Note: Descriptions are shown in the official language in which they were submitted.
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BENZOCYCLE-SUBSTITUTED TRIAZINE AND PYRIMIDINE ULTRAVIOLET
LIGHT ABSORBERS
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates generally to novel benzocycle-substituted pyrimidines
and
triazines and their use as protectants against degradation by environmental
forces, including
ultraviolet light, actinic radiation, oxygen, moisture, atmospheric pollutants
and
combinations thereof.
Description of Related .Art
Exposure to sunlight and other sources of ultraviolet radiation is known to
cause
1 S degradation of a variety of materials, especially polymeric materials. For
example,
polymeric materials such as plastics often discolor and may become brittle as
a result of
exposure to ultraviolet light. Accordingly, a large body of art has been
developed directed
towards materials such as ultraviolet light absorbers and stabilizers which
are capable of
inhibiting such degradation.
A class of materials known to be ultraviolet light absorbers are o-
hydroxyphenyltriazines, in which at least one substituent on the 1, 3 or 5
carbon on the
triazine ring is a phenyl group with a hydroxyl group ortho to the point of
attachment to the
triazine ring. In general this class of materials is well known in the art.
For example, United States Patent No. 3,843,371 discloses
hydroxyphenyltriazines
for use in photographic materials. The triazines in this patent, however, show
poor
solubilities and poor stabilities.
United States Patent No. 3,896,125 discloses hydroxyphenyl triazines, but
these, too
are poorly soluble and discolor with time.
The use of hydroxyphenyltriazines alone or in combination with other light
stabilizers such as hydroxyphenylbenzotriazoles, benzophenones, oxanilides,
cyanoacrylates, salicylates, and hindered amine light stabilizers (HALS), for
the
stabilization of polymers is also well known. For example, United States
Patent Nos.
4,853,471, 4,921,966, and 4,973,701, 4,973,702 disclose such combinations.
Typically, the aforementioned aryl ring with the hydroxyl group ortho to the
point of
attachment to the triazine ring is based on resorcinol and, consequently, this
aryl ring also
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contains a second substituent (either a hydroxyl group or a derivative
thereof) para- to the
point of attachment to the triazine ring. For example, United states Patents
No. 3,118,837
and 3,244,708 disclosep-alkoxy-o-hydroxyphenyl triazines with improved UV
protection,
but many embodiments of such triazines exhibit poor compatibility and
solubility, and poor
yellowing performance.
This para- substituent can be "non-reactive," as in the case of an alkyloxy
group, or
"reactive" as in the case of a hydroxyalkyloxy (active hydrogen reactive site)
or
(meth)acryloyl (ethylenic unsaturation reactive site) group. For the purposes
of the present
invention, the former are referred to as "non-bondable" benzocycle-substituted
pyrimidines
I 0 and triazines and the latter are referred to as "bondable" benzocycle-
substituted pyrimidines
and triazines.
Low volatility is an important characteristic of stabilizers used in any
applications
where high temperatures are encountered. High temperatures are used in the
processing of
thermoplastics and in the curing of thermoset resins and coatings. High
temperatures are
1 S also often present in the end-use applications for the stabilized
material. Low volatility will
prevent loss of the stabilizer during processing, curing, and high temperature
end-uses.
Besides reducing losses of stabilizer during processing or curing, low
volatility will
minimize processing problems such as die lip build-up and plate-out.
Many polymer additives (such as ultraviolet light stabilizers) migrate out of
the
20 polymer substrate to be protected, or are adsorbed (chemicall;y or
physically) by one or more
systems components (such as pigments), thereby diminishing their
effectiveness. Such
migration and adsorption problems are examples of the general problems of lack
of
solubility and compatibility found for many commercial polymer additives.
Bondable triazines are well known in the art. For example, United States
Patent
25 Nos. 3,423,360, 4,962,142 and 5,189,084 disclose various bondable and the
incorporation of
these compounds into polymers by chemical bonding. Bondable stabilizers have a
potential
advantage in this respect in that, depending on the bondable functionality and
the particular
polymer system to be stabilized, they can be chemically incorporated into a
polymer
structure via reaction of the bondable functionality either during polymer
formation (such as
30 in the case of polymerizing monomers or a crosslinking polymer system) or
subsequently
with a preformed polymer having appropriate reactive functionality.
Accordingly, due to
such bonding, migration of these UV absorbers between layers of mufti-layer
coatings and
into polymer substrates is greatly reduced.
-2-
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SUMMARY O~ TI IT: 1NV1?N'I'I(~N
'!'hc present invcntiun provides a new class ul' bcn~ueye:le:-suhstitute;d
pyrinudinc;s
and triazines depicted below, in which a substituent attached to the triazine
or pyl'11111d111~
ring is a fused benzocyclic group:
S
S
XO
0
wherein X signifies hydrogen or a blocking group, A can be a nitrogen or
optionally
substituted methine, and the fused ring designated by S is a non-aromatic 4 to
12 membered
ring, optionally containing one or more heteroatoms; any of the three rings
may bear one or
more additional substituents. These fused benzocyclic-substituted triazines
and pyrimidines
1 S have the advantage of being highly soluble in and compatible; of having
extremely low
volatility, and therefore low losses during high temperature processing or
curing; of being
highly effective in inhibiting yellowing; and of being highly effective in
preventing
degradation of polymers and coatings due to the action of actinic radiation,
heat, oxygen,
and moisture.
The benzocyclic substituted triazine and pyrimidine LJV absorbers of the
present
invention possess exceptionally low volatility, lower than mast current art UV
absorbers.
Furthermore these benzocyclic triazine UV absorbers, impart improved
weatherability and
yellowing resistance to polymers compared to current art UV absorbers. None of
the
previously available triazine UV stabilizers and absorbers combine the
unexpected low
volatility along with the weatherability, yellowing resistance, solubility,
and compatibility of
the benzocyclic substituted triazine and pyrimidine absorbers and stabilizers
of the present
invention.
More specifically, the new benzocycle-substituted pyrimidines and triazines of
the
present invention have general formula (I):
35
-3-
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(CH2)n
G' ~G
~Rz)a "~ ~
(CH2)m (~H~)"
( R, 'Z
(I)
wherein
I 5 each A is independently nitrogen or methine optionally substituted with
R2, and at least two
A are nitrogen;
each of T and T' is independently a direct bond, carbon, oxygen, nitrogen,
sulfur,
phosphorous, boron, silicon, or functional groups containing these elements.
