Note: Descriptions are shown in the official language in which they were submitted.
- 1 - 1 3 1 07~6
Rigid polyvinyl chLoride is utilized for a variety of
applications including~ for example, siding for houses and
window frames. The rigid polyvinyl chloride is generallY
formulated with high levels of titanium dioxide, e.g.
12-15 parts per hundred, in order to provide proper
pigmentation and prevent significant color variation upon
exposure to UV radiation and with a tin mercaptide
compound as a heat and process stabili7er. The combina-
tion of the titanium dioxide and the tin mercaptide is
included to permit the resin to be ut;tized outdoors, an
essent;al characteristic, without undergoing excess;ve
photodegradation. This is required by manufacturers who
seek assurance that the siding, window frames, and the
l;ke, w;ll be functional for substantial periods of time
without significant color change, reduced physical
properties or resin degradation.
There are, however, certa;n disadventages to these
systems. Thus, the tin mercaptides do not provide
adequate protection against the UV light-induced degrada-
tion commonly encountered during long-term outdoor use.
The use of blends of tin mercaptides and organotin
carboxylates has been resorted to in an attempt to resolve
this difficulty~ While improvement has been noted with
the latter blends~ further protection during such long-
term outdoor use is still required.
There are also certain d;sadvantages to the use of
the indicated high levels of titanium dioxide. Of pr;mary
importance, the high content causes excessive wear and
early failure, i.e. scoring and uneven wear of extruder
barrels and screws in the polyvinyl chloride processing
1 3 ~ 07~6
-- 2
equipment, necessitating expens;ve and frequent
replacement of parts. A further major shortcom;ng of
rigid polyvinyl chlor;de conta;n;ng these h;gh t;tan;um
dioxide levels is that s;d;ngs prepared therefrom can only
be in ~h;te or pastel colors. Darker shades of s;d;ng are
not available because of the h;gh levels. Attempts to
lower the titanium dioxide level have resulted in
siqnificant reductions ;n light stability of the polyvinyl
chlor;de as evidenced by unacceptable color changes, loss
o~ impact strength and surface crazing.
It has ~urther been proposed to use piperidine light
3tabili ers together with organotin stabil;zers in order
to improve the propert;es of polyvinyl chloride ;n
general, 'or example together with lead compounds as
further stabilizers~ The use of lead compounds, however,
leads to further dra~backs, inter alia because of ecological
problem~ caused by lead compounds.
It has now been determined that rigid polyvinyl
~hloride products can be prepared with excellent resis
tance to thermal degradation during processing and
improved long term resistance to UV degradation and which
p~lyvinyl chloride products do not exhibit the drawbacks
mention~d hereinbefore, or exhibit said drawbacks to a
m~l~h less extent. In addition, levels of titanium dioxide
~an b~ si~nificantly reduced or eliminated totalLy without
3ign;f;cant impact on performance, thereby reducing the
wear on and resulting failure of processing equipment
Nh;le giving siding and frame manufacturers greater
flexibility in the color of the manufactured item, i~e~
availability of darker colors~ All these advantages are
I 3 ~ 0786
-- 3 --
obtained by the composition of this invention.
The composition of this invention is a rigid
polyvinyl chloride composit;on, which comprises ;n addition
to said polyvinyl chlor;de, (A) at least one 2,2,6,6-tetra-
alkylpiperidine compound which contains at least one group
of the formula
RCH2
5H3 ~R
/---\ ( 1 )
~r-o
2 CH3
~herein R is hydrogen or methyl;
and (B) at least one organotin compound of the formulae
oz1
1 2
(Z) 2Sn-OZ
(z)2Sn(OOC-Z3)2
( IZ)2 ( IZ)2
Z -COO-Sn-O-Sn-OOC-Z
(Z)msn(ooccH=cHcooz )4-m
wherein 2 and Z4 independently are C1-C20 alkyl, C3-C20
alkenyl, cycloalkyl, aryl, alkaryl or aralkyl;
z1 is C10-C30 alkyl or phenyl substituted by one or
C8 12 alkyl;
1 ~ I U7~6
Z is Z or -Sn(OZ1)(Z)2;
Z is C1-C30 alkyl, C3-C20-alkenyl~ cycloalky~, aryl,
alkaryl or aralkyl; and
m is an integer from 1 to 3.
The 2~2,6,o-tetraalkyl piperidine compounds to be
used according to the invention are generally known and
are recognized for their ab;lity to combat light degrada-
tion in a variety of substrates including polyvinyl
chloride. U~Sa 3,542,729, U.S. 3,547,874, U.S. 3,640,928,
U~S. 3,840,494, U~S. 4,021,432, U.S. 4,049,647,
U.S. 4,064,102, U.S. 4,086,204 and U~Sa 4,265,805 are
typ;cal of the numerous patents that disclose such
piper;dine light stabilizers.
The 2,2,6,6-tetraalkylpiperidine compounds containing
at least one group of the formula I to be used according
to the invention include in particular the following
pre~erred classes of compounds:
a) Compounds of the formula II
RCH 2\ CH 3/R
R~ ~ _R2 ( I I ),
RCH2~ \CH3
n
1 31 07~6
in which n is a number from 1 to 4, preferably 1 or 2, R is
hydrogen or methyl, R1 is hydrogen, oxyl, C1-C18-alkyl,
C3-cg-alkenyl~ C3-Cg-alkynyl~ C7-C12-aralkyl, C1-C8-
alkanoyl, C3-C5-alkenoyl, glycidyl or a group -CH2CH(OH)-Z,
with Z being hydrogen, methyl or phenyl, R preferably being
Cl-Cl~-alkyl, allyl, benzyl, acetyl or acryloyl, and R2, if
n = l, is hydrogen, C1-C1g-alkyl which may be interrupted by
one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a
monobasic radical of an aliphatic, cycloaliphatic, arali-
phat;cr unsaturated or aromatic carboxylic acid, carbamic
a~id or phosphorus-containing acid or a monovalent silyl
radic3l, preferably a radical of an aliphatic carboxylic
ac;d having 2 to 1~ C atoms, cycloaliphatic carboxylic acid
having 7 to 15 C atoms, an ~,~-unsaturated carboxylic acid
having 3 to S C atoms or an aromatic carboxylic acid having
7 to 15 C atoms, or, if n = 2, R2 is C1-C12-alkylene, C4-C12-
alkenylene, xylylene, a dibasic radical of an aliphatic,
cycloaliphatic, araliphatic or aromatic dicarboxylic acid,
dicarbamic acid or phosphorus-containing acid or a divalent
silyl radical, preferably a radical of an aliphatic dicar-
boxylic acid having 2 to 36 C atoms, a cycloaliphatic or
aromatic dicarboxylic acid having 8 - 14 C atoms or an ali-
phatic, cycloaliphatic or aromatic dicarbamic acid having
8 - 14 C atoms, or, if n = 3, R2 is a tribasic radical of an
aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an
aromatic tricarbamic acid or a phosphorus-containing acid or
3 trivalent silyl radical, and, if n = 4~ R2 is a tetra-
basic radical of an aliphatic, cycloaliphatic or aromatic
tetracarboxylic acid.
Any C1-C12-alkyl substituents are, for example,
m~thyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl,
n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl
or n-dodecyl.
