
condensed
during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids,
polyhydantoins
and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from
hydroxycarboxylic acids or
the corresponding lactones, for example polyethylene terephthalate,
polybutylene terephthalate,
poiy-1,4-dimethyioicyciohexane terephthalate and polyhydroxybenzoates, as well
as block
CA 02299754 2000-02-23
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copolyether esters derived from hydroxyl-terminated polyethers; and also
polyesters modified
with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols,
ureas and
melamines on the other hand, such as phenol7formaidehyde resins,
urea/formaldehyde resins
and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and
unsaturated
dicarboxylic acids with polyhydric alcohols and vinyl compounds as
crosslinking agents, and
also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for
example epoxy acrylates,
urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with
melamine resins, urea
resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aGphatic, cycloaliphatic,
heterocyclic or aromatic
glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and
bisphenol F, which are
crosslinked with customary hardeners such as anhydrides or amines, with or
without
accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically
modified homologous
derivatives thereof, for example cellulose acetates, cellulose propionates and
cellulose
butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins
and their
derivatives.
CA 02299754 2000-02-23
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28. Blends of the aforementioned polymers (polybiends), for example PP/EPDM,
Poly-
amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA,
PC/PBT,
PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,
POM/acrylate,
POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PAIPPO,
PBT/PC/ABS
or PBT/PET/PC.
29. Naturally occurring and synthetic organic materials which are pure
monomeric compounds
or mixtures of such compounds, for example mineral oils, animal and vegetable
fats, oil and
waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates,
adipates, phosphates
or trimellitates) and also mixtures of synthetic esters with mineral oils in
any weight ratios,
typically those used as spinning compositions, as well as aqueous emulsions of
such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or
latices of carbo-
xylated styrene/butadiene copolymers.
31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for
example, in U.S.
Patent No. 4,259,467; and the hard polyorganosiloxanes described, for example,
in U.S. Patent
No. 4,355,147.
32. Polyketimines in combination with unsaturated acrylic polyacetoacetate
resins or with
unsaturated acrylic resins. The unsaturated acrylic resins include the
urethane acrylates,
polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups
and the
acrylated melamines. The polyketimines are prepared from polyamines and
ketones in the
presence of an acid catalyst.
33. Radiation curable compositions containing ethylenically unsaturated
monomers or
oligomers and a polyunsaturated aliphatic oligomer.
34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an
epoxy functional
coetherified high solids melamine resin such as LSE-4103 (Monsanto).
In general, the compounds of the present invention are empioyed in from about
0.01 to
about 5% by weight of the stabilized composition, although this will vary with
the particular
CA 02299754 2000-02-23
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substrate and application. An advantageous range is from about 0.05 to about
3%, and
especially 0.05 to about 1%.
The stabilizers of the instant invention may readily be incorporated into the
organic
polymers by conventional techniques, at any convenient stage prior to the
manufacture of
shaped articles therefrom. For example, the stabilizer may be mixed with the
polymer in dry
powder form, or a suspension or emulsion of the stabilizer may be mixed with a
solution,
suspension, or emulsion of the polymer. The resulting stabilized compositions
of the invention
may optionally also contain from about 0.01 to about 5%, preferably from about
0.025 to about
2%, and especially from about 0.1 to about 1% by weight of various
conventional additives,
such as the materials listed below, or mixtures thereof.
1. Antioxidants
1.1. Alkylated monoflhenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-
tert-butyl-4,6-di-
methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-
butylphenol, 2,6-di-tert-butyl-
4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-
dimethylphenoi,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-
meth-
oxymethyiphenol, nonylphenots which are linear or branched in the side chains,
for example,
2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenoi, 2,4-
dimethyl-6-(1'-
methytheptadec-1'-yl)phenol, 2,4-dirnethyl-6-(1'-methyltridec-1'-yl)phenol and
mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-
butylphenol, 2,4-dioctyl-
thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-
dodecylthiomethyl-4-
nonylphenol.
1.3. Hydroguinon s and alkylated hvdroauinones, for example 2,6-di-tert-butyl-
4-methoxy-
phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-
diphenyl-4-octade-
cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-
hydroxyanisole, 3,5-di-tert-butyl-
4-hydroxyanisole, 3,5-di-tert-butyi-4-hydroxyphenyl stearate, bis-(3,5-di-tert-
butyl-4-hy-
droxyphenyl) adipate.
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1.4. Toco heroIs, for example a-tocopherol, 0-tocopherol, y-tocopherol, S-
tocopherol and
mixtures thereof (Vitamin E).
1.5. Hvdroxylated thiodighsnvl ethers, for example 2,2'-thiobis(6-tert-butyl-4-
methylphenol), 2,2'-
thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-
thiobis(6-tert-butyl-2-
methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-
hydroxyphe-
nyl)disulfide.
1.6. AlkylidenebisQhenols, for example 2,2'-methylenebis(6-tert-butyl-4-
methylphenol), 2,2'-
methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-
methylcyclohexyl)-
phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-
nonyl-4-me-
thylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-
ethyiidenebis(4,6-di-tert-butylphe-
noI), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methyienebis[6-
(a-methylbenzyl)-4-
nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-
methylenebis(2,6-
di-tert-butyiphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1 -
bis(5-tert-butyl-4-
hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-
4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyi-
4-hydroxy-2-methyl-
phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-
4'-
hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-
phenyl)dicyclopentadiene, bis[2-(3'-
tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-
methylphenyl]terephthalate, 1,1-bis-(3,5-
dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-
hydroxyphenyl)propane, 2,2-bis-(5-
tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecyimercaptobutane, 1,1,5,5-tetra-
(5-tert-butyt-4-
hydroxy-2-methylphenyl)pentane.
1.7. O-. N- and S-benzvl comuounds, for example 3,5,3',5'-tetra-tert-butyi-
4,4'-dihydroxydibenzyl
ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-
hydroxy-3,5-di-tert-
butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-
hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-
hydroxybenzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxvbenzv, .ated malonates, for example dioctadecyl-2,2-bis-(3,5-di-
tert-butyl-2-hy-
droxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-
malonate, di-
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dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
bis[4-(1,1,3,3-te-
tramettiyi butyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hvdroxvbenzyl compQunds, for example 1,3,5-tris-(3,5-di-tert-
butyl-4-hydroxy-
benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-
2,3,5,6-tetrame-
thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine Comp4unds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-
butyl-4-hydroxy-
anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-
hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,
2,4,6-tris(3,5-di-tert-
butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-
hydroxyben-
zyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-
dimethylbenzyl)isocyanurate, 2,4,6-tris-
(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-
tert-butyl-4-hydroxy-
phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-
hydroxybenzyl)iso-
cyanurate.
1.11. Benzvtohosphqnates, for example dimethyl-2,5-di-tert-butyl-4-
hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-
butyl-4-hy-
droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-
methylbenzylphosphonate, the
calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-
hydroxybenzyiphosphonic acid.
1.12. AcvlaminQrahenols, for example 4-hydroxylauranilide, 4-
hydroxystearanilide, octyl N-(3,5-
di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of 8-(3.5-di-tert=butyl-4-hydrogyohenyl)orQoionic acid with mono-
or polyhydric
alcohols, 'e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-
hexanediol, 1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene
glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,
N,N'-bis(hy-
droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylol-
propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of f~-(5-tert-butvi-4-hydroxy-3-methyll2henvllQrooionic acid with
mono- or polyhydric
alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-
hexanediol, 1,9-
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nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene
glycol, - triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-bis-
(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol, trimethyl-
olpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of 8-(3 5-dicvclohexvl-4-hy~iroxyphenyl) rp oDjonic acid with
mono- or polyhydric
alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, tri-
ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-
bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-
1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxvahenyI acetic acid with mono- or
polyhydric alcohols,
e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-
nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene
glycol, triethylene
glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-
bis(hydroxyethyl)oxamide, 3-
thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-
hydroxymethyl-l-
phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of Q-(3.5-di-tert-butvl-4-hvdroxyphenyllprooionig acid e.g. N,N'-
bis(3,5-di-tert-butyl-
4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-
hydroxy-
phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)-
hydrazide, N,N'-bis[2-(3-(3,5-di-tert-butyl-4-
hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau'
gard XL-1 supplied by Uniroyal).
1.18. Ascd.rbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenyienediamine,
N,N'-di-sec-butyl-
p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-
bis(1-ethyl-3-
methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicy-
clohexyl-p-phenylenediamine, N,N'-diphenyi-p-phenylenediamine, N,N'-bis(2-
naphthyl)-p-
phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-
dimethylbutyl)-N'-phenyl-
p-phenylenediamine, N-(1 =methylheptyl)-N'-phenyl-p-phenylenediamine, N-
cyclohexyl-N'-
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phenyi-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-
N,N'-di-sec-
butyl-p=phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-
isopropoxydiphenylamine,
N-phenyl-l-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-
naphthylamine,
octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-
butylaminophenol, 4-
butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octa-
decanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-
dimethylaminomethyl-
phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-
tetramethyl-4,4'-
diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-
bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-
phenyl-1 -
naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-
octyldiphenylamines, a mixture
of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated
dodecyldiphenylamines, a mixture of mono- and dialkylated
isopropyvisohexyldiphenylamines, a
mixture of mono- und dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-
dimethyl-4H-1,4-
benzothiazine, phenothiazine, a mixture of mono- und dialkylated tert-
butyl/tert-
octyiphenothiazines, a mixture of mono- und dialkylated tert-octyl-
phenothiazines, N-
allylphenothiazin, N,N,N',N'-tetraphenyl-l,4-diaminobut-2-ene, N,N-bis(2,2,6,6-
tetramethyl-
piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-
yl)sebacate, 2,2,6,6-
tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV absorbers and liaht stabilisers
2.1. 2-(2'-Hydroxvphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-
methylphenyl)-benzo-
triazole, 2-(3',5'-di-tert-butyi-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-
butyl-2'-hydroxyphe-
nyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-
tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-
butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-
5'-methylphenyl)-5-
chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-
hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-
4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-
hydroxyphenyl)benzotriazole, 2-(3',5'-bis-
(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-
octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-
(2-ethylhexyloxy)-
carbonylethyi]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-
methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-meth-
oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbonyl-
ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)carbonylethyl]-2'-hydroxy-
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phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-
hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-
bis[4-(1,1,3,3-
tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product
of 2-[3'-tert-butyl-5'-
(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene
glycol 300;
[R-CH2CH2 COO-CH2CH2+ where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-
2
ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-
phenyl]-
benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(a,a-
dimethylbenzyl)-phenyl]ben-
zotriazole.
2.2. 2-Hydroxvbenzoohenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy,
4-decyloxy,
4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy
derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-
tertbutyl-phenyl
salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl)
resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-
hydroxybenzoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-
hydroxybenzoate, 2-
methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Ac Iryates, for example ethyl a-cyano-R,P-diphenylacrylate, isooctyl a-
cyano-O,O-diphe-
nyiacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-R-methyl-p-methoxy-
cinnamate,
butyl a-cyano-[i-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-
methoxycinnamate
and N-(R-carbomethoxy-R-cyanovinyl)-2-methylindoline.
2.5. Nickel communds, for example nickel complexes of 2,2'-thio-bis-[4-
(1,1,3,3-tetramethyl-
butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional
ligands such as n-
butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate,
nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-
hydroxy-3,5-di-tert-
butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-
methylphenyl
undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole,
with or without
additional ligands.
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2.6. Stericallv hindered amines, for example bis(2,2,6,6-tetramethyl-4-
piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-
piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-
pentamethyl-4-piperidyl) n-
butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-
hydroxyethyl)-2,2,6,6-
tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic
condensates of N,N'-
bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-
2,6-dichloro-
1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-
piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-ethanediyi)-bis(3,3,5,5-
tetrame-
thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-
2,2,6,6-tetramethyl-
piperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-
tert-butylbenzyl)-
malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,
bis(1-octyloxy-
2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-
tetramethylpiperidyl)succinate,
linear or cyclic condensates of N,N'-bis-(2,2,6,6-tetramethyl-4-
piperidyl)hexamethylenediamine
and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-
bis(4-n-butylamino-
2,2,6,6-tetramethylpiperidyl )-1,3,5-triazine and 1,2-bis(3-
aminopropylamino)ethane, the
condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentarnethylpiperidyl)-
1,3,5-triazine and
1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-
1,3,8-
triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-
piperidyl)pyrrolidin-2,5-
dione, 3-dodecyl-l-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a
mixture of 4-
hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation
product of N,N'-
bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-
2,6-dichloro-
1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane
and 2,4,6-
trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine
(CAS Reg. No.
[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N-
(1,2,2,6,6-
pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-l-
oxa-3,8-diaza-4-
oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-
l-oxa-3,8-diaza-
4-oxospiro [4,5]decane und epichlorohydrin, 1, 1 -bis(1,2,2,6,6-pentamethyl-4-
piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-
bis(2,2,6,6-tetramethyl-
4-piperidyl)hexamethylenediamine, diester of 4-methoxy-methylenemalonic acid
with 1,2,2,6,6-
pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-
tetramethyl-4-
piperidyl)]siloxane, reaction product of maleic acid anhydride-a-olefin-
copolymer with 2,2,6,6-
tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
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2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide,
2,2'-dioctyloxy-5,5'-
di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-
ethyloxanilide, N,N'-
bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and
its mixture with 2-
ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-
disubstituted oxanilides
and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-
octyloxyphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 2-(2,4-
dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-
4-propyl-
oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis(4-
methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 2-[2-
hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-
triazine, 2-[2-
hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-
triazine, 2-[4-
(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-
dimethylphenyl)-1,3,5-
triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-
dimethylphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-
(2-hydroxy-4-
methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-
hydroxy-
propoxy)pheny!]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-
phenyl-1,3,5-
triazine, 2,{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-
4,6-bis(2,4-
dimethyiphenyl)-1,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-
salicyloyl hydrazine,
N,N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl) hydrazine, 3-
salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide,
isophthaloyl
dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyl-
oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and Qhosahonites, for example triphenyl phosphite, diphenyl
alkyl phosphites,
phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,
trioctadecyl phos-
phite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)
phosphite, diisodecyl
pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol
diphosphite, bis(2,6-di-
tert-butyl-4-methylphenyl)-pentaerythritoi diphosphite,
diisodecyloxypentaerythritol diphosphite,
CA 02299754 2000-02-23
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bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythrito! diphosphite, bis(2,4,6-
tris(tert-butyl-
phenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite,
tetrakis(2,4-di-tert-butylphenyl)
4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-
dibenz[d,g]-1,3,2-
dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,
bis(2,4-di-tert-butyl-6-
methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-
dibenz(d,g]-1,3,2-
dioxaphosphocin, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyi-1,1'-
biphenyi-2,2'-
diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-
diyl)phosphite, 5-butyl-5-
ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
Especially preferred are the following phosphites:
Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168, Ciba-Geigy),
tris(nonylphenyl) phosphite,
(CH3)3C ~ C(CH3)3 (CH3)3C C(CH3)3
O` O
(A) H3C-CH P-F P-O-CH2CH2 N (8)
O '' O
(CH3)3C
C (CH3)3 C(CH3)3
(CH3)3C 3
(CH3)3C C(CH3)3
O
P- O- CH2CH(C4H9)CH2CH3 (C)
O
(CH3)3C
C(CH3)3
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O 'xii> (CH3)3C', ~ ~ O-P` -OO (p)
C(CH3)3 (CH3)3C
C(CH3)3 (CH3)3C
/ 0 0
H3C ~~ O- P
\ x f P- O CH3
- O p (E)
C(CH3)3 (CH3)3C
CI H3
H3C-C-CH3
(F) H37Ct8 O-P 0 0 P-O-C18H37 O P-OCH2CH3 (G)
O O HsC
H C~C CH3
3 CH3 2
5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-
diethylhydroxylamine, N,N-
dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-
ditetradecylhydroxylamine, N,N-
dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-
octadecylhydrox-
ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
derived from
hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-
nitrone, N-octyl-
alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-
tridcyl-nitrone, N-
hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-
hexadecyl-alpha-
heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-
heptadecyl-
nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-
dialkylhydroxylamine
derived from hydrogenated tallow amine.
7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl
thiodipropionate.
CA 02299754 2000-02-23
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8. Peroxide scavengers, for example esters of 0-thiodipropionic acid, for
example the lauryl,
stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercapto-
benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide,
pentaerythritol tetrakis((3-
dodecylmercapto)propionate.
9. Polyamide stabilisers, for example, copper salts in combination with
iodides and/or phos-
phorus compounds and salts of divalent manganese.
10. Ba ic co-stabilisers, for example, melamine, polyvinylpyrrolidone,
dicyandiamide, triallyl
cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali
metal salts and alkaline earth metal salts of higher fatty acids for example
calcium stearate, zinc
stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium
paimitate, antimony pyrocatecholate or zink pyrocatecholate.
11. Nucleating aoents, for example, inorganic substances such as talcum, metal
oxides such as
titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of,
preferably, alkaline
earth metals; organic compounds such as mono- or polycarboxylic acids and the
salts thereof,
e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium
succinate or sodium
benzoate; polymeric compounds such as ionic copolymers (ionomers). Especially
preferred are
1,3:2,4-bis(3',4'-dimethylbenzyfidene)sorbitol, 1,3:2,4-
di(paramethyldibenzylidene)sorbitol, und
1,3:2,4-di(benzylidene)sorbitol.
12. Fillers and reinforcinq agents, for example, calcium carbonate, silicates,
glass fibres, glass
bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and
hydroxides, carbon black,
graphite, wood flour and flours or fibers of other natural products, synthetic
fibers.
13. Other additives, for example, plasticisers, lubricants, emulsifiers,
pigments, rheology
additives, catalysts, flow-control agents, optical brighteners, flameproofing
agents, antistatic
agents and blowing agents.
14. Benzofuranones and indotinones, for example those disclosed in U.S.
4,325,863;
U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611;
CA 02299754 2000-02-23
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DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-
acetoxyethoxy)-
phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-
stearoyloxyethoxy)phe-
nyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-
hydroxyethoxy]phenyl)benzofuran-2-one],
5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-
dimethylphenyl)-5,7-di-
tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-
butyl-benzofuran-2-
one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-
dimethylphenyl)-5,7-di-
tert-butyl-benzofuran-2-one.
15. Amine oxides, for example amine oxide derivatives as disclosed in U.S.
Patent Nos.
5,844,029 and 5,880,191, didecyl methyl amine oxide, tridecyl amine oxide,
tridodecyl amine
oxide and trihexadecyl amine oxide. U.S. Patent Nos. 5,844,029 and 5,880,191
disclose the
use of saturated hydrocarbon amine oxides towards the stabilization of
thermoplastic resins. It
is disclosed that the thermoplastic compositions may further contain a
stabilizer or mixture of
stabilizers selected from phenolic antioxidants, hindered amine light
stabilizers, ultraviolet light
absorbers, organic phosphorus compounds, alkaline metal salts of fatty acids
and
thiosynergists. The co-use of amine oxides with other stabilizers towards
stabilizing polyolefins
is not exemplified.
The amine oxides costabilizers are of Formula (I)
O
E/ E3 (j)
E2
wherein
E, and E2 are independently a straight or branched chain alkyl of 6 to 36
carbon atoms, aryl
of 6 to 12 carbon atoms, aralkyl of 7 to 36 carbon atoms, alkaryl of 7 to 36
carbon atoms,
cycloalkyl of 5 to 36 carbon atoms, alkcycloalkyl of 6 to 36 carbon atoms or
cycloalkylalkyl of 6
to 36 carbon atoms;
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E3 is a straight or branched chain alkyl of 1 to 36 carbon atoms, aryl of 6 to
12 carbon
atoms, aralkyl of 7 to 36 carbon atoms, alkaryl of 7 to 36 carbon atoms,
cycloalkyl of 5 to 36
carbon atoms, alkcycloalkyl of 6 to 36 carbon atoms or cycloalkylalkyl of 6 to
36 carbon atoms;
with the proviso that at least one of E,, E2 and E3 contains a carbon-hydrogen
bond; and
wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and
cycloalkylalkyl groups may
be interrupted by one to sixteen -0-, -S-, -SO-, -S02-, -COO-, -OCO-, -CO-, -
NE4-, -CONE4- and
-NE4CO- groups, or wherein said alkyl, aralkyl, alkaryl, cycloalkyl,
alkcycloalkyl and
cycloalkylalkyl groups may be substituted by one to sixteen groups selected
from -OE4i -SE4,
-COOE4, -OCOE4, -COE4, -N(E4)2, -CON(E4)2, -NG4COE4 and 5- and 6-membered
rings
containing the -C(CH3)(CH2Rx)NL,(CH2RX)(CH3)C- group or wherein said alkyl,
aralkyl, alkaryl,
cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups are both interuppted and
substituted by the
groups mentioned above; and
wherein
E4 is independently hydrogen or alkyl of 1 to 8 carbon atoms;
Rx is hydrogen or methyl, preferably hydrogen;
L, is a C1.30 straight or branched chain alkyl moiety, a-C(O)R30 moiety
wherein R30 is a
C1.30 straight or branched chain alkyl group, or a-OR3o moiety wherein R30 is
a C1.30 straight or
branched chain alkyl group; and
wherein said aryl groups may be substituted by one to three halogen, alkyl of
1 to 8 carbon
atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof.
A preferred structure of formula (I) is where E, and E2 are independently
benzyl or
substituted benzyl. It is also possible for each of EI, E2, and E3 to be the
same residue. E, and
E2 are also preferably alkyl groups of 8 to 26 carbon atoms and most
preferably alkyl groups of
to 26 carbon atoms and E3 is preferably an alkyl group of 1 to 22 carbon atoms
and most
preferably methyl or substituted methyl. Also, preferred amine oxides include
those wherein E
E2, and E3 are the same alkyl groups of 6 to 36 carbon atoms. Preferably, all
of the
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aforementioned residues for E,, E2, and E3 are saturated hydrocarbon residues
or saturated
hydrocarbon residues containing at least one of the aforementioned -0-, -S-, -
SO-,
-C02-, -CO-, or -CON- moieties. Those skilled in the art will be able to
envision other useful
residues for each of E,, E2, and E3 without detracting from the present
invention.
The saturated amine oxides may also includes poly(amine oxides). By poly(amine
oxide) is
meant tertiary amine oxides containing at least two tertiary amine oxides per
molecule.
Illustrative poly(amine oxides), also called "poly(tertiary amine oxides)",
include the tertiary
amine oxide analogues of aliphatic and alicyclic diamines such as, for
example, 1,4-
diaminobutane; 1,6-diaminohexane; 1, 1 0-diaminodecane; and 1,4-
diaminocyclohexane, and
aromatic based diamines such as, for example, diamino anthraquinones and
diaminoanisoles.
Also included are tertiary amine oxides derived from oligomers and polymers of
the
aforementioned diamines. Useful amine oxides also include amine oxides
attached to
polymers, for example, polyolefins, polyacrylates, polyesters, polyamides,
polystyrenes, and the
like. When the amine oxide is attached to a polymer, the average number of
amine oxides per
polymer can vary widely as not all polymer chains need to contain an amine
oxide. All of the
aforementioned amine oxides may optionally contain at least one -0-, -S-, -SO-
, -C02-,
-CO-, or -CONE4- moiety. In a preferred embodiment, each tertiary amine oxide
of the
polymeric tertiary amine oxide contains a C, residue.
The groups E,, E2 and E3 of formula (I) may be attached to a molecule
containing a
hindered amine. Hindered amines are known in the art and the amine oxide of
the present
invention may be attached to the hindered amine in any manner and structural
position of the
hindered amine. Useful hindered amines when part of a compound of the amine
oxide
coadditive include those of the general formulas (II) and (III):
CA 02299754 2000-02-23
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RxCH2 CH3 RX
L (II)
RxCH2 CH3
3
RXCH2 CH
Li N N (III)
/yi
RxCH2 CH3 O
wherein L, and Rx are as described above. Also included are amine oxides
containing
more than one hindered amine and more than one saturated amine oxide per
molecule. The
hindered amine may be attached to a poly(tertiary amine oxide) or attached to
a polymeric
substrate, as discussed above.
The co-stabilizers, with the exception of the benzofuranones listed under 11,
are added
for example in concentrations of 0.01 to 10%, relative to the total weight of
the material to be
stabilized.
Further preferred compositions comprise, in addition to components (a) and (b)
further
additives, in particular phenolic antioxidants, light stabilizers or
processing stabilizers.
Particutarly preferred additives are phenolic antioxidants (item 1 of the
list), sterically hin-
dered amines (item 2.6 of the list), phosphites and phosphonites (item 4 of
the list) and per-
oxide-destroying compounds (item 5.) of the list.
CA 02299754 2000-02-23
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Additional additives (stabilizers) which are also particularly preferred are
benzofuran-2-
ones, such as described, for example, in US-A-4,325,863, US-A-4,338,244 or US-
A-5,175,312.
The phenolic antioxidant of particular interest is selected from the group
consisting of n-
octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl
tetrakis(3,5-di-tert-butyl-
4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-
hydroxybenzylphosphonate, 1,3,5-
tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-
tert-butyl-4-
hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di=tert-butyl-4-
hydroxybenzyl)benzene,
3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-
di-tert-butyl-p-
cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-
4-tert-butyl-3-
hydroxybenzyl)isocynurate, 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-
butylphenyl)butane, 1,3,5-tris[2-
(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanur ate, 3,5-di-(3,5-
di-tert-butyl-4-
hydroxybenzyl)rnesitol, hexamethylene bis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate), 1-(3,5-
di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N'-
hexamethylene-bis(3,5-di-tert-
butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-
hydroxybenzyl-
phosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate],
octyl 3,5-di-tert-butyl-
4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamoyl)hydrazide, and
N, N'-bis[2-(3, 5-di-te rt-butyl-4-hyd roxyhyd roci nnamoyloxy)-ethyl]-
oxamide.
A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-
tert-butyl-4-
hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,
1,3,5-tri-
methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-
tert-butyl-4-
hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-
bis(4,6-di-tert-
butylphenol).
The hindered amine compound of particular interest is selected from the group
consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
bis(1,2,2,6,6-pentamethylpiperidin-4-yi) sebacate,
di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-
hydroxybenzyl)butylmalonate,
4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-
tetramethylpiperidine, 3-n-octyl-
7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,
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1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane, 2,2,4,4-tetramethyl-7-
oxa-3,20-diaza-21-
oxodispiro[5.1.11.2] heneicosane, polycondensation product of 2,4-dichloro-6-
tert-octylamino-s-
triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
polycondensation
product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid,
polycondensation product of 4,4'-hexamethylenebis-(amino-2,2,6,6-
tetramethylpiperidine) and
1,2-dibromoethane,
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate,
tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate,
polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-
hexarnethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N',N",N"'-
tetrakis[(4,6-bis(butyl-
1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-y I]-1,10-diamino-4,7-
diazadecane,
polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-
hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine), mixed [2,2,6,6-
tetramethylpiperidin-
4-yI/R,[i,R',[i'-tetramethyl-3,9-(2,4,8 ,10-tetraoxaspiro[5.5]-undecane)
diethyl] 1,2,3,4-
butanetetracarboxylate,
mixed [1,2,2,6,6-pentamethylpiperidin-4-yl/[i,0,(3',[3'-tetramethyl-3,9-(2,4
,8,10-tetraoxaspiro[5.5]-
undecane)diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis(2,2,6,6-
tetramethyl-
piperidin-4-carboxylate),
4,4'-ethylenebis(2,2,6,6-tetramethytpiperazin-3-one), N-2,2,6,6-
tetramethylpiperidin-4-yi-n-
dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yi-n-
dodecylsuccinimide, N-1-acetyl-
2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide, 1-acetyl3-dodecyl-
7,7,9,9-tetramethyl-
1,3,8-triazaspiro[4.5]decane-2,4-dione, di-(1-octyloxy-2,2,6,6-
tetramethylpiperidin-4-yl)
sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethyipiperidin-4-yl) succinate, 1 -
octyloxy-2,2,6,6-
tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-
diyl][2-(1-cyclohexyloxy-
2,2,6,6-tetramethytpfperidin-4-yl)imino-hexamethylene-(4-(1-cyclohexyloxy-
2,2,6,6-tetramethyl-
piperidin-4-yl)imino], 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-
tetramethylpiperidin-4-yl)-n-
butylamino]-s-triazine,
2-(2-hydroxyethylamino)-4,6-bis{N-[1-(cyclohexyloxy)-2,2,6,6-
tetramethylpiperidin-4-yi]-
butylamino-s-triazine, oligomer of N-{[2-(N-2,2,6,6-tetramethylpiperidin-4-
yl)butylamino]-s-
triazin-4-yl}-N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine
terminated with 2,4-
bis(dibutylamino)-s-triazin-6-yl, N,N',N"-tris{2,4-bis[N-(1,2,2,6,6-
pentamethylpipe(din-4-yl)butyl-
amino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine, N,N',N"'-tris{2,4-
bis[N-(1,2,2,6,6-
CA 02299754 2000-02-23
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pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3'-
ethylenediiminodipropylamine and
N, N',N",N"'-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-
yl)butylamino]-s-triazin-6-yl}-
3,3'-ethylenediiminodipropylamine; N,N',N"-tris{2,4-bis[N-(1-cyclohexyloxy-
2,2,6,6-tetramethyl-
piperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine,
N,N',N"'-tris{2,4-
bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yi)butylamino]-s-triazin-
6-yl)-3,3'-ethylene-
diiminodipropylamine, N,N',N",N'"-tetrakis{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-
tetramethyl-
piperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine,
oligomer of N-{2-[(1-
propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N'-
bis(1-propoxy-2,2,6,6-
tetramethylpiperidin-4-yl)-1,6-hexanediamine terminated with 2,4-
bis(dibutylamino)-s-triazin-6-yl,
or the condensation product of 2-morpholino-4,6-dichloro-s-triazine with N,N'-
bis(1,2,2,6,6-
pentamethylpiperidin-4-yl)-1,6-hexanediamine.
A most preferred hindered amine compound is bis(2,2,6,6-tetramethylpiperidin-4-
yl)
sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-
pentamethylpiperidin-
4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensation
product of 1-(2-
hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the
polycondensation
product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-
hexamethylenebis(amino-2,2,6,6-
tetramethylpiperidine), N,N',N",N"'-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-
pentamethylpiperidin-4-
yl)amino)- s-triazine-2-yl]-1,10-diamino-4,7-diazadecane. di-(1-octyloxy-
2,2,6,6-tetramethyl -
piperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-
yl) succinate, 1-
octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-
triazin-2,4-diyl][2-(1-
cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethyiene-[4-(1-
cyclohexyloxy-
2,2,6,6-tetramethylpiperidin-4-yl)imino], or 2,4,6-tris[N-(1-cyclohexyloxy-
2,2,6,6-tetramethyl-
piperidin-4-yl)-n-butylamino]-s-triazine.