X is independently selected from hydrogen and a blocking group;
each of R' and Rz is independently a hydrocarbyl group, a functional
hydrocarbyl group,
hydroxy, alkoxy, hydrogen, halogen, cyano, or isocyano;
each of Y, Z, R3 and R4 are independently a hydrogen, hydrocarbyl group, a
functional
hydrocarbyl group, halogen, hydroxyl, cyano, -O(hydrocarbyl), -O(functional
hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl), -N(functional
hydrocarbyl)(functional
hydrocarbyI), -N(hydrocarbyl)(functional hydrocarbyl), -S(hydrocarbyl),
-S(functional hydrocarbyl), -S02(hydrocarbyl), -SOZ(hydrocarbyl),
-S03(hydrocarbyl), -S03(functional hydrocarbyl), -COO(hydrocarbyl),
-COO(functional hydrocarbyl), -CO(hydrocarbyl), -CO(functional hydrocarbyl,
-OCO(hydrocarbyl), -OCO(functional hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl),
-CONH2, -CONH(hyrdocarbyl), -CONH(functional hyrdocarbyl),
-CON(hydrocarbyl)(hyrdocarbyl), -CON(hydrocarbyl)(functional lyrdocarbyl),
-CON(functional hydrocarbyl)(functional hyrdocarbyl), -S(functional
hydrocarbyl),
-S02(functional hydrocarbyl), -S03(functional hydrocarbyl), -COO(functional
hydrocarbyl), -CO(functional hydrocarbyl), -OCO(functional hydrocarbyl), or a
hydrocarbyl group substituted by any of the above groups;
-4-
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each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorous,
boron,
silicon, selenium, tellurium, or functional groups containing these elements;
each of m, n, and o is independently an integer between 0 and 4, provided that
when
both G are direct bonds, the sum of m, n and o is between 2 and 10, and that
when one G is a direct bond, the sum of m, n and o is between 1 and 9, and
when neither G is a direct bond, the sum of m, n and o is between 0 and 8;
p is an integer between 0 and 3; and
q is an integer between 0 and 20.
Preferably, T' is an oxygen atom and Y is a group L, to give a mono-resorcinol
derived benzocycle-substituted pyrimidine or triazine of formula (II):
(C H2)n
~G
(R2)q-'~"
(CH2)m (CH2)o
20
(R1) ~TZ
' ZO~'A
R3
L
(II)
wherein
L is def ned as Y, Z, R3 and R4 as defined above; and
substituents A, G, T, X, Y, Z, R' to R4, and subscripts m, n, o, p, and q, are
defined
as above for general formula (I).
35
-5-
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More preferably, TZ in formula (II} is a resorcinol derivative of formula
(IIIa) or
(IIIb):
OL
o r R3 R4
L
(IIIa) (IIIb)
to give a mono benzocycle bis-resorcinol derived triazine of formulas (IVa)
and (IVb):
j H2\n
G G
I S ~ ~R2
or
(IVa) (IVb)
More Preferably, each L in formulas III and IV are independently selected from
the group
consisting of
hydrogen;
an alkyl of 1 to 24 carbon atoms optionally substituted by one or more
hydroxy,
alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups,
and which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain;
an alkenyl of 2 to 24 carbon atoms optionally substituted by one or more
hydroxy,
alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxy groups,
and which may contain one or more carbonyl groups, oxygen atoms or
nitrogen atoms in the chain;
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an aralkyl of 7 to 24 carbon atoms optionally substituted by one or more
hydroxy,
alkoxy, chloro, cyano, carboxy, carboalkoxy, amino, amido, carbamato, or
epoxy groups, and which may contain one or more carbonyl groups, oxygen
atoms or nitrogen atoms in the chain;
a polyoxyalkylene radical of the formula XII
-CHZ-CH(OH)-CHz-O-{CHz-(CHz)"-O-)mm Di (XII)
wherein D, is hydrogen,
-CHz-CH(OH)-CHz-OH, -CH2-CH\O HZ
or Rzs;
a polyoxyalkylene radical of the formula XIII
-CO-(CHz)"-O-(CHz-(CHz)"O-)mm Dz (XIII)
wherein Dz is -(CHz)~-CO-Rzz or Rzs;
a polyoxyalkylene radical of the formula VIII
1 S -YY-O-CO-(CHz)~-O-(CHz-(CH2)~ O-)mm D3 (XIV)
wherein D3 is '(CHz)~-CO'Rzz or Rzs;
a polyoxyalkylene radical of the formula XV
-(CHZ)kk-CH(Rz')-CO-B~-(CnnHznr; O-)mrn CnnHznn-Bt-D4 XV
wherein D4 is hydrogen of Rzs;
a polyoxyalkylene radical of the formula XVI
-CO-CHz-CHz-NH-(CnnHznri O-)mm'CnnHz",~ Ds (XVI)
wherein Ds is -NHz, -NH-(CHz)z-COO-Rz3 or -O-Rzs;
a polyoxyalkylene radical of the formula XVII
-YY-O-CO-CHz-CHz-NH-(C""HZn~ O-)mm CnnHzn~ Ds (XVII)
wherein Ds is as defined under formula (XVI};
a polyoxyalkylene radical of the formula XVIII
-(CnnHzn~ O-)mm-CnnHzno D6 (XVIII)
wherein D6 is -NH-CO-Rz4, -ORzs, OH or H;
a polyoxyalkylene radical of the formula XIX
C H-C H2-(OC H-C H2)n,-D7
(XIX)
wherein D7 is -ORzs, -NHCORz4 or -OCHZCH20Rzs;
R2~ is hydrogen or C,-C,6 alkyl;
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R22 is halogen or -O-RZ';
Rz3 is hydrogen, C,-C6 alkyl, C3-C6 alkenyl, aryl, or
aryl-C,-C4-alkyl;
R24 is hydrogen, C,-C,2 alkyl or aryl;
RZS is C,-C,6 alkyl, Cs-C,2 cycloalkyl, C3-C6 alkenyl,
C,-C,2 alkylaryl or aryl-C,-C4 alkyl;
R26 is hydrogen or C,-C4 alkyl;
RZ' is hydrogen, C,-C,8 alkyl, C3-C6 alkenyl, C,-C,8 alkoxy, halogen or aryl-
C,-C4-
alkyl;
R28 and Rz9 independently of one another are hydrogen,
C,-C,8 alkyl, C3-C6 alkenyl, C,-C,g alkoxy, or halogen;
R'° is hydrogen, C,-C4 alkyl or CN;
YY is unsubstituted or substituted Cz-CZ° alkyl;
kk is zero or an integer from 1-16;
1 S B, is O or NH;
mm is an integer from 2 to 60;
nn is an integer from 2 to 6;
a is an integer from 1 to 4.
Preferred in the present invention are compounds of formula (IV) wherein
both G are direct bonds, m = 4, n; o, p and q are 0, and all A are nitrogen of
formula (IVc):
30
{IVc)
Even more preferred in the present invention are bis-benzocycle-substituted
pyrimidines and triazines of formula (V):
-g_
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R2)q
)P
wherein all substituents are as defined above for general formulas (I) to
(IV).
Most preferred in the present invention are compounds of formula 5 wherein all
G
are direct bonds; m = 4; n, o, p, and q are 0; and all A are nitrogen, said
compound having
formula:
25
wherein
L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or a functional
hydrocarbyl group of 1 to 24 carbon atoms;
X is independently selected from hydrogen and a blocking group; and
R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl,
halogen,
hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl),
-SOz(hydrocarbyl), -S03(hydrocarbyl), -COO(hydrocarbyl),
-CO(hydrocarbyl), -OCO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl),
-9-
(CH2)n (CH2)n
G/ vG G/ vG
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-S(functional hydrocarbyl), -SOZ(functional hydrocarbyl), -S03(functional
hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl),
-OCO(functional hydrocarbyl), -N(functional hydrocarbyl)(functional
hydrocarbyl) or cyano.