;1 3 1 ~7~6
-- 6 --
C1-C1g-alkyl radicals R1 or R2 can be, for example,
the groups listed above and in addition also, for example,
n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octa-decyl.
A C3-C8-alkenyl radical R1 can be, for example, 1-
propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl,
2-octenyl or 4-tert.-butyl-2-butenyl.
A C3-Cg-alkynyl radical R1 is preferably propargyl.
A C7-C12-aralkyl radical R1 is in particular
phenethyl or especially benzyl.
A C1-C8-alkanoyl radical R1 is~ for example, formyl,
propionyl, butyryl, octanoyl or preferably acetyl, and
C3-C5-alkenoyl is especially acryloyl.
If R2 is a monobasic radical of a carboxylic acid,
this is, for example, an acetic acid, caproic acid, stearic
acid, acryl;c acid, methacrylic acid, benzoic acid or ~-
(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid radical.
If R2 is a dibasic radical of a dicarboxylic acid,
it is, for example, a malonic acid, adipic acid, suberic
ac;d, sebacic acid, maleic acid, phthalic acid, dibutylmal-
onic acid, dibenzylmalonic acid, butyl-(3,5-di-tert.-butyl-
4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic
acid radical
If R is a tribasic radical of a tr;carboxyl;c
acid, it is, for example a trimellitic acid or nitrilotri-
acetic acid radical.
If R2 is a tetrabasic radical of a tetracarboxylic
acid, it is, for example, the tetrabasic radical of butane-
1,2,3,4-tetracarboxylic acid or of pyromellitic ac;d.
If R2 is a dibasic radical of a dicarbamic acid,
it is, for example, a hexamethylene-dicarbamic acid or
2,4-toluylene-dicarbamic acid radical.
Those compounds of the formula II should be
13 1 U7.,6
especially mentioned in which n is 1 or 2, R is hydrogen, R1
is hydrogen~ o~y~, C1-C6-alky~, C3-Cg-alkenyl~ ~or example
llyl, benzyl~ C2-C6-alkanoy~ C3-C5-alkenoyl, for example
acryloyl or methacryloyl, g~ycidyl or -C~2CH(OH)-Zl with Z1
being hydrogen or methy~, and R2, if n = 1, is hydrogen, C1-
C12-alkyl, benzyl or the radical of an aliphatic carboxylic
acid having ~-18 C atoms, an ~ unsaturated carboxylic acid
having 3-5 C atoms or an aromatic carboxylic acid having 7-
l~ C atoms, and, if n = 2, R2 is C1-C6-alkylene, C4-C8-
alkenylene or the radical of an aliphatic saturated or un-
satur3ted d;carboxylic acid having 2-18 C atoms.
Examples of tetraalkylpiperidine compounds from this
~13~ ~re the follow;ng compounds: 1) 4-hydroxy-2,2,6,6-
tetram2thylpiperidine, 2) 1 allyl-4-hydroxy-2,2,6,6-tetra-
methylpiperidine, 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethyl-
piperidine, 4) 1-t4-tert~-butyl-2-butenyl)-4-hydroxy-2,2,
6,~-tetramethylpiperidine, S) 4-stearoyloxy-2,2,6,6-tetra-
methylpiperidine, 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetra-
methylpiperidine, 7) 4-methacryloyloxy-1,2,2,6,6-penta-
methylpiperidine, 8) 1,2,2,6,6-pentamethylpiperid-4-yl
~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate, 9) di-
(l-benzyl-2,2,6,6-tetramethylpiperid-4-yl) maleate, 10) di~
~2,2,6,6-tetramethylp;perid-4-yl) adipate, 11~ di-(2,2,6,6-
tetramethylpiperid-4-yl) sebacate, 12) di-(1,2,3,6-tetra-
methyl-2~6-diethyl-Piperid-4-yl) sebacate, 13) di-(1-allyl-
~,~,6,6-tetramethylpiperid-4-yl) phthalate, 14) 1-propargyl-
4-~-cyanoethoxy-2,2,6,6-tetramethylpiperidine, 15) 1-acetyl-
,6-tetramethylpiPerid-4-yl acetate, 16) tri-(2,2,6,6-
tetramethylp;perid-4-Yl) trimellitate, 17) 1-acryloyl-4-
ben2yloxy-2,2,6,6-tetramethYlpiperidine~ 18) c1i-(1,2,2,6,6-
pent3methylpiperid-4-Yl) dibutylmalonate, 19) di-(1,2,2,6,6-
pentamethylpiPerid-4-yl) butyL-(3,5-di tert.-butyl-4-hydroxy-
benzyl)-malonate, 20) di-(1,Z,2,6,6-pentamethylpiperjd-4-
yl) dibenzylmalonate, 21) d~ 2~3~6-tetramethyl-2~6-diethyl
piperid-4-yl) dibenzylmalonate, 22) hexane-1',6'-bis-(4-
carbamoyloxy-1-n-butYl-2~2~6~6-tetramethylpiperidine)~
23) toluene-2',4'-biS-(4-carbamoyloxy-1-n-propyl-2~2~6~6
131U7~6
-- 8 --
tetramethylpiperidine), 24) dimethyl-bis-(2,2,6,6-tetra-
methylpiperid-4-yloxy)-silane, 25) phenyl~tris-(2,2,6,6-
tetramethylpjperid-4-yloxy)-silane~ 26) tris-(1-propyl-
2,2,~,6-tetramethylpiperid-4-yl) phosphite, 27) tris-(1-
pr~pyl-2,2,6,6-tetramethylpiperid-4-yl) phosphate, 28) bis-
(1,2,2,b,6-pentamethylpiperid-4-yl) phenylphosphonate,
29~ di-(1,2,2,6,6-pentamethylpiperid-4-Yl) sebacate,
~9a) 4-hydroxy-1,2,2,6,6-PentamethYlPiperidine~ 29b) 4-hyd-
roxy-N-hydroxyethyl-2~2~6~6-tetramethylpiperidine~ 29c) 4-
hydroxy-,~-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine
~nd 29d) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperid;ne,
and part;cularly the compounds
bis~,2,~,c,-tetramethyl-4-piperidinyl)sebacate,
bis~l-3cetyl-2~2~6~6-tetramethyl-4-piperidinyl) sebacate~
bis~-ben2yl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate or
N-butyl-(3,5-di-tert.butyl-4-hydroxybenzyl)-bis-
~ ,6,6-pentamethyl-4-piperidinyl)malonate.
b) Compounds of the formula (III)
RCH
R~ -R~ (III~
RCH2 CH3 n
in which n is the number 1 or 2, R and R1 are as defined
under a~ ;nclud;ng the preferred definitions, R3 is hydro-
9~R, Cl-C12-alkyl, C2-C5-hydroxyalkyl, C5-C7-cycloalkyl"
C7-C~-aralkyl, c2-C1g-alkanoyl, C3-Cs-alkenoyl or benzoyl
and R4, if n = 1, is hydrogen, Cl-Clg-alkyl~ C3-C8-
alkenyl, Cs-C7-cycloalkyl~ C1-C4-alkyl substituted by a
hydroxyl, cyano, alkoxycarbonyl or carbamide group, gly-
cidyl or a group of the formula -CHz-CH(OH)-Z or of the
formula -CONH-Z, ~ith Z being hydrogen, methyl or phenyl,
1 3 1 07~6
or, if n = 2, R is C2-C12-alkylene, CS-C12-arylene,
xylylene, a -CH2-cHtOH)-cH2- group or a -CH2-CH(OH)-CH2-0-
D-o-cH2-rH(oH)-cH2- sroup~ with D being C2-C10-alkylene,
C6-C15-arylene or C6-C12-cycloalkylene, or R4, provided
that R3 is not alkanoyl, alkenoyl or benzoylr can also be
a dibasic radical of an aliphatic, cycloaliphatic or aro-
matic dicarboxYliC acid or dicarbamic acid or the group
-CO-, or R and R together, if n = 1, can be the dibasic
radical of an aliphatic, cycloaliphatic or aromatic 1,2-
or 1,3-dicarboxylic acid.