The instant composition can additionally contain another UV absorber selected
from the
group consisting of the s-triazines, the oxanilides, the hydroxybenzophenones,
benzoates and
the a-cyanoacrylates.
Particularly, the instant composition may additionally contain an effective
stabilizing
amount of at least one other 2-hydroxyphenyl-2H-benzotriazole; another tris-
aryl-s-triazine; or
hindered amine or mixtures thereof.
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Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from the group
consisting
of
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
2-[2-hydroxy-3,5-di (a,a-dimethylbenzyl)phenyi]-2H-benzotriazole;
2-[2-hydroxy-3-(a,a-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;
2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-
octa(ethyleneoxy)carbonyl)ethyl]phenyl}-
2H-benzotriazole; and
2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-
benzotriazole.
Preferably the 2-hydroxyphenyl-2H-benzotriazole may also be selected from the
group
consisting of
(a) 5-trifluoromethyl-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-
benzotriazole;
(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazoie;
(c) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;
(d) 2,2'-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-
octylphenol];
(e) methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2'-[4-tert-octyl-
6-(5-trifluoro-
methyl-2H-benzotriazol-2-yl)phenol];
(f) 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-
hydroxyhydrocinnamic acid;
(g) methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-
hydrocinnamate;
(h) isooctyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-
hydrocinnamate;
(i) 5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-
benzotriazole;
(j) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-
benzotriazole;
(k) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-
benzotriazole;
(I) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-
benzotriazole;
(m) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-
benzo-
triazole;
(n) 5-trifluoromethyi-2-(2-hydroxy-3-a-cumyl-5-tert-butylphenyl)-2H-
benzotriazole;
(o) 5-trifluoromethyl-2-(2-hydroxy-3-a-cumyl-5-nonylphenyl)-2H-benzotriazole;
(p) 5-trifluoromethyl-2-(2-hydroxy-3-a-cumyl-5-(2-hydroxyethyl)phenyl]-2H-
benzotriazole;
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(q) 5-trifluoromethyl-2-[2-hydroxy-3-a-cumyl-5-(3-hydroxypropyl)phenyl]-2H-
benzo-
triazole;
(r) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
(s) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
(t) 5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methytphenyl) 2H-benzotriazole;
(u) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-
benzo-
triazole;
(v) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-
benzo-
triazole;
(w) 5-trifiuoromethyl-2-(2-hydroxy-5-(2-hydroxyethyl)phenyl)-2H-benzotriazole;
(x) 5-trifluorornethyl-2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole;
(y) 5-fluoro-2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole;
(z) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole;
(aa) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
(bb) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;
and
(cc) 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.
Preferably, the other tris-aryl-s-triazine is selected from the group
consisting of
2,4-bis(2,4-dimethyl phenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;
2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;
2,4-bis(2,4-di methyl phenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-
hydroxypropoxy)-
phenyl]-s-triazine; and
2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-
tetramethylpiperidin-
4-yl)amino]-s-triazi ne.
Other materials to be stabilized according to the invention are recording
materials. By such
materials are meant, for example, those described in Research Disclosure 1990,
31429 (pages
474-480) for photographic reproduction and other reprographic techniques.
The novel recording materials comprise, for example, those for pressure-
sensitive copying
systems, microcapsule photocopier systems, heat-sensitive copier systems,
photographic
material and ink-jet printing.
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The novel photographic material can be a black and white or a colour
photographic material;
colour photographic material is preferred. Further details on the structure of
colour photographic
material, and the components which can be employed in the novel material, can
be found, inter
alia, in US-A-5,538,840, column 27, line 25, to column 106, line 16, and in
the publications cited
therein. Application of the novel compounds is essentially as
described for UV absorbers or hindered amine stabilizers
in this reference. Further important components, especially couplers, are
described in US-
5,578,437.
The acrylic resin lacquers which can be stabilized against light, moisture and
oxygen in
accordance to the instant invention are conventional acrylic resin stoving
lacquers or
thermosetting resins including acrylic/melamine systems which are described,
for example, in H.
Kittel's "Lehrbuch and Beschichtungen", Vol. 1, Part 2 on pages 735 and 742
(Berlin 1972),
"Lackkunstharze" (1977) by H. Wagner and H. F. Sarx on pages 229-238, and in
S. Paul's
"Surface Coatings: Science and Technology", (1985).
The polyester lacquers which can be stabilized against the action of light and
moisture
are conventional stoving lacquers described e-.g: in H. Wagner and H. F. Sarx,
op. cit., on
pages 86-99.
The alkyd resin lacquers which can be stabilized against the action of light
and moisture
in accordance with the instant invention.are the conventional stoving lacquers
which are used in
particular for coating automobiles (automobile finishing lacquers), for
example lacquers based
on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and
H. F. Sarx,
"Lackkunstharze" (1977), pages 99-123). Other crosslinking agents include
glycoluril resins,
blocked or unblocked isocyanates or epoxy resins. Other lacquers which can be
stabilized
include those with crosslinkable functionalities such as carbamate and
siloxane.
The lacquers stabilized in accordance with the invention are suitable both for
metal finish
coatings and solid shade finishes, especially in the case of retouching
finishes, as well as
various coil coating applications. The lacquers stabilized in accordance with
the invention are
preferably applied in the conventional manner by two methods, either by the
single-coat method
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or by the two-coat method. In the latter method, the pigment-containing base
coat is applied first
and then a covering coat of clear lacquer over it.
Although major emphasis in this application is directed to acid-catalyzed
baked finishes,
it is also to be noted that the compounds of the present invention are
applicable for use in non-
acid catalyzed thermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd,
acrylic and
polyester resins, optionally modified with silicon, isocyanates or
isocyanurates. The epoxy and
epoxy-polyester resins are crosslinked with conventional crosslinkers such as
acids, acid
anhydrides, amines and the like. Correspondingly, the epoxide may be utilized
as the
crosslinking agent for various acrylic or polyester resin systems that have
been modified by the
presence of reactive groups on the backbone structure.
The amount of instant stabilizer compound used is 0.1 to 5% by weight, based
on the
solvent-free binder, preferably 0.5 to 2% by weight. The binders can be
dissolved or dispersed
in customary organic solvents or in water or can be solvent-free.
When used in two-coat finishes, the compounds of the instant invention can be
incorporated in the clear coat or both in the clear coat and in the pigmented
base coat.
To attain maximum light stability, the concurrent use of other conventional
light
stabilizers can be advantageous. Examples are UV absorbers of the
benzophenone,
benzotriazole, acrylic acid derivatives, oxalanilide, aryl-s-triazine or metal-
containing types (e.g.
organic nickel compounds). In two-coat systems, these additional light
stabiliiers can be added
to the clear coat and/or the pigmented base coat.
If such combinations of stabilizers are used, the sum of all light stabilizers
is 0.2 to 20%
by weight, preferably 0.5 to 5% by weight, based on the film-forming resin.
When water-soluble, water miscible or water dispersible coating are desired
ammonium
salts of acid groups present in the resin are formed. Powder coating
composition can be
prepared by reacting glycidyl methacrylate with selected alcohol components.
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It is also contemplated that the instant compounds would find particular value
when used
with water-soluble inks and related polar oriented utilities where the
presence of the OH moiety
would pr.ovide for better compatibility and properties related to such aqueous
environments.
The instant compounds are also useful in the stabilization of acid catalyzed
thermoset
resins which are disclosed in United States Patent No. 5,112,89Q.
These resins are used in baked enamels or stoving lacquers. Hindered amine
light
stabilizaers are well known to be effective in stabilizing a host of organic
substrates including
polymers from the deleterious effects of oxygen and light. Such hindered amine
light stabilizers
have been used in the stabilization of hot-crosslinkable alkyd or acrylic
metallic stoving lacquers
(see U.S. Patent No. 4,426,472) and in stabilizing acid-catalyzed stoving
lacquers based on hot-
crosslinkable acrylic polyester or alkyl resins (see U.S. Patent Nos.
4,344,876 and 4,426,471).
None of the hindered amine light stabilizers of these patents possess
structures having an 0-
substituted hydroxyl group substituted directly on the N-atom of the hindered
amine. The instant
compounds have such substitution and additionally are even less basic than the
NOR
compounds described in U.S. Patent No. 5,112,890 as is seen in instant working
Example 114.
In their industrial uses, enamels with high solids content based on
crossiinkable acrylic,
polyester, urethane or alkyd resins are cured with an additional acid
catalyst. Light stabilizers
containing a basic nitrogen group are generally iess than satisfactory in this
application.
Formation of a salt between the acid catalyst and the light stabilizer leads
to incompatibility or
insolubility and recipitation of the salt and to a reduced level of cure and
to reduced light
protective action and poor resistance to moisture.
The acid catalyzed thermoset enamels must be stabilized in order to function
acceptably
in end-use applications. The stabilizers used are hindered amines, preferably
those substituted
on the N-atom by an inert blocking group in order to prevent precipitation of
the basic amine
with the acid catalyst with a concomitant retardation in cure, optionally in
combination with UV
absorbers as described above.
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The stabilizers are needed to impart greater retention of durability to the
cured enamels
(as measured by 20 gloss, distinction of image, cracking or chalking); the
stabilizers must not
retard cure (normal bake for auto finishes at 121 C; and low bake repair at
82 C) as measured
by hardness, adhesion, solvent resistance and humidity resistance; the enamel
should not
yellow on curing and further color change on exposure to light should be
minimized; the
stabilizers should be soluble in the organic solvents normally used in coating
applications, such
as methyl amyl ketone, xylene, n-hexyl acetate, alcohol and the like.
The instant hindered amine light stabilizers on the N-atom by an 0-substituted
moiety
containing a free hydroxyl group fulfill each of these requirements and
provide alone or in
combination with a UV absorber outstanding light stabilization protection to
the cured acid
catalyzed thermoset enamels.
The instant invention also pertains to resin systems capable of being fully
cured under
ambient conditions. For example, applicable resins include alkyd, acrylic,
polyester and epoxide
resins as described in S. Paul's "Surface Coatings: Science and Technology"
(1985), pages 70-
310. Various acrylic and modified acrylic resins are described in H. Kittel's
"Lehrbuch der Lacke
unde Beschichtungen", Vol. 1, Part 2, on pages 735 and 742 (Berlin 1972), and
in "Lack-
kunstharze" (1977) by H. Wagner and H. F. Sarx, op. cit, on pages 229-238.
Typical
crosslinkable polyester resins which can be stabilized against the action of
light and moisture
are described e.g. in H. Wagner and H. F. Sarx, op. cit., on pages 86-99. The
unmodified and
modified alkyd resins which can be stabilized are conventional resins which
are used in trade
sales, maintenance and automotive refinish coatings. For example, such
coatings are based on
alkyd resins, alkyd/acrylic resins and alkyd/silicon reins (see H. Wagner and
H. F. Sarx, op. cit.,
pages 99-123) optionally crosslinked by isocyanates or epoxy resins.
In addition various acrylic lacquer coating compositions are disclosed in U.S.
Patent No.
4,162,249. Other acrylic/alkyd resins with polyisocyanate additives are
disclosed in U.S. Patent
No. 4,471,083; and acrylic resins containing either pendant amino ester groups
or glycidyl
groups are described in U.S. Patent No. 4,525,521.
The ambient cured coatings stabilized by the instant compounds are suitable
both for
metal finish coatings and solid shade finishes, especially in the case of
retouching finishes. The
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lacquers stabilized by the instant compounds are preferably applied in a
conventional manner
by two methods, either by the single-coat method or by the two-coat method. In
the latter
method, the pigment-containing base coat is applied first and a covering coat
of clear lacquer
applied over it. When used in two-coat finishes, the instant hindered amine
compound can be
incorporated in the clear coat or both in the clear coat and in the pigmented
base coat.
The instant invention also pertains to abrasion-resistant coating compositions
suitable
for coating over polycarbonates. Such coatings as described in U.S. Patent No.
5,214,085
comprise a silyl acrylate, aqueous colloidal silica, a photoinitiator and
optionally a polyfunctional
acrylate as well as UV absorbers. Such coatings provide resistance after
prolonged outdoor
exposure to sunlight, moisture, thermal cycling causing yellowing,
delamination and formation of
microcracks and decreasing transparency.
Related hindered amine stabilizers have been utilized individually and in
combination
with UV absorbers to improve the performance characteristics of ambient cured
coating
systems. Notwithstanding such improvements, there still exists a need to
further retard the
photooxidation and photodegradation of such ambient cured systems and thereby
provide
increased effectiveness by maintaining the physical integrity of the coatings.
Such effectiveness
can be manifested by prevention of embrittiement, cracking, corrosion,
erosion, loss of gloss,
chalking and yellowing of the coating.
It has now been determined that the aforementioned improvements canbe achieved
by
substitution of the N-atom of the hindered amines with an -OR moiety and by
the utilization of
such derivatives in ambient cured coating systems as is taught in United
States Patent
No. 5,124,378. The instant compounds are even less basic
than the compounds of U.S. 5,124,378 and are particularly well
suited for this task. In particular, the physical integrity of the coatings is
maintained to a higher
degree with significant reduction in loss of gloss and in yellowing.
Accordingly, the instant
invention relates to the use of the instant NOR compounds, where the R moiety
is further
substituted by a hydroxyl group, optionally together with further stabilizers,
for stabilizing
ambient cured coatings based on alkyd resins; thermoset acrylic resins;
acrylic alkyds; acrylic
alkyd or polyester resins optionally modified with silicon, isocyanates,
isocyanurates, ketimines
or oxazolidines; and epoxide resins crosslinked with carboxylic acids,
anhydrides, polyamines
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or mercaptans; and acrylic and polyester resin systems modified with reactive
groups in the
backbone thereof and crosslinked with epoxides; against the degradative
effects of light,
moisture and oxygen.
The instant invention also relates to electrodeposited coatings applied to
metal
substrates where various top coats may be applied thereover. The inclusion of
the instant
compounds in the E-coat provides delamination resistance to said E-coats. The
primary resins
in said E-coats are acrylic or epoxy resins. These E-coats are described in
European patent
application EP 0 576 943 Al.
The instant invention also pertains to UV-cured coating systems using
unsaturated
acrylic resins, polyurethane acrylates, epoxy acrylates, polyester acrylates,
unsaturated
polyester/styrene resins and silyl acrylates.
Powder Coatin4s
The instant invention also pertains to powder coating formulations which
require
resistance to photodegradation. Resin systems which would be applicable
include glycidal
methacrylate or acrylate-functional acrylic or acrylic hybrids, crosslinked
with diacids or
anhydrides; acid or anhydride functional acrylic or polyester resins
crosslinked with TGIC;
hydroxyl functional acrylic or polyester resins crosslinked with isocyanates.
The stabilized
coating may be a single layer applied to a substrate, or may be a clearcoat
applied over a
waterborne or solvent-borne basecoat.
The stabilized coating may also contain a UV absorber, consisting of one of
the
aforementioned compounds.
Radiation-Cured Systems
The instant invention also pertains to radiation-cured coating systems. These
systems
would consist of :
a. Ethylenically unsaturated polymerizable comopounds
b. At least one photoinitiator
.. . . . : , ... . ,,. . .. . .. . . .. ,. . . ... . . . . .. _ . . . . . : .
. . . . . . . . .. . . . _. .
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c. One or more of the instant stabilizing compounds
The coating composition may also include a UV absorbing stabilizer,
represented by one
of the classes mentioned..
The coating may also include pigments or other colorants designed to provide
opacity or
aesthetic properties.
The ethylenically unsaturated polymerizable compounds can contain one or more
than
one olefinic double bond. They may be low molecular (monomeric) or high
molecular
(oligomeric) compounds.
Typical examples of monomers containing one double bond are alkyl or
hydroxyalkyl
acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl and
2-hydroxyethyl
acrylate, isobornyl acrylate, and methyl and ethyl methacrylate. Further
examples of these
monomers are acrylonitrile, acrylamide, methacrylamide, N-substituted
(meth)acrylamides, vinyl
esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether,
styrene, aikylstyrenes,
halostyrenes, N-vinylpyrrolidone, vinyl chloride and vinylidene chloride.
Examples of monomers containing more than one double bond are ethylene glycol
diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate,
hexamethylene glycol
diacrylate, bisphenol A diacrylate, 4,4'-bis(2-
acryloyloxyethoxy)diphenylpropane,
trimethylolpropane triacrylate, pentaerythritol triacrylate and tetraacrylate,
pentaerythritol divinyl
ether, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate,
triallyl phosphate, triallyl
isocyanurate or tris(2-acryloylethyl)isocyanurate. Examples of high molecular
weight
(oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated
polyethers,
acrylated polyurethanes and acrylated polyesters. Further examples of
unsaturated oligomers
are unsaturated polyester resins, which are usually prepared from maleic acid,
phthalic acid and
one or more diols and which have molecular weights of greater than about 500.
Unsaturated
oligomers of this type are also known as prepolymers.
Typical examples of unsaturated compounds are esters of ethylenically
unsaturated
carboxylic acids and polyols or polyepoxides, and polymers containing
ethylenically unsaturated
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groups in the chain or in side groups, including unsaturated polyesters,
polyamides and
polyurethanes and copolymers thereof, polybutadiene and butadiene copolymers,
polyisoprene
and isoprene copolymers, polymers and copolymers containing (meth)acrylic
groups in side-
chains, as well as mixtures of one or more than one such polymer.
Illustrative examples of unsaturated carboxylic acids are acrylic acid,
methacrylic acid,
crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids such as
linolenic acid or oleic
acid. Acrylic and methacrylic acid are preferred.
Suitable polyols are aromatic and, preferably, aliphatic and cycloaliphatic
polyols.
Aromatic polyols are typically hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-bis(4-
hydroxyphenyl)propane, as well as novolacs and cresols. Polyepoxides include
those based on
the cited polyols, preferably on the aromatic polyols and epichlorohydrin.
Further suitable
polyols are polymers and copolymers which contain hydroxyl groups in the
polymer chain or in
side groups, for example polyvinyl alcohol and copolymers thereof or
hydroxyalkyl
polymethacrylates or copolymers thereof. Other suitable polyols are
oligoesters carrying
hydroxyl end groups.
Illustrative examples of aliphatic and cycloaliphatic polyols are
alkylenediols containing
preferably 2 to 12 carbon atoms, including ethylene glycol, 1,2- or 1,3-
propanediol, 1,2-, 1,3- or
1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene
glycol, triethylene
glycol, polyethylene glycols having molecular weights of preferably 200 to
1500, 1,3-
cyclopentanediol, 1,2-, 1,3-or 1,4-cyclohexanediol, 1,4-
dihydroxymethylcyclohexane, glycerol,
tris(O-hydroxyethyl)amine, trimethylolethane, trimethylolpropane,
pentaerythritol,
dipentaerythritol and sorbitol.
The polyols may be esterified partially or completely with one or with
different
unsaturated carboxylic acids, in which case the free hydroxyl groups of the
partial esters may be
modified, for example etherified, or esterified with other carboxylic acids.
Illustrative examples of esters are: Trimethylolpropane triacrylate,
trimethylolethane
triacrylate, trimethylolpropane trimethacrylate, trimethylolethane
trimethacrylate, tetramethylene
glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol
diacrylate,
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pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol
tetraacrylate,
dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol
tetraacrylate,
dipentaerythritol pentacrylate, dipentaerythritol hexacrylate,
tripentaerythritol octacrylate,
pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,
dipentaerythritol dimethacrylate,
dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate,
pentaerythritol
diitaconate, dipentaerythritol trisitaconate, dipentaerythritol
pentaitaconate, dipentaerythritol
hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-
butanediol
dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol
tetraacrylate,
pentaerythri:tol-modified triacrylate, sorbitol tetramethacrylate, sorbitol
pentacrylate, sorbitol
hexacrylate, oligoester acrylates and methacrylates, glycerol di- and-
triacrylate, 1,4-
cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene
glycol having
molecular weights of 200 to 1500, or mixtures thereof. Polyfunctional monomers
and oligomers
are available for example from UCB Chemicals, Smyrna, Georgia, and Sartomer,
Exton,
Pennsylvania.
Suitable ethylenically unsaturated polymerizable compounds are also the amides
of
identical or different unsaturated carboxylic acids of aromatic;
cycloaliphatic and aliphatic
polyamines containing preferably 2 to 6, more particularly 2 to 4, amino
groups. Exemplary of
such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3-
or 1,4-
butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine,
dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine,
phenylenediamine,
bisphenylenediamine, bis(O-aminoethyl) ether, diethylenetriamine,
triethylenetetramine, bis(0-
aminoethoxy)ethane or bis(O-aminopropoxy)ethane. Other suitable polyamines are
polymers
and copolymers which may contain additional amino groups in the side-chain and
oligoamides
containing amino end groups.
Exemplary of such unsaturated amides are: Methylenebisacrylamide, 1,6-
hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide,
bis(methacrytamidopropoxy)ethane, R-methacrylamidoethylmethacryiate, N-[(a-
hydroxyethoxy)ethyljacrylamide.
Suitable unsaturated polyesters and polyamides are derived typically from
maleic acid and
diols or diamines. Maleic acid can be partially replaced by other dicarboxylic
acids such as
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fumaric acid, itaconic acid, citraconic acid, mesaconic acid or chloromaleic
acid. To control the
reactivity of the polyester and to influence the crosslinking density and
hence the product
properties, it is possible to use in addition to the unsaturated dicarboxylic
acids different
amounts of saturated dicarboxylic acids such as phthalic acid, isophthalic
acid, terephthalic
acid, tetrahydrophthalic acid, succinic acid or adipic acid. The unsaturated
polyesters can be
used together with ethylenically unsaturated comonomers such as styrene. The
polyesters and
polyamides can also be derived from dicarboxylic acids and ethylenically
unsaturated diols or
diamines, especially from those with long chains containing typically from 6
to 20 carbon atoms.
Polyurethanes are typically those derived from saturated or unsaturated
diisocyanates and
unsaturated and saturated diols.
Suitable polyester acrylates or acrylated polyesters are obtained by reacting
oligomers,
typically epoxides, urethanes, polyethers or polyesters, with acrylates such
as hydroxyethyl
acrylate or hydroxypropyl acrylate.
Polybutadiene and polyisoprene and copolymers thereof are known. Suitable
comonomers
include olefins such as ethylene, propene, butene, hexene, (meth)acrylates,
acrylonitrile,
styrene or vinyl chloride. Polymers containing (meth)acrylate groups in the
side-chain are also
known. They may typically be reaction products of epoxy resins based on
novolak with
(meth)acrylic acid, homo- or copolymers of polyvinyl alcohol or their
hydroxyalkyl derivatives
which are esterified with (meth)acrylic acid or homo- and copolymers of
(meth)acrylates which
are esterified with hydroxyalkyl(meth)acrylates.
Preferred monomers are typically alkyl- or hydroxyaikyl acrylates or
methacrylates, styrene,
ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol
diacrylate,
hexamethylene glycol diacrylate or bisphenol A diacrylate, 4,4'-bis(2-
acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate,
pentaerythritol triacrylate or
tetraacrylate, preferably acrylates, styrene, hexamethylene glycol or
bisphenol A diacrylate, 4,4'-
bis(2-acryloyloxyethoxy)diphenylpropane or trimethylolpropane triacrylate.
Particularly preferred (oligome(c) polyunsaturated compounds are polyester
acrylates or
unsaturated polyester resins which are prepared from maleic acid, fumaric
acid, phthalic acid
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and one or more than one diol, and which typically have molecular weights from
about 500 to
3000. -
Preferred unsaturated carboxylic acids are acrylic acid and methacrylic acid.
The photopolymerizable compounds are used by themselves or in any desired
mixtures. It
is preferred to use mixtures of.polyol(meth)acrylates.
Binders may also be added to the unsaturated photopolymerizable compounds. The
addition of binders is particularly useful if the photopolymerizable compounds
are liquid or
viscous substances. The amount of binder may be from 5-95, preferably 10-90
and, most
preferably, 40-90, percent by weight, based on the entire composition. The
choice of binder will
depend on the field of use and the desired properties therefore, such as the
ability of the
compositions to be developed in aqueous and organic solvent systems, adhesion
to substrates
and susceptibility to oxygen.
Suitable binders are typically polymers having a molecular weight of about
5,000 to
2,000,000, preferably 10,000 to 1,000,000. Illustrative examples are: Homo-
and copolymers of
acrylates and methacrylates, including copolymers of methyl methacrylate/ethyl
acrylate/methacrylic acid, poly(alkyEmethacrylates), poly(alkylacrylates);
cellulose esters and
ethers such as cellulose acetate, cellulose acetobutyrate, methyl cellulose,
ethyl cellulose;
polyvinyl butyral, polyvinyl formal, cyclized rubber, polyethers such as
polyethylene oxide,
polypropylene oxide, polytetrahydrofuran; polystyrene, polycarbonate,
polyurethane, chlorinated
polyolefins, polyvinyl chloride, copolymers of vinyl chloride/vinylidene
chloride, copolymers of
vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate,
polyvinyl acetate,
copoly(ethylene/vinyl acetate), polymers such as polycaprolactam and
poly(hexamethylene
adipamide), polyesters such as poly(ethylene glycol terephthalate) and
poly(hexamethylene
glycol succinate).
The unsaturated compounds can also be used in admixture with non-
photopolymerizable
film-forming components. These components may be physically drying polymers or
solutions
thereof in organic solvents, for example nitrocellulose or cellulose
acetobutyrate. The
photopolymerizable unsaturated monomers may be a component of a free radical-
ionic curable
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blend, such as a#ree radical-cationic curable blend. Also of importance are
systems that
undergo both thermal and photo-induced curing cycles, such as are used in
powder coatings,
laminates, certain adhesives and conformal coatings.
Mixtures of a prepolymer with polyunsaturated monomers which, additionally
contain a
further unsaturated monomer are frequently used in paint systems. The
prepolymer in this
instance primarily determines the properties of the paint film and, by varying
it, the skilled
person can influence the properties of the cured film. The polyunsaturated
monomer acts as
crosslinking agent that renders the paint film insoluble. The mono-unsaturated
monomer acts
as reactive diluent with the aid of which the viscosity is lowered without
having to use a solvent.
Moreover, properties of the cured composition such as curing rate,
crosslinking density and
surface properties are dependent on the choice of monomer.
Unsaturated polyester resins are usually used in two-component systems,
together with a
mono-unsaturated monomer, preferably with styrene.
Binary electron-rich/electron-poor monomer systems are often employed in thick
pigmented coatings. For example, vinyl ether/unsaturated polyester systems are
employed in
powder coatings and styrene/unsaturated polyester systems are used in gel
coats.
A preferred process is that wherein the ethylenically unsaturated
polymerizable
compounds are a mixture of (i) at least one oligomeric compound and (ii) at
least one monomer.
An interesting process is that wherein the ethylenically unsaturated
polymerizable
compounds are a mixture of (i) unsaturated polyesters, especially those that
are prepared from
maleic acid, fumaric acid and/or phthalic acid and one or more than one diol,
and which have
molecular weights of 500 to 3,000, and (ii) acrylates, methacrylates or
styrene or combinations
thereof.
An important process is also that wherein the ethylenically unsaturated
polymerizable
compounds are a mixture of (i) unsaturated polyesters and (ii) acrylates or
methacrylates or
combinations thereof.
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Another interesting process is that wherein the ethylenically unsaturated
polymerizable
compounds are a mixture of (i) unsaturated polyester acrylates and (ii)
acrylates or
methacrylates or combinations thereof.
Synthesis of Cornpgunds
The instant compounds may be prepared by the reaction of tributyltin hydride
and a
halogen substituted alcohol to produce carbon centered radicals that are
trapped by nitroxyl
compounds.
The instant compounds may also be prepared by coupling an N-oxyl hindered
amine
with a carbon centered radical generated by the photochemical or thermal
decomposition of a
perester or dialkyl peroxide in the presence of an alcohol. The bridge
compounds described
above can be formed when two nitroxyl radicals couple with the same solvent
molecule,
especially when the amount of solvent is reduced.
The preferred method of preparation of the instant compounds is to react an N-
oxyl
hindered amine with a carbon centered radical generated by mixing an aqueous
or alcoholic
solution of a metal ion such as Fe2+, Fe3+, Cu2' or Cu+ and a peroxide such as
tert-butyl
hydroperoxide or hydrogen peroxide in the presence of an alcohol solvent at a
temperature of
20-80 C. Especially effective is the combination of ferrous chloride, ferric
chloride or ferrous
sulfate, particulariy ferrous chloride, or ferric chloride, and hydrogen
peroxide. Water may be
added to the alcohol at the beginning of the reaction to improve solubility of
the metal salt or to
dissolve an alcohol which is solid at the reaction temperature. A ligand such
as 2,2'-dipyridyl,
2,2':6',2"-terpyridyl, may be added to the reaction mixture. Two nitroxyl
radicals can sometimes
couple with the same solvent molecule to produce bridged compoundsdescribed in
some
formulas listed earlier. The formation of bridge compounds is more favored
when the amount of
solvent is reduced.
Some of the instant hydroxy-substituted N-alkoxy compounds may be reacted with
monofunctional or difunctional esters, acids or acid chlorides or isocyanates
to form polymeric
ester or urethane derivatives.
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Thus, another object of the invention is a process for the synthesis of the N-
(hydroxyalkoxy) substituted hindered amines of formula IV
Gi~G2
T N-O-E-(OH) b (IV)
G\/'G
2
wherein
G, and G2 are independently alkyl of 1 to 4 carbon atoms, or G, and G2
together are pentamethylene;
T is a divalent organic radical required to complete a five- or six-membered
ring containing the hindered amine nitrogen atom and two quaternary carbon
atoms
substituted by G, and G2;
E is a (b + 1) valent alkylene radical of 2 to 18 carbon atoms, an alkenylene
radical of 3 to 19 carbon atoms, a cycloalkylene radical of 5 to 12 carbon
atoms, a
cycloalkenylene radical of 5 to 12 carbon atoms or an alkylene radical of 2 to
4
carbon atoms substituted by phenyl or by phenyl substituted by one or two
alkyl of 1
to 4 carbon atoms; and
b is 1, 2 or 3; with the proviso that b cannot exceed the number of saturated
carbon atoms in E, and when b is 2 or 3, each hydroxyl group is bonded to a
different
carbon atom in E;
which process comprises
reacting a N-oxyl hindered amine of formula V
G1~GZ
T N-O- (V)
,G2
G::::'`
with an alcohol of formula VI
E-(OH)b (VI)
in the presence of a peroxide or organic hydroperoxide and a catalytic amount
of a
metal salt or metal-ligand complex.