The benzocycle-substituted pyrimidines and triazines of the present invention
further comprise oligomeric species of formulas (VI) and (VII):
(CH2)n
~G
(R2)q-.-~
(CH2)m (CH2)o
(R' )
A
R4
ZT A'~~'Y
(VI)
wherein
A, T, T', Y, Z, R' - R4, G, m-q, and X, are as defined above;
r is an integer between 2 and 4;
D when r is 2, is selected from the group consisting of CZ C,6 alkyl, C4 C,z
alkenyl,
xylylene, C3-CZO alkyl which is interrupted by one or more oxygen atoms,
hydroxy-substituted C3 CZO alkyl which is interrupted by one or more oxygen
atoms, --CHZCH(OH)CH20-R'S-OCHzCH(OH)CH2,
-CO-R'6-CO--, -CO-NH-R"-NH--CO-,
'-{CHZ)., COO-R'8-OCO--(CHZ)s
a polyoxyalkylene bridge member of the formula XX
-CHZ-CH(OH)-CHZ-O-(CHZ-(CHZ)"O-)n,m-CH2-CH(OH)-CHZ-
a polyoxyalkylene bridge member of the formula XXI
-CO-(CHZ)~-O-(CHz-(CHZ)~ O-)mm-(CI-I,)~ CO- (XXI)~
a polyoxyalkylene bridge member of the formula XXII
-YY-O-CO(CHZ)~-O-(CHZ-(CHZ)~-O-)m,r,-(CHZ)~-COO-YY- (XXII),
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a polyoxyalkylene bridge member of the formula XXII1
-(CI-Iz)~~-CII(R''')-CO-I3,v(C~~l-lz~~-O-)mm~=n~l.lz~~ B~-CO-CH(Itz')_
(CH2)kk- (VIII),
a polyoxyalkylene bridge member of the formula XXIV
-COCHCHZNH(CnnH2nn0)mCnnH2nn-NHCH2-CHCO- (XXIV) ;
21 ~21
a polyoxyalkylene bridge member of the formula XXV
-YY-O-CO-(CHz)z-NH-(C""H2""O-)mm-C""Hz""NH-
(CHz)zC00-YY-
V)>
a polyoxyalkylene bridge member of the formula XXVI
-(CnnHznn-O-)mm-CnnH2rui (~'lI)~
and a polyoxyalkylene bridge member of the formula XXVII
-CH(CH3)-CHz-(O-CH(CH3)-CHz)8 (O-CHz-CHz)b-(O-CHz-
CH(CH3)~ (XXVII),
wherein a + c = 2.5 and b = 8.5 to 40.5 or a + c = 2 to 33 and b = 0,
Rz' is hydrogen or C,-C,6 alkyl,
Rzz is halogen or -O-Rz',
Rz3 is hydrogen, C,-C6 alkyl, C3-C6 alkenyl, aryl, or aryl-C,-C4-alkyl,
Rza is hydrogen, C,-C,z alkyl or aryl,
Rzs is C,-C,6 alkyl, CS-C,z cycloalkyl, C3-C6 alkenyl,
C,-C,z alkylaryl or aryl-C,-C4 alkyl,
Rz6 is hydrogen or C,-C4 alkyl,
Rz7 is hydrogen, C,-C,8 alkyl, C3-C6 alkenyl, C,-C,8 alkoxy, halogen
or aryl-C,-C4 alkyl,
Rz8 and Rz9 independently of one another are hydrogen, C,-C,g alkyl,
C3-C6 alkenyl, or
C,-C,a alkoxy, or halogen;
R3° is hydrogen, C,-C4 alkyl or CN,
YY is unsubstituted or substituted Cz-Czo alkyl,
kk is zero or an integer from 1-16,
B, is O or NH,
mm is an integer from 2 to 60,
nn is an integer from 2 to 6,
a is an integer from 1 to 4;
-11-
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when r is 3, D is
---~ (CH2)S--COO-- R~ 9
3
and when r is 4, D is
---~ (CH2)S-COO-- R2~ <,
4
wherein R'9 is C3 C,° alkanetriyl and RZ° is C4-C,°
alkanetetryl; and
s is I-6;
R'S is CZ-C,° alkyl, Cz-C,° oxaalkyl or CZ-C,°
dithiaalkyl, phenyl, naphthyl,
diphenyl, or CZ-C6 alkenyl, or phenylene-XX-phenylene wherein XX
is -O-, -S-, -Spz , -CHz , or -C(CH3 i ;
R'6 is Cz-C,° alkyl, CZ-C,° oxaalkyl or Cz-C,°
dithiaalkyl, phenyl, naphthyl,
diphenyl, or Cz-C6 alkenyl provided that when r is 3 the alkenyl has at
least 3 carbons;
R" is Cz-C,° alkyl, phenyl, naphthyl, diphenyl, or CZ-C6 alkenyl,
methylenediphenylene, or C4-C,5 alkylphenyi; and
R'8 is Cz-C,° alkyl, or C4-C~° alkyl interrupted by one or more
oxygen atoms;
and
~CH2)n
~G
tCH2)m (CH2)o
(R' )
AOA O X~
TY
r
(VII)
-12-
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wherein A, T, T', Y, Z, R' - R4, G, m-q, and X, are as defined above; r is 2
or 3; X', when r is
2, is -CO-R'6-CO-, -COz-R'6--COz-, -SOZ-Ryb-SOz-,
-CO-NH-R"-NH-CO-, a polyoxyalkylene bridge member of formula -CO-(CHz)~-
O-(CHz-(CHz)"O-)mm-(CHz)"CO-, or
-COCHCH2NH(CnnH2nn~)mCnnH2nn'NHCH2-CHCO- (XXIV) ;
21 ~21
when r = 3, X' is:
_(-COz_R'6)R~9, -(_CONH-R'6)R'9, -(-SOz-Rib)Ri9
wherein R'6, R", R'g, and R'9 are as defined above.
The benzocycle-substituted pyrimidines and triazines of the present invention
also
comprise oligomeric species of the formulas (VIII) and (IX):
(CH2jn
G~ ~G
(R2)q-'t-
(CH~m (~I
R4
(R1) i
H
(VIII)
wherein A, T, T', Y, Z, R' through R3, G, m through q, and X, are as defined
above;
R4 is selected from the group consisting of straight chain alkyl of 1 to 12
carbon
atoms, branched chain alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12
carbon atoms, alkyl substituted by cyclohexyl, alkyl interrupted by
cyclohexyl, alkyl substituted by phenylene, alkyl interrupted by phenylene,
benzylidene, -S-, -S-S-, -S-E-S- -SO- -SOz-,
' '
-SO-E-SO-, -SOz-E-SOz-, -CHz-NH-E-NH-CHz-, and
~ H3 CHs
-C
CH
3
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wherein E is selected from the group consisting of alkyl of 2 to 12 carbon
atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted by cyclohexyl of
8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8 to 12 carbon
atoms; and
r is an integer between 2 and 4.