Any C1-C12- or C1-C18-alkyl substituents are as
already defined under a).
Any Cs-C7-cycloalkyl substituents are especially
cyclohexyl.
A C7-Cg-aralkyl radical R3 is in particular
phenylethyl or especially benzyl. A C~-Cs-hydroxyalkyl
radical R3 is especially 2-hydroxyethyl or 2-hydroxypropyl.
A C2-C1g-alkanoyl radical R3 is, for example pro-
pionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or
octadecanoyl, and preferably acetyl, and C3-Cs-alkenoyl is
especially acryloyl.
A C2-Cg-alkenyl radical R4 is, for example, allyl,
methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
A C1-C4-alkyl radical R4 which is substituted by
a hydroxyl, cyano, alkoxycarbonyl or carbamide group can
be, for example, 2-hydroxyethyL, 2-hydroxypropyl, 2-cyano-
ethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-amino
carbonylpropyl or 2-(dimethylaminocarbonyl)-ethyl.
Any C2-C12-alkylene substituents are, for example,
ethylene, propylene, 2,2-dimethylpropylene~ tetramethylene,
hexamethylene, octamethylene, decamethylene or dodeca-
methylene.
1 3 1 0786
- 10 -
Any C6-C15-arylene substituents are~ for example,
~r m- or p-phenylene, 1,4-naphthylene, 4,4'-diphenylene or
. _ . . _ .
~ C(DI)(D2)--\ ~-- in ~hich D1 and D2 independently
.--. ~=.
o~ one another are hydrogen or methyl.
A C6-C12-cycloalkylene radical D is especially
cyclohexylene.
Those compounds of the formula III should especially
be mentioned in ~hich R and R1 have the preferred meanings
defined under a), R3 is hydrogen or C1-C6-alkyl and R4, if
n - l, ;s hydrogen, C1-C12-alkyl, C3-Cg-alkenyl, C1-C4-
31kyl sub~tituted by hydroxyl, cyano or carbamido,
~N7~(0~ Z or CONH-Z and~ if n = 2, R4 iS as defined under
the formula III, with the exception of R3+R4 combined.
Examples of tetraalkylpiperidine compounds from this
Cl3ss are the following compounds: 30) N,N'-bis-~2,2,6,6-
tetramethylpiperid-4-yl)-hexamethylene-1,6-diamine, 31)
N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-hexamethylene-1,6-
diacetamide, 32) 1-acetyl-4-(N-cyclohexylacetamido)-2,2,6,6-
tetramethylpiperidine, 33) 4-benzoylamino-2,2,6,6-tetra-
methylpiperidine, 34) N,N'-bis-(2,2,6,6-tetramethylpiPerid-
4-yl~-N,N'-dibutyl-adipamide, 35) N~N'-bis-(2,2,6,6-tetra-
methylpiperid-4-yl)-N,N'-dicyclohexyl-2-hydroxypropylene-
1~3-diamine, 36) N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-
p-xylylenediamine, 37) the compound of the formula
1310786
\~/ o ~4Hg
GH3~cH2-cH(OH)-cH2- 1
CH3 CH3 /
i!, ~!
CH3-¢-CH3
~i ~t
CH3~ ~CH3 \
CH3- ~-CH2-CH(OH)-CH2-
CH3 \CH3 4Hg
38~ 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiper-
;dine, 39) 4-(3-methyl-4-hydroxy-5-tert.-butyl-benzamido)-
2,2,6,6-tetramethylpiperidine and 40) 4-methacrylamido-
1,2,2,6,6-pentamethylpiperidine.
c) Compounds of the formuLa (IV)
~ RCH2~ ~CH3~ ol
¦ RCH 5 \CH3 ~ (IV)
;n wh;ch n is the number 1 or 2, R and R1 are as defined
under a) including the preferred defin;tions and R5, if
n = 1, is C2-Cg-alkylene or -hydroxyalkylene or C4-C22-
acyloxyalkylene and, if n = 2, is the group (-CH2)2C(CH2-)2
A C2-Cg-alkylene or -hydroxyalkylene radical R5 is,
for example, ethylene, 1-methylethylene, propylene, 2-ethyl-
propylene or 2-ethyl-2-hydroxymethylpropylene.
A C4-C22-acyloxyalkylene radical RS is, for example,
2-ethy~-2-acetoxymethylpropylen2
1 3 1 0786
- 12 -
Thus, in the case of n = 2, R5 is the complement to
form a spiro-6-ring and, in the case of n = 1, preferably
is the complement to form a spiro-5- or -6-ring.
Examples of tetraalkylpiperidine compounds ~rom this
class are the following compounds: 41) 9-aza-8,8,10,10-
tetramethyl-1,5-dioxaspiro[5.5]undecaner 42) 9-aza-8,8,10r10-
tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane, 43) 8-aza-
2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane, 44) 9-aza-
3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro
t5.5]undecane, 45) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-
8,8,10~10-tetramethyl-1,5-dioxaspiro[5~5]undecane and 46)
2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-
spiro-5"-(1",3"-dioxane)-2"-spiro-4"'-(2"',2"',6"',6"'-tetra-
methylpiperidine).
d) Compounds of the formulae VA, VB and VC
RCff2\ ~CH3/R 1~
= (VA)
RCH2 \CH3 ~ n- R7
RCHz~ /CH3~ l
--'--T 2
~ ~ (VB)
~7 '=0
RCH2/ \CH3
RCH2\ ~CH
RCHa/ C113 B --R7
- 13 - I 3 1 07~6
in wh;ch n is the number 1 or 2, R and R1 are as defined
under a) including the preferred definitions, R6 is hydro-
gen, C1-C12-alkyl, allyl, benzyl, glycidyl or Cz-C6-alkoxy-
alkyl and R7, if n = 1, is hydrogen, C1-C12-alkyl, C3-Cs-
~lkenyl, C7-Cg-aralkyl~ Cs-C7-cycloalkyl, C2-C4-hydroxy-
alkyl, C2-C6-alkoxyalkyl, C6-C10-aryl, glycidyl or a group
of the formula -tCH2)p-COO-Q or of the formula
-~C~2)p-0-CO-~, wherein p is 1 or 2 and Q is C1-C4-alkyl
or phenyl, or, if n = 2, R7 is Cz-C12-alkylene, C4-C12-
alkenylene, C6-C12-arylene, a group
-CH2-CH(OH)-CH2-0-D-O-CH2-CH(OH)-CH2-, wherein D is C2-C10-
alkylene, C6-C1S-arylene or C6-C12-cycloalkylene or a group
-~H~C~O~')CH2-(OCH2-CH(OZ')CH2)2- ~herein Z' is hydrogen,
~1-Clg-alkyl, allyl, benzyl, C2-C12-alkanoy or benzoyl, and
Tl and T2 independently of one another are hydrogen, C1-C18-
3lkyl or are C6-C1o-aryl or C7-Cg-aralkyl which are unsubsti-
tuted or substituted by halogen or C1-C4-alkyl, or T1 and ~2
together with the C atom linking them, form a Cs-C12-cyclo-
alkane ring.