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The N-oxyl compounds of formula V may be prepared by the reaction of the
corresponding N-H hindered amine with hydrogen peroxide and sodium tungstate
as
described by E. G. Rozantsev et al., in Synthesis, 1971, 192; or with tert-
butyl
hydroperoxide and molybdenum (VI) as taught in United States Patent No.
4,691,015.
More specifically, the instant process involves the reaction of a mixture of 5
to 100 moles of the alcohol of formula VI, 1 to 15 moles of hydrogen peroxide
or
organic hydroperoxide, and 0.001 to 0.5 moles of metal salt or metal-ligand
complex
per mole of N-oxyl compound of formula V. The reaction is preferably carried
out at a
temperature in the range of 20 to 100 C.
The alcohol may serve two functions both as reactant and as solvent for the
reaction. A mixture of products may result if the alcohol contains non-
equivalent
carbon-hydrogen bonds which are reactive in the instant process. For example,
tert-
butyl alcohol can give only one product whereas tert-amyl alcohol can give
three
distinct reaction products. A cosolvent may be used if the alcohol is a solid
at the
temperature of the reaction or if the metal salt or metal-ligand complex is
not very
soluble in the alcohol. Typical cosolvents are water, methanot and ethylene
glycol.
The instant process mainly uses a less than stoichiometric amount, based
on peroxide, of a transition metal salt or a metal-ligand complex with the
metal
chosen from groups IVA, VA, VIIA, VIIIA or 1B (transition metals, metals of
lowest
weight in these groups being Ti, V, Mn, Fe, Co, Ni, Cu) of the periodic table.
Iron(1I),
iron(Iil), copper(l) and copper(II) are the most effective catalysts. The
metal may be in
the form of a simple salt such as a metal chloride or sulfate, a metal salt of
an organic
acid such as acetic acid, or a metal oxide which may also contain a cation
from group
IA or IIA of the periodic table, such as sodium metavanadate. The metal may
also be
complexed with a ligand such as 2,2'-dipyridyl, ethylenediaminetetraacetic
acid or its
disodium salt, triphenylphosphine oxide, or the anion of acetylacetone. These
metal
ligand complexes are items of commerce or may be formed in situ by mixing a
metal
salt with the ligand. The amount of ligand may be less than the amount
required to
completely complex the metal based on its oxidation state. The metal salt or
metal-
ligand complex may be bound to a solid support such as silica gel so that it
can be
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recovered and reused.
A mineral acid or sulfonic acid may be added to the reaction mixture in an
amount corresponding to up to one mole per mole of nitroxyl moiety.
The instant process can be run in air or in an inert atmosphere such a
nitrogen or argon.
There are several variations of the instant process. One variation involves
the addition of a solution of aqueous hydrogen peroxide or organic
hydroperoxide to a
mixture of the N-oxyl hindered amine, the alcohol and cosolvent (if used) and
acid (if
used), and metal salt or metal-ligand complex which has been brought to the
desired
temperature for reaction. The proper temperature is maintained by controlling
the rate
of peroxide addition and/or by using a heating or cooling bath. After the
peroxide is
added, the reaction mixture is stirred till the starting N-oxyl compound of
formula V
has disappeared or is no longer being converted to the compound of formula IV.
The
reaction is best monitored by thin layer chromatography, gas chromatography or
liquid chromatography. Additional portions of metal salt or metal-ligand
complex can
be added while the reaction is in progress. After the initial peroxide charge
has been
added to the reaction mixture, more peroxide can be added dropwise to bring
the
reaction to completion.
A second variation of the instant process is to simultaneously add separate
solutions of the peroxide and the nitroxyl compound to a mixture of the
alcohol,
cosolvent (if used), acid (if used) and metal salt or metal-ligand complex.
The nitroxyl
compound may be dissolved in water or the alcohol solvent used in the
reaction.
Some of the nitroxyl compound may be introduced into the reaction mixture
prior to
starting the peroxide addition, and all of the nitroxyl compound should be
added prior
to completing the peroxide addition.
Another variation of the instant process involves the simultaneous addition of
separate solutions of the peroxide and of the aqueous or alcohol solution of
the metal
salt or metal-ligand complex to a mixture of the nitroxyl compound, alcohol,
cosolvent
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(if used), and acid (if used). Some of the metal may be introduced into the
reaction
mixture prior to starting the peroxide addition.
Still another variation of the instant process is the simultaneous addition of
separate solutions of the peroxide, of the aqueous or alcohol solution of the
nitroxyl
compound, and of an aqueous or alcohol solution of the metal salt or metal-
ligand
complex to the alcohol, cosolvent (if used) and acid (if used). A portion of
the nitroxyl
compound and/or metal salt or metal-ligand complex may be introduced into the
reaction mixture prior to starting the peroxide addition. All of the nitroxyl
compound
should be added prior to completing the peroxide addition.
If acid is used in the reaction, the acid may be added in one portion at the
beginning of the reaction, or a portion of acid may be added at the beginning
of the
reaction and the remainder added while the reaction is in progress; or all of
the acid
may be added while the reaction is in progress. Some or all of the acid may be
mixed
with the metal salt if the metal salt is added as a solution while the
reaction is in
progress.
If a metal-ligand complex is prepared in situ, the metal salt and ligand are
most effectively mixed prior to contact with the nitroxyl compound.
At the end of the reaction, the residual peroxide should be carefully
decomposed prior to
the isolation of any products.
Preferred Processes
G, and G2 in formula (IV) and (V) are preferably methyl. T is preferably 2-
hydroxy-1,3-propanediyl or 2-oxo-1,3-propanediyl.
When b is 1, -E-(OH) is a carbon centered radical formed preferably from 2-
methyl-2-propanol (= tert-butyl alcohol), 2-propanol, 2,2-dimethyl- 1 -
propanol, 2-
methyl-2-butanol, ethanol, 1 -propanol, 1 -butanol, 1 -pentanol, 1 -hexanol, 1
-nonanol,
1 -decanol, 1 -dodecanol, 1 -octadecanol, 2-butanol, 2-pentanol, 2-ethyl- 1 -
hexanol, 2-
octanol, cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-
phenyl-1-
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ethanol; and -E-(OH) is most preferably formed from 2-methyl-2-propanol (=
tert-butyl
alcohol) or cyclohexanol.
When b is 2, -E-(OH)2 is a carbon centered radical formed preferably from
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-
1,3-
propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-
cyclohexanediol
or 1,4-cyclohexanediol; and -E-(OH)2 is formed most preferably from 1,4-
butanediol,
2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-
cyclo-
hexanediol.
When b is 3, -E-(OH)3 is a carbon centered radical formed preferably from
1,1,1-tris(hydroxymethyl)ethane, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol,
1,2,4-
butanetriol or 1,2,6-hexanetriol; and -E-(OH)3 is formed most preferably from
1,1,1-
tris(hydroxymethyl)ethane or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol.
b is preferably 1 or 2; most preferably 1.
Preferred products of the instant process are the compounds of formulae (1)
to (30) described above.
Preferably the peroxides are hydrogen peroxide, the addition compound of
urea and hydrogen peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide
and
cumene hydroperoxide. More perferably the peroxides are hydrogen peroxide and
the
addition compound of urea and hydrogen peroxide; and most perferably hydrogen
peroxide.
The hydrogen peroxide may be 15 to 50% by weight solution in water,
preferably 30 to 50% by weight solution in water.
Preferably, the metals are chosen from the groups IVA, VA, VIIA, VIIIA and
IB of the periodic table. More preferred are iron(11), iron(III), copper(l),
copper(II),
cobalt(II), cobalt(III), manganese(II), manganese(III), vanadium(II),
vanadium(I11),
cerium(III) and titanium(III). Most preferred are iron(II), iron(III),
copper(l) and
copper(II).
Preferably the counterions for the above metals are chloride, sulfate, acetyl-
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acetonate (acac), acetate, citrate, oxalate, nitrate, perchlorate, cyanide,
hydroxide,
phosphate, pyrophosphate and oxide.
Preferably the ligands for the above metals are 2,2'dipyridyl, 2,2':6,2"-
terpyridyl, 1,10-phenanthroline, ethylenediaminetetraacetic acid,
ethylenediamine-
tetraacetic acid disodium salt, pyridine, picolinic acid, 2-pyrazinecarboxylic
acid,
aromatic diimines formed from the reaction of aniline or substituted anilines
with 1,2-
diketones such as 2,3-butanedione, and triphenylphosphine oxide.
Preferably the metal salts are ferrous chloride, ferric chloride, ferric
acetyl-
acetonate, ferric phosphate, ferric pyrophosphate, ferrous phosphate, ferrous
sulfate,
ferric sulfate, ferrous acetate, ferric citrate, ferrous oxalate, ferric
oxalate, ferric
nitrate, ferrous perchlorate, ferric perchlorate, cuprous chloride, cupric
chloride,
cuprous sulfate, manganous chloride, sodium metavanadate, titanous chloride,
vandium(II) chloride and vanadium(Iil) chloride. Most preferred metal salts
are ferrous
chloride, ferric chloride, ferric acetylacetonate, ferric phosphate, ferric
pyrophosphate,
ferrous phosphate, ferrous sulfate, ferric-sulfate and cupric sulfate.
Preferably the metal-ligand complexes are those from iron(II), iron(111),
copper(I) or copper(Ii) salts and 2,2'-dipyridyl, triphenyiphosphine oxide,
ethylene-
diaminetetraacetic acid or ethylenediaminetetraacetic acid disodium salt. Most
preferably, the metal-ligand complex are those from ferrous chloride or ferric
chloride
and 2,2'-dipyridyl.
Preferably the acids are hydrochloric acid, sulfuric acid, methanesulfonic
acid, oxalic acid, trifluoroacetic acid, polyphosphoric acid and phosphoric
acid; most
preferably, the acid is methanesulfonic acid, polyphosphoric acid or
phosphoric acid.
The preferred amount of alcohol solvent for the instant process depends to
some extent on the relative number of reactive hydrogens on the alcohol
reactant and
the hindered amine nitroxyl compound. The reaction is typically carried out
with a
ratio of 5 to 100 moles of solvent per mole of nitroxyl moiety with the
preferred ratio
being 10 to 50 moles per mole of nitroxyl moiety, and the most preferred ratio
being
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-73-
to 30 moles of solvent per mole of nitroxyl moiety. A cosolvent may be
present,
which is preferably selected from water, methanol, ethylene glycol, or
mixtures
thereof.
The preferred amount of hydrogen or organic hydroperoxide is 1 to 20 moles
per mole of nitroxyl moiety, with the more preferred amount being 1 to 5 moles
of
peroxide per mole of nitroxyl moiety and the most preferred amount being 1 to
3
moles of peroxide per mole of nitroxyl moiety.
The preferred amount of metal salt or metal-ligand complex is 0.001 to 0.5
molar equivalent per mole of nitroxyl moiety, with a ratio of 0.001 to 0.05
moles of
metal salt or metal-ligand complex per mole of nitroxyl moiety being the most
preferred.
If an acid is used in the instant process, the preferred amount of acid is
0.01
to 1 molar equivalent per mole of nitroxyl moiety, with a ratio of 0.01 to 0.5
molar
equivalents of acid per mole of nitroxyl moiety being most preferred.
The reaction is usually run at 20 to 100 C; preferably at 60 to 100 C.
The following examples are for illustrative purposes only and are not to be
construed to
limit the instant invention in any manner whatsoever. Room temperature depicts
a temperature
in the range 20-25 C.
Abbreviations:
v parts by volume
w parts by weight
' Hnmr nuclear magnetic resonance (NMR) of 'H
m/z mass spectrometry (atomic units)
amu molecular weight in g/mol (= atomic units).
Examples Pl-P63 illustrate the novel process for preparing the
compounds of the invention.
Example P1 illustrates the use of ferric chloride in the instant
process.
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Exam I~ e P1
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 9.4 g (140 mmol) of 50% aqueous hydrogen peroxide mixed with 20
mL of
tert-butyl alcohol is added over four hours at 45-50 C to a mixture of 3.44 g
(20.0 mmol) of 4-
hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 0.125 g (0.77 mmol) of anhydrous
ferric chloride,
30 mL of tert-butyl alcohol and 10 mL of water. The temperature is then
maintained at 45-50 C
for 19 hours. Analysis by gas chromatography shows less than 1% of the
starting nitroxyl
compound is present.
Example P2 shows recycling a metal catalyst on a solid support.
Examgle P2
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6=tetramethylpiperidine
2,2'-Dipyridyl (0.16 g, 1.0 mmol) and 2.54 g (0.80 mmol) of 5% ferric chloride
on silica
gel are stirred together in 30 mL of tert-butyl alcohol which is heated to 45
C. To the mixture are
added 3.44 g (20.0 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and
10 mL of water.
A solution of 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide mixed with 20
mL of tert-
butyl alcohol is added over four hours at 45-50 C to the reaction mixture. The
temperature is
maintained at 45-50 C for 30 minutes. Analysis by gas chromatography shows
that the starting
nitroxyl compound is completely reacted to form greater than 90% of the title
compound.
The silica gel is separated by filtration and the above experiment is repeated
using the
recovered silica gel. After nearly all the peroxide is added to the reaction
mixture in 4.5 hours,
gas chromatography shows 36% of the starting nitroxyl compound is still
present. After the
reaction mixture is heated for an additional 19 hours at 45-50 C, only 5% of
the starting nitroxyl
compound still remains.
Example P3
Reaction of 4-Hydroxy-1 -oxyl-2,2,6,6-tetra-
methylpiperidine with Isopropyl Alcohol
2,2'-Dipyridyl (0.156 g, 1 mmol) is added to a mixture of 0.20 g (1 mmol) of
ferrous
chloride tetrahydrate in 30 mL of isopropyl alcohol at 40 C. To this mixture
are added 3.44 g(20
CA 02299754 2000-02-23
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mmol) of 4-hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine and 10 mL of water. A
solution of 9.4 g
(138 mr'rmol) of 50% aqueous hydrogen peroxide in 20 mL of isopropyl alcohol
is added over
seven hours at 40-45 C to the above mixture. The crude reaction mixture is
cooled and reacted
with 0.5 g of sodium borohydride. Gas chromatography/mass spectrometry
analyses indicate
the major component of the reaction mixture is 4-hydroxy-1-(2-hydroxypropoxy)-
2,2,6,6-tetra-
methylpiperidine (m/z = 231).
Examgle P4
Reaction of 1-Oxy1-2,2,6,6-tetramethyl
piperidin-4-one with tert-Amyl Alcohol
2,2'-Dipyridyl (0.078 g, 0.50 mmol) is added to a mixture of 0.99 g (5.0 mmol)
of ferrous
chloride tetrahydrate is 150 mL of tert-amyl alcohol at 25 C. To this mixture
is added 0.2 g of
tetrabutylammonium chloride and 17.2 g (101 mmol) of 1-oxyl-2,2,6,6-
tetramethylpiperidin-4-
one. A solution of 29.5 g (434 mmol) of 50% aqueous hydrogen peroxide is added
over three
hours at 25-30 C to the above mixture. Aqueous sodium sulfite solution is
added to decompose
peroxides. The reaction mixture is thoroughly extracted with ethyl acetate to
afford 23.4 g of an
orange oil. Gas chromatography/mass spectrometry analyses indicate that the
oil contains three
major reaction products in a nearly 2:2:1 ratio (area percent). The three
products are consistent
with the reaction of the starting nitroxyl compound with each of the possible
carbon radicals
formed from tert-amyl alcohol.
Examole P5
Reaction of 1-Oxyl-2,2,6,6-tetramethyl
piperidin-4-one with 1 -Butanol
The procedure of Example P4 is repeated with 150 mL of n-butyl alcohol in
place of
tert-amyl alcohol. Work-up of the reaction mixture yields 19.2 g of an orange
oil. Gas
chromatography/mass spectrometry analyses indicate that three of the
components of the
product mixture correspond to the reaction of the starting nitroxyl compound
with radicals
formed by hydrogen abstraction from 1-butanol.
Example P6
Reaction of 1 -Oxyl-2,2,6,6-tetramethyl
piperidin-4-one with Neopentyl Glycol
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The procedure of Example P4 is repeated with a mixture of 400 mL of 2,2-
dimethyl-1,3-
propanediol (= neopentyl glycol) and 55 mL of water in place of tert-amyl
alcohol. Work-up of
the reaction mixture yields 14.0 g of a brown oil.
Examgle P7
Reaction of 1 -Oxyl-2,2,6,6-tetramethyl
piperidin-4-one with 2-Octanol
The procedure of Example P4 is repeated with a mixture of 150 mL of 2-octanol
in
place of tert-amyl alcohol. The peroxide is added over a period of six hours
at 25-30 C and the
reaction mixture is stirred ovemight at room temperature. Work-up of the
reaction mixture gives
19.4 g of an orange oil. Gas chromatography/mass spectrometry analyses
indicate that five of
the components of the product mixture correspond to the reaction of the
starting nitroxyl
compound with radicals formed by hydrogen abstraction from 2-octanol.
Examples P8-P12 indicate the use of mineral acid with various iron salts in
the instant
process.
Examnle P8
4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 17.2 g (100 mmol) of 4-hydroxy-1 -oxyl-2,2,6,6-
tetramethylpiperidine
dissolved in 40 mL of water and three-fourths of a solution of 25.0 g (0.37
mol) of 501/0 aqueous
hydrogen peroxide are added simultaneously over three hours at 40 C to a
mixture of 1.12 g
(4.0 mmol) of ferrous sulfate heptahydrate, 25 mL of water, 0.5 mL of 98%
sulfuric acid and 200
mL of tert-butyl alcohol. At the conclusion of the nitroxyl addition, 0.145 g
(0.5 mmol) of ferrous
sulfate heptahydrate, 0.1 mL of 98% sulfuric acid, and 1-2 mL of water are
added to the reaction
mixture. The remainding one-fourth of the peroxide solution is added over one
hour at 40 C.
One hour later, a solution of 2.9 g. (40 mmol) of 50% aqueous hydrogen
peroxide is added
dropwise to the reaction mixture. After another 1.3 hours, a solution of 0.14
g (0.5 mmol) of
ferrous sulfate heptahydrate, 0.15 mL of 98% sulfuric acid and 1-2 mL of water
are added in one
portion. The reaction mixture is stirred an additional 40 minutes at 40 C.
After the peroxides are
decomposed with sodium sulfite, the reaction mixture is treated with sodium
hydroxide and
sodium borohydride and concentrated. The residue is dissolved in ethyl acetate
and passed
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through silica gel to afford 20.5 g (84% yield) of the title compound as a
white solid.
Example P9
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 34.5 g (200 mmoi) of 4-hydroxy-l-oxyl-2,2,6,6-
tetramethy{piperidine
dissolved in 75 mL of water and a solution of 49.5 g (0.73 mol) of 50% aqueous
hydrogen
peroxide are added simultaneously over seven hours at 40 C to a mixture of
1.61 g (8.1 mmol)
of ferrous chloride tetrahydrate, 50 mL of water, 1.6 mL of 37% hydrochloric
acid and 390 mL of
tert-butyl alcohol. About four hours into the addition, a solution of 0.22 g
(1.1 mmol) of ferrous
chloride tetrahydrate, 0.2 mL of 37% hydrochloric acid and 1-2 mL of water are
added to the
reaction mixture. The reaction mixture is stirred ovemight at room
temperature. The reaction is
then completed by adding a solution of 0.11 g (0.55 mmol) of ferrous chloride
tetrahydrate, 0.1
mL of 37% hydrochloric acid and 1-2 mL of water and a solution of 5.8 g (85
mmol) of 50%
aqueous hydrogen peroxide while heating the reaction mixture at 40 C. The
reaction mixture is
filtered to remove solids, quenched with sodium sulfite, treated with sodium
hydroxide and
sodium borohydride and concentrated. The residue is dissolved in ethyl acetate
and passed
through silica gel to afford 42.6 g (87% yield) of the title compound as a
white solid.
Exarrple P 10
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 17.2 g(100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-
tetramethyipiperidine
dissolved in 50 mL of water and a solution of 25.3 g (0.37 mol) of 50% aqueous
hydrogen
peroxide are added simultaneously over 3-3.5 hours at 40 C to a mixture of
0.27 g (1.0 mmol) of
ferric chloride hexahydrate, 25 mL of water, 1.1 mL of 37% hydrochloric acid
and 200 mL of tert-
butyl alcohol. About two hours into the addition, 0.5 mL of 37% hydrochloric
acid is added to the
reaction mixture. After the peroxide addition is complete, 1.2 mL of 37%
hydrochloric acid is
added and the reaction mixture is heated at 40-50 C for 3.5 hours. The
reaction mixture is
stirred overnight at room temperature. The reaction is completed by adding two
portions of 0.3
mL of 37% hydrochloric acid while heating the reaction mixture at 45 C for 5.5
hours. Work-up
is done as in Example P9 and affords 21.5 g (88% yield) of the title compound
as a white solid.
Gas chromatography shows the product has a purity greater than 96%.
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ExamQle P11
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 17.2 g (100 mmol) of 4-hydroxy-1 -oxyl-2,2,6,6-
tetramethylpiperidine
dissolved in 40 mL of water and three-fourths of a solution of 25.0 g (0.37
mol) of 50% aqueous
hydrogen peroxide are added simultaneously over 2.5 hours to 40 C to a mixture
of 1.46 g (4.1
mmol) of ferric acetylacetonate, 25 mL of water, 0.5 mL of 98% sulfuric acid
and 200 mL of tert-
butyl alcohol. At the conclusion of the nitroxyl addition, 0.18 g (0.5 mmol)
of ferric acetyl-
acetonate is added to the reaction mixture. The remaining one-fourth of the
peroxide solution is
added over one hour at 40 C. After heating for two hours, gas chromatography
shows less than
10% nitroxyl compound remaining in the reaction mixture. Sulfuric acid (0.3
mL) and a solution
of 4.9 g (72 mmol) of 50% aqueous hydrogen peroxide are added to the reaction
mixture at
40 C, and the reaction mixture is stirred overnight at room temperature. Work-
up as in Example
P9 affords 18.1 g (74% yield) of the title compound as a white solid.
Example P12
4-Hydroxy-1-(2-hydroxy-2-methyipropoxy)-
2,2,6,6-tetramethylpiperidine
When the procedure of Example P11 is repeated without the addition of sulfuric
acid,
69% of the starting nitroxyl compound remains present 1.5 hours after the
peroxide addition is
completed. This compares with only 10% nitroxyl compound remaining at a
comparable time as
seen in Example P11.
ExamlpeP13
1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-one
A solution of 23.6 g (347 mmol) of 50% aqueous hydrogen peroxide is added over
7.5
hours to a mixture of 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-
4-one, 0.994 g (5
mmol) of ferrous chloride tetrahydrate, 1 mL of 37% hydrochloric acid, 360 mL
of tert-butyl
alcohol, and 120 mL of water. The reaction is saturated with potassium
chloride and the
aqueous layer is extracted with tert-butyl alcohol. The combined organic
layers are concentrated
to an orange oil. The oil is dissolved in methylene chloride and purified by
flash chromatography
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on silica gel with 4:1 (v/v) hexane:ethyl acetate. The resulting yellow oil is
crystallized to afford
8.3 g of a white solid melting at 57-60 C. The isolated product is injected
into a gas
chromatograph and has the same retention time as an authenic sample of the
title compound.
Examples P14, P15 and P16 illustrate the effect of various ligands of formula
(IV)
x x
(IV)
N~ N
H ~CH
3c 3
on the formation of the compound of Example P13.
Examole P14
1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-one
To a mixture of 0.994 g (5 mmol) of ferrous chloride tetrahydrate and 150 mL
of tert-
butyl alcohol at 35 C are added, sequentially, 1.18 g (5.0 mmol) of N,N'-(1,2-
dimethyl-1,2-
ethanediylidene)bis(benzenamine), where in formula IV, X is hydrogen, and 17.0
g (100 mmol)
of 1-oxyl-2,2,6,6-tetrarnethylpiperidin-4-one. A solution of 47.5 g (700 mmol)
of 50% aqueous
hydrogen peroxide mixed with 60 mL of tert-butyl alcohol is added over eight
hours at 35-40 C
to the above mixture. The reaction is stirred an additional 16 hours at 40 C.
Analysis by gas
chromatography shows less than 4% starting nitroxyl present. Solids are
removed by filtration,
and the filtrate is reacted with aqueous sodium sulfite to decompose excess
peroxide. The
reaction mixture is thoroughly extracted with ethyl acetate to afford, after
concentration, 21.4 g
of crude product containing greater than 93% of the title compound as based on
gas
chromatography.
Examgle P 15
1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-one
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Example P14 is repeated using 1.48 g (5 mmol) of N,N'-(1,2-dimethyl-1,2-ethane-
diylide'ne)bis(4-rnethoxybenzenamine), where in formula IV, X is methoxy, in
place of N,N'-(1,2-
dimethyl-1,2-ethanediylidene)bis(benzenamine), where in formula IV, X is
hydrogen. Analysis by
gas chromatography shows 3% starting nitroxyl compound present at the end of
the reaction
time. After work-up, the reaction mixture affords 17.7 g of an orange material
which contains
97% of the title compound as seen by gas chromatography.
ExamRIe P 16
1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-one
Example P14 is repeated using 5.0 mmol of N,N'-(1,2-dimethyl-1,2-
ethanediylidene)-
bis(4-chlorobenzenamine), where in formula IV, X is chlorine, in place of N,N'-
(1,2-dimethyl-1,2-
ethanediylidene)bis(benzenamine), where in formula IV, X is hydrogen.
Exam la e P17
4-Benzoyloxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 18.4 g(0.27 mol) of 50% aqueous hydrogen peroxide mixed with 50
mL of
tert-butyl alcohol is added over two hours to a mixture of 24.9 g (0.090 mol)
of 4-benzoyloxy-l-
oxyl-2,2,6,6-tetramethylpiperidine, 7.13 g (0.036 mol) of ferrous chloride
tetrahydrate, 3.7 g
(0.030 mol) of picolinic acid, and 150 mL of tert-butyl alcohol at 60 C. The
reaction temperature
is maintained at 60 C for five hours after the peroxide addition is complete.
The reaction mixture
is filtered to remove solids, and the filtrate is stirred for 30 minutes with
1 liter of 10% aqueous
sodium sulfite solution to decompose excess peroxide. The aqueous solution is
extracted three
times with methylene chloride, and the combined organic layers are dried over
anhydrous
magnesium sulfate and finally concentrated to an orange oil. Purification by
flash
chromatography on silica gel with 4:1 (v/v) hexane:ethyl acetate affords 12.0
g of an amber oil.
The product is confirmed to be the title compound by nmr and mass spectrometry
analyses.
Example P18 shows the effect of omitting the picolinic acid from Example P17.
Example P18
4-Benzoyloxy-1-(2-hydroxy-2-methylpropoxy)-
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2,2,6,6-tetramethylpiperidine
'A solution of 20.4 g (0.30 mol) of 50% aqueous hydrogen peroxide mixed with
25 mL of
tert-butyl alcohol is added over three hours to a mixture of 27.6 g(0.10 mol)
of 4-benzoyloxy-1-
oxyl-2,2,6,6-tetramethylpiperidine, 7.13 g (0.036 mol) of ferrous choride
tetrahydrate and 115
mL of tert-butyl alcohol at 40 C. The reaction temperature is maintained at 40
C for twenty
hours after the peroxide addition is complete. The crude reaction mixture is
purified by flash
chromatography on silica gel to afford 16.2 g of the title compound.
ExampI e P19
Reaction of Bis(1-oxyl-2,2,6,6-tetramethyl-
piperidin-4-y!) Sebacate with Neopentyl alcohol
Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetra-
methylpiperidin-4-yl) sebacate and ferrous chloride in neopentyl alcohol
according to
the procedure of Example P18.
Examale P20
Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethyl-
piperidine with Neopentyl Glycol
Aqueous hydrogen peroxide is added to a mixture of 4-hydroxy-l-oxyl-
2,2,6,6-tetramethylpiperidine and ferrous chloride in neopentyl glycol
according to the
procedure of Example P18.
Example P21
Reaction of 4-Octadecanoyloxy- 1 -oxyl-2,2,6,6-
piperidine with tert-Amyl Alcohol
Aqueous hydrogen peroxide is added to a mixture of 4-octadecanoyloxy-l-
oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride in tert-amyl alcohol
according
to the procedure of Example P18.
ExamAle P22
Reaction of 4-Octadecanoyloxy-l-oxyl-2,2,6,6-
piperidine with tert-Butyl Alcohol
Aqueous hydrogen peroxide is added to a mixture of 4-octadecanoyloxy-1 -
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oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride in tert-butyl alcohol
according
to the procedure of Example P18.
Examnle P23
Reaction of 4-Benzoyloxy- 1 -oxyl-2,2,6,6-
tetramethylpiperidine with Propylene Glycol
Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-1-oxyl-
2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in propylene
glycol
according to the procedure of Example P18.
Exam IeP24
Reaction of 1-bxyl-2,2,6,6-tetramethyl
piperidin-4-one with Trimethylene Glycol
Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetra-
methylpiperidine-4-one and ferrous chloride tetrahydrate in trimethylene
glycol
according to the procedure of Example P18.
Example P25
Reaction of Bis(1-oxyl-2,2,6,6-tetramethyl-
pipe(din-4-yl) Sebacate with 2-Propanol
Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetra-
methylpiperidin-4-yl) sebacate and ferrous chloride tetrahydrate in 2-propanol
according to the procedure of Example P18.
Example P26
Reaction of 4-Benzoyloxy-1 -oxyl-2,2,6,6-tetramethyl-
piperidine with 1,4-Butanediol
Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-1-oxyl-
2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in 1,4-
butanediol
according to the procedure of Example P18.
Examale P27
Reaction of 4-Hexyloxy-l-oxyl-2,2,6,6-tetramethyl-
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piperidine with Pinacol
Aqueous hydrogen peroxide is added to a mixture of 4-hexyloxy-1 -oxyl-
2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in pinacol
according to
the procedure of Example P18.
Examgle 28
Reaction of 4-Hydroxy-1 -oxyl-2,2,6,6-tetramethyl-
piperidine with 2-Ethyl-l-hexanol
Aqueous hydrogen peroxide is added to a mixture of 4-hydroxy-l-oxyl-2,2,6,6-
tetra-
methylpiperidine and ferrous chloride tetrahydrate in 2-ethyl-1 -hexanol
according to the
procedure of Example P18.
Examples P38-P47 show the effectiveness of various metals in the instant
process.
ExamQ!e P38
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethyipiperidine
A solution of 50% aqueous hydrogen peroxide is added at a rate of
approximately 100 mmol per hour and, simultaneously, a solution of 17.2 g (100
mmol) of 4-hydroxy-l-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40-45 mL
of
water is added at a rate of 35-50 mmol per hour to a mixture of metal salt,
acid if
used, 25 mL of water and 200 mL of tert-butyl alcohol maintained at 35-45 C.