GC H2)~
I (C H2)~~ ,(C Hy)m
~)P
R4 AOA
IS
A T
R3 OX
r
wherein
(IX)
each A is independently nitrogen or methine optionally substituted with R2,
and at
least two A are nitrogen;
each of T and T' is independently a direct bond, carbon, oxygen, nitrogen,
sulfur,
phosphorous, boron, silicon, or a functional group containing these elements;
each of Y, Z, R', and RZ is independently a hydrocarbyl group, a functional
hydrocarbyl group, hydrogen, halogen, cyano, or isocyano;
each G is independently a direct bond, nitrogen, sulfur, oxygen, phosphorous,
boron,
silicon, selenium, tellurium, or functional groups containing these elements;
each of m, n, and o is independently an integer between 0 and 4, provided that
when
both G are direct bonds, the sum of m, n and o is between 2 and 10, and that
when one G is a direct bond, the sum of m, n and o is between 1 and 9, and
when neither G is a direct bond, the sum of m, n and o is between 0 and 8;
p is an integer between 0 and 3;
q is an integer between 0 and 12;
X is independently hydrogen or a blocking group;
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R3 and R4 are independently hydrogen, hydrocarbyl, functional hydrocarbyl,
halogen,
hydroxyl, -O(hydrocarbyl), -O(functional hydrocarbyl), -S(hydrocarbyl),
-SOZ(hydrocarbyl), -S03(hydrocarbyl), -COO(hydrocarbyl),
-CO(hydrocarbyl), -0CO(hydrocarbyl), -N(hydrocarbyl)(hydrocarbyl),
-S(functional hydrocarbyl), -SOZ(functional hydrocarbyl), -S03(functional
hydrocarbyl), -COO(functional hydrocarbyl), -CO(functional hydrocarbyl),
-OCO(functional hydrocarbyl), N(functional hydrocarbyl)(functional
hydrocarbyl) or cyano;
r is an integer between 2 and 4;
D, when r is 2, is selected from the group consisting of C2 C,balkylene,
CQ C,zalkenylene, xylylene, C3 CZ°alkylene which is interrupted by
one or more oxygen atoms, hydroxy-substituted C3 CZ°alkylene which
is interrupted by one or more oxygen atoms, -OOCR14C00-,
-CH~CH(OH)CH20-R'S-OCHzCH(OH)CH~,
1 S -CO-R'6-CO-, -CO-NH-R "-NH-CO-, and
-(CH~).~-COO-R'8-OCO-(CHz).,.-; and
when r is 3, D is
-- f (CH2)S-COO-- R~ g
and when r is 4, D is
--~ (CH2)S--~00~-- R2o
4
wherein
R'9 is C3 Cl°alkanetriyl and RZ° is C4
C,°alkanetetryl;
s is 1-6;
r is an integer between 2 and 4;
D, when r is 2, is selected from the group consisting of Cz C,6alkylene,
C4 C,Zalkenylene, xylylene, C3 CZ°alkylene which is interrupted by
one or more oxygen atoms, hydroxy-substituted C3 CZ°alkylene which
is interrupted by one or more oxygen atoms,
-CHZCH(OH)CHZO-R'S-OCHZCH(OH)CH,,
-CO-R'b-CO-, -CO-NH-R"-NH-CO-, and
-(CHZ)s COO-R'8-OCO--(CHZ),. ; and
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whenris3,Dis
--~ (CHAS-COO-~-- R~ g
3
andwhenris4,Dis
--~ (CH2)s-X00-~-- R2° ..
4
wherein R'9 is C3 C,°alkanetriyl and RZ° is C4
C,°alkanetetryl;
s is 1-6;
Rg is C,-C,8 alkyl, C3-C,e alkenyl, C3-CZ° alkyl, which is interrupted
by O, N, or S,
and/or substituted by OH, C,-C4 alkyl which is substituted by -P(O)(OR'4)2,
-N(R9) (R'°), or -OCOR", and/or OH, or is glycidyl, cyclohexyl or C7-C,
~
phenylalkyl;
I S R9 and R'° are each independently of the other, C,-C,~ alkyl, C3-
C,Z alkoxyalkyl, C4-
C,6 dialkylaminoalkyl or CS-C,Z cycloalkyl, or R9 and R'°, when
taken
together, are C3-C9 alkylene or C3-C9 oxaalkylene of C3-C9 azaalkylene;
R" is C,-C,8 alkyl, Cz-C,8 alkenyl or phenyl;
R'Z is C,-C,8 alkyl, CZ-C,8 alkenyl, phenyl, C,-C,2 alkoxy, phenoxy, C,-C,2
alkylamino; phenylamino, tolylamino or naphthylamino;
R'3 is C,-C,Z alkyl, phenyl, naphthyl or C~-C,4 alkylphenyl;
R'4 is C,-C,2 alkyl or phenyl;
R'S is Cz-C,° alkylene phenyIene or a phenylene-x-phenylene- group,
wherein X is
-O-, -S-, -SOZ-, --CHZ-, or --C(CH3)z-
R'6 is CZ-C,° alkylene, CZ-C~° oxaalkylene or CZ-C,°
dithiaalkylene, phenylene,
naphthylene, diphenylene or CZ-C6 alkenylene;
R" is CZ-C,° aIkylene, phenylene, naphthylene, methylenediphenylene or
C~-C,5
alkylphenylene, and
R'g is Cz-C,° alkylene or C4-CZ° alkylene which is interrupted
by one or more oxygen
atoms.
The benzocycle-substituted pyrimidines and triazines of the present invention
may
optionally have the added benefit of being capable of being chemically bonded
to
appropriate polymer systems via functionality attached to the benzocycle,
pyrimidine and
triazine groups {e.g., by a hydroxyl, ethylenic unsaturated and/or activated
unsaturated group
in one or more of R', R2, Y or Z).
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These benzocycle-substituted pyrimidines and triazines may in general be
prepared
via a number of procedures well known in the art, for example, those described
in Brunetti,
H; Luethi, C.; Helv. ChemicaActa, 55 (1972) pp. 1566-1595; Tanimoto, S.;
Yamagata, M.
Senryo to Yukahin, 40 (1995) pp 339ff; United States Patent Nos. 5,106,972,
5,288,868,
5,438,138, and 5,478,935; EP 395,938; EP 577,559; EP 649,841; EP 779,280; WO
9,628,431; GB 884,$02; and Japanese Patent Kokai Tokkyo Koho 9,059,263 all of
which
are incorporated herein by reference for all purposes as if fully set forth.
The novel benzocycle-substituted pyrimidines and triazines of the present
invention
are particularly useful as ultraviolet light absorber agents for stabilizing a
wide variety of
materials including, for example, organic compounds, oils, fats, waxes,
cosmetics, dyes and
biocides, and particularly various organic polymers (both crosslinked and non-
crosslinked)
used in applications such as photographic materials, plastics, fibers or dyed
fibers, rubbers,
paints and other coatings, and adhesives. The present invention, consequently,
also relates
to (1) a method of stabilizing a material which is subject to degradation by
actinic radiation
1 S (e.g., an organic material such as an organic polymer in the form of a
film, fiber, shaped
article or coating) by incorporating into said material an amount of an
actinic radiation
stabilizer composition effective to stabilize the material against the effects
of actinic
radiation, wherein the actinic radiation stabilizer composition comprises the
inventive
benzocycle-substituted 1,3,5-triazine or pyrimidine; and {2) the material so
stabilized.
The novel benzocycle-substituted pyrimidines and triazines of the present
invention
are also effective as ultraviolet Iight screening agents in applications such
as sunscreens and
other cosmetic preparations, capstock layers for extruded polymers, dyed
fibers and
laminated UV-screening window films, among others. The present invention,
consequently,
also relates (1) to a method of protecting a substrate against degradation by
actinic radiation
by applying to the substrate an actinic radiation screening layer (e.g., a
coating film or
capstock layer) containing an actinic radiation screening composition in an
amount effective
to reduce the amount of actinic radiation impinging on the substrate, wherein
the actinic
radiation screening composition comprises the inventive benzocycle-substituted
pyrimidines and triazines; and (2) the substrate so protected.