Any C1-C12-alkyl substituents are, for example,
methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl,
n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl
or n-dodecyl.
Any C1-C1g-alkyl substituents can be, for example,
the groups l;sted above and additionally also, for example~
n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Any C2-C6-alkoxyalkyl substituents are, for example,
m~thoxymethyl, ethoxymethyl, propoxymethyl, tert.-butoxymethyl,
eeho~yethyl, ethoxypropyl, n-butoxyethyl, tert~-butoxyethyl,
i~opropoxyethyl`or propoxypropyl.
A C3-Cs-alkenyl radical R7 is, for example,
1 3 1 07~6
- 14 -
1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
C7-Cq-aralkyl radicals R7, T1 and T2 are in par-
ticular phenethyl or especially benzyl. T1 and T2 forming
a cycloalkane ring together with the C atom can be, for
example, a cyclopentane, cyclohexane, cyclooctane or
cyclododecane ring.
A C2-C4-hydroxyalkyl radical R7 is, for example, 2-
hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxy-
butyl.
C6-C10-aryl radicals R7, T1 and T2 are in particu-
lar phenyl or ~- or ~-naphthyl which are unsubstituted or
substituted by halogen or C1-C4-alkyl.
A C2-C12-alkylene radical R7 is, for example, eth-
ylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexa-
methylene, octamethylene, decamethylene or dodecamethylene.
A C4-C12-a~kenylene radical R7 is in particular
Z-butenylene, 2-pentenylene or 3-hexenylene.
A C6-C12-arylene radical R7 is, for example, o-,
m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
A C2-Cl2-alkanoyl radical Z' is, for example, propio-
nyl, butyryl, octanoyl or dodecanoyl, and preferably acetyl.
A C2-C10-alkylene, C6-C1s-arylene or C6-C12-cyclo-
alkylene radical D is as preferably defined under b).
Examples of tetraalkylpiperidine compounds from this
class are the following compounds: 47) 3-benzyl-1~3,8-tr;aza-
7,7,9,9-tetramethylsp;roC4.5]decane-2,4-d;one, 48) 3-n-octyl-
1~3,8-triaza-7,7,g,9-tetramethylsp;roC4.5]decane-2,4-d;one,
49) 3-allyl-1,3,8-tr;aza-1,7,7,9,9,-pentamethylspiro[4~5]-
decane-2,4-d;one, 50) 3-glycidyl-1,3,8-tr;aza-7,7,8,9,9-penta-
methylsp;roC4.5]decane-2,4-d;one, 51) 2-;sopropyl-7,7,9,9-
tetramethyl-1-oxa-3,8-diaza-4-oxo-spiroC4.5]decane, 52) 2,2-
dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-d;aza-4-oxo-spiro[4.5]-
decane, 53) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-
d;spiroC5.1.11.2]heneicosane, 54) 2-butyl-7,7,9,9-tetramethyl-
1-oxa-4,8-diaza-3-oxo-sp;ro[4.5]decane and 54a) 8-acetyl-3-
dodecyl-1,3,8-tr;aza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-
dione or the compounds of the following formulae:
. ~ ,
t 7i 1 078~
U~
~.
5:
~'i i'~
Z
"\ A /''
N C,~ O I_
~ C;><
T~
3 T~ ;~, U.
O
o
~, , ,
^
` X
I ) I 0786
- 16 -
e) Compounds of the formula VI
~8
R9 W -Rl (VI),
in which n is the number 1 or 2 and R8 is a group of the
formula
~CH3~ ~CH2R
--E-~A) ~ _
CH3 CH2R
in wh;ch R and R1 are as defined under a) including the
preferred definitions, E is -O- or -NR11-, A is C2-C6-
alkylene or -(CH2)3-0- and x is one of the numbers O or 1,
R9 is identical to R8 or one of the groups -NR11R12,
-oR13, -NHCH2oR13 or -N(CH2oR13)2, R10 is, if n = 1,
identical to R8 or R9 and, if n = 2, a group -E-B-E-
~wherein B is C2-C6-alkylene which may be interrupted by
-N(R11)-, R11 is C1-C12-alkyl, cyclohexyl, benzyl or
C1-C4-hydroxyalkyl or a group of the formula
~CH3~ ~CH2R
~ Rl
CH3 CH2R
R1~ is C1-C12-alkyl, cyclohexyl, benzyl or C1-C4-hydroxy-
alkyl and Rl3 is hydrogen, C1-C12-alkyl or phenyl, or
R11 and R12 together are C4-Cs-alkylene or -oxaalkylene,
~ar e~ample
-CH2CH2~ -CH2CH2
~. , or a group of the formula ~N--R
-CH2CH2 ff H2CH2
1 3 t 07~S
- 17 -
or R11 and R12 can also each be a group of the formula
N~ N~-A-
C4Hs~~
Ca3\i \~~CH3
CH 3 b' CH 3
Any C1-C12-alkyl substituents are, for example,
methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl,
n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl
or n-dodecyl.
Any C1-C4-hydroxyalkyl substituents are, for
example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,
2-hydroxybu~yl or 4-hydroxybutyl.
A C2-C6-alkylene radical A is, -for example, ethylene,
propylene, 2,2-dimethylpropylene, tetramethylene or hexa-
methylene.
If R11 and R12 together are C4-C5-alkylene or
oxaalkylene, they are, for example, tetramethylene, penta-
methylene or 3-oxapentamethylene.
Examples of tetraalkylpiperidine compounds from this
class are the compounds of the following formulae:
I ~ 1 07~6
- 18 -
ÇH3
H3C\ /~\ /CH3
H3C'~ \CH3
59) ~-C4Hg
(CH3CH2)2N~ ~ CH2CH3)2
~(CIHs) 2
CH3\ /CH3 ~ CH3\ /CH3
~0) C2Hg~ -C2Hs
CH3' \CH3 2~s 2Hs CH3' \CH3
~ H3C\ /CH3
61) ~ ~ with R = -NH-CH2CH2CH2-0~ CH3
R ~ R H3C/ CH3
131~)786
c~`
.\.
~s~
x ~
r~
ro
\,A ~
~ ~ ~ ! ! ~ ~ ,~ ;3~ o o
T ~
S~ 7; :1:1 ~"~ ,o
N
_
~ ~\~
T
~1 1,' ~ I i t5,
:Z ~ o~ Z ",
,~
.
.