The
reaction mixture is maintained at 35-45 C after all reactants are added, and
in some
cases the reaction mixture is stirred overnight at room temperature. The
reaction is
monitored by gas chromatography. Results are tabulated below.
Table I
Formation of 4-Hydroxy-l-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine Using Hydrogen
Peroxide and Various Metals
mol % metal8 mol % acida moles H,U20 yieldc
4% CoCI2 10% HCI 2.9 3%
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11 % MnCI2 10% HCI 3.6 16%
4% NaVO3 none 1.5 <1%
4% CeCI3 none 1.5 <1%
4% TiCI3 60% HCI 3.5 2%
4% VCI2 10% HCI 2.2 1%
4% VCI3 10% HCI 3.6 6%
(a) moles per mole of nitroxyl starting material;
(b) moles of peroxide added to reaction per mole of nitroxyl starting
material; and
(c) gas chromatographic yields based on integrated area of title compound with
respect to total area of all hindered amine components present in the reaction
mixture.
Exam IQ e P39
1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-one
A solution of 1.0 g (15 mmol) of 50% aqueous hydrogen peroxide in 5 mL of
tert-butyl alcohol is added over 30 minutes at 60 C to a mixture of 0.5 g (2.9
mmol) of
1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 0.1 g (0.16 mmol) of N,N'-bis(3,5-
di-tert-
butylsalicylidene)-1,2-cyclohexanediaminomanganese(II) chloride (Jacobsen's
catalyst), and 10 mL of tert-butyl alcohol. The reaction is stirred ovemight
at 60 C.
Gas chromatography shows 2.5% of the title compound is present in the reaction
mixture.
Examole P40
1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-one
The procedure of Example P39 is repeated using 0.25 g (1.05 mmol) of
cobalt(II) chloride hexahydrate in place of the Jacobsen's catalyst. Gas
chromatography shows 9% of the title compound is present in the reaction
mixture.
Example P41
4-Hydroxy-l-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
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A solution of 0.25 g(1.0 mmol) of copper(II) sulfate pentahydrate in 5 mL of
water is added to a solution of 0.16 g (1.0 mmol) of 2,2'-dipyridyl in 120 mL
of tert-
butyl alcohol. To this solution is added 8.6 g (50 mmol) of 4-hydroxy-1-oxyl-
2,2,6,6-
tetramethylpiperidine. A solution of 13.6 g (200 mmol) of 50% aqueous hydrogen
peroxide mixed with 13 mL of tert-butyl alcohol is added dropwise to the
reaction
mixture at 23-40 C over three hours. The mixture is then stirred at ambient
temperature for 72 hours. Gas chromatography shows 9% of the title compound is
present in the reaction mixture.
Exanale P42
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 34.5 g (200 mmol) of 4-hydroxy-1 -oxyl-2,2,6,6-tetramethyl-
piperidine dissolved in 75 mL of water and a solution of 48.1 g (0.71 mol) of
50%
aqueous hydrogen peroxide are added simultaneously over six hours at 35-45 C
to a
mixture of 0.79 g (8.0 mmol) of copper(l) chloride, 50 mL of water, 1.6 mL of
37%
hydrochloric acid, and 400 mL of tert-butyl alcohol. The reaction mixture is
stirred
overnight at room temperature. The reaction mixture is heated to 40-45 C and
treated
with a total of 1.78 g of copper(l) chloride, 4.4 mL of 37% hydrochloric acid,
and 85 g
(1.25 mol) of 50% aqueous hydrogen peroxide to react completely the remaining
nitroxyl compound. Work-up according to the procedure of Example P9 affords
38.6 g
of a tan solid containing 88% of the title compound based on gas
chromatographic
analysis.
Examgle P43
4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 17.2 g (100 mmol) of 4-hydroxy-l-oxyl-2,2,6,6-tetramethyl-
piperidine dissolved in 50 mL of water and a solution of 31.5 g(0.46 mol) of
50%
aqueous hydrogen peroxide are added simultaneously over three and 4.5 hours
respectively to a mixture of 0.69 g (4.0 mmol) of copper(II) chloride
dihydrate, 25 mL
of water, 0.8 mL of 37% hydrochloric acid, and 200 mL of tert-butyl alcohol at
35-
50 C. The reaction mixture is maintained at 45-50 C and treated with a total
of 0.32 g
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of copper(II) chloride dihydrate, 0.6 mL of 37% hydrochloric acid, and 35.5
g(0.52
mol) of '50% aqueous hydrogen peroxide to react completely the remaining
nitroxyl
compound. Work-up according to the method of Example P9 affords 17.1 g of an
off-
white solid containing 90% of the title compound based on gas chromatographic
analysis.
Exam lo e P44
4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-
piperidine dissolved in 50 mL of water and a solution of 29.3 g (0.43 mol) of
50%
aqueous hydrogen peroxide are added simultaneously over three and 4.25 hours
respectively to a mixture of 1.0 g (4.0 mmol) of copper(il) sulfate
pentahydrate, 25 mL
of water, 0.6 mL of 98% sulfuric acid, and 200 mL of tert-butyl alcohol at 35-
50 C.
The reaction mixture is maintained at 45-50 C and treated with a total of 0.44
g of
copper(II) sulfate pentahydrate, 0.4 mL of 981% sulfuric acid, and 6.7 g (98
mmol) of
50% aqueous hydrogen peroxide to react completely the remaining nitroxyl
compound. Work-up according to the method of Example P9 affords 19.1 g of a
white
solid containing 95% of the title compound based on gas chromatographic
analysis.
Example P45
4-Hydroxy-l-(2-hydroxy-2-methyipropoxy)-
2,2,6,6-tetramethy{piperidine
A solution of 7.4 g (109 mmol) of 50% aqueous hydrogen peroxide in 10 mL
of water is added dropwise over five hours at 43-60 C to a mixture prepared by
the
sequential addition of 5 mL of water, 0.5 mL of glacial acetic acid, 60 mL of
tert-butyl
alcohol and a solution of 5.4 g (31.4 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-
tetramethyl-
piperidine in 5 mL of water to 0.166 g (0.95 mmol) of ferrous acetate. A fresh
solution
of 4.4 g (65 mmol) of 50% aqueous hydrogen peroxide and 4 mL of water is then
added to the reaction mixture at 60 C. The mixture is stirred overnight at
room
temperature.
Analysis by gas chromatography shows that the reaction mixture contains
52% of the title compound and 41% unreacted starting material based on the
original
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nitroxyl content.
Exam .~le P46
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine ,
The procedure of Example P9 is repeated using a mixture of ferrous chloride
and ferric chloride.
Examle~P47
4-Hydroxy-1-(2-hydroxy-2-methytpropoxy)-
2,2,6,6-tetramethylpiperidine
The procedure of Example P9 is repeated using a mixture of ferric chloride
and iron powder in place of ferrous chloride.
Examples P48 and P49 show the reaction where tert-butyl hydroperoxide is
used in place of hydrogen peroxide.
ExamRle P48
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 5.2 g (30 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-
piperidine dissolved in 20 mL of water and a solution of 7.8 g (61 mmol) of
70%
aqueous tert-butyl hydroxperoxide are added simultaneously over one hour at 35-
50 C to a mixture of 0.33 g (1.2 mmol) of ferric chloride hexahydrate, 8 mL of
water,
0.2 mL of 37% hydrochloric acid, and 60 mL of tert-butyl alcohol. The reaction
mixture
is maintained at 45 C for one hour after the addition and is then stirred at
room
temperature for three days. Gas chromatography shows 3% of the title compound
is
present in the reaction mixture.
Example P49
4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
The procedure of Example P48 is repeated using ferrous chloride in place of
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ferric chloride.
Example P50
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
This example uses the addition compound formed from urea and hydrogen
peroxide in place of 50% aqueous hydrogen peroxide.
A solution of 52.2 g (555 mmol) of urea-hydrogen peroxide addition
compound dissolved in 75 mL of water and a solution of 3 mL of concentrated
sulfuric
acid dissolved in 29 mL of water are prepared. Portions of both solutions are
added
simultaneously over two hours at a temperature of 40 C to a mixture of 0.17 g
(61
mmol) of ferrous sulfate heptahydrate, 34.75 g (202 mmol) of 4-hydroxy-l-oxyl-
2,2,6,6-tetramethylpiperidine, 410 mL of tert-butyl alcohol and 70 mL of
water. A fresh
portion of 0.485 g of ferrous sulfate heptahydrate is added and the reaction
mixture is
stirred overnight at 45 C for 16 hours. The remaining peroxide and acid
solutions are
added simultaneously to the reaction mixture over seven hours at 45 C.
Concentrated
sulfuric acid (1.8 mL) is added and the mixture is stirred at room tempetature
for 64
hours. After the reaction mixture is heated at 45-50 C for 6.5 hours, 1.8 mL
of
concentrated sulfuric acid and 0.101 g of ferrous sulfate heptahydrate are
added. The
reaction mixture is then heated at 45 C for 16 hours to bring the nitroxyl
concentration
to less than 1 k of its original value. The reaction mixture is worked up
following the
procedure similar to that described in Example 20 to afford 38.1 g(77 !o
yield) of
product as a white solid.
Anaylsis by gas chromatography shows the reaction product contains
approximately 94% of the title compound.
Examc>le P51
4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
Examples 51-54 show the effect of different acids on the instant process.
A solution of 17.2 g (100 mmol) of 4-hydroxy-l-oxyl-2,2,6,6-tetramethyl-
piperidine in 35 mL of water and a solution of 23.3 g (342 mmol) of 50%
aqueous
hydrogen peroxide are added simultaneously over 2.5 hours and 6.5 hours,
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respectively, to a mixture of 0.527 g(3.0 mmol) ferrous acetate, 20 mL of
water, 2.3 g
of trifluoroacetic acid, and 200 mL of tert-butyl alcohol which is maintained
at 43 C.
Near the end of the peroxide addition, a solution of 0.347 g (2.0 mmol) of
ferrous
acetate and 1.25 g of trifluoroacetic acid in 5 mL of water is added to the
mixture. A
fresh portion of 5.1 g (75 mmol) of 50% aqueous hydrogen peroxide is then
added
over 90 minutes, and the reaction mixture is stirred for 15 hours at 42-45 C.
The
reaction mixture is worked up following a procedure similar to that described
in
Example P9 to afford 17.5 g(71 % yield) of product as a white solid.
Analysis by gas chromatography shows the reaction product contains
approximately 92% of the title compound.
Example P52
4-Hydroxy-l-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 17.2 g(100 mmol) of 4-hydroxy-l-oxyl-2,2,6,6-tetramethyl-
piperidine in 35 mL of water and a solution of 31.6 g (464 mmol) of 50%
aqueous
hydrogen peroxide are added simultaneously over 2.5'hours and 15 hours,
respectively, to a mixture of 0.561 g (3.1 mmol) of ferrous oxalate dihydrate,
20 mL of
water, 1.26 g of oxalic acid dihydrate, and 200 mL of tert-butyl alcohol which
is
maintained at 43-65 C. After the peroxide is added, the reaction mixture is
stirred for
seven hours at 50-60 C. Oxalic acid dihydrate (1.26 g) and 0.380 g (2.2 mmol)
of
ferrous oxalate dihydrate are added to the reaction mixture and stirring is
continued at
65-80 C for seven hours.
Analysis by gas chromatography shows the reaction mixture comprises
approximately 86% of the title compound and less than 4% of the starting
material
based on hindered amine content.
Examp Ie P53
4-Hydroxy-l-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-
piperidne in 35 mL of water and a solution of 23.4 g (344 mmol) of 50% aqueous
hydrogen peroxide are added simultaneously over 2.5 hours and 6 hours,
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respectively, to a mixture of 0.563 g (2.0 mmol) ferrous sulfate heptahydrate,
10 mL
of water, 1.3 mL of methanesulfonic acid, and 200 mL of tert-butyl alcohol
which is
maintained at 45 C. The reaction mixture is stirred at 45 C for two hours
after the
completion of the peroxide addition.
Analysis by gas chromatography shows the reaction mixture comprises 85%
of the title compound and less than 2% of the starting material based on
hindered
amine content.
Exam la e P54
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 46.5 g (270 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-
piperidine in 120.5 g of tert-butyl alcohol and 108 mL of water and a solution
of 37.4 g
(550 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over 3
hours and 11.5 hours, respectively, to a mixture of 3.5 g (12.9 mmol) ferric
chloride
heptahydrate, 32 mL of water, 1.3 g of 85% phosphoric acid, and 292 mL of tert-
butyl
alcohol which is maintained at 80 C. The reaction mixture is maintained at 80
C for
30 minutes after completion of the peroxide addition.
Analysis by gas chromatography shows less than 1% of the starting nitroxyl
compound remains. Excess peroxide is destroyed by sodium sulfite and the crude
product is filtered and treated with sodium borohydride in 14 molar aqueous
sodium
hydroxide to afford 71 % yield of the title compound as analyzed by gas
chromatography.
Example P55
4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
This example shows that a solution of the metal salt can be added dropwise
to the reaction mixture throughout the course of the reaction.
A solution of 1.62 g (8.1 mmol) of ferrous chloride tetrahydrate, 2 mL of 37%
hydrochloric acid, and 50 mL of water and a solution of 35.7 g(525 mmol) of
50%
aqueous hydrogen peroxide are added simultaneously over 13 hours and 16 hours,
respectively, to a mixture of 34.5 g (200 mmol) of 4-hydroxy- 1 -oxyl-2,2,6,6-
tetra-
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methylpiperidine in 100 mL of water and 400 mL of tert-butyl alcohol which is
maintained at a temperature of 38-45 C. The reaction mixture is heated at 40-
45 C
for eight hours after completion of the peroxide addition.
Analysis by gas chromatography shows that the reaction mixture contains
86% of the title compound and less than 5% of the starting nitroxyl compound.
ExamQle P56
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethytpiperidine
Examples 56-57 show the effect of increasing the reaction temperature.
A solution of 2 mL of 98% sulfuric acid in 30 mL of water and a solution of
27.1 g (398 mmol) of 50% aqueous hydrogen peroxide are added simultaneously
over 5.5 hours to a solution of 0.119 g (0.43 mmol) of ferrous sulfate
heptahydrate, 70
mL of water, 34.6 g (201 mmol) of 4-hydroxy- 1 -oxyl-2,2,6,6-
tetramethylpiperidine and
410 mL of tert-butyl alcohol which is maintained at a temperature of 43-45 C.
The
reaction mixture is heated at 45 C for 20 hours after completion of the
peroxide
addition.
Analysis by gas chromatography shows that the reaction mixture contains
73% of the title compound and 18% of the starting nitroxyl compound.
Example P57
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 27.7 g (407 mmol) of 50% aqueous hydrogen peroxide and
90% of a solution of 2.2 mL of 98% sulfuric acid in 30 mL of water are added
simultaneously over 5.25 hours and 6.5 hours, respectively, to a solution of
0.115 g
(0.41 mmol) of ferrous sulfate heptahydrate, 70 mL of water, 34.6 g(201 mmol)
of 4-
hydroxy-l-oxyl-2,2,6,6-tetramethylpiperidine and 410 mL of tert-butyl alcohol
which is
maintained at a temperature of 63-68 C. All of the peroxide is consumed after
6.5
hours.
Analysis by gas chromatography shows that the reaction mixture contains
76% of the title compound and 12% of the starting nitroxyl compound.
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Example P58
4-Hydroxy-1-(2-hydroxy-2-methyipropoxy)-
2,2,6,6-tetramethyipiperidine
A solution of 10.0 g (58.1 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-
piperidine in 20 mL of water and a solution of 15 g(220 mmol) of 50% aqueous
hydrogen peroxide are added simultaneously over 1.5 hours and 7 hours,
respectively, to a solution of 0.394 g (1.77 mmol) of fen7c phosphate
tetrahydrate, 13
mL of water, and 120 mL of tert-butyl alcohol which is maintained at a
temperature of
63-81 C. The reaction mixture is stirred overnight at room temperature. A
fresh
portion of 1.0 g(15 mmol) of 50% aqueous hydrogen peroxide is added, and the
reaction mixture is stirred for 24 hours at 80 C to bring the amount of the
nitroxyl
compound to less than 1.5% of the original amount. Excess peroxide is
decomposed
with sodium sulfite.
Analysis by gas chromatography shows the reaction mixture contains
approximately 89% of the title compound based on total hindered amine content.
Example P59
4-Hydroxy-1-(2-hydroxy-2-methyipropoxy)-
2, 2, 6,6-tetramethyipiperidi ne
A solution of 10.1 g (58.7 mmol) of 4-hydroxy-l-oxyi-2,2,6,6-tetramethyl-
piperidine in 30 mL of water and a solution of 16.3 g(240 mmol) of 50% aqueous
hydrogen peroxide are added simultaneously over 2 hours and 6 hours,
respectively,
to a solution of 1.31 g (1.76 mmol) of ferric pyrophosphate, 20 mL of water,
and 120
mL of tert-butyl alcohol which is maintained at a temperature of 60-79 C. The
reaction
mixture is stirred ovemight at room temperature. To the reaction mixture are
added a
solution of 15 mL of tert-butyl alcohol, 0.34 g (0.46 mmol) of ferric
pyrophosphate,
and 3.8 g (56 mmol) of 50% aqueous hydrogen peroxide. The mixture is then
heated
for ten hours at 75-80 C. Excess peroxide is decomposed with sodium sulfite.
The
reaction mixture is worked up in a procedure similar to that described in
Example P9
to afford 10.2 g(71 ! yield) of product as a white solid which is consistent
with the
title compound according to gas chromatography analysis.
Exampie P60
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4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
This example illustrates the effect of combining two different metal salts in
the instant process.
A solution of 0.13 g (0.52 mmol) of cupric sulfate pentahydrate, 1 mL of 98%
sulfuric acid, and 15 mL of water and a solution of 13.6 g(200 mmol) of 50%
aqueous
hydrogen peroxide are added simultaneously over 3.5 hours and 4.25 hours,
respectively, to a solution prepared by the addition of 17.4 g(101 mmol) of 4-
hydroxy-
1-oxyl-2,2,6,6-tetramethylpiperidine in 50 mL of water to a mixture of 0.14 g
(0.50
mmol) of ferrous sulfate heptahydrate, 10 mL of water and 200 mL of tert-butyl
alcohol. The reaction mixture is kept at 40-45 C during the addition, and then
stirred
ovemight at room temperature.
Analysis by gas chromatography shows that 77% of the starting compound
is converted to the title compound.
Examale P61
Mixture of Bis[1-(2-hydroxy-2-methytpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl] Adipate and
Bis[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl] Glutarate
A solution of 159 g (2.34 mol) of 50% aqueous hydrogen peroxide is added
dropwise to a mixture of 168.4 g of a mixture of bis[1-oxyl-2,2,6,6-
tetramethyl-
piperidin-4-yl] adipate and bis[1-oxyl-2,2,6,6-tetramethylpiperidin-4-yi]
glutarate
prepared from DBE-3 (dibasic ester, DuPont having approximately 9:1 dimethyl
adipate:dimethyl glutarate), 2.03 g (7.5 mmol) of ferric chloride hexahydrate,
1.5 mL
of 37% hydrochloric acid, 1.9 mL of tert-butyl alcohol and 262 mL of water at
a
temperature of 40 C. After a total reaction time of 30 hours, the temperature
is
increased to 70 C and a solution of 71 g (1A4 mol) of 50% aqueous hydrogen
peroxide is added to the mixture over six hours. After the mixture is stirred
for 13
hours at 65 C, another 71 g portion of 50% aqueous hydrogen peroxide is added
over
six hours, and the mixture is stirred at 65 C for 17 hours. Excess peroxide is
decomposed with sodium sulfite. The mixture is filtered to remove solids, and
most of
the tert-butyl alcohol and water are removed by co-distillation with heptane.
The
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residue is extracted with ethyl acetate, and the solution is washed with
saturated
sodium'chloride solution. Solvent is evaporated, and the residue is purified
by flash
chromatography on silica gel with hexane/ethyl acetate to afford 84.1 g of a
white
solid melting at 131.5-133 C. A second crop of 16.3 g of a white solid melting
at 128-
130 C is also obtained.
NMR analysis shows the structure of the white solid to be consistent with the
expected adipate/glutarate reaction product.
Examgle P62
Mixture of Bis[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl] Adipate and
Bis[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl] Glutarate
The procedure outlined in Example P61 is repeated using a mixture of bis[1-
oxyl-2,2,6,6-tetramethylpiperidin-4-yl] adipate and bis[1-oxyl-2,2,6,6-
tetramethyl-
piperidin-4-yiJ glutarate prepared from DBE-2 (dibasic ester, DuPont having
approximately 3:7 dimethyl adipate:dimethyl glutarate) in place of bis[1-oxyl-
2,2,6,6-
tetramethylpiperidin-4-yl] adipate and bis[1-oxyl-2,2,6,6-tetramethyipiperidin-
4-yl]
glutarate prepared from DBE-3 described in Example P61.
Example P63
4-Hydroxy-l-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-
piperidine in 50 mL of water and a solution of 25.2 g (370 mmol) of 50%
aqueous
hydrogen peroxide are added simultaneously over four hours and eight hours,
respectively, to a mixture of 1.12 g (4.0 mmol) of ferrous sulfate
heptahydrate, 20 mL
of water and 1 mL of methanesulfonic acid and 400 mL of tert-butyl alcohol
which is
maintained at 80-85 C. A solution of 0.506 g (1.8 mmol) of ferrous sulfate
heptahydrate and 0.3 mL of methanesulfonic acid in 2 mL of water is added to
the
reaction mixture during the peroxide addition. The mixture is stirred at 80-85
C for 30
minutes after the peroxide is added. Gas chromatography shows that less than
1% of
the starting nitroxyl remains. The reaction is worked up following a procedure
similar
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to that of Example P9 to afford 40.8 g of a white solid which contains 98% of
the title
compoi,nd by gas chromatography analysis.
Further examples illustrating the novel compounds are the following:
Example
Reaction of 1- xyl-2,2,6,6-tetrarnethyl-
piperidin-4-one with Cyclohexanol
A solution of 55 g (0.49 mol) of 30% aqueous hydrogen peroxide is added
dropwise over
a 4.25 hour period to a mixture of 23.5 g (0.14 mol) of 1-oxyl-2,2,6,6-
tetramethyl-piperidin-4-one
and 4.0 g (0.020 mol) of ferrous chloride tetrahydrate in 14 g (0.14 mol) of
cyclohexanol and 150
g of cyclohexane. The reaction temperature is maintained at approximately 40 C
throughout the
addition. The reaction mixture is stirred at 40 C for three hours after the
peroxide addition is
complete. A second portion of 30% aqueous hydrogen peroxide (10 g, 0.09 mol)
is added and
the reaction mixture is heated at 40 C for seven hours. After the mixture is
cooled to room
temperature, sodium sulfite (5 g) is added. The reaction temperature is
carefully brought to 60 C
for one hour to decompose excess peroxide. Upon cooling, the organic layer is
separated, dried
over anhydrous magnesium sulfate, and concentrated to give 22.6 g of a brown
oil. The oil is
dissolved in cyclohexane and passed through silica gel with cyclohexane and
then 1:2 (v/v)
ethanol/cyclohexane to afford 16.5 g of a yellow oil.
Analysis by gass chromatography and mass spectrometry shows the product to be
a
mixture which contains at least four isomers of 1-(hydroxycyclohexyioxy)-
2,2,6,6-tetramethyi-
piperidin-4-one.
Example 2
Bis(1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethyipiperidin-4-yi)] Sebacate
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A solution of 73 g (0.64 mol) of 30% aqueous hydrogen peroxide is added
dropwise over
a 3.5 hbur period to a mixture of 30.0 g (0.059 mol) of bis(1-oxyl-2,2,6,6-
tetramethylpiperidin-yl)
sebacate and 4.7 g (0.024 mol) of ferrous chloride tetrahydrate in 150 g of
tert-butyl alcohol and
6 g of water. The reaction temperature is kept at approximately 40 C
throughout the peroxide
addition. The reaction mixture is stirred at 40 C for four hours after the
addition is complete. The
reaction mixture is diluted with 150 g of ethyl acetate. A colution of 100 g
of 20% aqueous
sodium sulfite solution is added and the reaction mixture is stirred for 1.5
hours at 45-60 C to
decompose excess peroxide. The aqueous layer is extracted with 100 g of ethyl
acetate, and
the combined organic layers are washed with 200 g of 5% sulfuric acid. Solvent
is evaporated to
obtain 39.4 g of a pale yellow liquid which is purified by flash
chromatography on silica gel with
a 4:1:5 part mixture (by volume) of ethyl acetate:isopropanol:hexane to afford
19.1 g (49% yield)
of the title compound as a pale yellow oil.
'Hnmr (CDCI3): S = 3.65 ppm (4H, -NOCH2-)
Exam In e 3
Reaction of 6is(1-oxyl-2,2,6,6-tetramethyl-
piperidin-4-yl) Sebacate with Cyclohexanol
A solution of 70 g(0.62 mol) of 30% aqueous hydrogen peroxide is added
dropwise over
2.75 hours to a mixture of 32.4 g (0.063 mol) of bis(1-oxyl-2,2,6,6-
tetramethylpiperidin-yl)
sebacate and 5.0 g (0.025 mol) of ferrrous chloride tetrahydrate in 100 g of
cyclohexanol. The
reaction temperature is maintained at 40-45 C during the addition. The
reaction mixture is then
stirred at 40 C for five hours and during this time, fresh 50% aqueous
hydrogen peroxide (5.0 g,
0.074 mol) is added to the reaction mixture in two equal portions. The
following day, the reaction
mixture is heated to 40 C, another portion of 50% aqueous hydrogen peroxide
(2.5 g, 0.037
mol) is added, and the mixture is maintained at 40 C for another five hours. A
solution of 100 g
of 20% aqueous sodium sulfite is added to the mixture and the reaction
temperature is
maintained at 70 C for 45 minutes to decompose excess hydrogen peroxide. The
combined
organic layers are concentrated to give 151 g of crude product. Water is
added, and residual
cyclohexanol is removed by steam distillation. The remaining 50 g of crude
product is purified by
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fiash chromatography on silica gel with a 10:1:10 part mixture of ethyl
acetate:ethanol:hexane to
afford 32.9 g of an oil.
NMR analysis shows that the oil contains bis[1-(trans-2-hydroxycyciohexyioxy)-
2,2,6,6-tetra-
methyipiperidin-4-ylJ sebacate in addition to other structural isomers of said
sebacate
compound.
Ecamnig4
Reaction of 4-Hydroxy-l-oxyl-2,2,6,6-
tetramethyipiperidine with Cyclohexanol
A solution of 50 g(0.74 mol) of 50% aqueous hydrogen peroxide is added
dropwise over
a 1.75 hour period to a mixture of 35.0 g (0.20 mol) of 4-hydroxy-1 -oxyl-
2,2,6,6-tetramethyl-
piperidine and 10.0 gr (0.050 mol) of ferrous chloride tetrahydrate in 100 g
of cyclohexanol. The
reaction temperature is maintained at approximately 40-45 C throughout the
addition. After the
peroxide addition is complete, the reaction mixture is stirred at 40 C for
five hours. The mixture
is cooled to room temperature and a solution of 100 g of 20% aqueous sodium
sulfite is added.
The reaction mixture is carefully heated at 60 C for one hour to decompose
excess peroxide.
After acetone is added to the organic layer, the crude product mixture is
filtered to remove solids
and the filtrate is concentrated. Water is added and residual cyclohexanol is
removed by steam
distillation. The crude product is purified by flash chromatography on silica
gel with 2:1 (v/v)
hexane/ethyl acetate to afford 36.3 g of a yellow oil.
Analysis by mass spectrometry shows the oil to be a mixture of isomers of 1-
(hydroxycycio-
hexyioxy)-4-hydroxy-2,2,6,6-tetramethyipiperidine and 1-
(dihydroxycyciohexyioxy)-4-hydroxy-
2,2,6,6-tetramethyipiperidine.
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Examnle 5
Reaction of 2,4-Bis[N-( i -oxyl-2,2,6,6-tetramethyl
piperidin-4-yl)butylamino-6-chloro-s-triazine with Cyclohexanol
A solution of 30 g (0.44 mol) of 50 aqueous hydrogen peroxide is added over a
2 hour
period to a mixture of 39.4 g (0.070 mol) of 2,4-bis[N-(1-oxyl-2,2,6,6-
tetramethytpiperidin-4-yl)-
butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferrous chloride
tetrahydrate in 150 g of
cyclohexanol at a temperature of 40-45 C. The reaction mixture is stirred at
40 C for ten hours
after the peroxide addition is complete, and during this time, another 19 g
(0.28 mol) portion of
5W6 aqeuous hydrogen peroxide is added. Another portion of 50% aqueous
hydrogen peroxide
(25 g, 0.37 mol) is added while the reaction mixture is heated at 50-65 C for
four hours. The
reaction mixture is treated with a solution of 100 g of 20% aqueous sodium
sulfite at 60 C for
one hour to decompose residual peroxide. The organic layer is concentrated to
a brown oil
which is extracted thrice with cyclohexane and once with ethyl acetate. The
combined extracts
are concentrated to afford 43.4 g of a yellow solid.
Examnle 5A
2,4-Bis(N-[1-(trans-2-hydroxycyclohexyloxy)-
2,2,6,6-tetramethylpiperidin-4-yl}butylamino)-
6-(2-hydroxyethyl)amino-s-triazine
The product obtained in Example 5 is reacted with ethanolamine and sodium
hydroxide
solution. The crude reaction mixture is duluted with ethyl acetate and washed
with water. The
aqueous layer is extracted with ethyl acetate, and the combined organic layers
are
concentrated. The residue is dissolved in ethyl acetate and cyclohexane is
added. A brown oil is
removed. The remaining solution is concentrated to give 13.7 g of crude
product. The crude
product is purified by flash chromatography on silica gel with 2:1 (v/v) ethyl
acetate/hexane and
then 8:1 (v/v) ethyl acetate/methanol to afford 6.4 g of a yellow oil. The oil
is dissolved in ethanol
and treated with decolorizing carbon at 60 C for one hour. Solids are removed
by fittration and
the solvent is evaporated to give 6.5 g of an off-white solid, melting at 67-
80 C.
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NMR analysis shows the solid contains the title compound in addition to a
mixture of hydroxy-
cyclohexyloxy and dihydroxycyclohexyloxy structural isomers.