The novel benzocycle-substituted pyrimidines and triazines of the present
invention
may also be employed to form light.stabilizing compositions. Such Iight
stabilizing
compositions may include a variety of other components known in the art
including other
ultraviolet light absorbers of the triazine class, other ultraviolet light
absorbers of different
classes (e.g. benzotriazoles, benzophenones), hindered amine light
stabilizers, radical
scavengers, antioxidants and the like.
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These and other features and advantages of the present invention will be more
readily understood by those of ordinary skill in the art from a reading of the
following
detailed description.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The Benzocvcle-substituted nvrimidines and triazines
As used herein, the term "benzocycle-substituted pyrimidines and triazines"
broadly
refers to any compound of formulas (I) through (IX), above.
As used herein, the term "benzocycle" broadly refers to any compound or
substituent
of general formula (X):
(CH2)n
~G
(RZ)q'_'.~
(CH2)m (CH2)o
1S
(
(X)
Wherein substituents G, R', RZ, and subscripts m, n, o, p, and q, are defined
as above for
general formulas (I), (II), (III), and (IV);
The term "hydrocarbyl" in the context of the present invention, and in the
above
formulas, broadly refers to a monovalent hydrocarbon group in which the
valency is derived
by abstraction of a hydrogen from a carbon atom. Hydrocarbyl includes, for
example,
aliphatics (straight and branched chain), cycloaliphatics, aromatics and mixed
character
2S groups (e.g., aralkyl and alkaryl). Hydrocarbyl also includes such groups
with internal
unsaturation and activated unsaturation. More specifically, hydrocarbyl
includes (but is not
limited to) such groups as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl,
cycloalkenyl and
alkynyl, preferably having up to 24 carbon atoms. A hydrocarbyl may optionally
contain a
carbonyl group or groups (which is/are included in the carbon count) andlor a
heteroatom or
heteroatoms (such as at least one oxygen, sulfur, nitrogen or silicon), in the
chain or ring.
The term "functional hydrocarbyl" in the context of the present invention, and
in the
above formulas, broadly refers to a hydrocarbyl possessing pendant and/or
terminal reactive
and/or latent reactive functionality and/or leaving groups. "Reactive"
functionality refers to
functionality which is reactive with common monomer/polymer functionality
under normal
3S conditions well understood by those persons of ordinary skill in the
relevant art. As non-
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limiting examples of reactive functionality may be mentioned active hydrogen-
containing
gro«ps such as lZydroxyl, amino, carboxyl, thin, amido, carbamoyl and
activated mcthylcnc;
isocyanato; cyano; epoxy; ethylenically unsaturated groups such as allyl and
methallyl; and
activated unsaturated groups such acryloyl and methacryloyl, and maleate and
maleimido
(including the Diels-Alder adducts thereof with dienes such as butadiene).
"Latent reactive"
functionality within the meaning of the present invention and, as would
clearly be
understood by those persons of ordinary skill in the art, refers to reactive
functionality which ~~
is blocked or masked to prevent premature reaction. As examples of latent
reactive
functionality may be mentioned ketimines and aldimines (amines blocked,
respectively, with
ketones and aldehydes); amine-carboxylate salts; and blocked isocyanates such
as alcohol
(carbamates), oxime and caprolactam blocked variations. A "leaving" group
within the
meaning of the present invention, as would clearly be understood by those
persons of
ordinary skill in the relevant art, is a substituent attached to the
hydrocarbyl chain or ring
which during reaction is dislodged or displaced to create a valency on a
carbon or
heteroatom in the hydrocarbyl chain or ring, said valency being filled by a
nucleophile. As
examples of leaving groups may be mentioned halogen atoms such as chlorine,
bromine and
iodine; hydroxyl groups (protonated and unprotonated); quaternary ammonium
salts (NT4+);
sulfonium salts (ST3+); and sulfonates (-OS03T); where T is, e.g., methyl or
para-tolyl. Of
all these classes of reactive functionality, the preferred functionality
includes hydroxyl,
-COORs, -CR6=CHZ, -CO-CR6=CHZ, Cl, an isocyanate group, a blocked isocyanate
group
and -NHRS, wherein
RS is selected from hydrogen and a hydrocarbyl (preferably of up to 24 carbon
atoms); and
R6 is selected from hydrogen and an alkyl of 1 to 4 carbon atoms (preferably
hydrogen and methyl).
The term "hydrocarbylene" in the context of the present invention is a
divalent
hydrocarbon group in which both valencies derive by abstraction of hydrogens
from carbon
atoms. Included within the definition of hydrocarbylene are the same groups as
indicated
above for hydrocarbyl and functional hydrocarbyl with, of course, the extra
valency (for
example, alkylene, alkenylene, arylene, alkylaryl, etc.).
The term "functional hydrocarbylene" in the context of the present invention
refers to
a species of hydrocarbylene possessing pendant reactive functionality, latent
reactive
functionality and/or leaving groups. The term "non-functional hydrocarbylene"
in the
context of the present invention refers generally to a hydrocarbyiene other
than a functional
hydrocarbylene.
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The benzocycle-substituted pyrimidines and triazines in accordance with the
present
invention also relate to latent stabilizing compounds against actinic
radiation of the general
formulas (I), (III), and (IV), wherein at least one of the hydroxyl groups on
an aryl ring ortho
to the point of attachment to the triazine or pyrimidine ring is blocked, that
is, wherein at
least one X is other than hydrogen. Such latent stabilizing compounds liberate
the effective
stabilizers by cleavage of the O-X bond, e.g., by heating or by exposure to UV
radiation.
Latent stabilizing compounds are desirable because they have many favorable
properties,
i.e., good substrate compatibility, good color properties, a high cleavage
rate of the O-X
bond and a long shelf life. The use of latent stabilizing compounds is further
described in
United States Patent Nos. 4,775,707, 5,030,731, 5,563,224 and 5,597,854, which
are
incorporated herein for all purposes as if fully set forth.
Latent stabilizing compounds comprising the benzocycle-substituted pyrimidines
and triazines in accordance with the present invention can be prepared from
compounds of
the general formulas (I), (II) and (IV) through (IX), wherein at least one X
is hydrogen, by
subjecting said compounds to a further reaction to form latent stabilizing
compounds, as
described in the immediately preceding incorporated references.
As preferred examples of blocking groups X may be mentioned one or more of the
following groups: allyl, -CORa, -SOZR", -SiR'RdRe, -PR~Rs or -POR~R6, -LONHR",
wherein
each Ra is independently selected from C,-C8 alkyl, halogen-substituted C,-Cg
alkyl,
CS C,2 cycloalkyl, CZ C8 alkenyl, -CHz CO-CH3, C,-C,2 alkoxy, and phenyl
or phenoxy which is unsubstituted or substituted by C,-C,2 alkyl, C,-C4
alkoxy, halogen and/or benzyl;
each R" is independently selected from C,-C,2 alkyl, C6 C,o aryl and C~ C,8
alkylaryl;
each R', Rd and R' is independently selected from C,-G,g alkyl, cyclohexyl,
phenyl
and C,-C, 8 alkoxy;
each Rf and Rs is independently selected from C,-C,Z alkoxy, C,-C,2 alkyl, CS
C,Z
cycloalkyl, and phenyl or phenoxy which is unsubstituted or substituted by
C,-C,2 alkyl, C,-C4 alkoxy, halogen and/or benzyl; and
each R" is independently selected from C,-C8 alkyl, CS C,2 cycloalkyl, Cz Cg
alkenyl,
-CHz CO-CH3, and phenyl which is unsubstituted or substituted by C,-C,2
alkyl, CZ C8 alkenyl, C,-C4 alkoxy, halogen and/or benzyl.