- 20 - ~3107~
CH3~ ~CH3
C8HI7~ H
~ ~ CH3 CH3
64) C.3HI7 ~ H(CHz)3- - _
CH3~ CH3
CH3 H~ CH3 2
ÇH2cH2oH
CH3~ ~CH3
CH3~ \CH3
65) ~-C4Hg
CH3~ ~CH3 ~ ~ CH3~ ~CH3
H0-CH2CH2~ -CH2CH2-OH
CH3 CH3 CH3 CH3
ÇH2-CH=CH2
H3C~ CH3
H3C/I\ ~I\CH3
~-C4H~
(66~ H3C~ ~CH3 ~ ~ . f, 3
H2CaHC-H2C~ N~ -CH2-C~kCH2
,~. 4Hg 4Hg ._.
H3C CH3 CH3~ \CH3
13107~6
- 21 -
f) Compounds of the formula VII
\ 3 \ / 2
O
/ ~N 1~ (VII)
O--9
CH/ \CH R n
;n which n is the number 1 or 2; R is as def;ned under
the formula (I)~ and R14 when n i s '1~ iS C-4~C18 alkyL, .
C -C 2 aralkyl, the group -CO-R15, or C1-C4 alkyl which is
substituted by -CN, -COOR16, -OH, -OCOR17 or
CH -CH(OH)-~ wherein R15 is C1 C12 Y ~ 2 4
~k~nyl or phenyl~ R16 is C1-C18 alkyl, R17 1 18
alkyl, C2-C10 alkenyl, cyclohexyl, ben~yl or C6-C10 aryl;
ar R14 when n is 2 is C4-C12 alkylene, 2-butenylene-1,4,
xylylene, the group H2 2 18 2 2
group -CH2-OOC-R19-COO-CH2- wherein R18is C2-C10 alkylene~
phenylene or cyclohexylene, and R19 is C2-C10 alkylene,
xylylene or cyclohexylene.
If any substituents are C1~C12 alkyl, they are for
example methyl, ethyl, n-propyl, n-butyl, sec-butyl,
tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl~ n-nonyl,
n-~ecyl, n-undecyl or n-dodecyl.
Any subst;tuents which are C1-C18 alkyl can be for
example the groups ment;oned above~ and in addition for
example n-tridecyl, n-tetradecyl, n-hexadecyl or n-
octadecyl.
- 22 - ~ 6
If any groups are C2-C~O alkylene, these are in
particular ethylene, propylene, 2,2-dimethylpropyLene,
tetramethylene, hexamethylene, octamethylene or deca-
methylene.
As C4-C18 alkyl, R14 is for example n-butyl, sec-butyl,
tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, 1~1-dimethyl-
2-tert-butylethyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl~
n-tetradecyl, n-hexadecyl or n-octadecyl.
If R14 is a C1-C4 alkyl group substituted by -CN, ;t
is for example cyanomethyl, cyanoethyl, 3-cyano-n-propyl
or 4-cyano-n-butyl.
If R14 is C4-C12 alkylene, it is for example 2 2-
dimethylpropylene, tetramethylene, hexamethylene, octa-
methylene, decamethylene or dodecamethylene.
If R14 is C7-C12 aralkyl, ;t ;s in particular phenethyl,
p-methyl-benzyl or especially benzyl.
As C2-C4 alkenyl, R15 is for example vinyl, ~-propenyl,
allyl, methallyl or 2-butenyl.
As C2-C10 alkenyl, R17 ;s for example the groups
mentioned for R15 as alkenyl, and in addition for example
crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.
If Rj7 is C6-C10 aryl, it is for example phenyl which
is unsubstituted or substituted in the o- or p-position
by methyl, ethyl, isopropyl, n-butyl or tert-butyl.
:
1 3 1 07~
- 23 -
The following compounds are examples of polyalkyl-
piperidine light stabilizers of this class:
67) bis-[~-(2,2,6,6-tetramethylpiperidino)-ethyl]~
sebacate,
68) a-(2,2,6,6-tetrame~hylpiperidino)-acetic acid-
n-octyl ester, and
~9) 1,4-bis-(2,2,6,6-~teiramethylpiperidino)-2-butene.
9) Compounds of the formula VIII
RCH2 / CH3 R
E CO-NH-CH2-OR20 (VIII )
RCH / \CH
tR21) or -0-; E is C1-C3 alkylene, the
yroup -CH2~CH(Z4)-0- wherein Z4 is hydrogen, methyl or
phenyl, the group -(CH2)3-NH- or a s;ngle bond; R is
hydrogen or methyl; R1 is hydrogen, C1-C18 alkyl~, C3-C8
3 l kenyl, C3-C8 alkynyl, C7-C12 aralkyl, C1-C8 alkanoyl,
C3-C5 alkenoyl or glycidyl; R20-is hydrogen or C1-C18
3lkyl; R.21 is hydrogen, C1-C18 alkyl, C5-C7 cycloalkyl~
C7-C12 aralkyl, cyanoethyl, C6-C10 aryl, the group
-CH2-CHt~4)-QH, a group of the formula
2\ ~CH3 /R
`~
~ ~ ~ 0
~ 3 ~
- 24 -
or a group of the formula
--G~E--C~O-NH-CH2-OR20
/ \ /
CH3~¦ I 3
RCH2 \~/ CH2R
wherein G can be C2-C6 alkylene or C6-C12 arylene; or
R21 is a group ~E-CO-NH-CH2-OR20.
If any substituents are C1-C18 alkyl, they are for
~xample methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-
butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl,
n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl
or n-octadecyl.
If any substituents are C7-C12 aralkyl, they are for
example phenethyl or in particular benzyl.
If R1 is C3-C8 alkenyl, it can be for example 1-
propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl,
2-hexenyl, 2~octenyl or 4~tert-butyl-2-butenyl.
As C3-C8 alkynyl, R1 is preferably propargyl. As
C1-C~ alkanoyl, R1 ;s for example formyl, propionyl,
butyryl, octanoyl but preferably acetyl; and as C3-C5
alkenoyl, R1 is espec;ally acryloyl.
As C5-C7 cycloalkyl, R21 ;s in part;cular cyclohexyl~
As C6-C10 aryl, R21 is particularly phenyl, or a- or
13~07~6
~-naphthyL which is unsubstituted or substituted with
halogen or C1-C4 alkyl~ As ~1-C3 alkylene, E is for example
methylene, ethylene or propylene.
As C2-C6 alkylene, G is for example ethylene, propylene,
2,2-dimethylpropylene~ tetramethylene or hexamethylene;
and as C6-C12 arylene, G is, for example, o-, m- or
p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
Thè'follQwing compounds are examples o~ polyalkyl-
piperidine light stabilizers of this class:
70) N-hydroxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-
urea,
71) N-methoxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-
urea,
72) N-methoxymethyl-N'-n-dodecyl-N'-2,2,6,6-tetramethyl-
piperidin-4-yl-urea, and
73) 0-(2,2,6,6-tetramethylpiperidin-4-yl)-N-methoxy-
methyl-urethane.
h) Oligomeric or polymeric compounds, the recurrent
structural unit of which contains a 2,2,6,6-tetraalkylpiper-
idine radical of the formula (I), in particular polyesters,
polyethers, polyamides, polyamines, polyurethanes, polyureas,
polyaminotriazines, poly~meth)acrylates, poly(meth)acryl-
amides and copolymers thereof, which contain such radicals~
Examples of 2,2,6,6-tetraalkylpiperidine light stab-
ilizers from this class are the compounds of the following
~ormulae, m being a number from 2 to 200.