Example 6
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 50.7 g (0.75 mol) of 50% aqueous hydrogen peroxide mixed with 25
mL of
tert-butyl alcohol is added over two hours to a mixture of 25.8 g (0.15 mol)
of 4-hydroxy-l-oxyl-
2,2,6,6-tetramethylpiperidine, 8.95 g (0.045 mol) of ferrous chloride
tetrahydrate and 110 mL of
tert-butyl alcohol at 50 C. The reaction mixture is then maintained at 50 C
for six hours and
monitored by gas chromatography. Another 17.7 g(0.26 mol) of 50% hydrogen
peroxide is
added and the reaction mixture is heated at 50 C for two more hours to bring
about complete
reaction of the starting nitroxyl compound. The reaction mixture is filtered
to remove solids, and
the filtrate is diluted with water. The tert-butyl alcohol-water solution is
extracted three times with
methylene chloride and the aqueous layer is thoroughly extracted with ethyl
acetate to afford 7.4
g of the title compound. The combined organic layers are washed once with
saturated sodium
chloride, dried over anhydrous magnesium sulfate and concentrated to give 21.7
g of an orange
oil. The orange oil is purified by flash chromatography on silica gel with 3:2
heptane:ethyl
acetate to afford another 12.4 g of the title compound and 4.2 g of a compound
which has the
same retention time by gas chromatography as an authenic sample of 1-(2-
hydroxy-2-rnethyl-
propoxy)-2,2,6,6-tetramethylpiperidin-4-one.
Examples 6A to 6D illustrate the effect of adding a ligand to the procedure
described in
Example 6.
Examole 6A
4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
Ferrous chloride tetrahydrate (0.99 g, 5.0 mmol) is added to 400 mL of tert-
butyl
alcohol which is heated to 40 C. The mixture is stirred for 15 minutes and
0.78 g (5.0 mmol) of
2,2'-dipyridyl is added to the tert-butyl alcohol solution. The solution is
then stirred for five
minutes and 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-
tetramethylpiperidine is added. A
solution of 49 g (0.72 mol) of 50% aqueous hydrogen peroxide mixed with 100 mL
of tert-butyl
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alcohol is added to the reaction mixture over a 10-hour period at 40-45 C.
Another 6 g(0.088
mol) of 50% aqueous hydrogen peroxide is then added while the reaction mixture
is heated at
45 C for four hours until the starting nitroxyl compound is reacted. Analysis
by gas
chromatography shows the reaction mixture contains 6 area % of 1-(2-hydroxy-2-
methyl-
propoxy)-2,2,6,6-tetramethylpiperidin-4-one compared to 22 area % in Example
6. Solids are
removed by filtration, and after 1.5 g of sodium borohydride is added, the
filtrate is stirred for
one hour. The filtrate is diluted with water, and the mixture is thoroughly
extracted with ethyl
acetate. The extract is concentrated to afford 24.2 g of a light tan
crystalline solid which has the
same gas chromatography retention time as an authenic sample of the title
compound. In a
similar experiment, the final product is recrystallized several times from
heptane to obtain 16.9 g
(69% yield) of the title compound, melting at 127-131 C.
Examgle 6B
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 32.3 g (475 mmol) of 50% aqueous hydrogen peroxide mixed with 35
mL
of tert-butyl alcohol is added over six hours at 45-50 C to a mixture prepared
by adding
sequentially 0.362 g (1.2 mmol) of ethylenediaminetetraacetic acid, 55 mL of
tert-butyl alcohol
and 17.2 g (100 mmol) of 4-hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine to a
solution of 0.80 g
(4 mmol) of ferrous chloride dissolved in 5 mL of water. Analysis by gas
chromatography shows
15% starting nitroxyl compound remains at the end of the peroxide addition.
The reaction
mixture is stirred for one hour at 45-50 C and then for 72 hours at 25 C to
complete the
reaction. Analysis by gas chromatography shows the reaction mixture contains a
ratio of 7 parts
of the title compound to 1 part of 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetrarnethylpiperidin-4-
one.
Exarnale 6C
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
The procedure of Example 6B is repeated using triphenytphosphine oxide in
place of
the ethylenediaminetetraacetic acid.
Exam It~ e 6D
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4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
The procedure of Example 6B is repeated using ethylenediaminetetraacetic acid
disodium salt in place of ethylenediaminetetraacetic acid.
x le 7
Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl] Adipate
Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-
tetramethyl-
pieridin-4-yl) adipate and ferrous chloride tetrahydrate in tert-butyl alcohol
at 30-50 C. Excess
peroxide is decomposed with aqeuous sodium sulfite solution. The organic layer
is concentrated
and the crude product is purified by flash chromatography on silica gel to
afford the title
compound.
Example
Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl] Glutarate
Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-
tetramethyl-
pieridin-4-yl) glutarate and ferrous chioride tetrahydrate in tert-butyl
alcohol at 30-50 C. Excess
peroxide is decomposed with aqeuous sodium sulfite solution. The organic layer
is concentrated
and the crude product is purified by flash chromatography on silica gel to
afford the title
compound.
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Examl2le 9
Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl] Succinate
Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-
tetramethyl-
pieridin-4-yl) succinate and ferrous chloride tetrahydrate in tert-butyl
alcohol at 30-50 C. Excess
peroxide is decomposed with aqeuous sodium sulfite solution. The organic layer
is concentrated
and the crude product is purified by flash chromatography on silica gel to
afford the title
compound.
Exam la e 10
Bis[1-(2-hydroxy-1-phenethoxy)-2,2,6,6-
tetramethylpiperidin-4-yl] Sebacate
Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-
tetramethyl-
pieridin-4-yl) sebacate and ferrous chloride tetrahydrate in. phenethyl
alcohol at 30-50 C. Excess
peroxide is decomposed with aqeuous sodium sulfite solution. The organic layer
is concentrated
and the crude product is purified by flash chromatography on silica gel to
afford the title
compound.
Examole 11
2,4-Bis(N-[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-
6-chloro-s-triazine
A total of 40 g (0.59 mol) of 50% aqueous hydrogen peroxide is added in two
portions
over five hours to a mixture of 43.2 g (0.076 mol) of 2,4-bis[N-(1-oxyl-
2,2,6,6-tetramethyl-
piperidin-4-yl)butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferrous
chloride
tetrahydrate in 150 g of tert-butyl alcohol and 15 g of water. Another portion
of 50% aqueous
hydrogen peroxide (3 g, 0.044 mol) is added to the reaction mixture while the
temperature is
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maintained at 40-45 C for 2.25 hours. The reaction mixture is diluted with 100
g of ethyl acetate.
A solution of 100 g of 20% aqueous sodium sulfite is added and the reaction
mixture is heated
at 60 C for one hour to decompose residual peroxide. The aqueous layer is
extracted with ethyl
acetate, and the combined organic layers are concentrated. The crude product
is purified by
flash chromatography on silica gel with 1:1 (v/v) hexane/ethyl acetate to
afford 54.1 g of the title
compound.
Examnle 12
2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-
2,2,6, 6-tetramethylpiperidi n-4-yl]butylamino}-
6-(2-hyd roxyethyl)amino-s-triazine
The title compound is prepared by the reaction of the intermediate prepared in
Example
11 with ethanolamine and sodium hydroxide. The aqueous layer is removed, and
the remaining
layer is extracted with cyclohexane. Solvent is evaporated at reduced
pressure, and the crude
product is purified by flash chromatography on silica gel with 1:2 (v/v)
hexane/ethyl acetate to
afford 4.1 g of the title compound as a white solid, melting at 110-120 C.
'Hnmr (CDCI3): S= 3.54 ppm (q,2H, NCH2); 3.59 ppm (s,4H, NOCH2).
Example 13
Reaction of the Product of Example 11 with
N, N'-Bis(3-aminopropyl)ethylenediami ne
The product prepared in Example 11 is reacted with N,N'-bis(3-
aminopropyl)ethylene-
diamine in a 3:1 molar ratio. The product mixture includes N,N',N"-tris{2,4-
bis[N-[1-(2-hydroxy-2-
methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-
3,3'-ethylenediimino-
dipropylamine and N,N',N"'-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethyl-
piperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropyiamine.
Example 14
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2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-
2,2, 6,6-tetramethylpiperidin-4-yl]butylamino}-
6-octylam i no-s-triazi ne
The reaction of the compound prepared in Example 11 with excess octylamine
yields the
title compound as an off-white glass melting at 68-86 C.
Exam .21e 15
N,N'-Bis(4,6-bis(N-[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-
s-triazin-2-yl}-1,6-diaminohexane
The title compound is prepared by the reaction of the compound prepared in
Example 11
with hexamethylenediamine.
Example 16A
Reaction of 4-Hydroxy-l-oxyl-2,2,6,6-
tetramethylpiperidine with tert-Butyl Alcohol
A solution of 50% aqueous hydrogen peroxide is added to a mixture of 4-hydroxy-
l-oxyl-
2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in tert-butyl
alcohol at 30-60 C.
Excess peroxide is decomposed with aqeuous sodium sulfite. The organic layer
is concentrated
and the crude product is purified by flash chromatography on silica gel to
afford a sample of 4-
hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.
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Example 16B
1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yi Methacrylate
The title compound is prepared by reaction of the compound prepared in Example
16A
with methyl methacrylate.
Examole 17
4-Allyloxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A suspension of 8.4 g (0.21 mol) of 60% sodium hydride in mineral oil is added
in
portions at 50 C to a solution of 49.1 g (0.20 mol) of the compound obtained
in Example 16A in
500 ml of anhydrous diglyme. Allyl bromide (20.8 ml, 29.1 g, 0.24 mol) is then
added to the
reaction mixture over several hours, and the mixture is stirred at 50 C for 7
hours. The reaction
is cooled and quenched with 2N hydrochloric acid solution. After the addition
of a saturated
solution of sodium bicarbonate to neutralize excess acid, the organic layer is
concentrated to
afford 47.5 g (83% yield) of the title compound, which is a yellow oil.
Example 18
4-(2,3-Epoxypropoxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
The title compound is prepared by the reaction of the compound prepared in
Example
16A with epichlorohydrin.
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Example 19
1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-
piperidin-4-yl 3-{[[[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yloxy]carbonyl]-
amino]methyl}-3,5,5-trimethylcyclohexylcarbamate
The title compound is prepared by the reaction of the compound prepared in
Example
16A with 5-isocyanato-l-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (=
isophorone
diisocyanate).
Exam la e 20
Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl] 1,6-Hexanedicarbamate
The title compound is prepared by the reaction of the compound prepared in
Example
16A with hexamethylene diisocyanate.
Examale 20A
Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyipiperidin-4-yl] toluene-
2,4-
dicarbamate
The title compound is prepared from the reaction of the compound obtained in
Example
16A with toluene-2,4-diisocyanate.
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Examole 20B
1,3,5-tris{[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-
yloxy]carbonylaminohexyl}-2,4,6-trioxo-s-triazine
The title compound is prepared from the reaction of the compound obtained in
Example
16A with 1,3,5-tris[6-isocyanatohexyl]-2,4,6-trioxo-s-triazine (DESMODUR N-
3390).
Examole 21
1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethyipiperidin-4-yl Acrylate
The title compound is prepared by the reaction of the compound prepared in
Example
16A with methyl acrylate.
Example 22
2,4,6-Tris{N-[1-(2-hydroxy-2-methytpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-
s-triazine
A solution of 40 g (0.35 mol) of 30% aqueous hydrogen peroxide is added over
1.25
hours to a mixture of 11.7 g (0.011 mol) of 2,4,6-tris[N-(1-oxyl-2,2,6,6-
tetramethylpiperidin-4-yl]-
butyiamino}-s-triazine and 3.0 g(0.015 mol) of ferrous chloride tetrahydrate
in 100 g of tert-butyl
alcohol and 9 g of water. The reaction temperature is maintained at 60-65 C
during the peroxide
addition. Two equal portions (2 g, 0.29 mol) of 50% aqueous hydrogen peroxide
are added to
the reaction mixture while the temperature is maintained at 60 C for 9.5
hours. After the reaction
mixture is diluted with ethyl acetate and cooled to room temperature, a
solution of 100 g of 20%
aqueous sodium sulfite is added. The reaction mixture is heated at 60 C for
one hour to
decompose the excess peroxide. The aqueous layer is extracted with ethyl
acetate, and the
combined organic layers are concentrated. The crude product is purified by
flash
chromatography on silica gel with 2:1 (v/v) cyclohexane/ethyl acetate to
afford a material which
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is triturated with 1:1 (v/v) cyclohexane/acetone to give 4.0 g of the title
compound as a white
solid, melting at 172-176 C.
Exam Ig e 23A
Reaction of 1-Oxyl-2,2,6,6-tetramethyl-
piperidin-4-one with tert-Butyl Alcohol
Aqueous hydrogen peroxide is added to a mixture of 1 -oxyl2,2,6,6-
tetramethylpiperidin-
4-one and ferrous chloride in tert-butyl alcohol at 30-60 C. Excess peroxide
is decomposed with
aqueous sodium sulfite. The organic layer is concentrated and the residue is
purified by flash
chromatography to afford the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethyl-
piperidin-4-one.
ExamAle 23B
4-Butylamino-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A mixture of butylamine, the compound prepared in Example 23A and a catalytic
amount
of 5% platinum on carbon is hydrogenated at 3 atmospheres using a Parr
apparatus. The
catalyst is removed by filtration, and the solvent is evaporated to afford the
title compound.
Example 24
4-Trimethylsilyloxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethyl piperidine
Chlorotrimethylsilane (6.4 ml, 0.050 mol) is added over 15 minutes at 60 C to
a mixture
of 12.25 g (0.050 mol) of the compound obtained in Example 16A, 8.5 ml of
triethylamine and
125 ml of anhydrous tetrahydrofuran. The reaction mixture is stirred at 60 C
for 2 hours, then
stirred at room temperature for 1 hour. Solvent is evaporated, and the residue
is partitioned
~. _
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between water and dichloromethane. The organic layer is dried over magnesium
sulfate and
concentrated to obtain 14.6 g (92% yield) of the title compound as a yellow
oil.
Exam Ip e 25
4-Benzoyloxy-1 -(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine
A solution of 50% aqueous hydrogen peroxide is added slowly to a mixture of 4-
benzoyl-
oxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in
tert-butyl alcohol at
30-60 C. Excess peroxide is decomposed by aqueous sodium sulfite solution. The
organic layer
is concentrated and the residue is purified by flash chromatography to afford
the title compound.
Example 26
1-(2-Hydroxy-2-methylpropoxy)-4-[3-(trimethyl-
silyl)propoxy]-2,2,6,6-tetramethylpiperidine
The title compound is prepared by reacting the compound prepared in Example 17
with
trimethylsilane and hydrogen hexachloroplatinate(IV) in isopropyl alcohol.
Exampie 26A
1-(2-Hydroxy-2-methylpropoxy)-4-[3-(diethylmethylsilyl)propoxy]-2,2,6,6-
tetramethylpiperidine
A mixture of 28.5 g(0.10 mol) of the compound obtained in Example 17, 14.5 ml
(0.10
mol) of diethylmethylsilane, and 1 ml of a solution of 2% hydrogen
hexachloroplatinate(IV) in
isopropyl alcohol is heated at reflux for 4 hours. The reaction mixture is
distilled under vacuum
to obtain a viscous, pale yellow oil. Mass spectroscopy reveals that the
reaction product has a
molecular ion of 387, which is consistent with formation of the title
compound.
Example 27
. , . .. . . . . . . ....., . .. ,. . .... . ..
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Tetrakis{3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yloxy]propyl}-
1,3,5,7-tetramethylcyclotetrasiloxane
The title compound is prepared by heating a mixture of 30.3 g(0.106 mol) of
the
compound obtained in Example 17, 6.3 rnl (0.026 mol) of 1,3,5,7-
tetramethylcyclotetrasiloxane,
and 1 ml of a 2% solution of hydrogen hexachloroplatinate(IV) in isopropyl
alcohol at 1000 C for
4 hours. The reaction mixture is cooled and partitioned between
dichloromethane and water.
The organic layer is filtered and concentrated at reduced pressure to obtain
31.7 g (98% yield)
of the title compound as a viscous orange oil.
Exam Ip e 28
Poly{(3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yloxy]propyl]methyl}silane
The title compound is prepared by the reaction of the compound prepared in
Example 17
with poly(methylsilane) and hydrogen hexachloroplatinate(IV) in isopropyl
alcohol.
Example 29
Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-
yloxy]propyl]methyl}siloxane, terminated with trimethylsiloxy
The title compound is prepared by heating a mixture of 29.6 g(0.104 mol) of
the
compound obtained in Example 17, 6.8 g (0.004 mol) of
poly(methylhydrosiloxane), terminated
with trimethylsiloxy, average molecular weight 1700, and 1 ml of a 1 %
solution of hydrogen
hexachloroplatinate(IV) in isopropyl alcohol at 100 C for 1 hour. The
resulting poiymeric mass
is partially dissolved in hot dichloromethane, and the suspension is extracted
with hot water.
The organic layer is concentrated to obtain 34.7 g of the title compound as a
white, rubbery
solid.
Anal. Calcd. for C439.5H91oN25.501033i27.5 (n=25.5 in starting material): C,
58.82; H, 10.21; N, 3.97
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Found C, 59.62; H 10.11, N 3.08
Example 30
Mixture of Bis[1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl] Glutarate
and Bis [1- (2-Hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl] Adipate
A mixture of the compound prepared in Example 16A,
DBE-2 dimethyl ester mixture (DuPont), and lithium amide is
heated at reflux in xylene. Methanol is distilled from the
reaction mixture. The reaction mixture is quenched with dilute
mineral acid, and the organic layer is washed with water and
dried over anhydrous magnesium sulfate. The xylene solution is
evaporated at reduced pressure to afford the title compound
mixture.
Example 30A
Mixture of Bis[1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl] Adipate and
Bis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl] Glutarate
A solution of aqueous 50% hydrogen peroxide is added
dropwise to a mixture of ferric chloride, aqueous hydrochloric
acid, water, t-butyl alcohol, and bis(l-oxyl-2,2,6,6-tetra-
methylpiperidin-4-yl) adipate and bis(1-oxyl-2,2,6,6-tetra-
methylpiperidin-4-yl) glutarate, prepared from DBE-3 dibasic
ester (DuPont-). Excess peroxide is decomposed with aqueous
sodium sulfite solution. The reaction mixture is filtered and
solvents are evaporated. The residue is purified by flash
chromatography on silica gel with hexane/ethyl acetate to
afford the title compound as a white solid, mp 131.5-133.
Example 30B
Mixture of Bis[1-(2-Hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl] Glutarate
and Bis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl] Succinate
When the procedure of Example 30 is repeated with
DBE-9 a dimethyl ester mixture (DuPont), the title mixture is
prepared.
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Example 31
Reaction of Bis.(1-oxyl-2,2,6,6-tetramethyl-
piperidin-4-yl) Sebacate with Neopentyl alcohol
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Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-
tetramethyl-
piperidin-4-yl) sebacate and ferrous chloride in neopentyl alcohol according
to the procedure of
Example 25.
Example 32
Reaction of 1-oxyl-2,2,6,6-tetramethyl- piperidin-4-one with Neopentyl Glycol
Aqueous hydrogen peroxide is added to a mixture of 1-oxy1-2,2,6,6-
tetramethylpiperidin-
4-one and ferrous chloride in neopentyl glycol according to the procedure of
Example 25.
Examale 33
Reaction of 4-Octadecanoyloxy-l-oxyl-2,2,6,6-
piperidine with tert-Amyl Alcohol
Aqueous hydrogen peroxide is added to a mixture of 4-octadecanoyloxy-1-oxyl-
2,2,6,6-
tetramethylpiperidine and ferrous chloride in tert-amyl alcohol according to
the procedure of
Example 25.
Examgle 33A
Reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-methyl-2-
butanol
A solution of 34.5 g (0.20 mol) of 4-hydroxy-1 -oxyl-2,2,6,6-
tetramethylpiperidine in 50 ml
of water and a solution of 22.5 g of 50% aqueous hydrogen peroxide are added
at 90-95 C to a
mixture containing a total of 1.88 g of ferrous sulfate heptahydrate, 2.05 g
of methanesulfonic
acid, 20 ml of water, and 450 ml of 2-methyl-2-butanol (t-amyl alcohol). The
reaction is
completed in 6 hours. The reaction mixture is filtered to remove solids, and
the filtrate is stirred
with sodium sulfite followed by basic sodium borohydride. The aqueous layer is
removed, and
the organic layer is concentrated and purified by flash chromatography on
silica gel with
hexane/ethyl acetate to afford 46.3 g of a yellow oil. Analysis by gas
chromatography-mass
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spectroscopy reveals that the product is a mixture of 3 major components, all
with molecular
weight 259, which correspond to the addition of t-amyl alcohol to the starting
nitroxyl compound.
Examole 33B
Transesterification of the reaction product of Example 33A with methyl
stearate
A mixture of 44.8 g(0.173 mol) of the reaction product obtained in Example
33A, 47.1 g
(0.158 mol) of methyl stearate, 0.223 g of lithium amide, and toluene is
heated at reflux.
Methanol is distilled from the reaction mixture along with some of the
toluene. The reaction
mixture is quenched with dilute acetic acid, and washed successively with
water, dilute aqueous
sodium bicarbonate solution, and saturated sodium chloride solution. The
toluene solution is
dried over magnesium sulfate, filtered, and concentrated to obtain a solid.
Purification by flash
chromatography on silica gel with hexane/ethyl acetate affords 70.0 g of an
off white solid
product, mp 38-43.
Examgle 34
4-Benzoyloxy-l-(2-hydroxycyclohexyloxy)-
2,2,6,6-tetramethylpiperidi ne
Tributyltin hydride is added dropwise to a solution of 2-bromocyclohexanol and
excess
4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The
mixture is heated to
facilitate reaction. The crude reaction mixture is passed through silica gel
with heptane and then
heptane/ethyl acetate to afford the title compound as a mixture os cis/trans
isomers.
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Example 35
4-Hydroxy-1 -(2-hydroxycyclohexyloxy)-
2,2,6,6-tetramethylpiperidine
The title compound is prepared by heating the compound prepared in Example 34
in a
solution of potassium hydroxide in methanol.
Example 36
Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6-
tetramethylpiperidine with Propylene Glycol
Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-l-oxyl-2,2,6,6-
tetra-
methylpiperidine and ferrous chloride tetrahydrate in propylene glycol
according to the
procedure of Example 25.
Example 37
Reaction of 4-Benzoyloxy-l-oxyl-2,2,6,6-
tetramethylpiperidine with Trimethylene Glycol
Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-l-oxyl-2,2,6,6-
tetra-
methylpiperidine and ferrous chloride tetrahydrate in trimethylene glycol
according to the
procedure of Example 25.
Examgle 38
Bis[1-(2-hydroxyethoxy)-2,2,6,6-
tetramethylpiperidin-4-ylJ Sebacate
Tributyltin hydride is added dropwise to a solution of 2-iodoethanol and
excess bis(1-
oxyl-_2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The crude
reaction mixture
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is passed through silica gel with heptane and then heptane/ethyl acetate to
afford the title
compound.
Example 39
Reaction of Bis(1-oxyl-2,2,6,6-tetramethyl-
piperidin-4-yl) Sebacate with Isopropanol
Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-
tetramethyl-
piperidin-4-yl) sebacate and ferrous chloride tetrahydrate in isopropanol
according to the
procedure of Example 25.
Example 40
Reaction of 4-Benzoyloxy-l-oxyl-2,2,6,6-tetramethyl-
piperidine with 1,4-Butanediol
Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-1 -oxyl-
2,2,6,6-tetra-
methylpiperidine and ferrous chloride tetrahydrate in 1,4-butanediol according
to the procedure
of Example 25.
Example41
Reaction of 4-Hexyloxy-l-oxyl-2,2,6,6-tetramethyl-
piperidine with Pinacol
Aqueous hydrogen peroxide is added to a mixture of 4-hexyloxy-1-oxyl-2,2,6,6-
tetra-
methylpiperidine and ferrous chloride tetrahydrate in pinacol according to the
procedure of
Example 25.
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ExamQle 42
Reaction of 1-Oxyl-2,2,6,6-tetramethyl-
piperidin-4-one with Glycerol
Aqueous hydrogen peroxide is added to a mixture of 1 -oxyl-2,2,6,6-
tetramethylpiperidin-
4-one and ferrous chloride tetrahydrate in glycerol according to the procedure
of Example 25.
Example 43
Reaction of 4-Hydroxy-l-oxyl-2,2,6,6-tetramethyl-
piperidine with 2-Ethyl-l-hexanol
Aqueous hydrogen peroxide is added to a mixture of 4-hydroxy-1 -oxyl-2,2,6,6-
tetra-
methylpiperidine and ferrous chloride tetrahydrate in 2-ethyl-1 -hexanol
according to the
procedure of Example 25.
Example 44
1-(2-Hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-
2,2, 6,6-tetramethylpiperidine
A mixture of 12.11 g (49.4 mmol) of the compound obtained in Example 16A,
12.11 g
(44.8 mmol) of methyl hexadecanoate (methyl paimitate), 0.76 g of lithium
amide, and toluene is
heated at reflux. Methanol is distilled from the reaction mixture along with
some of the toluene.
The reaction mixture is quenched with dilute acetic acid, and washed
successively with
aqueous methanol, dilute aqueous sodium bicarbonate solution, and saturated
sodium chloride
solution. The toluene solution is dried over magnesium sulfate, filtered, and
concentrated to
obtain a solid. Purification by flash chromatography on silica gel with
hexane/ethyl acetate
affords 18 g of a solid. Recrystallization from methanol yields 10.7 g of the
title compound as a
white solid, mp 60-64.
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Examole 44A
1-(2-hydroxy-2-methylpropoxy)-4-eicosanoyloxy-2,2,6,6-tetramethylpiperidine
A mixture of 8.40 g (34.2 mmol) of the compound obtained in Example 16A, 10.17
g
(31.1 mmol) of methyl eicosanoate, 0.35 g of lithium amide, and toluene is
heated at reflux. The
reaction mixture is quenched with dilute acetic acid, and washed successively
with aqueous
methanol, dilute aqueous sodium bicarbonate solution, and saturated sodium
chloride solution.
The toluene solution is dried over magnesium sulfate, filtered, and
concentrated to obtain a
solid which is purified by flash chromatography on silica gel with
hexane/ethyl acetate to afford
9.9 g of the title compound as a white solid, mp 69-73.
Example 44B
1-(2-hydroxy-2-methylpropoxy)-4-(2-ethylhexanoyioxy)-2,2,6,6-
tetramethylpiperidine
A mixture of 51.6 g (0.210 mol) of the compound obtained in Example 16A, 30.6
g
(0.193 mol) of methyl 2-ethylhexanoate, 1.26 g of lithium amide, and toluene
is heated at reflux.
Methanol is distilled from the reaction mixture along with some of the
toluene. The reaction
mixture is quenched with dilute acetic acid, and washed successively with
aqueous methanol,
dilute aqueous sodium bicarbonate solution, and saturated sodium chloride
solution. The
toluene solution is dried over magnesium sulfate, filtered, and concentrated
to obtain a yellow
liquid. Purification by flash chromatography on silica gel with hexane/ethyl
acetate affords 51.0
g of the title compound as a pale yellow oil.
Example 44C
1-(2-hydroxy-2-methylpropoxy)-4-dodecanoyloxy-2,2,6,6-tetramethytpiperidine
A mixture of 72.7 g (0.297 mol) of the compound obtained in Example 16A, 51.9
g
(0.242 mol) of methyl dodecanoate (methyl laurate), 0.43 g of lithium amide,
and toluene is
heated at reflux. Methanol is distilled from the reaction mixture along with
some of the toluene.
The reaction mixture is quenched with dilute acetic acid, and washed
successively with
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aqueous methanol, dilute aqueous sodium bicarbonate solution, and saturated
sodium chloride
solution: The toluene solution is dried over magnesium sulfate, filtered, and
concentrated to
obtain a solid. Purification by flash chromatography on silica gel with
hexane/ethyl acetate
affords 96.7 g of the title compound as a white solid, mp 46-8.
Ecam ~~ lo e 45
Reaction of N,N',N",N"'-Tetrakis{2,4-bis[N-(1-oxyl-
2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-t(azin-
6-yl)-3,3'-ethylenediiminodipropylamine with Cyclohexano!
A mixture of N,N',N",N"'-tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-
tetramethylpiperidin-4-yl]butyl-
amino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine in cyclohexanol is
reacted with aqueous
hydrogen peroxide and ferrous chloride tetrahydrate according to the method of
Example 4. A
white solid melting at 133-175 C is obtained.
Examg I e 46
Reaction of 2,4,6-Tris(N-(1-oxyl-2,2,6,6-tetramethyl-
piperidin-4-yl]butylarnino)-s-triazine with Cyclohexanol
A mixture of 2,4,6-tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-
yl]butylamino}-s-triazine
and cyclohexanol is reacted with aqueous hydrogen peroxide and ferrous
chloride tetrahydrate
according to the procedure of Example 4. A light brown oil is obtained.
... . . . ..: .... :.. . ...... .. , ., . .., ..... . .... ., . .. . . . ... .
. , . . ... .. ... .. .
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Exam Ip e 47
Bis[1-(3-hydroxypropoxy)-2,2,6,6-tetramethyl-
piperidin-4-yl] Sebacate
Tributyltin hydride is added dropwise to a solution of 3-bromo-l-propanol and
excess
bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The
mixture is heated to
facilitate reaction. The crude reaction mixture is passed through silica gel
with heptane and then
heptane/ethyl acetate to afford the title compound.
Exam le 48
Bis(i -(12-hydroxy-1-dodecyloxy)-2,2,6,6-
tetramethylpiperidn-4-yl] Sebacate
Tributyltin hydride is added dropwise to a solution of 12-bromo-1-dodecanol
and excess
bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The
mixture is heated to
facilitate reaction. The crude reaction mixture is passed through silica gel
with heptane and then
heptane/ethyl acetate to afford the title compound.
Example 49
Bis(1-(2-hydroxypropoxy)-2,2,6,6-tetramethyl-
piperidin-4-yl] Sebacate
Tributyltin hydride is added dropwise to a solution of 1 -bromo-2-propanol and
excess
bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The
mixture is heated to
facilitate reaction. The crude reaction mixture is passed through silica gel
with heptane and then
heptane/ethyl acetate to afford the title compound.
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Example 50
Reaction of the Product of Example 11 with
N, N'-Bis(3-aminopropyl)ethylened iam ine
N,N'-Bis(3-aminopropyl)ethylenediamine and the product prepared in Example 11
are
reacted in a 1:3.0 to 1:3.5 molar ratio. The product mixture includes N,N',N"-
tris{2,4-bis[N-[1-(2-
hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-
triazin-6-yl}-3,3'-
ethyienediiminodipropylamine, N,N',N"'-tris{2,4-bis[N-[1-(2-hydroxy-2-
methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yi}-3,3'-
ethylenediiminodipropylamine, and
N,N',N", N"'-tetrakis{2,4-bis[N-[1-(2-hydroxy 2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-
yi]butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine.