The reaction to give the latent stabilizing compounds of the present invention
of the
general formula (I), (III), and (IV), in which X is allyl, -CORB, -SOZRb, -
SiR'RdR', -PRfRg or
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WO 99/67225 PCT/US99/13708
-POR'Rg, can be carried out, for example, by reaction of the compounds of the
general
formula (III) through (X), wherein at least one X is hydrogen with the
corresponding halides
such as allyl chloride, Cl-COR', Cl-SOZRb, Cl-SiR'RdR', Cl-PRfRs, or Cl-
PORfRs. The
reaction to give the latent stabilizing compounds of the present invention of
the general
formulas (III) through (X) in which X is -CONHR" can be carned out, for
example, by
reaction of the compounds of the general formulas (III) through (X), wherein
at least one X
is hydrogen with the corresponding isocyanates. Furthermore, acylated
compounds can be ~~
obtained by reaction with anhydrides, ketenes or esters, such as lower alkyl
esters, as is well
known to one skilled in the art. The above-described reagents may be used in
approximately
equimolar amounts or in excess, for example, from 2 to 20 mol with respect to
the hydroxyl
groups desired to be made latent in the starting compound of the general
formula (I), (III), or
(IV).
Catalysts customarily used for acylation, sulfbnylation, phosphonylation,
silylation
or urethanation reactions may be used in forming the latent stabilizing
benzocycle-
substituted pyrimidines and triazines of the present invention. For example,
acylation and
sulfonylation reaction catalysts such as tertiary or quaternary amines, such
as triethylamine,
dimethylaminopyridine or tetrabutylammonium salts, may be used for forming
these latent
stabilizing compounds.
The reaction may be carried out in the presence of a solvent, such as
relatively inert
organics, e.g., hydrocarbons such as toluene and xylene, chlorinated
hydrocarbons such as
carbon tetrachloride or chloroform, or ethers such as tetrahydrofuran or
dibutyl ether, or
without a solvent. Alternatively, the reagents) may be emplayed as the
solvent. The
reaction temperature is usually between room temperature and about
150°C, for example, up
to the boiling point of the solvent when a solvent is used.
In preferred embodiments, each X is hydrogen.
In preferred embodiments, L is selected from the group consisting of hydrogen,
C,-C24 alkyl or mixtures thereof; C,-C24 branched alkyl or mixtures thereof;
C3-C6 alkenyl; -COR'2; -COOR'Z; -CONHR'2; -SOZR'3; C,-C,8 alkyl which is
substituted with one or more of the groups: hydroxy, C,-C,g alkoxy, C3-C,8
alkenoxy, halogen, phenoxy, C,-C,g alkyl-substituted phenoxy, C,-C,8
alkoxy-substituted phenoxy, halogen-substituted phenoxy, -COOH,
-COORB, -CONH2, -CONHR9, -CON(R9){R'°), -NH2, -NHR9, -
N(R9)(R'°),
-NHCOR", -N(R9)COR", -NHCOOR", -N(R4)COOR", -CN, -OCOR",
-OC(O)NHR9, -OC(O)NHR9, -OC(O)N(R9)(R'°); CZ-Cs° alkyl which is
interrupted by one or more oxygen atoms or carbonyl groups and optionally
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WO 99/67225 PCT/US99/13708
substituted by one or more substituents selected from the group consisting of
hydroxy, C,-C,z alkoxy, and glycidyloxy; t;lycidyl; and cyclohexyl optionally
substituted with hydroxyl or -OCOR".
R9 and R'° independently of one another are C,-C,z alkyl, C3-C,z
alkoxyalkyl, C4-C,6
dialkylaminoalkyl, or Cs-C,z cycloalkyl, or R9 and R'° taken together
are
C3-C9 alkylene or C3-C9 oxoaalkylene or C3-C9 azaalkylene.
R" is C,-C,8 alkyl, Cz-C,8 alkenyl, or phenyl. "
Some of these groups as well as others are described in U.S. 5,106,891, U.S.
5,189,084, U.S. 5,356,995, U.S. 5,637,706, U.S. 5,726,309, EP 434,608, EP
704,437, WO
I O 96/28431, and GB 2,293,823 which are incorporated herein by reference for
all purposes as
if fully set forth.
L may also be an alkyl of 1 - 24 carbon atoms substituted by a hindered amine
light
stabilizer (HALS) group of the general formula XI. Triazines containing
tetramethylpiperidine groups are described in U.S. 4,161,592 and 5,376,710,
which are
1 S hereby incorporated by reference herein as if fully set forth.
R~'
Rs~ r Ray
3 K
(Xla) (Xlb)
wherein
J is -O-, NR3°-, -T--(CH2)2 NR3°- wherein T is -O- or -S-,
and
R3° is C,-C,z alkyl or hydrogen;
R" is hydrogen or C,-C8 alkyl;
R3z is hydrogen, oxygen, C,-Cz, alkoxyalkyl, C~-C8 aralkyl, 2,3-epoxypropyl,
and
aliphatic acyl group with 1-4 C atoms or one of the groups --CHzCOOR'3,
-CHz-_'CH(R34~R3s, --COOR36 or --CONHR36, wherein R33 is C,-C,z
alkyl, C3-C6 alkenyl, phenyl, C7-C8 aralkyl or cyclohexyl, R34 is a hydrogen,
methyl or phenyl, R35 is hydrogen, an aliphatic, aromatic, araliphatic or
alicyclic acyl group with 1-8 C atoms, wherein the aromatic part is
unsubstituted or is substituted by chlorine, C,C4 alkyl, C,-C8 alkoxy or by
hydroxyl, and R36 is C,-C,z alkyl, cyclohexyl, phenyl or benzyl;
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WO 99/67225 PCT/US99/13708
R" is hydrogen, -OH or one of the groups --O--C',O-R38 or NR36-CO-R3g,
wherein R'8 is C,-C,2 alkyl or phenyl; and
K is -O--(CmmHzmm~-- ,herein mm is 1 to 6,
Preferred among the sterically hindered amines are members of the group
consisting of
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1,2,2,6,6-
pentamethylpiperidin-4-
yl)sebacate; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; the
condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-
octylamino-
2,6-dichloro-1,3,5-triazine; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-
yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; 3-
dodecyl-1-
(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-1-(1-acetyl-
2,2,6,6-
tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; a mixture of 4-hexadecyloxy-
and 4-
stearyloxy-2,2,6,6-tetramethylpiperidine, and mixtures thereof.
Most preferably, each L group is independently selected from hydrogen, an
alkyl of 1
to 24 carbon atoms, or mixtures thereof; an alkyl of 4 to 20 carbon atoms
containing one or
more oxygen atoms in the chain and optionally substituted with one or more
hydroxyl
groups, or mixtures thereof.