~ 3 1 07~6
~ 26
~6) CH3\ ~CH3
~C--CH2--CH2~ CH2--CH2--N~ ~-~;;
CH3~ \CH3
77)CH3\ /CH3 CH3~ ~CH3
CH2-CH2~ -O-C-(CH2~4-C-0-~\ ~ -CH2-CH2-0-C-(CHz)4-C
CH3 CH3 CH3 CH3
7B)CH3~ /C2Hs CH3~ /C2Hs
- ~CH 2)3 - ~ ~. - NH-~ t -C-NH--\ ~ -(CH 2 )3-NH~
CH3 C2Hs ~ CH; C2Hs ~-
79) H3 H3
~H ~ - CH2- --CH3
.~ CH3 H3
(CH2)
~I t~ CH3\~ i/cH3
80) CH3 ~ CH3 CH3 ~ CH3
[ ~ --CH2--CH(OII)--CH2~
CH t' 't CH
CH3 ~ CH3
81) CH3\ ~CH3 CH3\ /CH3
CH2--CH=CH--CH2--h~~- ~ C--~--C
CH3 CH3 CH3 CH3
_ ~ (CH 2 ~ 6 - ~ ]~
~ 3~1 t/ 3 CH ~ & H
CH3\t/ \t~CH3 CH3/ ~ ~CH3
CH3 ~ \CH3
1 3 t 07~,
- 27 -
83) CH3\ ~CH3 CH3\ /CH3
_ -0-~ CH2~ -CH2- ~o-8-(CHz)~- ~ _
._, .=, ,_.
CH3 CH3 CH3 CH3 m
~4)
CH3\ /CH3
-o--CH2-CH2- ~ /-
CH3 CH3
~S) H3
CH2 ~
CH3 CH3
O= , \./
~,/ ~ - CH3
CH3f \CH3
86) H3
E ---CH2 ~
CH3\ /CH3
O=
C~Hl3- 1-~/ ~ - CH3
CH3/ \CH3
,/o\~
\~
,~ , ~ ~ (CH~)
CH 1~ \i CH CH / \ CH
CH3/ ~ \CH3 CH3/ y \CH3
88) (CH2)6 ~ - CHz-CH2
CH t' ' CH
CH3f ~ \CH3 CH3 ~ CH3
1 3 1 07~6
- 28 -
89)
[ ~ -~cH2)6 ~ 8_ CH2- 8
CH I~ `- CH CH3~, i/CH3
CH3 ~ CH3 CH3 ~ CH3
with compounds 76 and 79 be;n~ preferred.
;) Compounds of the formula IX
2\ / 3~R
L RC~ CH3 nR23 (IX)
wherein n is an integer of 1 to 4, preferably 2,
R22 is H, OH or C1-C8 alkoxy, and
;f n is 1, R23 is C1-C20 alkyl, C5 C12 y
C7-C14 aralkyl, and
;f n ;s 2~ R23 is C2-C12 alky~ene, C6 C12 Y
C8-C16 c~cloalkylene-dialkylene~ C8-E14 aralkylene,
C4-C9 mono- or dioxaalkylene, and
23 3 12 lkane triyl and
' 23 4 12 ane tetrayl,
and R and R1 are as defined before.
1 3 t 07~6
- 29 -
Preferred piperidine compounds carry polar substituents
in the 4-position of the piperidine ring or carry
a spiro ring in this position. Particularly preferred
piperidine compounds are those of the above mentioned
classes a~ to e~ and h).
The organotin carboxylates and alcoholates to be
used according to the invention (component (B)) are
generally known and are recognized for their ability
to combat thermal degradation in polyvinyl chloride.
When the ~ substituents in the organotin compounds
of component (B) of the composition according to this
inv~ntion are alkyl, they may typically contain from
1 to ~0 or 10 to 30, respectively, carbon atoms in a linear
or branched chain including~ for example, methyl, ethyl,
n-propyl, isopropyl, n-butyl~ isobutyl, sec-butyl,
tert-butyl, n-amyl, neopentyl, isoamyl, n-hexyl, isohexyl
heptyl, octyl, decyl, dodecyl, tetradecyl, octadecyl and
eicosyl. When they are cycloalkyl, they may typically be
C5-C8 cycloalkyl, for example cyclopentyl, cyclohexyl,
cycloheptyl, or cyclooctyl. When they are aralkyl, they
may typically be C7-C15-aralkyl, preferably phenyl-C1-C4-
alkyl~ Examples are benzyl, ~-phenylethyl~ y-phenylpropyl
or ~-phenylpropyl. When they are aryl, they may typ;cally
b~ C6-Cl4-aryl, for example naphthyl or preferably phenyl.
~hen they are alkaryl, they may typically be naphthyl or
~r~-ferably phenyl substituted by 1 to 3, preferably 1 or 2,
most preferably 1, C1-C18(preferably C1-C12) alkyl group(s).
E~amples are tolyl, xylyl, p-ethylphenyl or p-nonylphenyl.
This may also be substituted in that they may bear
substituents such as alkyl, aryl, cycloalkyl, aralkyl,
1 3 1 07~6
- 30 -
alkaryl, alkoxy, etc. Typical substituted aryl radicals
include anisyl and biphenyl. Substi-tuted aralkyl includes
chlorobenzyl, p-phenylbenzyl and p-methylbenzyl.
Substituted alkaryl includes 2,6-di-tert-butyl-4-methyl-
phenyl.
Illustrative of these organotin carboxylates and
alcoholates are the following:
dibutyl-t;n d;tetradecyl ox;de,
dibutyl-tin di-isotridecyl oxide,
dibutyl-tin-bis-(p-oc~ylphenyl ox;de),
d;octyl-t;n-b;s-(p-nonylphehyl ox;de),
dioctyl-tin (ditetradecyl oxide),
bis(dibutyl-p-nonylphenyloxy-tin) oxide,
bis(dioctyl-p-octylphenyloxy-tin) oxide,
bis(dibutyl-isotridecyloxy-t;n) ox;de,
bis(d;butyl-tetradecyloxy-tin) oxide,
d;butylt;n d;laurate,
b;s(dibutyl-;sodecanoylt;n)oxide,
dibutyltin d;-isooctadecyiate
butylt;n tr;octanoate,
d;phenylt;n d;laurate,
1 3 1 07~6
- 31 -
dibutyltin bis(isooctylmaleate), dibutyltin dipelargonate,
d;butyltin distearate, dihexyltin dioleate, dioctyltin
ditallate, dioctyltin diundecylenate, dibutyltin
b;s~(neodecanoate), dioctyltin bis-~neotridecanoate),
dibutyltin bis-(monomethyl maleate3, dihexyltin
bis-(monohexyl maleate), dihexyltin bis-~monoisooctyl
maleate), dibutyltin bis~(monocetyl maleate3, dibutyltin
bis-(monooctadecyl maleate), dibutyltin bis-(mono-
2-ethoxyethyl maleate), dioctyltin bis-(monocyclohexyl
maleate), dihexyltin bis-(monobenzyl maleate) and
butylhexyltin bis(mono-tert.butylbenzyl maleate).