Examnle 51
N,N',N", N"'-Tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methyl-
propoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-
s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine
The title compound is prepared by the addition of aqueous hydrogen peroxide to
a
mixture of N,N',N",N"'-tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-
4-yl]butylamino]-s-
triazin-6-yl}-3,3'-ethylenediiminodipropylamine, ferrous chloride and tert-
butyl alcohol according
to the procedure of Example 7.
Examgle 51 A
N,N',N"'-Tris{2,4-bis[N-[1-(2-hydroxy-2-methyl-
propoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-
s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine
The title compound is prepared by the addition of aqueous hydrogen
peroxide to a mixture of N,N',N"'-tris{2,4-bis[N-(1-oxyl-2,2,6,6-
tetramethylpiperidin-4-
yl)butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine, ferrous
chloride and
tert-butyl alcohol according to the procedure of Example 7.
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Examole 518
N, N',N"-Tris{2,4-bis[N-[1-(2-hydroxy-2-methyl-
propoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-
s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine
The title compound is prepared by the addition of aqueous hydrogen
peroxide to a mixture of N,N',N"-tris{2,4-bis[N-(1-oxyl-2,2,6,6-
tetramethylpiperidin-4-
yl)butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine, ferrous
chloride and
tert-butyl alcohol according to the procedure of Example 7.
Exam Ip e 52
Reaction of the Product of Example 11 with
N,N'-Bis(3-aminopropyl)ethylenediamine
N,N'-Bis(3-aminopropyl)ethylenediamine and the product prepared in Example 11
are
reacted in a 1:4.0 molar ratio. The product mixture includes N,N',N"-tris{2,4-
bis[N-[1-(2-hydroxy-
2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-
3,3'-ethylene-
diiminodipropylamine, N,N',N"'-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetra-
methylpiperidin-4-yi]butylamino]-s-triazin-6-yl}-3,3'-
ethylenediiminodipropylamine, and
N,N',N", N"'-tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-
yl]butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine.
Examole 53A
2-{N-[1-(2-Hydroxy-2-methyipropoxy)-2,2,6,6-tetrarnethyl-
pipe ridin-4-yl]butylamino}-4,6-dichloro-s-triazine
The compound prepared in Example 23B is reacted with an equimolar amount of
cyanuric chloride and sodium bicarbonate at 0 C to give the title compound.
Examole 53B
N,N'-Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
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tetramethylpiperidin-4-yl]-1,6-hexanediamine
The title compound is prepared by the hydrogenation at 50 psi of the compound
obtained in Example 23A, hexamethylenediamine, methanol and a catalytic amount
of 5%
platinum on carbon.
Example 53C
N, N'-Bis{2-[N-(2-hyd roxy-2-methylpropoxy)-2,2,6,6-tetra-
methylpiperidin-4-yl]butylamino]-4-chloro-s-triazin-6-yl}-
N,N'-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl]-1,6-hexanediamine
The title compound is prepared by reaction of the two compounds prepared in
Examples
53A and 53B in a 2:1 molar ratio in xylene at 60-80 C with sodium hydroxide as
the acid
acceptor.
Exam la e 53D
Oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-
methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-
N,N'-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl]-1,6-hexanediamine
terminated with 2,4-bis(dibutylamino)-s-triazin-6-yl
The compounds prepared in Examples 53B and 53C are mixed together in a 2:1
molar
ratio in xylene solution at 100-160 C with sodium hydroxide as the acid
acceptor. The reaction
mixture is then treated with 2,4-bis(dibutylamino)-6-chloro-s-triazine under
the same conditions
to give an oligomeric product having a low number (2, 4, 6, 8) of repeating
units terminated by
the 2,4-bis(dibutylamino)-s-triazin-6-yI moieties as seen in the structure
below.
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CfH, CfB,
Ca, ) 6 N'0 I N-- (ca, )6 N1~~--N
CaHf NN NN N~N CENf
TN N-C 8
CaN ~CENf x + f N C4f C4N9
O O O O
gO NO O HO 80
8O
2,4,6
Examole 54
Oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-
methylpiperidin-4-yl]butylaminoJ-s-triazin-4-yl}-
N,N'-bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl]-1,6-hexanediamine
terminated with 2,4-bis(dibutylamino)-s-triazin-6-yl
N,N'-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine and N,N'-bist2-
[N-(2,2,6,6-
tetramethylpiperidin-4-yl)butylamino]-4-chloro-s-triazin-6-yl}-N, N'-
bis(2,2,6,6-tetramethyl-
piperidin-4-yl)-1,6-hexanediamine are mixed together in a 2:1 molar ratio in
xylene at 100-160 C
with sodium hydroxide as the acid acceptor. The reaction mixture is then
treated with 2,4-
bis(dibutylamino)-6-chloro-s-triazine under the same conditions. The resulting
mixture of
oligomers is heated with tert-butyl hydroperoxide and a catalytic amount of
molybdenum trioxide
in an inert solvent such as 1,2-dichloroethane to form the corresponding N-
oxyl compounds.
Aqueous hydrogen peroxide in then added to the mixture of the N-oxyl compounds
and ferrous
chloride tetrahydrate in tert-butyl alcohol according to the procedure of
Example 7. The final
products is a mixture of oligomers as in Example 53D although the ratios of
the individual
components may not be the same as in Example 53D.
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Exam Ip e 55
Oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-
methylpiperidin-4-yl]butylami no]-s-triazin-4-yl}-
N,N'-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl]-1,6-hexanediamine
terminated with 2-butyiamino-4-{N-[1-(2-hydroxy-
2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-
butylamino-s-triazin-6-yl
The title compound is prepared by heating a mixture of the compounds prepared
in
Examples 53A and 53B, in a 1.33 to 1.0 molar ratio in xylene at 100-160 C
using sodium
hydroxide as the acid acceptor. Dibutylamine is then added to the reaction
mixture under the
same conditions to complete the reaction. The product is a mixture of
oligomers that include 1-4
repeating units as seen in the structure below.
CdH9 C~H9
\ N N ( CH2
N C4 He
C~H ~ Ny N NT
4H9
A
C&Hy N N C
O O
N
o HO HC o
HO HO
1-4
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Examnle 56
Oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-
methylpiperidi n-4-yl]butylamino]-s-triazin-4-yl}-
N,N'-bis[1-(2-hydroxy-2-methyipropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl]-1,6-hexanediamine
terminated with 2-butylamino-4-{N-[1-(2-hydroxy-
2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-
butylamino-s-triazin-6-yl
The title compound is prepared by heating a mixture of the compounds prepared
in
Examples 53B and 53C, in a 0.5:1 molar ratio in xylene at 100-160 C using
sodium hydroxide
as the acid acceptor. Dibutylamine is then added to the reaction mixture under
the same
conditions to complete the reaction. The product is a mixture of oligomers
that include 1, 3, 5
and 7 repeating units as seen in the structure below.
:2~-( CH2 T~ N/
\
N N N C4H
4H9
C~H9 N N N C
O O
N N
O HO HO O
HO Ho
1,3,5,7
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Exam Ip e 57
Oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-
methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-
N,N'-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl]-1,6-hexanediamine
terminated with 2-butylamino-4-{N-[1-(2-hydroxy-
2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-
butylamino-s-triazin-6-yl
N,N'-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine and N,N'-bis{2-
[N-(2,2,6,6-
tetramethylpiperidin-4-yl)butylamino]-4-chloro-s-triazin-6-yl}-N, N'-
bis(2,2,6,6-tetramethyl-
piperidin-4-yl)-1,6-hexanediamine are mixed together in a 0.5:1 molar ratio in
xylene at 100-
160 C with sodium hydroxide as the acid acceptor. The reaction mixture is then
treated with
dibutylamine under the same conditions. The resulting mixture of oligomers is
treated with tert-
butyl hydroperoxide and a catalytic amount of molybdenum trioxide in an inert
solvent such as
1,2-dichloroethane to form the corresponding N-oxyl compounds. Aqueous
hydrogen peroxide
in then added to a mixture of the N-oxyl compounds and ferrous chloride
tetrahydrate in tert-
butyl alcohol according to the procedure of Example 7. The final product is a
mixture of
oligomers such as prepared in Example 56 although the ratios of the individual
components
may not be the same as those in the product of Example 56.
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Example
58 Oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethypiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N'-bis[1-(2-hydroxy-2-
methylpropoxy)-2,2,6,6-tetramethypiperidin-4-yl]-1,6-hexanediamine,
terminated with acetyl
The compounds prepared in Examples 538 and C are mixed together in a 2:1
molar ratio in xylene solution at 100-160 C with sodium hydroxide as the acid
acceptor. After the reaction is complete, the reaction mixture is concentrated
at
reduced pressure. Acetic anhydride is added to the reaction mixture at room
temperature, and the mixture is then heated at 130 C. The crude mixture is
cooled and neutralized with potassium carbonate. The reaction mixture is
concentrated at reduced pressure. The product is a mixture of oligomers that
include 2, 4, and 6 repeating units as seen in the structure below.
0 0
H3C N (CH2 )6 N (CH2) 6 CH3
NN
7I C~Hs
N N
N
O O O O
N
HO HO O HO HO
HO
2,4,6
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Examole 59
Oligomer of N-t2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-
methylpiperidin-4-yl]buty{aminoJ-s-triazin-4-yl}-
N,N'-bis[i -(2-hydroxy-2-methyipropoxy)-2,2,6,6-
tetramethylpiperidin-4-yI]-1,6-hexanediamine
terminated with Acetyl
Example 54 is repeated except that acetic anhydride Is used in place of 2,4-
bis(dibutyl-
amino)-6-chloro-s-triazine according to the procedure of Example 58. The final
product is a
mixture of oligomers as described in Example 58 although the ratios of the
components may not
be identical to those of the product prepared in Example 58.
Examnle 60
Poly[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethyipiperidin-4-yi Methacrylate
The title compound is prepared from the free radical polymerization of the
compound
obtained in Example 16B. The average molecular weight of the polymer is 1500-
3000 amu.
Examflle 61
Poly[1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidin-4-yl Acrylate
The title compound is prepared from the free radical polymerization of the
compound
obtained in Example 21. The average molecular weight of the polymer is 1500-
3000 amu.
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Exampte 62
1,4-Bis(4-hydroxy-2,2,6,6-tetramethyl
piperidin-1 -yloxy)-2-butanol
Tributyltin hydride is added dropwise to a solution of 1,4-dibromo-2-propanol
and excess
4-hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The mixture
is heated to
facilitate the reaction. The crude reaction mixture is passed through silica
gel with heptane and
then heptane/ethyl acetate to afford the title compound.
Examgle63
1,3-Bis(4-hydroxy-2,2,6,6-tetramethyl
piperidin-1 -yloxy)-2-propanol
Tributyltin hydride is added dropwise to a solution of 1,3-dibromo-2-propanol
and excess
4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The mixture
is heated to
facilitate the reaction. The crude reaction mixture is passed through silica
gel with heptane and
then heptane/ethyl acetate to afford the title compound.
ExamDle 64
2-Hydroxy-2-methylpropane-1,3-diyi bis{[1-(2-hydroxy-
2-methylpropoxy)-2,2,6,6-tetramethylpiperidi n-4-yi]
(1-oxy-2,2,6,6-tetramethylpipe(din-4-yl) Sebacate
The title compound is isolated by high pressure liquid chromatography from the
crude
reaction product obtained in Example 2.
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Examole 65
1,3-Bis(4-octadecanoyloxy-2,2,6,6-tetrarnethyl
pipe(din-1-yloxy)-2-methyl-2-propanol
Aqueous hydrogen peroxide is added to a mixture of 4-octadecanoyloxy-1 -oxyl-
2,2,6,6-
tetramethylpiperidine and ferrous chloride tetrahydrate in tert-butyl alcohol
at 30-50 C. Excess
peroxide is decomposed with aqueous sodium sulfite solution. The organic layer
is concentrated
to obtain a mixture which includes 1-(2-hydroxy-2-methylpropoxy)-4-
octadecanoyloxy-2,2,6,6-
tetramethylpiperidine and the title compound. The title compound is separated
from the mixture
by high pressure liquid chromatography.
Example 66
1,3-Bis(4-hydroxy-2,2,6,6-tetramethyl
piperidin-1-yloxy)-2-methyl-2-propanol
The title compound is isolated by high pressure liquid chromatography from the
crude
reaction product obtained in Example 16A.
Examale 67
1,3-Bis(4-oxo-2,2,6,6-tetramethyl
piperidin-1-yloxy)-2-methyl-2-propanoi
The title compound is isolated by high pressure liquid chromatography from the
crude
reaction product obtained in Example 23A.
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Examale 68
1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl Hexanoate
The title compound is prepared by heating a mixture of methyl hexanoate, the
compound
prepared in Example 16A, lithium amide and xylene at reflux while methanol is
removed by
distillation.
Exarngle 69
4-6enzoyloxy-1-(2-hydroxyethoxy)-
2,2,6,6-tetramethylpiperidine
Tributyltin hydride is added dropwise to a solution of 2-iodoethanol and 4-
benzoyloxy-1 -
oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The crude reaction
mixtuire is passed
through silica gel with heptane and then heptane/ethyl acetate to afford the
title compound.
Examg1e 70
4-Hydroxy-l-(2-hydroxyethoxy)-
2,2,6,6-tetramethylpiperidine
The title compound is prepared by heating a methanolic solution of the
compound
obtained in Example 69 with potassium hydroxide.
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Examole 71
Poly[4-hydroxy-1-(2-hydroxyethoxy)-
2,2,6,6-tetramethylpiperidin-4-yl succinate]
The title compound is prepared by the reaction of approximately equimolar
amounts of
dimethyl succinate and the compound prepared in Example 70.
Exam Ip e 72
Poly[4-hydroxy-1-(2-hydroxycyclohexyloxy)-
2,2,6,6-tetramethytpiperidin-4-yl succinate]
The title compound is prepared by the reaction of approximately equimolar
amounts of
dimethyl succinate and the compound prepared in Example 35.
Exam lu e 73
1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-
2,2,6,6-tetramethylpiperidine
A mixture of methyl stearate, the compound prepared in Example 16A and a
catalytic
amount of lithium amide is heated at reflux in xylene. Methanol is distilled
from the reaction
mixture. The reaction is quenched with dilute acid. The organic layer is
concentrated and the
crude product is purified by flash chromatography on silica gel to afford the
title compound as a
white solid melting at 51-56 C.
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Example 73A
1-(4-Octadecanoyloxy-2,2,6,6-tetramethyl
piperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane
The title compound is prepared by the reaction of the compound prepared in
Example
16A with excess methyl stearate and a catalytic amount of lithium amide in
xylene.
Example 74
4-Hydroxy-1 -(2-hydroxy-1 -phenethoxy)-
2,2,6,6-tetramethylpiperidine
The title compound is prepared by heating a methanolic solution of the
compound
obtained in Example 10 with potassium hydroxide.
Egample 75
Poly[4-hydroxy-1-(2-hydroxy-1-phenylethoxy)-
2,2,6,6-tetramethylpiperidin-4-yl succinate]
The title compound is prepared by the reaction of approximately equimolar
amounts of
dimethyl succinate and the compound obtained in Example 74.
Examnle 76
Stabilization of Thermoplastic Olefins
Molded test specimens are prepared by injection molding thermoplastic olefin
(TPO)
pellets containing pigments, a phosphite, a phenolic antioxidant or
hydroxylamine, a metal
stearate, ultraviolet light absorbers or a hindered amine stabilizer or a
mixture of UV absorber
and hindered amine stabilizer.
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Pigmented TPO pellets are prepared from pure pigment or pigment concentrate,
coadditives and commercially available TPO by mixing the components in a
Superior/MPM 1"
single screw extruder with a general all-purpose screw (24:1 UD) at 400 F (200
C), cooled in a
water bath and pelletized. The resulting pellets are molded into 60 mil (0.006
inch), 2"x2"
plaques at about 375 F (190 C) on a BOY 30M Injection Molding Machine.
Pigmented TPO formulation composed of polypropylene blended with a rubber
modifier
where the rubber modifier is an in-situ reacted copolymer or blended product
containing
copolymers of propylene and ethylene with or without a ternary component such
as ethylidene
norbornene are stabilized with a base stabilization system consisting of an
N,N-dialkylhydroxyl-
amine or a hindered phenolic antioxidant with or without an organophosphorus
compound.
All additive and pigment concentrations in the final formulation are expressed
as weight
percent based on the resin.
Formulation contained thermoplastic otefin pellets and one or more of the
following
components:
0.0 to 2.0% pigment,
0.0 to 50.0% talc,
0.0 to 0.1 % phosphite,
0.0 to 1.25% phenolic antioxidant,
0.0 to 0.1 % hydroxylamine
0.05 to 0.10 calcium stearate,
0.0 to 1.25% UV absorber
0.0 to 1.25% hindered amine stabilizer.
The components are dry-blended in a tumble dryer prior to extrusion and
molding.
Test plaques are mounted in metal frames and exposed in an Atlas Ci65 Xenon
Arc
Weather-Ometer at 70 C black panel temperature, 0.55 W/m2 at 340 nonometers
and 50%
relative humidity with intermittent light/dark cycles and water spray (Society
of Automotive
Engineers - SAE J 1960 Test Procedure). Specimens are tested at approximately
625 kilojoule
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intervais by performing color measurements on an Applied Color Systems
spectrophotometer
by reflectance mode according to ASTM D 2244-79. Data collected include delta
E, L*, a* and
b* values. Gloss measurements are conducted on a BYK-Gardner Haze/Gloss Meter
at 600
according to ASTM D 523.
UV Exposure Testing
Test speciments exposed to UV radiation exhibit exceptional resistance to
photodegration when stabilized with light stabilizer systems comprising a
combination of 2-(2-
hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazoie (TINUVIN0328, Ciba ), the
compound of
Example 73 and N,N',N",N'"-tetrakis[4,6-bis(butyl-(1,2,2,6,6-
pentamethylpiperidin-4-yl)amino)-s-
triazin-2-yl]-1,10-diamino-4,7-diazadecane (CHIMASSORBO 119, Ciba). The
control sample
consists of a stabilizer formulation commonly used in the industry to impart
UV stability. All of
the samples contain a pigment, Pigment Red 177, and talc.
The test plaques described earlier contain the following (all concentrations
are weight
percent based on resin):
Polymer substrate is commercially available polyolefin blend POLYTROPE TPP
518-01
supplied by A. Schulman Inc. Akron, Ohio)
Color package is 0.025% Red 3B -Pigment Red 177, C.I. #65300.
Each plaque contains:
0.2% TINUVINO 328;
0.1 k calcium stearate; and
15% talc.
The Control plaques additionally contain
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0.1 % IRGANOX B225 (50:50 blend of IRGANOX3 1010, Ciba (neopentanetetrayl
tetrakis(4-hydroxy-3,5-di-tert-butylhydrocinnamate) and IRGAFOS 168, Ciba
[tris-(2,4-di-tert-
butylphenyl) phosphite;
0.2% TINUVIN 770, Ciba [bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate];
0.2% CHIMASSORB 944, Ciba [polycondensation product of 4,4'-hexamethylene-
bis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-
triazine].
The two test plaques (NOR-1 and NOR-2) each contain 0.05% N,N,-diaikylhydroxyl-
amine;
NOR-1 additionally contains
0.2% of CHIMASSORB 119; and
0.2% of TINUVIN 123, Ciba, [bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate].
NOR-2 additionally contains
0.2% of CHIMASSORB'o 119; and
0.2% of the compound of Example 73.
The results of the UV testing are given in the table below.
DE* Gloss Value % Gloss Value
0 3000 0 3000 0 3000
Sample K'IJm2 K'/m2 K' mz K'I/m2 K' m2 K' m2
control 0.0 4.7 66.6 5.4 100 8.1
NOR-1 0.0 4.0 65.5 16.9 100 25.8
NOR-2 0.0 3.8 64.9 45.3 100 69.8
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The compound of Example 73 present in test plaques NOR-2 specifically shows
greatly
improved gloss retention compared to the less effective control system and in
fact is also more
effective that a related hindered amine compound (TINUVIN 123) present in
test plaques NOR-
1. Resistance to color change upon UV exposure is also enhanced.
Polymer blends containing an unsaturated temary component, such as EPDM
blends,
are especially benefited with the more efficient instant light stabilizer
systems described above.
In all cases, the light stabilized formulations show much greated resistance
to
photodegradation than unstabilized specimens which fail quickly under the UV
exposure
conditions outlined above.
Example 77
Paintable TPO
Molded test specimens are prepared by injection molding thermoplastic olefin
(TPO)
pellets containing the instant compounds, pigments and other coadditives as
described in
Example 76.
The light stable formulations are painted with one-pack paint systems and
tested for
TPO/paint interactions. Before painting, the test specimens are first washed
in accordance with
GM998-4801 and dried for 15 minutes at 200 F (94 C). Adhesion promoter is
applied to the dry
film thickness of 0.2-0.4 mils. The samples are dried for five minutes before
a 1 K basecoat is
applied to a film thickness of 1.2-1.4 mils. The painted panels are dried for
three minutes, a
clearcoat is then applied to a dry film thickness of 1.2-1.5 mils followed by
ten minutes flash
drying and a 30 minute oven bake at 250 F (121 C).
Paint adhesion is measured by Aggressive Adhesion Testing (proprietary test
procedure
conducted at Technical Finishing, Inc.) and Taber Scuff. Painted panels which
retain greater
than 80% of the paint finish are considered acceptable. After Aggressive
Adhesion Testing,
samples with less than 5% paint loss are deemed acceptable.
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Samples are tested to evaluate the TPO/paint interactions as follows:
Aggresive HALS
Formutation' Taber Scuff Test Adhesion Test 2K
A 100% removed 6% Loss (fail) 9.1
B 0% removed 4% Loss (pass) 4.6
C 0% removed 3% Loss (pass) 4.0
Formulation A contains 0.2% CHIMASSORB 944, 0.2% TINUVIN 328, 500 ppm
calcium
stearate and 750 ppm N,N-dialkylhydroxylamine in reactor-grade TPO.
A also contains 0.2% of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate
(TINUVINi 770, pKa of
9.1).
Formulations B and C contain 0.2% CHIMASSORBe 119, 0.2% TINUVIN 328, 500 ppm
calcium stearate and 750 ppm N,N-dialkylhydroxylamine in reactor-grade TPO.
B also contains 0.2% of bis(i-octyloxy-2,2,6,fi-tetramethylpiperidin-4-yi)
sebacate (TINUVIN
123, pKa of 4.6).
C also contains 0.2% of 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy
2,2,6,6-tetramethyl-
piperidine (compound of Example 73, pKa of 4.0)
The data in the table indicate that, although formulation A failed in both the
Taber Scuff
and Aggressive Adhesion Tests, both formulations B and C passed both paint
adhesion tests.
However, as inspection of the pK, values attests, the lower the pKa, value
(less basic) for the test
hindered amine compound the less paint loss results in this Aggressive
Adhesion Test. The
instant compound of Example 73 having the hydroxyl moiety present has the
lowest pKa value
and also the least paint loss even better than the close prior art compound
where no hydroxyl
moiety is present.
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Exam I
Stabilization of Polypropylene Molded Articles
Molded test specimens are prepared by injection molding polypropylene pellets
containing pigments, a phosphite, a phenolic antioxidant or hydroxylamine, a
metal stearate,
ultraviolet light absorbers or a hindered amine stabilizers or a mixture of UV
absorbers and
hindered amine stabilizers.
Pigmented polypropylene pellets are prepared from pure pigment or pigment
concentrates, stabilizers, co-additives and commercially available
polypropylene by mixing the
components in a Superior/MPM 1" single screw extruder with a general all-
purpose screw (24:1
UD) at 475 F (250 C), cooled in a water bath and pelletized. The resulting
pellets are molded
into 60 mil (0.06 inch thick) 2"x2" plaques at about 475 F (250 C) on a BOY
30M Injection
Molding Machine.
Pigmented polypropylene formulations composed_of polypropylene homopolymer or
polypropylene copolymer are stabilized with a base stabilization system
consisting of an N,N-
dialkylhydroxylamine or a hindered phenolic antioxidant with or without an
organophosphorous
compound.
All additive and pigment concentrations in the final formulations are
expressed as weight
percent based on the resin.
Formulations contained polypropylene pellets and one or more of the following
components;
0.0% - 2.0% pigment,
0.0% - 50.0% talc,
0.0% - 50.0% calcium carbonate,
0.0% - 0.1% phosphite,
0.0% - 1.25% phenolic antioxidant,
0.0% - 0.1% hydroxylamine,
0.05% - 0.10% calcium stearate,
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0.0% - 1.25% UV absorber,
0.0% -1.25% hindered amine stabilizer.
The components are dry blended in a tumble dryer prior to extrusion and
molding.
Test plaques are mounted in metal frames and exposed in an Atlas Ci65 Xenon
Arc
Weather-o-meter at 70 C black panel temperature, 0.55 W/m2 at 340 nanometers
and 50%
relative humidity with intermittent light/dark cycles and water spray (Society
of Automotive
Engineers - SAE J 19601`est Procedure). Specimens are tested at approximately
625 kilojoule
intervals by performing color measurements on an Applied Color Systems
spectrophotometer
by reflectance mode according to ASTM D 2244-79. Data collected included delta
E, L*, a* and
b* values. Gloss measurements are conducted on a BYK-GARDNER Haze/Gloss Meter
at 60
according to ASTM D523.
UV Exposure Testing
Test specimens exposed to UV radiation exhibit exceptional resistance to
photodegradation when stabilized with light stabilizer systems comprised of a
combination of
Tinuvin 328, the compound of Example 73 and CGL 2020. CGL 2020 is oligomer of
N-([2-(N-
2,2,6, 6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl)-N, N'-
bis(2,2,6,6-tetramethylpiperidin-
4-yl)-1,6-hexanediamine terminated with 2,4-bis(dibutylamino)-s-triazin-6-yl.
The Control
sample consists of a stabilizer formulation commonly used in the industry to
impart UV stability.
All of the samples contain Pigment Red 177.
DE* Gloss Values % Gloss
Retention
Red 3B Formulations 0 Kj/M2 3000 0 Kj/m 3000 0 Kj/m 3000
K' m2 K'/m2 K'/m2
Comp. 1 Comp. 2 Comp. 3
Control 0.14% 0.20% 0.2% Tin. 0 6.5 88% 24% 100% 28%
T 123 CGL 328
2020
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OE' Gloss Values % Gloss
Retention
Red 3B Formulations 0 Kj/m2 3000 0 3000 0 Kj/m 3000
K' mZ K' m2 K' m2 K'/m2
Comp.1 Comp. 2 Comp. 3
Ex. 73 0.10% Ex. 0.10% 0.1 % Tin. 0 0.6 88% 77% 100% 88%
73 CGL 2020 328
NOR 2 0.10% 0.10% 0.1 % Tin. 0 8.2 87% 13% 100% 14%
NOR 2 CGL 2020 328
= All formulations are base stabilized with 0.05% dialklyhydroxylamine in the
final resin
formulation.
= Polymer substrate is a commercially available polypropylene homopolymer -
Profax 6501
(commercial supplier Montell Polyolefins).
= Color package is 0.25% Red 3B - Pigment Red 177, C.I. # 65300 in the final
resin
formulation.
= Each formulation contains a hydroxyphenyl benzotriazole UV absorber -
Tinuvin 328, 2-(2-
hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole.
= NOR 2 is bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate.
= Each formulation contains 0.1% calcium stearate.
= Samples are 60 mil thick 2" x 2" injection molded plaques.
= UV exposures conducted under SAE J 1960 - Exterior Automotive conditions.
All additive and pigment concentrations in the final formulations are
expressed as weight
percent on the resin.
The formulation containing the subject compound of Example 73 specifically
shows
greatly improved gloss retention compared to the less effective Control
stabilizer system even at
a lower total concentration. Resistance to color change upon UV exposure is
also significantly
enhanced. The subject compound of Example 73 is also significantly more
effective in
maintaining appearance when compared with another solid N-O-R HALS (NOR 2) of
similar
molecular at equal concentrations.
In all cases, the light stabilized formulations show much greater resistance
to
photodegradation than unstabilized specimens which fail quickly under the UV
exposure
conditions outlined above.
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Examole 79
Polypropylene Fiber
Fiber samples are prepared by extruding fiber-grade polypropylene with the
instant
compounds, coadditives and pigments. Typical formulations contain the instant
compounds at
levels from 0.05 to 2.0%, a metal stearate such as calcium stearate at 0.05 to
0.5%, pigments
from 0 to 5%, UV absorbers at levels of 0.05 to 2.0%, phosphites at 0 to 0.1%,
phenotic
antioxidants at 0 to 1.25%, N,N-dialkylhydroxylamines at 0 to 0.1% and
optionally other
hindered amines at levels of 0 to 2.0%. All additive and pigment
concentrations in the final
formulations are given as weight percent based on the resin.
Pigment concentrates are prepared from pure pigment and polypropylene (PROFAX
,
Hercules) by mixing the two components in a high shear mixer in a ratio of 25%
pigment and
75% resin, pressing the resulting resin/pigment mixture on a Wabash
Compression molder
(Model # 30-1515-4T3) into a thin sheet and dividing the sheet into fine chips
for dispersion in
polypropylene at reduced concentrations. Aitematively, pigment concentrates
areobtained as
pigment dispersions in a suitable carrier resin for subsequent blending in
fiber at reduced
concentrations.
Formulations containing polypropylene, 0.05-0.1 % phosphite, 0-1.25% phenolic
antioxidant, 0-0.1% dialkylhydroxylamine, 0.05-0.1% calcium stearate, 0-1.25%
UV absorber, 0-
1.25% hindered amine are dry blended in a tumble dryer, extruded on a
Superior/MPM 1" single
screw extruder with a general all-purpose screw (24:1 L/D) at 475 F (246 C),
cooled in a water
bath and pelletized. The resulting pellets are spun into fiber at about 475 F
(246 C) on a HILLS
Research Fiber Extruder (Model # REM-3P-24) fitted with a 41 hole, delta
configuation
spinneret. The spun tow is stretched at a draw ratio of 3.2:1 producing a
final denier of 615/41.
Fiber samples are knitted into socks on a Lawson-HemphillFiber Analysis
tCnitter, cut
into appropriate lengths and exposed in an Atlas Ci65 Xenon Arc Weather-O-
meter at 89 C
black panel temperature, 0.55 W/m2 at 340 nanometers and 50% relative humidity
(Society of
Automotive Engineers - SAE J 1885 Test Procedure).
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Fiber samples are tested by performing color measurements on an Applied Color
Systems spectrophotometer by reflectance mode according to ASTM D 2244-79.
Identical, but
separate, fiber samples are examined for catastrophic failure and the time to
failure is recorded.
The samples containing the instant compounds exhibit good stabilization
performance
against the deleterious effects of UV light.