Each R' and R2 is independently selected from hydrogen, chloro, an alkyl of 1
to 8
carbon atoms, an alkyloxy of 1 to 8 carbon atoms optionally containing an
oxygen atom in
the chain, a hydroxyalkyl of 1 to 8 carbon atoms group optionally containing
an oxygen
atom in the chain, a hydroxyalkyloxy of 1 to 8 carbon atoms group optionally
containing an
oxygen atom in the chain, an acyl group of 2 to 12 carbon atoms and an acyloxy
of 2 to 12
carbon atoms. Especially preferred is when each R' and RZ is independently
selected from
hydrogen, chloro, an alkyl of 1 to 4 carbon atoms, and alkoxy of 1 to 4 carbon
atoms, and
particularly hydrogen, methyl, and methoxy.
Each of R3 and R4 is independently selected from hydrogen, a hydrocarbyl group
of 1
to 24 carbon atoms, a hydrocarbyloxy group of 1 to 24 carbon atoms, an acyl
group of 2 to
24 carbon atoms and an acyloxy group of 2 to 24 carbon atoms. More preferably,
each R' is
independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms
optionally
containing an oxygen atom in the chain; an alkyloxy of 1 to 24 carbon atoms
optionally
containing an oxygen atom in the chain; an alkenyl of 2 to 24 carbon atoms
optionally
containing an oxygen atom in the chain; an alkenyIoxy of 2 to 24 carbon atoms
optionally
containing an oxygen atom in the chain; an acyl group of 2 to 12 carbon atoms;
an acyloxy
group of 2 to 12 carbon atoms; and optionally substituted benzoyl. Still more
preferably,
each R' is independently selected from hydrogen, an alkyl of 1 to 8 carbon
atoms, an
alkyloxy of 1 to 8 carbon atoms optionally containing an oxygen atom in the
chain, a
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WO 99/67225 PCT/US99/13708
hydroxyalkyl of 1 to 8 carbon atoms group optionally containing an oxygen atom
in the
chain, a hydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing an
oxygen
atom in the chain, an acyl group of 2 to I2 carbon atoms and an acyloxy of 2
to 12 carbon
atoms. Some ofthese groups as well as others are described in U.S. 5,189,084,
U.S.
5,354,794, U.S. 5,543,518, U.S. 5,637,706, EP 434,608, EP 704,437, and WO
96/28431,
which are incorporated herein by reference for all purposes as if fully set
forth.
In preferred embodiments, each of R' and R4 is independently selected from
hydrogen, halogen, an acyl of 2 to 24 carbon atoms, benzoyl, alkyl of 1 to 24
carbon atoms,
an alkenyl of 2 to 24 carbon atoms, a cycloalkyl of 5 to 24 carbon atoms; and
an aralkyl of 7
to 24 carbon atoms.
In another preferred embodiment, R3 and R4 are independently methylene,
alkylidene, or benzylidene substituted by a benzophenone UV absorber or a
benzotriazole
UV absorber. Related triazine - benzotriazole and triazine - benzophenone
hybrid UV
absorbers are disclosed in U.S. 5,585,422 which is incorporated by reference
herein for all
I S purposes fully set forth. In a related preferred embodiment, R3 and R4 are
independently
methylene, alkylidene, or benzylidene substituted by a second triazine UV
absorber.
Related triazine dimers (and oligomers) are disclosed in U.S. 5,726,309 and EP
704,437
which are incorporated by reference herein for all purposes fully set forth.
Preferred benzotriazoles comprise at least one member of the group consisting
of 2-
(2'-hydroxy-5'-methylphenyl)-benzotriazole; 2-(3',5'-di-tert-butyl-2'-
hydroxyphenyl)benzotriazole; 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(2'-
hydroxy-S'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-
butyl-2'-
hydroxyphenyl)-5-chlorobenzotriazole; 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'-octoxyphenyl)benzotriazole; 2-(3',5'-di-tert-amyl-2'-
hydroxphenyl)benzotriazole;
2-(3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole; a mixture of
2-(3'-tert-
butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-
(3'-tert-
butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-
benzotriazole, 2-
(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-S-chloro-
benzotriazole, 2-(3'-
tert-butyl-2'-hydroxy-S'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-
tert-butyl-2'-
hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-
[2-(2-
ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-
hydroxy-5'-
methylphenyl)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
isooctyloxycarbonylethyl)phenylbenzotriazole; 2,2-methylenebis[4-(1,1,3,3-
tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product
of 2-[3'-tert-
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WO 99/67225 PC'T/US99/13708
butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with
polyethylene glycol
300; [R-CHzCH-COO(CHZ)3]i - where R=3'-tert-butyl-4'-hydroxy-5'-2H-
benzotriazol-2-
ylphenyl; and derivatives thereof. Most preferred benzotriazoles are members
of the group
consisting of 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;
2-(3',5'-di-
tert-amyl-2'-hydroxphenyl)benzotriazole; 2-(3',5'-bis(a,a-dimethylbenzyl)-2'-
hydroxyphenyl)-benzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbonylethyl)phenyl)benzotriazole, the transesteriiication product of
2-[3'-tert-
butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenylJbenzotriazole with
polyethylene glycol
300 and mixtures thereof.
In preferred embodiments, R" is selected from hydrogen and hydrocarbyl of 1 to
24
carbon atoms which may optionally be substituted by hydroxyl or alkoxy of 1 to
4 carbon
atoms and/or contain one or more oxygen and/or nitrogen atoms in the chain.
More
preferably, R" is selected from hydrogen and hydrocarbyl of 1 to 24 carbon
atoms which
may optionally be substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms.
1 S In preferred embodiments, R'Z is selected from hydrogen and an alkyl of 1
to 4
carbon atoms. More preferably, R'~ is selected from hydrogen and a methyl
group.
In preferred embodiments, R" is selected from hydrogen, a hydrocarbyl group of
1 to
8 carbon atoms, or phenyl. More preferably, R'3 is hydrogen or methyl.
In preferred embodiments, G is a direct bond, m and o are 0, and n is 4.
Further preferred embodiments may include any combination of the parameters
mentioned above.
Methods of Preparation
The term "Lewis acid" is intended to include aluminum halides, alkylaluminum
halides, boron halides, tin halides, titanium halides, lead halides, zinc
halides, iron halides,
gallium halides, arsenic halide, copper halides, cadmium halides, mercury
halides, antimony
halides, and the like. Preferred Lewis acids include aluminum trichloride,
aluminum
tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc
dichloride,
titanium tetrachloride, tin dichloride, tin tetrachloride, or a mixture
thereof.
As used herein, the term "step-wise" means a reaction sequence wherein a
series of
reactions are conducted, the first reaction producing compounds of Formulas
(XXXII),
(XXXV), or (:KXXVI) and being carried out to between about 50% to about 100%
completion prior to addition of a compound of Formula (XXXIII) to produce
compounds of
Formulas (I), (IV a/b/c), or (V). Preferably the reaction is carried out to
between about 70%
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WO 99/67225 PCT/US99/13708
to about 100% completion prior to addition of compound of Formula (XXXIII),
and more
preferably to between about 75% to about 100% completion.
The novel benzocycle-substituted pyrimidines and triazines of the present
invention
can be prepared through the Friedel-Crafts reaction of a benzocycle moiety
(:KXX) with a
halogen-substituted pyrimidine or triazine compound of Formula (XXXI) or
(XXXIV). See
Schemes l, 2, and 3.