Preferred organotin components are mi~tures of at least
one compound of the formula (Z)zSn~ 2 and at least one
0~
compound of the formula (Z)2Sn(OOC-Z )2
Further preferred organotin compounds are dibutyltin
d;-;sotr;decylox;de, d;butyltin d;-isostearate, dibutyltin
d;-2-ethylhexanoate, d;butyltin dilaurate, dibutyltin
d;tetradecanoate or mixtures thereof.
Add;t;onal stab;lizers, especially tin stabilizers,
m~y be opt;onally blended w;th the above noted carboxylates
orland alcoholates to form the heat stabilizer component of
the compos;t;ons of this invention, such blends being pre-
~erred for use ;n the instant invention. Such additional tin
stab;l;~ers include, for example, organotin mercaptoesters
and/or organotin mercaptides. Preferred organotin
mercaptoesters correspond to the formula
(Z)msn(s-cpH2pcooz )4~m
21~89-711-~ 3 ~ 07~6
- 32 -
wherein ~, Z4 and m are as previously defined, and p is
an integer from 1 to 5, preferably 1 or 2, in particular 2
The aforementioned preferred members for these various
substituents likewise apply in this instance.
Examples of such compounds are octyltin
tris-~dodecyl-~-mercaptopropionate), dibutyltin
bis~;sotridecyl-~-mercaptopropionate), dibutyltin
bis~-ethylhexyl-~-mercaptopropionate), dibutyltin
bis~tetradecyl-~-mercaptopropionate~, octyltin
tris~alfyl-thioglycolate3, tributyltin isooctyl
thi~ col~te, butyltin tris(cyclohexyl thioglycolate),
~ty~tin tris(isooctyl mercaptoacetate) and the like, with
diblJ~yltin bis~isotridecyl-~-mercaptopropionate3,
dibutyltin bis~tetradecyl-~-mercaptopropionate~, octyltin
~r;stdodecyl-~-mercaptopropionate) or dibutyltin
bist~-ethylhexyl-~-mercaptopropionate) or mixtures thereof
being preferred.
As previously noted, the organotin carboxylates and
alc~h~lates as well as the organotin mercaptoesters and
m~th~ds f~r their preparat;on are generally known.
U.3~ 2,8~û,182~ U.S. 3,398,114, U.S. 3,562,305,
U~S. 3,o40,950, U.S. 3,640,947, U.S. 3,657,2Y4,
U.3~ 3~33,741, U.SO 4~193,913, U~S~ 4,358,555,
~nad;an 1,152~735 and Canadian 1,170,031 are typical of
~h~ numerous patents that disclose such organotin materials.
Mix~lres of carboxylates and mercaptoesters are particularly
d;sclosed, for example, in U,S. 3,562,305, U.S. 3,933,741,
~anadian 1,152,735 and Canadian 1,170,031.
As a further optional but preferred system~ the organo-
tin carboxylate or alcoholate by itself or inc~mbintaion with the
13 1 07~G
~ 7117
- 33 -
mercaptoester can be combined with an organotin
mercaptide. The organotin mercaptides are also com-
mercially available and well known to those skilled in the
art. Such mercaptides correspond, for example, to the
general formula (Z ~) Sn(Z )4 y wherein Z and Z are
individually selected from alkyl, cycloalkyl, aryl, alkaryl
or aralkyl radicals among others (specific substituents
listed hereinabove) and y is 1-3. A w;de variety of tin
mercaptides and methods for preparation thereof are
disclosed in U.S. 2,641,588~ U.S. 2,726,227,
U.S. 3,933,741 and U.S. 3,953,285. Likewise, mixtures of
carboxylates and mercaptides are disclosed, for example,
in U.S. 3,562,305 and U.S. 3,933,741.
Representive mercaptides include dibutyltin
bis(lauryl mercaptide), butyltin tris(lauryl mercaptide),
dibutyltin bis(octyl mercaptide), dibut~ltin bis(benzyl
mercaptide), dioctyltin bis(cyclohexyl mercaptide),
dioctyltin bis(octyl mercaptide), dimethyltin bis~lauryl
mercaptide) and dicyclohexyltin bis(lauryl mercaptide)n
With respect to concentrations of the components, the
2,2,6,6-tetraalkylpiperidine is preferably present in
amounts ranging from 0.1 to 3.0 /O~ by weight of resin, and
preferably 0.25 to 1.5 %, and the organot;n carboxylate
or alcoholate ;s preferably present ;n amounts ranging
from 1.0 to 5.0 %, by we;ght of resin, and preferably
1.5 to 4.0 %. When the organotin mercaptoester and/or the
tin mercaptide are present, they can replace, for example,
1 ~ 1 07~6
- 34 -
either individually or together a maximum of about 70 ~., by
weight, of the carboxylate and preferably up to about 40 %,
by weight.
The titanium dioxides that are conventionally utilized
in rigid polyvinyl chloride formulations are known and
comnlercially available~ The preferred titanium dioxides
are rutile grades. For purposes of th;s invention, for
e~ample 0 to 1G.0 ~ of titanium dioxide, per weight of
resin ;s applicable, with 1 to 10 ~, especially 2 to ~ %,
for example 4.0 to 6.0 % being preferred when said titanium
dioxide is present. These concentrations can provide
3dditional photodegradative inhibition when comb;ned with
the stabilization systems while substant;ally eliminating
the aforementioned disadvantages of high titanium d;oxide
levels.
The compos;t;on of th;s ;nvent;on preferably does not
contain any lead compounds (lead stab;l;zers) which are
frequently present in polyvinyl chloride compositions.
The instant ;nvention realtes to a composition of
r;3;d polyvinyl chloride, i.e. unplasticized polyvinyl
chlor;de resin, as well as materials containing at least
85 ~ of polyvinyl chloride resin. Such resins generally
conta;n further conventional additives including processing
3;ds, impact modifiers, lubricants, pigments, fillers, and
th~ l;ke~ It is also possible to combine the systems with
canvent;onal U~ absorbers and antioxidants such as
ben~oates, ben20triazoles, benzophenones, hindered phenols
~r mixtures thereof. Techniques for processing rigid
polyv;nyl chloride are also known to those skilled ;n the
art and such techniques are applicable herein.
1 3 1 07~6
- 35 -
Compounding follwed by extrusion is the conven~10nal
technique for siding manufacture.
As previously noted, the stabilized rigid polyvinyl
chlorides of this invention exhibit a broad range of
desirable properties. Of particular value they exhibit
excellent thermal and UV stabilization over prolonged
periods of time. They permit the reduction of titanium
dioxide levels without sacrificing the light stability and
impact strength provided by the high levels. In addition,
the lowerins or elimination of the titanium dioxide
content allows for significantly reduced wear on the
processing machinery and for an expansion of the number of
pigmented systems that can be readily utilized therein.
Thus~ wh;le the high titanium dioxide levels restrict the
ava;lable colors to white and pastels, the instant systems
are available in a broad range of light, pastel and dark
colors.
Ihe following example ;llustrates some preferred
embodiments of the invention. In this example, all parts
given are by weight unless otherwise specified.
Example
The following rig;d polyvinyl chloride base
~ormulat;ons are util;zed ;n the following tests.