Examale 80
Other socks of propylene fiber as prepared in Example 79 are exposed in a Blue
M
forced draft oven at 120 C. Failure is determined by the criterion set forth
in Example 79. The
longer it takes for the catastrophic failure to occur, the more effective is
the stabilizing system.
The socks containing the instant compounds exhibit good thermal stabilization
efficacy.
Example 81
Film grade polyethylene is dry blended with approximately 10% by weight of the
test
additives, such as the compound of Example 51, and then melt compounded at 200
C into
"Masterbatch" pellets. The fully formulated "Masterbatch" pellets are dry
blended with
polyethylene resin to get the desired final stabilizer concentrations. Typical
formulations contain
the instant compounds at levels from 0.05% to 2.0%, a metal stearate such as
calcium stearate
at 0.05% to 0.5%, a phosphite at 0% to 0.1 %, a phenolic antioxidant at 0% to
1.25%, an N,N-
dialkylhydroxylamine at 0% to 0.1 % and optionally a hindered amine at 0% to
2.0%. The This
stabilized fully formulated resin is then blown at 200 C into a 150 micron
thick film on a DOLCI
film line.
The blown films are exposed in an Atlas Xenon-Arc WeatherOmeter according to
ASTM
G26 at 63 C bpt, 0.35 W/m2 at 340 nm with no spray cycle. Films are tested
periodically for any
change in elongation using an Instron 112 tensile tester. Failure in this test
is determined by
observation of the loss of % elongation in the film. The longer it takes for
this loss to occur, th
more effective is the stabilizer system.
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The films containing the instant compound mixture show good light stabilizing
efficacy.
Exam lp e 82
Film grade polyethylene is dry blended with 10% loading of the test additives,
such as
the compound of Example 51, as described in Example 81, and then melt
compounded at
200 C into fully formulated master batch pellets. The master batch pellets are
dry blended with
the polyethylene resin to get the final stabilizer concentration. The fully
formulated resin is then
blown at 200 C into a 150 micron thick film using a DOLCI film line.
The resulting films are exposed on a greenhouse on galvanized iron backing.
Treatment
includes applications of pesticides on a regular basis (i.e. sodium N-
methyldithiocarbamate,
VAPAM' every six months and SESMETRIN' every month). Performance is measured
by
monitoring the percent residual elongation. Failure is defined as the time to
a 50% loss of
original elongation.
The films containing the instant compounds show good resistance to pesticides.
Examole 83
Master batch pellets prepared as described in Example 81 are dry blended into
polyethylene resin to get the final stabilizer cocentration. The fully
formulated resin is then blown
at 200 C into a 25 micron thick film using a DOLCI film line.
The resulting films are exposed on a soil to simulate agricultural mulch film
conditions.
Treatment includes exposure to methyl bromide fumigant for three days at 60
g/m3.
Performance is measured by monitoring the time to physical embrittlement.
The films containing the instant compounds show good resistance to fumigants.
Examgle 84
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Greenhouse film samples are prepared as described in Example 81, but in
addition to
the instant compounds also contain a metal stearate or a metal oxide. Typical
formulations
contain from 0.05 to 2% by weight of the instant hindered amines, 0.05 to 0.5%
of a metal
stearate such as calcium oxide, and 0.05 to 0.5% of a metal oxide such as zinc
oxide or
magnesium oxide.
Effectiveness is monitored as described in Example 82. The films containing
the instant
compounds exhibit good light stability.
Exam {~ 85
Polypropylene fiber is prepared as described in Example 79. In addition to the
instant
compounds, selected halogenated flame retardants are also included in the
formulation. The
flame retardants are tris(3-bromo-2,2-bis(bromomethyl)propyl)phosphate,
decabromodiphenyl
oxide, ethylene bis-(tetrabromophthalimide), or ethylene bis-(dibromo-
norbornane-
dicarboximide).
Using the criterion for light stabilization described in Example 79, the socks
knitted from
the polypropylene fiber containing the instant compounds exhibit good light
stability.
Exam !c e 86
Molding grade polypropylene is dry blended with test additives and then melt
compounded into pellets. In addition to the instant compounds, selected flame
retardants are
also included. The flame retardants are tris(3-bromo-2,2-
bis(bromomethyl)propyl)phosphate,
decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), or ethylene bis-
(dibromo-
norbomanedicarboximide). The pelletized fully formulated resin is then
injection molded into test
specimens using a Boy 50M laboratory model injection molder.
Test plaques are mounted in metal frames and exposed in an Atlas Ci65 Xenon
Arc
Weather-Ometer with intermittent light/dark cycles and water spray following
the ASTM G26 test
procedure. Specimens are tested at periodic intervals for changes in tensile
properties. Failure
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in this test is determined by the observation of the loss of tensile
properties. The longer it takes
for the loss in properties to occur, the more effective is the stabilizer
system.
The test samples containing the instant compounds exhibit good light
stabilization
properties.
Exam Ip e 87
Molded test specimens are prepared by injection molding thermoplastic olefin
(TPO)
pellets as described in Example 76. In addition to the instant compounds,
selected flame
retardants are also included in the test specimens. The flame retardants are
tris(3-bromo-2,2-
bis(bromomethyl)propyl) phosphate, decabromodiphenyl oxide, ethylene bis-
(tetrabromo-
phthalimide), or ethylene bis-(dibromo-norbornanedicarboximide).
The samples including the instant hindered amines exhibit good light
stabilizing activity.
Examgle 88
Film grade polyethylene is compounded and blown into film at 200 C as
described in
Example 82 using a DOLCI film line. In addition to the instant compounds,
selected flame
retardants are included in the formulation. The flame retardants are tris(3-
bromo-2,2-bis(bromo-
methyl)propyl) phosphate, decabromodiphenyl oxide, ethylene bis-
(tetrabromophthaFimide), or
ethylene bis-(dibromo-norbornanedicarboximide).
When tested for light stabilizing activity as described in Example 82, the
films containing
the instant compounds exhibit good stabilization.
Example 89
Molded test specimens are prepared by injection molding thermoplastic olefin
(TPO)
pellets containing the instant compounds, pigments and other coadditives as
described in
Example 77.
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The test specimens are painted with one-pack paint systems and tested for
TPO/paint
interactions. Before painting, the test specimens are first wiped with
isopropanol and air blasted
to remove any dust. After a five minute flash, these specimens are coated with
the adhesion
promoter, then the base coat, and then optionally a clear coat. Typical film
thickness of these
various coatings are 0.1-0.3 mils for the adhesion promoter, 0.6-0.8 mils for
the base coat, and
1.2-1.5 mils for the clear coat. After painting, the specimens are cured in an
over at 120 C for 30
minutes.
Samples are tested to evaluate the TPO/paint interactions as follows: In the
initial
adhesion test, a clear cellophane adhesive tape is used to pull on a 3 mm
cross hatched paint
surface or; in the humidity test, the painted plaques are exposed for 240
hours at 38 C in an
atmosphere having 98% relative humidity. The blister rating is tested by
visual observation
according to ASTM D 714.
The samples containing the instant compounds exhibit good TPO/paint
interaction
properties as determined by the criteria above.
Example 90
Thermoplastic Elastomers
Resin materials of the general class known as thermoplastic elastomers,
examples of
which include, copolymers of styrene with butadiene or isoprene and/or
ethylene-cobutylene
such as SBS, SEBS and SIS, are dry blended with the instant compounds and melt
compounded into pellets. Typical formulations contain the instant compounds at
levels from
0.05% to 2.0%, a metal stearate such as calcium stearate at 0.05% to 0.5%,
pigments from 0%
to 5%, UV absorbers at levels of 0.05% to 2.0%, phosphites at 0.0% - 0.1%,
phenolic
antioxidants at 0.0% - 1.25%, N,N-dialkylhydroxylamine at 0.0% - 0.1%, and
optionally other
hindered amine stabilizers at levels of 0.0% to 2.0%.
The pelletized fully formulated resin is then processed into a useful article
such as blown
or cast extrusion into film; injection molded into a molded article;
thermoformed into molded
articles; extruded into wire and cable housing; or rotational molded into
hollow articles.
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The materials containing the instant compounds exhibit stability against
deleterious
effects of UV light and thermal exposure.
Exam I
Articles prepared according to Example 90 which additionally contain selected
organic
pigments as well as the instant compounds also exhibit stability against the
deleterious effects
of actinic light and thermal exposure.
Example 92
Articles prepared according to Example 90 which additionally contain a
hindered
phenolic antioxidant selected from the group consisting of neopentanetetrayl
tetrakis(3,5-di-tert-
butyl-4-hydroxyhydrocinnamate, octadecyl 3,5-di-tert-butyl-4-
hydroxyhydrocinnamate, 1,3,5-
trimethyl-2,4,6-tris(3,5,-di-tert-butyl-4-hydroxybenzyl)benzene, 1,2-bis(3,5-
di-tert-butyl-4-
hydroxyhydrocinnamoyl)hydrazine, calcium [bis(monoethyl 3,5-ditert-butyl-4-
hydroxybenzyl)-
phosphonate], 1,3,5-tris(3,5-di-tert-butyl=4-hydroxybenzyl) isocyanurate and
1,3,5-tris(3-
hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurate, as well as the instant
compounds also
exhibit stability against the deleterious effects of actinic light and thermal
exposure.
Exam la e 93
Articles prepared according to Example 90 which additionally contain an
organophosphorus stabilizer selected from the group consisting of tris(2,4-di-
tert-butylphenyl)
phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-
nitrilo[triethyl-tris-
(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], tetrakis(2,4-
di-butylphenyl) 4,4'-
biphenylenediphosphonite, tris(nonylphenyl) phosphite, bis(2,4-di-tert-
butylphenyl)
pentaerythrityl diphosphite,
2,2'-ethylidenebis(2,4-di-tert-butylphenyl) fluorophosphite and 2-butyl-2-
ethylpropan-1,3-diyl
2,4,6-tri-tert-butylphenyl phosphite as well as the instant compounds of also
exhibit stability
against the deleterious effects of actinic light and thermal exposure.
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Example 94
Articles prepared according to Example 90 which additionally contain a
benzofuranone
stabilizer which is 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-2H-benzofuran-2-
one, as well as the
instant compounds also exhibit stability against the deleterious effects of UV
light and thermal
exposure.
ExamQle 95
Articles prepared according to Example 90 which additionally contain a dialkyl
hydroxyl-
amine stabilizer which is N,N-dialkylhydroxylamine made by the direct
oxidation of N,N-
di(hydrogenated tallow)amine as well as the instant compounds also exhibit
stability against the
deleterious effects of actinic light and thermal exposure.
Exam pI
Articles prepared according to Example 90 which additionally contain other
hindered
amine stabilizers selected from the group consisting of bis(2,2,6,6-
tetramethylpiperidin-4-yl)
sebacate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-
tetramethyl-4-hydroxy-
piperidine and succinic acid, N.N',N",N"'-tetrakis[4,6-bis(butyl-1,2,2,6,6-
pentamethyipiperidin-4-
yl)amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane, the polycondensation
product of 4,4'-
hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-
octylamino-s-
triazine, the polycondensation product of 4,4'-hexamethylenebis(amino-2,2,6,6-
tetramethyl-
piperidine) and 2,4-dichloro-6-morpholino-s-triazine, 2,2,6,6-
tetramethylpiperidin-4-yl
octadecanoate, 3-dodecyl-l-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-
pyrrolidin-2,5-dione,
1,3,5-tris(N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-
yl)ethyl]amino}-s-triazine,
poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane, the
polycondensation
product of 2,4-dichloro-6-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino)-s-
triazine and
2,2'ethylene-bis([2,4-(2,2, 6,6-tetramethylpiperidi n-4-yl) butylamino-s-
triazin-6-yl]amino-
trimethyleneamino} as well as the instant compounds also exhibit stability
against the
deleterious effects of actinic light and thermal exposure.
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Exam Ige 97
Articles prepared according to Example 90 which additionally contain other N-
hydro-
carbyloxy substituted hindered amines selected from the group consisting of
bis(1-octyloxy-
2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-
tetramethylpiperidin-4-yi)
adipate, bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-
cyclohexyloxy-
2,2,6,6-tetramethylpiperidin-4-yi) sebacate, and 1-cyclohexyloxy-2,2,6,6-
tetramethylpiperidin-4-
yl octadecanoate as well as the instant compounds also exhibit stability
against the deleterious
effects of actinic light and thermal exposure.
Examale 98
Articles prepared according to Example 90 which additionally contain a o-
hydroxyphenyl-
2H-benzotriazole, a hydroxyphenyl benzophenone or a o-hydroxyphenyl-s-triazine
UV absorber
selected from the group consisting of 2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-
benzotriazole, 2-
(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-tert-
butylphenyl)-2H-
benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, 2-(2-
hydroxy-3-a-cumyl-
5-tert-octylphenyl)-2H-benzotriazole, 2,4-di-tert-butylphenyl 3,5-di-tert-
butyl4-hydroxybenzoate,
2-hydroxy-4-n-octyloxybenzophenone and 2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-
4-octyloxy-
phenyl)-s-triazine as well as the instant compounds also exhibit stability
against the deleterious
effects of UV light and thermal exposure.
Exam Ir~ e 99
The hindered amine test stabilizers are incorporated into a two-component
polyester
urethane coating based on a commercially available polyester polyol
(DESMOPHENO 670-80)
and commercially available isocyanurate (DESMODUR N-3390) at a level of 2% by
weight
based on total resin solids. The coating system is catalyzed with 0.015%
dibutyl tin dilaurate
based on total resin solids.
Each coating formulation is applied by drawdown onto transparent glass slides
approximately 4" x 6" to a film thickness of about 2 mils (0.002") in
triplicate.
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These triplicate glass plates are processed as seen below:
Plate 1 - bake for 30 minutes at 180 F (82 C); age at room temperature; and
observe
daily.
Plate 2 - allow to air dry (ambient cure); age at room temperature; and
observe daily.
Plate 3- allow to air dry for one day; age in a 120 F (49 C) oven; observe
daily and
continue aging at 120 F (49 C).
Starting at time zero, all plates are evaluated for visual appearance, noting
the
development of any cloudiness within the coating and any exudate on the
surface of the
coating. The results of four days of observation are noted below.
Plate 1
m le' 0 DaY 1 Day 2 Day 3 av 4 18 months
A cl cl cI ci cl clear
B slh haze haze haze haze haze
C cl cl cl cl cI clear
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Plate 2
m I' p DM 1 Day 2 Qay 3 Day 4 18 months
A cl ci cl cl c1 clear
B sl h haze haze haze haze haze
C cl cl ci cl cl clear
Plate 3
Sample* 0 a 1 Dav 2 Day 3 Day 4 18 months
A cl cl cl cl cl clear
B sI h haze haze haze haze haze
C cl cl cl cl cl clear
*A is unstabilized.
B contains 2% by weight of bis(1-octytoxy-2,2,6,6-tetramethyipiperidin-4-yi)
sebacate
(TINUVIN 123).
C contains 2% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yi]
sebacate, compound of Example 2.
These data show that the instant compound having a hydroxy moiety present on
the
group attached to the 1-position of the hindered amine provides excellent
solubility and
compatibility for the polyester urethane coating that cannot be achieved with
the closest prior art
compound where said hydroxy moiety is absent.
Experience teaches that, if the instant compounds are soluble and compatible
in this
particular clearcoat, they will certainly be compatible and soluble in other
resin systems.
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Example 100
Approximately 50 mL of the same stabilized formulated two-component clear
coatings
described in Example 99 are alliowed to gel in a sealed 4 ounce jar. The
solidified coatings are
visually observed for clarity after solidification. The development of opacity
or cloudiness is
indicative of an incompatibility between the hindered amine stabilizer and the
formulated
coating.
Solidified coating in jar
Sam le* 0 Dav 1 pay 2 18 mo th
A clear clear clear clear
B clear cloudy cloudy cloudy
C clear clear clear clear
*A is unstabilized.
B contains 2% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate
(TINUVIN 123).
C contains 2% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-yl]
sebacate, compound of Example 2.
These data show that the instant compound having a hydroxy moiety present on
the
group attached to the 1 -position of the hindered amine provides excellent
solubility and
compatibility for the polyester urethane coating that cannot be achieved with
the closest prior art
compound where said hydroxy moiety is absent.
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xample 101
1-(2-Hydroxy-2-methylpropoxy)-4-[9-(methoxy-
carbonyi)nonanoyloxy]-2,2,6,6-tetramethylpiperidine
The title compound is prepared by the reaction of the compound prepared in
Example
16A with one equivalent or more of dimethyl sebacate and a catalytic amount of
lithium amide in
xylene.
Exam Ige 102
1-(2-Hydroxy-2-methylpropoxy)-4-[5-(methoxy-
carbonyl)pentanoyioxy]-2,2,6,6-tetramethylpiperidine
The title compound is made by the procedure of Example 101 where dimethyl
sebacate
is replaced by an equivalent amount of dimethyl adipate.
Examole 103
1-(2-Hydroxy-2-methylpropoxy)-4-[3-(methoxy-
carbonyl)propionytoxy]-2,2,6,6-tetramethylpiperidine
The title compound is made by the procedure of Example 101 where dimethyl
sebacate
is replaced by an equivalent amount of dimethyl succinate.
Example 104
1-(2-Hydroxy-2-methylpropoxy)-4-[4-(methoxy-
carbonyl)butyryloxy]-2,2,6,6-tetramethylpiperidine
The title compound is made the procedure of Example 101 where dimethyl
sebacate is
replaced by an equivalent amount of dimethyl glutarate.
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Example 104A
Mixture of 1-(2-Hydroxy-2-methylpropoxy)-4-[5-methoxy-carbonyl)pentanoyloxy]-
2,2,6,6-
tetramethylpiperidine and 1-(2-Hydroxy-2-methylpropoxy)-4-[4-methoxy-
carbony!)butyryloxy]-
2,2,6,6-tetramethylpiperidine
Example 101 is repeated with an equivalent amount of DBE-2 dibasic ester
(DuPonto) in
place of dimethyl sebacate.
Example 104B
Mixture of 1-(2-Hydroxy-2-methylpropoxy)-4-[5-methoxy-carbonyl)pentanoyloxy]-
2,2,6,6-
tetrarnethylpiperidine and 1-(2-Hydroxy-2-methylpropoxy)-4-[4-methoxy-
carbonyl)butyryloxy]-
2,2,6,6-tetramethylpiperidine
Example 101 is repeated with an equivalent amount of DBE-3 dibasic ester
(DuPont D) in
place of dimethyl sebacate.
Examale 105
Condensation Product of
4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-
2,2,6,6-tetramethylpiperidine with Hexamethylene
Diisocyanate, and Terminated with Methoxy
The title compound is prepared from the reaction of approximately equimolar
amounts of
the compound prepared in Example 16A with hexamethylene diisocyanate followed
by reaction
with excess methanol.
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Exam Ipe 106
Condensation Product of
4-Hydroxy-1 -(2-hydroxyethoxy)-2,2,6,6-tetra-
methylpiperidine with Hexamethylene
Diisocyanate, and Terminated with Methoxy
The title compound is prepared from the reaction of approximately equimolar
amounts of
the compound prepared in Example 70 with hexamethylene diisocyanate, followed
by reaction
with excess methanol.
Examgle 107
Condensation Product of
4-Hydroxy-1 -(2-hydroxy-1 -phenethoxy)-
2,2,6,6-tetramethylpiperidine with Hexamethylene
Diisocyanate, and Terminated with Methoxy
The title compound is prepared from the reaction of approximately equimolar
amounts of
the compound prepared in Example 74 with hexamethylene diisocyanate, followed
by reaction
with excess methanol.
Exam l
Stabilization of a Two-Component
Acrylic Urethane Clearcoat
The hindered amine test stabilizers are incorporated into a two-component
acrylic
urethane coating as described om Example 99. The system is catalyzed with
0.02% by weight
of dibutyltin dilaurate based on the total resin solids. The stabilizers are
added at the
appropriate level to the acrylic polyol portion of the two-component coating
which is then
combined with the isocyanate component immediately prior to application.
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Steel panels 3" x 4" primed with an electrocoat primer are then coated with a
light blue
metallic basecoat, then with the stabilized clearcoat. The basecoat is spray
applied to a
thickness of 1.0 mil (25 microns) dry film thickness and the stabilized
clearcoat is then applied to
a thickness of 2.0 mils (50 microns) dry film thickness. The coating is air-
dried and aged for two
weeks. The panels are then exposed in a Xenon-Arc Weather-Ometer under the
following
conditions:
Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray; 60
minutes light
only; 60 minutes dark and rear spray condensate.
Lamp filters are: quartz inner/borosilicate S outer.
Irradiance: 0.45 watts per square meter.
20 Gloss is measured before exposure and at 500 hour intervals during
exposure.
Higher gloss retention is desirable.
Percent Retention of 20 Gloss
Samr)le* 4500 hours 8500 hours 12000 hours
A 17 - -
B 60 22
C 47 17 -
D 34 22 -
'E 41 23 -
F 75 45 28
G 77 45 27
'A is unstabilized.
B contains 1% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate
(TINUVIN 123).
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C contains 0.9% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-
yl] sebacate, compound of Example 2.
D contains 1.04% by weight of 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-
tetramethylpiperidin-4-y!)-N-
butylamino]-6-(2-hydroxyethylamino)-s-triazine.
E contains 1.01 % by weight of the compound of Example 12.
F contains 2% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate
(TINUVIN 123).
G contains 1.8% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperidin-4-
yi] sebacate, compound of Example 2.
These data show that the instant hydroxy substituted compounds give comparable
20
Gloss Retention values to NOR compounds at equivalent molar concentrations.
Ex ma nle 109
Stabilization of a Two-Component
Acrylic Urethane Clearcoat
A clearcoat as prepared in Example 108 is applied by spin-coating to 1"
silicon disks to a
dry film thickness of approximately 25 microns. The initial optical film
thickness of each disk is
measured using a Zeiss interferometer. The disks are then exposed in a Xenon-
Arc Weather-
Ometer under the following conditions:
Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray; 60
minutes light
only; 60 minutes dark and rear spray condensate.
Lamp filters are: quartz inner/quartz outer.
Irradiance: 0.55 watts per square meter.
Optical film thickness is remeasured every 250 hours and film loss is
determined for
each formulation. The film loss caused by weathering after 3972 and 5561 hours
is tabulated in
the table below. A lower value for film loss is desirable.
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Film Loss (in microns)
Sample' 3972 hours 5561 hours
A 23.3 complete erosion
B 6.9 16.3
C 6.7 17.8
D 6.3 14.3
E 5.9 12.4
F 6.5 16.1
G 6.6 16.7
'A is unstabilized.
B contains 1% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate
(TtNUVIN 123).
C contains 0.9% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethylpiperldin-4-
yl) sebacate, compound of Example 2.
D contains 1.04% by weight of 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-
tetramethyipipe(din-4-yl)-N-
butylaminoj-6-(2-hydroxyethylami no)-s-triazine.
E contains 1.01 % by weight of the compound of Example 12.
F contains 0.78% by weight of 1 -octyloxy-2,2,6,6-tetramethyl-4-
hydroxypiperidine.
G contains 0.56% by weight of 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-
tetramethyl-4-hydroxy-
piperidine, compound of Example 16A.
These data show that the instant hydroxy substituted compounds give comparable
resistance to erosion as the closest NOR compounds at equivalent molar
concentrations.
Example 110
Coatings over Plastic Substrates
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A major application for non-basic hindered amines is in the protection of
automotive
topcoats applied over plastic substrates. However, many low molecular weight,
non-reactable
light stabilizers migrate into the plastic substrate during drying and cure.
As a consequence, a
significant portion of the light stabilizer may be lost from the topcoat into
the substrate and
hence be ineffective in protecting said topcoat.
The extent of migration of hindered amine stabilizers during application and
cure of the
coating is determined by comparing the concentration of hindered amine in the
cured clearcoat
applied over a plastic substrate versus the same clearcoat applied over a non-
permeable
substrate such as glass or steel.
Hindered amine stabilizers under test are incorporated into a flexible
thermoset
acrylic/melamine clear coating appropriate for use on automotive plastic
substrates. The
hindered amine is incorporated at a level of 1.5% by weight based on total
resins solids.
Each coating formulation is applied by an automatic spray appratus onto
automotive
grade RIM (Reacting Injection Molded) substrate and TPO (thermoplastic
polyolefin). Both
substrates are in form of 4" x 12" plaques. Each coating is applied to achieve
a dry film
thickness of approximately 2.0 mils (50 microns). The coatings are cured by
baking at 250 F
(121 C) for 20 minutes.
Triplicate samples of each cured coating formulation are removed from each
substrate
and cryoground to a fine powder. A known amount of each sample is extracted in
refluxing
toluene overnight. The hindered amine present is analyzed quantitatively by
dilution to a known
volume and analyzed by HPLC or SFC chromatography. Calibration curves for each
test
stabilizer compound are developed. The hindered amine content of each
extracted coating is
determined by this method.
When the instant hindered amine compounds substituted on the N-atom with an -O-
E-
OH moiety are compared to the corresponding -NOR compounds lacking such a
hydroxyl
moiety, a higher percent recovery of the instant hindered amine compound from
the clearcoat
over a plastic substrate is found indicating that much less of the instant
hindered amine
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stabilizer migrates into the plastic substrate allowing for better
stabilization of the clear topcoat
over such plastic substrates.
ExamgI e 111
Stabilization of Waterbome Wood Vamish
Waterbome coating comprise a significant and increasing proportion of the
coating in
use for a wide variety of applications including automotive basecoats,
industrial coatings and
trade sale coatings. These coatings may be pigmented or transparent. The
trends are also
towards higher solids formulation which in general depend on light stabilizers
to maintain
properties on exterior exposure, and towards lower levels of cosolvents. This
requires higher
solubility of stabilizers in such cosolvents (primarily water) or actual
solubility in water.
The test stabilizers are incorporated into a waterborne dispersion by
predissolution in a
cosolvent blend. The waterborne dispersion is a commercially available
acryliclurethane hydrid
resin. The cosolvent blend is a 1:1 mixture of TEXANOL (2,2,4-trimethyl-1,3-
pentanediol,
Texaco) and ARCOSOLVE TPM (tripropylene glyool methyl ether,
AtianticRichfield).
0.45 gram of the test stabilizer is predissolved in 10 g of the cosolvent
blend which is
then incorporated into the following composition:
PDW
FLEXTHANE 630 (Air Products) 100.0
Foamaster VF 0.1
Water 10.0
TEXANOUARCOSOLVE/hindered amine 10.5
UV absorber (TINUVIN 1130, Ciba) 1.2
BYK 346 0.5
MICHEMLUBE 162 2.0
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Each coating is brush applied onto 6" x 6" sections of cedar and pine boards.
The weight
of the coating applied is regulated by weighing the coating and brush before
and after
application and ensuring that the same weight of coating is applied to each
section.
The coated board sections are allowed to dry at ambient temperature for two
weeks,
then evaluated for visual appearance, gloss and Hunter L*, a* and b* color.
The sections are
exposed on racks at a 450 angle in South Florida for six months before being
returned and
evaluated for visual appearance, gloss, color change and any other signs of
degradation or
delamination.
The instant hindered amine compounds substituted on the N-atom with an -O-E-OH
moiety provide better stabilization efficacy to the sections in respect to
visual appearance, gloss
retention, resistance to color change and to delamination than do the
corresponding -NOR
compounds lacking such a hydroxyl moiety.
Exarr ,gle 112
Stabilization of Pigmented Automotive OEM Basecoat
A basecoat pigmented with a mixture of Pigment Red 177 and mica is stabilized
with 1%
by weight of a hindered amine stabilizer based on the total basecoat solids
(pigment plus resin).
The basecoat is spray applied at a dry film thickness of 1 mil (25 microns) to
primed 4" x 12"
steel panels, then topcoated with a high solids commercially available
automotive clearcoat.
The coated panels are cured in an over at 250 F (121 C) for 30 minutes. The
panels are then
exposed in a Xenon-Arc Weather-Ometer under the following conditions:
Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray; 60
minutes light
only; 60 minutes dark and rear spray condensate.
Lamp filters are: quartz innerlborosilicate S outer.
Irradiance: 0.55 watts per square meter.
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20 Gloss, Distinctness of Image, Hunter Color Space Values (L*, a*, b* and
AE) are
measu~ed before exposure and after 3000 hours of exposure.
The instant hindered amine compounds substituted on the N-atom with an -O-E-OH
moiety provide better stabilization efficacy to the panels in respect to
distinctness of image,
gloss retention and resistance to color change than do the corresponding -NOR
compounds
lacking such a hydroxyl moiety.
Examale 113
ABS Molding Applications
Thermoplastic materials composed of mixtures of copolymers derived from the
copolymerization of styrene monomer with acrylonitrile and the
copotymerization of stryrene
monomer with butadiene, generally referred to as ABS, are dry blended with the
instant
compounds and melt compounded into pellets. Typical formulations contain the
instant
compounds at levels from 0.05% to 2.0%, a metal stearate such as calcium
stearate at 0.05% to
0.5%, pigments from 0% to 5%, UV absorbers at levels of 0.05% to 2.0%,
phosphites at 0.0% -
0.1%, phenolic antioxidants at 0.0% - 1.25%, N,N-dialkylhydroxylamine at 0.0% -
0.1%, and
optionally other hindered amine stabilizers at levels of 0.0% to 2.0%.
The pelletized fully formulated resin is then processed into a useful article
such as
extrusion into sheet, film, profile and pipe ; molded into bottles; injection
molded into a molded
article; thermoformed into molded articles; or rotational molded into hollow
articles.
The materials containing the instant compounds exhibit stability against
deleterious
effects of UV light and thermal exposure.
Example 114
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pK, Values
In order to determine the pK, values of water insoluble materials, organic
references
with known pKa values in water are titrated non-aqueously. A plot of the half
neutralization
potential (HNP) versus the known aqueous pK, value of the reference material
is establed. The
HNP of the test material is determined and extrapolated to find the
corresponding pK, value of
the test material. Such organic reference materials include 2,2,6,6-
tetramethylpiperidine; 4-
hydroxy-2,2,6,6-tetramethylpiperidine; 1-hydroxyethyl-4-hydroxy-2,2,6,6-
tetramethyipiperidine;
triacetoneamine and N-methylaniline.
The reference materials, which are structurally at least peripherally related
to the instant
test materiais and are soluble in both water and 1:1 acetonitriie:chtoroform,
are used to make a
calibration plot in the non-aqueous titration (1:1 acetonitrile:chloroform
solvent and 0.1 N
perchioric acid/dioxane titrant) system. Approximately 0.5 milliequivalents of
test material is
weighed into a titration beaker. Thirty mL of acetonitriie is added to
dissolve the sample. Prior to
titration, 30 mL of chloroform is added. Titration is carried out and the HNP
is determined. The
electrolyte for the reference electrode is 2-(aminomethylpyridine. The
electrode is allowed to
stand in the solvent system for two hours after filling with the electrolyte
to achieve equilibration.