I ~ 1 07~6
- 36 -
parts
II III IV VVI VII
polyvinyl chloride resin1 100 1on ~ -- 100
polyv;nyl chloride res;n --- --- 100100 100 100 -~-
methacryl;c acid~ester
processing aid 1~0 1.0 2.02.0105 1.5 2.5
acrylic impact modifier4 7.0 7.07.07.0 7.0 7.0 ---
Calcium stearate --- --- 0.8 --- 0~8 ~~~ ~~~
paraffin wax 0.6 ---1.0 1.0 1.0 1-0 ~~~
polyethylene wax 0.3 0~20.2 0.2 2.0 0.2 ---
titanium dioxide (rutile,
non-chalking) variable
light stab;l;zer variable
heat stab;l;zer variable
1 - ~Diamond Shamrock 500
2 - ~ EON 103EP-76
3 - ~ACRYLOID K120N
!4 - ~ACRYLOID K323B
The ingred;ents are blended including the ;nd;cated
amounts of TiO2 and stab;lizer. The samples are milled on
a two roll mill (front roll ~ 171C - back roll @ 165C)
for a period of three minutes after band formation. The
resulting material is then compression molded (temperature
182C, 2 minutes contact pressure, 1 minute pump;ng
pressure, 2 m;nutes full pressure, cool to 38C) and cut
;nto test plaques (5~1 cm. x 5~1 cm.)
The follow;ng stab;l;zers are ut;l;zed in these
tests.
~2,6,6-t~tramethylpiperidine compounds
1 3 ~ Q7~6
- 37 ~
A - 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-tri-
azaspiro(4,5)decane-2,4-dione
B - bis~2,2,6,6-tetramethyl-4-piperidinyl)sebacate
C - bis(1-acetyl-2,2,6~6-tetramethyl-4-piperidinYl)-
sebacate
D - b;s(l-benzyl-2~2,6,6-tetramethyl-4-piperidinyl)-
sebecate
E - poly[6-(1,1~3,3-tetramethylbutyl)amino-1,3,5-triazine-
2,4-diyl-~2,2,6,6-tetramethyl-4-piperidinyl)imino-
hexamethylene-(2,2,6,6-tetramethyl-4-p;per;d;nyl)-
;mino] (= compound 79 above)
F - N-butyl-(3,5-d;-tert.butyl-4-hydroxybenzyl)-bis-
(1,2,2,6,6-pentamethyi-4-piperidinyl)malonate
- polysuccinate of 4~hydroxy-1-hydroxyethyl-2,2,6,6-
tetramethylpiperidine (= compound 76 above)
Tin Stabilizers
-
H - A blend of approximately 9:1, by weight, of m;xed
` d;butylt;n b;s(;sooctyl th;oglycolate)/butyltin tris
(;sooctyl th;oglycolate) and mixed butvlth;ostanno;c
acid/d;butyLtin sulfide
I - A blend o~ approx;mately 3:1, by we;ght, of dimethyl-
t;n bis(2-ethylhexylthioglycolate) and methylt;n
tris(2-ethylhexylthioglycolate)
J - A blend of apporximately 2:1, by weight, of mixed
dibutylt;n di-;sotridecyl oxide/dibutyltin
d;-;sostearate and dibutyltin bis(isotridecyl-
~-mercaptoprop;onate)
1 3 1 07~6
21~9-7117
- 38 -
K - A blend of approximately 2:1, by weight, of dibutyltin
bistmixed 2-ethylhexanoate and laurate) and dibutyltin
bis(tetradecyl-~-mercaptoporpionate)
L - A blend of 3 2, by weight, of dibutyltin bistmixed
2-ethylhexanoate and tetradecanoate) and dibutyltin
bis (isotridecyl-~-mercaptopropionate)
M - A blend of 2:1, by weight, of dibutyltin bis(mixed
2-ethylhexanoate and laurate) and dibutyltin bis
(isotridecyl-~-mercaptopropionate)
N - A blend of 2:1, by weight, of mixed dibutyltin
di-tetradecanoateldibutyltin di-isotridecyl oxide and
dibutyltin bis(isotridecyl-~ mercaptopropionate)
O - dibutyltin bis(methylmaleate~
Other Additives
P - 2-(2-hydroxy-3,5-diamylphenyl)benzotriazole
Q - 1,6-hexanediol-bis-(3,5-di-tert.butyl-4-hydroxy-
benzoate)
The formulated samples are submitted to the following
test procedures:
Test I - Dry Xenon Weatherometer Exposure
.. . . . _
G~
Exposed in Xenon Weatherometer at black panel
temperature of oO-66C and relative humidity of 25-35 %.
Samples are withdrawn at periodic intervals and yellowness
index measured according to ASTM D-1925-63T. Higher
values are indicative of lower stability. "Failure"
reflects a yellowness index greater than 40
.
1~107~6
- 39 -
Test II - Spray Xenon Weatherometer Exposure
Exposed as in Test I with identical bLack panel
temperature, relative humidity of 65-75 %, 102 m;nutes of
dry cycle and 18 minutes of water spray cycle. Me~sured
by yellowness index~
Test III - Arizona Exposure
Exposed outdoor in Arizona at an angle of 45 from
the horizontal facing south. Yellowness index measured
in;t;ally~ after n;ne months exposure at 140,000 langleys
and after twelve months exposure at 181,000 langleys~
The results obtained in these tests are noted in the
following tables:
Table I
Test Procedure I
Base Formulation II YeLLowness Index
Stab;lizers Conc. Conc.0 2045 4322
Stabilizers TiO2 hrs. hrs. hrs.
(parts) (parts~
A/J 1/2 5 10 16 21
B/J 1/2 5 11 14 25
C/J/P 1/2/1 5 1D 16 23
D/J/P 1/2/1 5 11 12 20
1 3 1 07$6
- 40 -
Table II
. . .
Test Procedure III
Base Formulation IV Yellowness Index
St~bilizers Conc. Conc~ 0 9 12
Stabilizers Tio2 months months months
(parts) (parts)
B/J 1/2 5 6 6 9
Table III
Test Procedure II
Base Formulation V Yellowness Index
Stabilizers Conc~ Conc 0 2500 3500
Stabilizers TiO2hrs. hrs.hrs.
(parts) (parts)
-
B/H 1/2 5 5 8 18
E/H 0.3/2 5 6 7 12
B~se For~ulation VI
~ .
B/K 1/2 5 4 5 8
B~K/P 1/2/1 5 3 3 6
E/K 0.3/2 5 5 3 5
F/K/P 0.3/2/1 5 4 5 7
B/J 1/2 5 3 2 4
E/J 0.3/2 5 3 4 8
B/L 1/2 5 4 5 11
B/M 1/2 5 3 3 6
B/N 1/2 5 3 2 6
B/N~Q 1/2/1 5 4 3 5
13107~6
- 41 -
Table IV
Test Procedure I
Base Formulation VII YelLowness Index
Stabilizers Conc. Conc, 0 400 700 1300 1900
StabiLizers TiO2 - hrs.h'rs.hrs.hrs.hrS.
_ _ (parts)(parts)
F/I 0.5/2.5 0 8 20 40 Fail Fail
G/I 0.5/2.5 0 8 16 41 Fail Fail
F/0 0~5/2.5 0 16 12 11 12 9
G/0 0~5/2~5 0 16 4 4 7 7