All samples are run in duplicate. The pK, values are seen in the table below.
Samole' HPN (my) Calculated pK.
I 523 3.9
I I 436 4.9
III 513 3.8
IV -- 4.6
V -- 3.8
VI -- 4.8
*1 is the compound of Example 73.
11 is 1-cyclohexyioxy-4-ocatadecanoyloxy-2,2,6,6-tetramethyipiperidine.
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III is the compound of Example 2.
IV is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
V is the compound of Example 50.
VI is the reaction product of 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-
tetramethylpiperidin-4-yl)butyl-
aminoj -6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine.
As can be seen from each of the above pairs of related compounds where the
individual
compounds differ from the other only by whether the 1 -position of the
piperidine ring is
substituted by an -O-R group or by an -O-E-OH, the instant -O-E-OH compounds
consisting
have a significantly lower pK, value meaning that said instant compounds are
distinguished by
consistently lower basicity than the prior art N-OR compounds.
Inspection of the results given in Example 77 shows that this lower basicity
and lower
pKõ values can be translated into superior performance for the instant
compounds compared to
the closely related prior art N-OR compounds in preventing paint loss on
paintable thermoplastic
polyolefins (TPO).
Example 115
Flame Retardancy
Fiber grade polypropylene, is dry blended with the test additives and then
melt
compounded at 234 C (450 F) into pellets. All formulations additionally
contain melt processing
stabilizer system. The pelletized fully formulated resin is then spun at 246 C
(475 F) into fiber
using a Hills laboratory model fiber extruder. The spun tow of 41 filaments is
stretch at a ratio of
1:3.2 to give a final denier of 615/41.
The fibers are then knitted into socks and on a Lawson-Hemphill Analysis
Knitter. Ten
replicates of each sample are tested under NFPA701-1996 Vertical bum
procedure. The time in
seconds for the knitted sock to extinguish after the insult flame is removed
is reported as "After
Flame". Efficacy as a flame retardant is demonstrated when low After Flame
times are
observed relative to a blank sample containing no flame retardant. The burning
time of the drips
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from the material and the weight loss are also recorded. The data demonstrates
that the instant
NOR HALS are effective as flame retardants.
Additive After flame (s) Drip Burn (s) Weight loss
(%)
BLANK, no FR 32 >50 63
Compound of 0.5 12.5 36
Example 73, 1.0%
Example 116
Flame Retardancy of Polypropylene Thick Sections
Molding grade polypropylene is dry blended with test additives and then melt
compounded into pellets. In addition to the instant compound, halogenated
flame retardants are
included in the formulation. Typical formulations contain the instant compound
and a flame
retardants such as: tris(3-bromo-2,2 bis (bromomethyl)propyl) phosphate (FMC
PB370); bis(2,3-
dibromopropyl ether) of bisphenol A (PE68); decabromodiphenyloxide (DBDPO);
ethylene bis-
tetrabromophthalimide (SATEX BT-93); ethylene bis-dibromonorbornanedi-
carboximide (SATEX
BN-451). Other formulations may contain Sb203 in addition to the brominated
flame retardants.
Other formulations may contain phosphorous based flame retardants such as
ethylene diamine
diphosphate (EDAP). The pelletized fully formulated resin is then compression
molded into test
specimens using a Wabash Compression Molder.
Test plaques are tested under UL-94 Vertical bum conditions. A minimum of
three
replicates are tested. The average time in seconds for the test sample to
extinguish after a first
and second insult flame is removed is reported. Efficacy as a flame retardant
is demonstrated
when low Flame times are observed. The instant compounds enhance the flame
retardancy of a
halogenated or phosphate flame retardant tested alone.
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Examole 117
Flame Retardancy in TPO Thick Sections
Molded test specimens were prepared by injection molding thermoplastic olefin
(TPO)
pellets containing the instant compounds. The TPO formulations may also
contain pigments, a
phenolic antioxidant, phosphite or hydroxylamine, a metal stearate,
ultraviolet light absorbers
(UVA) or a hindered amine stabilizers (HALS) or a mixture of UV absorbers and
hindered amine
stabilizers.
In addition to the instant compound, halogenated flame retardants are included
in the
formulation. Typical formulations contain the instant compound and a flame
retardants such as:
tris(3-bromo-2,2 bis (bromomethyl)propyl) phosphate (FMC PB370); bis(2,3-
dibromopropyl
ether) of bisphenol A (PE68); decabromodiphenyloxide (DBDPO); ethylene bis-
tetrabromophthalimide (SATEX BT-93); ethylene bis-dibromonorbornanedi-
carboximide (SATEX
BN-451). Other formulations may contain Sb203 in addition to the brominated
flame retardants.
Other formulations may contain phosphorous based flame retardants such as
ethylene diamine
diphosphate (EDAP).
Test plaques are tested under UL-94 Vertical burn conditions. A minimum of
three
replicates are tested. The average time in seconds for the test sample to
extinguish after a first
and second insult flame is removed is reported. The instant compounds enhance
the flame
retardancy of a halogenated or phosphate flame retardant tested alone.
Example 118
Light Stability in Flame Retardant ABS Molding Applications
Molding grade ABS is dry blended with test additives and then melt compounded
into
pellets. In addition to the instant compounds, selected flame retardants are
also included. The
flame retardants are tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate,
decabromodiphenyl
oxide, ethylene bis(tetrabromophthalimide) and ethylene
bis(dibromonorbornanedicarboximide).
The pelletized fully formulated resin is then injection molded into test
specimens using a BOY
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50M laboratory model injection molder. Other formulations may contain antimony
trioxide
(Sb203)'in addition to the brominated flame retardants. Other formulation may
contain
phosphorus based flame retardants such as ethylenediamine diphophate (EDAP).
Test plaques are mounted in metal frame and exposed in an Atlas Ci65 Xenon Arc
Weather-O-meter with intermittent light/dark cycles and water spray following
the ASTM G26
test procedure. Specimens are tested at periodic intervales for changes in
tensile properties and
for changes in color. The longer it takes for the loss in properties to occur
and the less the color
change as measured by DE, the more effective is the stabilizer system.
The test samples containing the instant compounds exhibit good retention of
tensile
properties and minimal color change during the accelerated weathering.
ExampI e 119
Light Stability in Flame Retardant HIPS Molding Applications
Molding grade high impact polystyrene is dry blended with test additives and
then melt
compounded into pellets. In addition to the instant compounds, selected flame
retardants are
also included. The flame retardants are tris[3-bromo-2,2-
bis(bromomethyl)propyl] phosphate,
decabromodiphenyl oxide, ethylene bis(tetrabromophthalimide) and ethylene
bis(dibromo-
norbornanedicarboximide). The pelletized fully formulated resin is then
injection molded into test
specimens using a BOY 50M laboratory model injection molder. Other
formulations may contain
antimony trioxide (Sb2O3) in addition to the brominated flame retardants.
Other formulation may
contain phosphorus based flame retardants such as ethylenediamine diphophate
(EDAP).
Test plaques are mounted in metal frame and exposed in an Atlas Ci65 Xenon Arc
Weather-O-meter with intermittent light/dark cycles and water spray following
the ASTM G26
test procedure. Specimens are tested at periodic intervales for changes in
tensile properties and
for changes in color. The longer it takes for the loss in properties to occur
and the less the color
change as measured by DE, the more effective is the stabilizer system.
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The test samples containing the instant compounds exhibit good retention of
tensile
properties and minimal color change during the accelerated weathering.
Examale 120
Stabilization of High Solids Acid-catalyzed
Thermoset Acrylic Resin Enamel
A high solids (50% by weight) thermoset acrylic resin enamel, catalyzed by
0.8% by
weight of dodecylbenzenesulfonic acid, based on the film-forming resin is
stabilized by the
addition of various instant compounds. The high solids thermoset acrylic resin
enamel
formulation (Acryloid AT 400 from Rohm and Haas) is based on hydroxyethyl
methacrylate,
methyl methacrylate, styrene, butyl acrylate and butyl methacrylate and a
melamine curing
agent.
Pieces of steel sheeting 4" x 12" (9.16 cm x 30.48 cm), coated with a primer
based on
polyester/epoxy resin, are then coated with a Ti02-pigmented base coat based
on a binder of
70% of monomers such as hydroxyethyl acrylate, styrene, acrylonitrile, butyl
acrylate and acrylic
acid with 30% of a melamine resin and an acid catalyst and finally with a
clear finishing enamel.
The base coat is sprayed onto the sheet to a thickness of about 0.8 mil
(0.0203 mm) and air
dried for three minutes. The clear finishing enamel is then sprayed onto the
sheet to a thickness
of about 2.0 mil. After 15 minutes air-drying, the coated sheets are baked for
30 minutes at
121 C.
The stabilizers under test are added to the thermoset acrylic resin finishing
enamel in a
concentration of 1% by weight before the enamel is coated onto the base coat.
The coated sheets, after storage for three weeks in an air-conditioned room
(23 C/50%
relative humidity), are subjected to weathering for 2000 hours according to
SAE J1920 in a
Xenon arc Weather-Ometer. In this apparatus, samples are subjected to
weathering in repeated
cycles of 180 minutes. The effectiveness of the stabilization is measured by
the retention of 20
gloss after weathering.
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The sheets stabilized by the instant compounds exhibit good retention of 20
gloss after
weathering under extreme weather conditions.
Exam ip e 121
The samples prepared in Example 120 are also evaluated on the basis of Knoop
Hardness (ASTM D-1474-68) on baked and overbaked samples; on the distinction
of image
(DOI); on Hunter Associates Apparatus; on 20 gloss (ASTM D-523-80); and on
cracking based
on visual observation.
The samples stabilized by the instant compounds exhibit a pattern of greater
retention of
20 gloss and DOI, and a longer absence of severe cracking after exposure.
Exanple 122
The thermoset acrylic enamel of Example 120 is formulated to include 3% by
weight of a
benzotriazole UV absorber and 1.5% by weight of an instant hindered amine test
compound.
The enamel is coated over a white base coat or over a silver metallic base
coat. Baking is
conducted at 121 C normal bake or at 82 C automotive low bake repair
temperature.
The coated panels are exposed in a Xenon arc exposure apparatus and 20 gloss
and
distinction of image (DOI) values are determined.
The samples stabilized by the instant compounds exhibit a pattern of greater
retention of
20 gloss and DOI.
Examale 123
Two thermoset acrylic enamles are formulated to include 3% by weight of a
benzotriazole UV absorber and 1% by weight of an instant hindered amine test
stabilizer.
The thermoset acrylic enamels are based on a binder of 70% of monomers such as
hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid
with 30% of a
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melamine resin and an acid catalyst such as p-toluenesulfonic acid,
dinonylnaphthalene-
disulfonic acid, dodecylbenzenesulfonic acid or phenyl acid phosphate.
Pieces of steel sheeting 4" x 12" (9.16 cm x 30.48 cm), coated with a prirner
based on
polyester/epoxy resin, are then coated with a base coat and finally with a
clear finishing enamel.
The base coat is sprayed onto the sheet to a thickness of about 0.8 mil
(0.0203 mm) and air
dried for three minutes. The clear finishing enamel is then sprayed onto the
sheet to a thickness
of about 2.0 mil. After 15 minutes air-drying, the coated sheets are baked for
30 minutes at
121 C.
The coated panels are exposed in a Xenon arc exposure apparatus and 20 gloss
and
distinction of image (DOI) values are determined.
The samples stabilized by the instant compounds exhibit a pattem of greater
retention of
20 gloss and DOI.
Examnle 124
A white polyester/melamine based oil-free alkyl coil coating is utilized in
this example.
The fully formulated paint is applied over a primed steel sheet using a wire
wound rod to give
0.6-0.8 mil dry film. The panels are baked for about 90 seconds at 220 C,
removed from the
oven and immediately quenched in water. The coated panels are exposed in a
Xenon Arc
Weather-Ometer, and in South Florida at an angle of 45 S to the sun. 20
gloss values are
determined.
The samples stabilized by the instant compounds exhibit a pattern of greater
retention of
20 gloss.
Example 125
The thermoset acrylic enamel of Example 124 including 0.8%
dodecylbenzenesulfonic
acid is formulated to include varying concentrations of benzotriazole or s-
triazine UV absorbers
and the instant hindered amine test compounds. The enamel is coated over a
silver metallic
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base coat pursuant to the procedure of Example 124 and baking is conducted for
30 minutes at
121 C the normal backe temperature.
The coated panels are exposed in a Xenon arc Weather-Ometer and the time to
the
50% loss of 20 gloss is determined.
The samples stabilized by the instant compounds and a UV absorber exhibit an
excellent retention of 200 gloss and a much longer time till 50% loss in 20
gloss is observed.
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Example 126
A thermoset acrylic enamel based on a binder of 70% of monomers such as
hydroxy-
ethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid with
30% of a melamine resin
and an acid catalyst such as p-toluenesulfonic acid,
dinonyinaphthalenedisulfonic acid or
dodecylbenzenesulfonic acid is formulated. Commercially available 9.16 cm x
30.48 cm
Uniprime panels are used as the substrate. The panels are coated with a silver
metallic base
coat and then with a clear finishing enamel. The base coat is stabilized with
1% of a
benzotriazole UV absorber and 1% of an instant hindered amine test compound
(based on solid
resin) and is sprayed onto the panel to a thickness of about 0.6-0.8 mil and
air dried for three
minutes. The clear coat including the above-noted stabilizers is then sprayed
to a thickness of
1.7-2.0 mils and after 10 minutes of air drying, the coated panels are baked
for 30 minutes at
121 C. The coated panels are then exposed in a Xenon arc apparatus and the 20
gloss values
are determined.
The samples stabilized by the instant compounds and a UV absorber exhibit
excellent
retention of 20 gloss.
Example 127: A water-borne acrylic melamine enamel is formulated as seen
below:
Parts Resin Solids
Synthacryl VSW 6483 30
(acrylic dispersion from Hoechst)
Synthacryl VSW 6484 42
(50% acrylic resin in butyl diglycol, Hoechst)
Maprenal MF 915 25
(70% melamine resin in isobutanol)
Maprenal MF 927 3
(melamine resin) 100
A water-based base coat/clear coat enamel is prepared by spray applying a 0.6-
0.8 mil
thick film of commercial silver metallic waterborne base coat (from BASF) over
an epoxy primed
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coil coated aluminum panel. This material is baked at 80 C for five minutes
and then clear
coated with 1.6-1.8 mil of the waterborne enamel. The system is baked at 80 C
for ten minutes
and then at 140 C for a further 30 minutes. Prior to application of the clear
coating, instant test
and light stabilizers dissolved in a minumum amount of butyl glycol acetate
are added to the
paint. The coated panels are exposed in a Xenon arc apparatus for 975 hours.
The distinction of
image (DOI) retention of the panels is measured.
The samples stabilized by the instant compounds exhibit greater retention of
DOI values.
Example 1 28
Stabilization of Tung Oil Phenolic Varnish
Pieces of 1.27 cm x 20.32 cm x 30.48 cm western red cedar panels having a fine
radial
cut are used to test a commercially available tung oil phenolic varish
(supplied by McCloskey).
One half of each panel is coated with two coats of unstabilized varnish. An
equal amount of
varnish containing 5% by weight (based on resin solids) of test stabilizers is
applied to the other
half of the panel in two coats. After storage for two weeks at ambient
temperature, the wood
panels are exposed outdoors at an angle of 45 S for a period of eight months.
The 60 gloss of
each half of the panel is measured at the top, middle and bottom portion of
the panel and
averaged according to ASTM D 523. Due to the lack of homogeneity of wood
substrates, the
gloss retention of the same varnish tends to differ slightly from panel to
panel. Thus, the
application of an unstabilized control varnish to every panel allows for a
more meaningful
measurement of the improvement in gloss due to the presence of the instant
test compound.
The panels stabilized by the instant compounds show excellent gloss retention
after long
exposure.
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Exam i~e 129
Stabilization of an Aromatic Urethane Vamish
A sample of commercial aromatic urethane varnish (Flecto-Varathane #90) is
tested by
the same method described in Example 128. After outdoor exposure at an angle
of 45 S for a
period of five months, the 60 gloss retention values of unstabilized and
stabilized portions of
the panels are determined.
The panels stabilized by the instant compounds show excellent gloss retention.
Example 130
Stabilization of a White Two-Component
Polyester Urethane Gloss Enamel
A white polyester is formulated as shown below:
Parts
Component I
Desmophen 670-90 (polyester glycol, Mobay) 132.4
Titanium Dioxide 198.6
Cellosolve Acetate 98.9
Sand Mill
Desmophen 670-90 94.98
Flow Aid 0.28
Tertiary Amine 0.015
Cellosolve Acetate 332.6
Com ~ on~a ent 11
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Desmodur N-100 (polyisocyanate, Mobay) 93.9
Cellosolve Acetate 58.7
This material is spray applied at a dry film thickness of 1.5-2.0 mil onto
Bonderite 40 cold
rolled steel panels that have been previously primed with a commerical epoxy
polyamide
maintenance primer (Sherwin-Williams Tile Clad II). Prior to application, the
instant test
compounds are added to the paint. After ambient storage for two weeks, three
panels of each
formulation are exposed outdoors at an angle of 45 S for a period of nine
months. Thereafter,
20 gloss retention is determined by ASTM D 523-80 at the top, middle and
bottom portions of
each panel. Thus, the average values for nine gloss retention measurements for
each triplicate
set of panels are obtained.
The panels stabilized by the instant compounds show excellent gloss retention.
Example 131
Stabilization of Acrylic Alkyd Refinish Enamel
A commercially available acrylic alkyd enamel pigments with non-leafing
aluminum
pigment and tinted a light blue is stabilized with a benzotriazole UV absorber
and an instant
hindered amine test compound and is then spray applied onto Bonderite 40
panels primed with
an alkyd primer. After the coating is allowed to cure at room temperature for
14 days, the panels
are exposed outdoors at an angle of 45 S for a period of eight months. The 20
gloss of the
exposed panels is measured.
The panels stabilized by the instant compounds show excellent gloss retention.
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Example 132
Stabilization of a Medium Oil Alkyd Enamel
A medium oil alkyd enamel pigmented with a non-leafing aluminum pigment and
tinted
light blue is stabilized with a benzotriazole UV absorber and an instant
hindered amine test
compound and is then sprayed applied onto cold rolled steel panels primed with
an epoxy
primer. After the coating is allowed to cure at room temperature for two
weeks, the panels are
exposed for accelerated weathering in a Xenon Arc Weather-Ometer for 840
hours. The 200
gloss values of the panels are determined before and after exposure.
The panels stabilized by the instant compounds show excellent gloss retention.
Example 133
Electrocoat Composition
A typical E-coat composition is prepared by adding the diglyicidyl ether of
bisphenol A,
polyethylene oxide diol, bisphenol A and xylene to a flask and heating to 135
C. The catalyst
dimethylbenzylamine in xylene is added and the temperature maintained at 143 C
for two hours.
The weight per epoxy (WPE) is measured and a previously prepared crosslinker
composed of
2,4-toluenediisocyanate, trimethylolpropane blocked with an alcohol is then
added and
temperature reduced to 100 C. The remaining epoxy groups are then capped with
two different
secondary amines, namely diketimine of diethylenetriamine and
methylethanolamine, in phenyl
cellosolve. The temperature is maintained for one hour at 110 C and the
crosslinker hexa-
methylenediisocyanate blocked with an alcohol is added. The temperature is
maintained near
100 C for 30 minutes and the resin mixture is added to deionized water,
surfactant and lactic
acid to give a resin emulsion.
To this resin emulsion is added the instant hindered amine compound,
additional epoxy
resin, carbon black, dibutyltin oxide catalyst, titanium dioxide, lead
silicate, water and UV
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absorber. After dispersion using a sand mill to achieve proper fineness, the
mixture is
incorporated into an electrocoat bath with water for electrocoating onto a
metal substrate.
The steel coating electrocoated with the above E-coat resin composition to a
thickness
of 23-30 m and cured for 20 minutes at a temperature of 176-201 C. A
pigmented resin layer is
coated thereover at a thickness of 20-51 m using an acrylic coating
composition in an organic
solver, pigments and a UV absorber. The coated panels are then baked at 121-
129 C to cure
the pigmented layer.
The panels are then exposed outdoors for four months. The panels containing
the
instant hindered amine compound, particularly when used with a UV absorber,
provided
excellent resistance to delamination of the E-coat layer from the metal
substrate.
Example 134
Abrasion-Resistant Coating Compositions
A solution in isopropanol of 50% (by weight) of 1,6-hexanediol, 10% 3-
methacryloyloxy-
propyltrimethoxysilane and 40% colodial silica (in form of a 34% aqueous
dispersion) is vacuum
stripped to remove volatiles and combined with an instant hindered amine
compound, a
benzotriazole UV absorber and 2,4,6-trimethylbenzoyldiphenylphosphine
photoinitiator. These
compositions show no gelation on storage.
The compositions above are applied by roller coating to a 15 mil film of
bisphenol A
polycarbonate and the coated films are passed under a mercury lamp at 43 C at
a line speed of
610 cm/min. The compositions are cured to a colorless and optically clear
coatings over the
polycarbonate substrate.
The coatings as measured by the Taber Abrasion Test (ASTM D1044) are abrasion
resistant.
, , .. .. . . . .. .. .. .. . . . . . .... . . . .. .. . . . .. .. ..... . ,
.. .. . _ .. .. . . . ..
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The test specimens are also subjected to accelerated aging tests using an
Atlas Ci35A
Xenon Arc Weather-Ometer. The results show that the coatings containing the
instant hindered
amine compound exhibit excellent resistance to yellowness and haze formation.
Example 135
Coating over Polycarbonate
A two-component polyester urethane coating is stabilized by the addition of an
instant
hindered amine compound. The high-solids polyester polyol (Desmophen 670-80,
Bayer) is
crosslinked with an isocyanate based resin (Desmodue N-3390, Bayer). The
coating is
catalyzed with 0.015% by weight of dibutyltin dilaurate catalyst.
Plaques of polycarbonate-based plastic substrate (Xenoy) 4" x 6" are coated
with the
formulated clear coat at a thickness of approximately 1.5 mils. The coating is
spray applied to
the substrate and then baked at 82 C for 20 minutes.
After storage for one week at room temperature, each plaque is cut into 2" x
3" strips
with five replicates being made for each formulation. Each strip is placed
into a 8-oz jar along
with 2 mL of distilled water and sealed. All samples are placed in an over at
54 C. A crosshatch
adhesion test is performed once a week on at least two of the replicate
samples until the
sample failed (5% adhesion loss) or until 40 days elapses.
The samples containing the instant hindered amine compounds exhibit excellent
resistance to delamination.
Example 136
Chromogenic photographic layers are prepared by hand-coating a gelatine
emulsion
containing silver bromide, yellow coupler and an additive on a polyethylene-
coated paper.
The composition of the layer is as given in following table, amounts are in
mg/m2:
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Component Amount in the layer
Gelatine 5150
AgBr 520
Yellow coupler 1.07 mmoUm
Coupler solvent solvi 33% of the coupler weight/m
Additive (cf table 4) 30% of the coupler weight/m
Hardener hal 300
Surfactant sul 340
The layers are dried for 7 days in a ventilated cabinet.
The dried samples are exposed to white light through a stepwedge of 0.3 logE
exposure
steps. They are developed with the P94 process for negative colour paper from
Agfa-Gevaert,
following the manufacturers' recommendations.
After exposure and processing, the remission density of the yellow dye is
measured in
the blue channel. The samples are then exposed in an Atlas WeatherOmeter
behind a separate
UV filter so as to receive 60kJ/cm2 light energy. The UV filter consists of an
emulsion coated
onto a polyester transparent support, such that the layer contains 1g/m2
Tinuvin B976 . The
temperature is 43 C and the relative humidity 50%. The density loss starting
from a blue-density
of 1 is determined. Low AD number are desired.
Table 1
Coupler Additive -AD(60kJ/cm2, from
OD=1)
CoupY1 none 63
CoupY 1 X 50
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CoupY1 B Y 59
CoupY2 none 40
CoupY2 A X 30
CoupY3 none 24
CoupY3 A X 20
CoupY3 B Y 22
CoupY4 none 36
CoupY4 A X 23
These results show that additives of the present invention improve the light
stability of
yellow photographic layers.
Exam I
Chromogenic photographic layers are prepared by hand-coating a gelatine
emulsion
containing silver bromide, yellow coupler and an additive on a polyethylene-
coated paper.
The composition of the layer is as given in following table, amounts are in
mg/m2:
Component Amount in the layer
Gelatine 5150
AgBr 520
Yellow coupler 1.07 mmol/m
Coupler solvent solvl 33% of the coupler weight/m
Additive (cf table 4) 30% of the coupler weight/m
Hardener hal 300
Surfactant su1 340
The layers are dried for 7 days in a ventilated cabinet.
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The dried samples are exposed to white light through a stepwedge of 0.3 logE
exposure
steps. They are developed with the P94 process for negative colour paper from
Agfa-Gevaert,
following the manufacturers recommendations.
After exposure and processing, the remission density of the yellow dye is
measured in
the blue channel. The samples are then subjected to storage in a Weiss
climatic cabinet for 28
days. The density loss starting from a blue-density of 1 is determined. Low AD
numbers are
desired.
Table 1
Coupler Additive -AD(28d at 80 C and
70%RH, from OD=1) in
%
CoupY1 none 22
CoupY1 X 16
CoupY1 Y 20
CoupY2 none 18
CoupY2 X 10
CoupY2 Y 10
CoupY2 Z 15
These previous results show that additives of the present invention also
improved the
dark stability of yellow photographic layers.
Components used in Examples 136 and 137:
CoupY1 CoupY2 ___T__CoUpY3
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H CiaO
O / HN-~)
HN S,n~/ p
~ O H H H =' ~ ~
p l ' N O~S`C H N
N Oy p p ~2 zs H
~ ~~ N-N p~Nrp CI
H N ~0 N
solvl hal su1
CtyU NyCl
Nf N SO,Na
O~/ OH
0
coaddl coadd2 CoupY4
~ I
y2CN
HO O / HO p O~ ~O H H
0 O
S OSO
X is the compound of Example 30.
Y is the compound of Example 73.
Z is the compound of Example 16A.
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Example 138
Stabiiization of Thermoplastic Polyolefins
Molded test specimens are prepared and tested as in Example 76 replacing N,N-
dialkylhydroxylamine base stabilizer in Sample NOR-2 with the amine oxide,
Genox" EP. Light
stabilizer formulations comprising a mixture of components outlined in Example
76, an amine
oxide and the instant compounds exhibit good stabilization performance against
deleterious
effects of UV light.
Examplg139
Paintable Thermoplastic Polyolefins
Molded test specimens are prepared as in Example 77 replacing N,N-
dialkylhydroxylamine base stabilizer in Sample NOR-2 with the amine oxide,
Genox" EP.
Formulations comprising a mixture of components outlined in Example 77, an
amine oxide and
the instant compounds exhibit good paint adhesion compared with a formulation
substituting the
close prior art compound where no hydroxyl moiety is present for the instant
compounds.
Examole 140
Stabilization of Polypropylene Fiber
Fiber specimens are prepared and tested as in Example 79 replacing N,N-
dialkylhydroxylamine base stabilizer in Sample NOR-2 with the amine oxide,
Genox"" EP. Light
stabilizer formulations comprising a mixture of components outlined in Example
79, an amine
oxide and the instant compounds exhibit good stabilization performance against
deleterious
effects of UV light.
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Example 141
Stabilization of a Glycidyl Methacrylate-based Powder Clearcoat
One of the major new coating technologies which can be used to meet
increasingly
stringent VOC solvent emission requirements is the use of powder coatings.
Applications
requiring the use of light stabilizers include clearcoats for finishing of
automotive topcoats,
finishing of garden implements, protection of automotive wheel covers. For
optimum
incorporation and shelf stability, stabilizers used in a powder coating should
be moderate-
melting (-100 C) solids, nonvolatile, and heat stable at typical powder
coating baking
temperatures (140-180 C).
Prior to incorporation of the Hindered Amine Light Stabilizers under test, a
premix of
commercially available GMA-based powder coating resin, UV absorber, and flow
aids is made
by extruding together at 145 C. The Hindered Amine Light Stabilizers under
test are then
incorporated into portions of this premix, along with a commercially available
1,12 dodecanoic
acid crosslinking resin. The final mix is extruded at 1000 C, then the
extrudate is milled on an
ultracentrifugal mill and powder cyclone, and sieved. The powders are
electrostatically sprayed
onto a basecoat to a film thickness of 60 microns. The coatings are cured for
30 minutes at
160 C.
The panels are weathered in a Xenon WeatherOmeter, and In Florida at 5 South
angle.
Gloss and color are measured.
The panels stabilized by the instant compounds show excellent gloss retention.
Example 142
Stabilization of an Oil Modified Urethane Alkyd for Wood Application
The Hindered Amine Light Stabilizers under test are incorporated into a
commercially
available solvent-borne urethane alkyd McWhorter 43-4355. A 2-hydroxy
benzotriazole UV
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absorber is also incoporated into all formulations. The Hindered Amine light
stabilizers are
added at equivalent piperidine levels. After mixing, the clear coatings are
applied by brushing to
white pine boards. Each board is divided into 8 sections separated by a groove
1/8" deep,
which is sealed with a film-forming clear varnish and the back and sides are
coated with a white
chlorinated pool paint. The stabilized coatings are applied in triplicate in
three coats to sections
of the boards in such a way as to ensure that a control formulation is present
on each of the
boards for comparison. The wood samples are allowed to dry for 1 week, then
placed on
exposure in Florida, Australia, and New York.
The panels stabilized by the instant compounds show good color retention,
cracking
resistance, and visual gloss retention.
Examole 143
Performed Films for Lamination to plastic parts
The instant invention also pertains to protective and decorative films which
are
performed, then applied to a substrate via a dry paint transfer process. These
films consist of a
single decorative layer which is applied to a carrier sheet, then laminated to
a self-supporting,
thermoformable backing sheet. The carrier sheet is then removed from the
opposite side of the
film, exposing the decorative layer. The composite film/backing sheet then is
thermoformed to a
three-dimensional shape. Additionally, these films may also consist of
multiple layers, where,
for example, a thermoplastic, thermoformable clearcoat is applied to the
carrier sheet, then
hardened to form an optically clear film. A color coat is then applied to the
exposed face of the
clearcoat, and hardened, resulting in a clear coat/color coat paint film
supported by the carrier.
This composite is then laminated to a thermoformable backing sheet, as above.
The carrier
sheet is removed, as above, and the composite clearcoat/colorcoat/backing is
then
thermoformed, as above.
The polymeric resins for the above application must be thermoplastic, and may
be
fluoropolymer/acrylic blends.