(CHZ)n
(R2~ G~ ~G Ha1 A TZ
"'m ((:Hy)o "
. Af Hal
al
(R )p
(rl)
VXO
G (CHy G R~ ~ G (C!"IZl'G
R i
(RZ~;~ -I (R~q~2)m (~H~o
~m (~H2~ Y
A TZ (xXXill)
(R, ~ ~ TZ
(rll)
Scheme 1
wherein Hal is bromine, chlorine, or iodine. Compound (XXX) is defined as a
protonated
compound of Formula (X), as defined above. In compounds (XXXI) and (XXXIV)
Hal, is a
halogen, preferably bromine, chlorine, or iodine, and A, T, and Z are as
defined above. In
compound (XXXIII) L, X, T', Y, R', and R4 are as defined above.
The relative amounts of the reactants are as follows. The amount of compounds
(XXXI) or (XXXIV) should be in sufficient amounts to react with benzocyclic
compounds
of Formula (XXX) to produce compounds of Formula (XXXII), (XXXV), or (XXXVI).
The
amount of benzocyclic compound of Formula (XXX) is important to ensure that a
sufficient
amount of benzocyclic compounds of Formula (XXXII), {XXXV), or (XXXVI) are
synthesized without excessive amounts of undesired side products such as
trisbenzocyclic
triazine or trisbenzocyclic pyrimidine. Moreover, excess amounts of
benzc~yclic
compounds can lead to undesired product distributions enriched in mono- and
tris-
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WO 99/67225 PCT/US99/13708
benzocyclic triazines, or mono- and tris-benzocyclic pyrimidines thus, making
product
separation and purification difficult and resource consuming.
(CHz)n
G' ~G
(R2~;~-- I Ha~~ Hal
w~2Jm (CHy)o . AI Hal
Rt ~ Hat
( )p
(XXX) (XXXiV)
(CH~n
IO (CH~n uxo o~ y
.G
;~ ,,,~ ~J
~~m (VH2)o
O"Hal (XXXIII) fH
(xxxv)
Scheme 2
The amount of benzocyclic compounds (XXX) should be in sufficient amounts to
synthesize 2-halo-4,6-bisbenzocyclic-1,3,5-triazine, 2,4-dihalo-6-benzocyclic-
1,3,5-triazine,
2-halo-4,6-bisbenzocyclicpyrimidine, 2,4-dihalo-6-benzocyclicpyrimidine or
convert 2-halo-
4,6-bisbenzocyclic-1,3,5-triazine into 2,4,6-trisbenzocyclic-1,3,5-triazine or
convert 2-halo-
4,6-bisbenzocyclicpyrimidine into 2,4,6-trisbenzocyclicpyrimidine. Preferably,
there should
be between about I to about 5 mol equivalents of benzocyclic compound of
Formula (~;XX)
to compound of Formula (XXXI) or (XXXIV). The amount of aromatic compound of
Formula (XXXIII) should be between about 0.5 to about 2.5 mol equivalents of
aromatic
compound of Formula (XXXIII) to compounds of Formula (XXXII), (XXXV), or
(XXXVI).
The amount of Lewis acid, AI(Hal)3 wherein Hal is a halide as defined above,
used
in the reaction should be in sufficient amounts to transform 2,4,6-trihalo-
1,3,5-triazine or
2,4,6-trihalo-pyrimidine to the preferred 2-halo-4,6-bisbenzocyclic-1,3,5-
triazine,
2,4,6-trisbenzocyclic-1,3,5-triazine, or 2-halo-4,6-bisbenzocycIicpyrimidine,
2,4,6-trisbenzocyclicpyrimidine, respectively. The amount of Lewis acid should
be between
about 0.5 to about 500 mol equivalents. Preferably, the amount of Lewis acid
should be
between about I to about S mol equivalents.
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WO 99/67225 PCT/US99/13708
(CHz)n
G C' Hat A Hat
(~~~m (~H~o r
AI Hal
(Rt) ~ Hal
S
(XXXIV)
L/XO
(CHZ3n (CH~n R R (CH~n (CH~n ..
i v IR=
G G Gi 'G Gi 'G G'i 'G
(R~'q~m I~H~o (CIH~m ~(R~~4 'Y ~ ((~m (~H~o (G~li~m ~oR~4
(XXXIII)
IO (R~) ~ (R~)p cR~ (R')P
Hal
(XXXVI)
1 S (V)
Scheme 3
The Lewis acid can be combined with either the benzocyclic compound of Formula
(XXX), compounds of Formula (XXXI) or (XXXIV), or both, in any manner. In situ
reaction mixture preparation comprises addition of at least one Lewis acid to
at least one
20 compound of Formula (XXXI) or (XXXIV), at least one benzocyclic compound of
Formula
(XXX), and optionally solvent, without regard to addition order. As used
herein, one or
more Lewis acids may be used, the first step and the second step Lewis acid
may be the
same or different.
The reaction should run for a sufficient amount of time, at a sufficient
temperature
25 and pressure to synthesize the desired triazine or pyrimidine compound. The
preferred
reaction time for the synthesis of compounds of Formula (XXXII), (;KXXV)~
(XXXVI), i.e.,
the first step, is between about S minutes and about 48 hours, more preferred
between about
1 S minutes and about 24 hours. The preferred reaction time for the synthesis
of compounds
of Formula (I), (IV a!b/c), (V), i.e., the second step, is between about 10
minutes and about
30 24 hours, more preferably time is between about 30 minutes and about 12
hours. The
reaction pressure is not critical and can be about 1 atm or higher if desired.
Preferably, the
reaction is carried out under an inert gas such as nitrogen or argon. One of
ordinary skill in
the art with little or no experimentation can determine the reaction
temperature necessary to
obtain the desired product.
3S
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WO 99/67225 PCT/US99/13708
The step-wise process comprises mixing at least one Lewis acid and compounds
of
Formula (XXXI) or (XXXIV) with one or more of the desired benzocyclic
compounds of
Formula (XXX), preferably until the reaction is between about 70% to about
100%
completed. Thereafter, the product is isolated and purified. The aromatic
compound of
Formula (XXXIII) is added to the purified product along with Lewis acid to
synthesize the
compounds of Formula (I), (IV a/b/c), or (V). The step-wise sequence allows
for the
isolation, purification, and storage of compounds of Formula (XXXII), (XXXV),
or
(XXXVI) prior to subsequent reaction with aromatic compounds of Formula
(XXXIII).
To synthesize compounds of Formula (I), (IV a/b/c), (V), the preferred
addition time
of the aromatic compound of Formula (XXXIII) to the reaction mixture is
between about 5
minutes to about 10 hours, more preferred addition time is between about 10
minutes to
about S hours, and most preferred addition time is between about 15 minutes to
about 2
hours.
The Lewis acid should be present in amounts sufficient to react with the
number of
halogens being substituted on compounds of Formula (XXXI) or (XXXIV). A range
of
between about 1 to about 5 mol equivalents of Lewis acid can be used. The
preferred Lewis
acid is aluminum chloride. A preferred amount of Lewis acid is between about 2
to about 4
mol equivalents to halo-triazine or halo-pyrimidine.
The synthesis of compounds of Formula (VI), (VII), VIII), or (IX) can be
performed
by methods commonly known in the art. One of ordinary skill in the art with
little or no
experimentation can determine the appropriate conditions to obtain the polymer
product
desired.
Uses of the benzocycle-substituted pyrimidines and triazines
As indicated earlier, the novel benzocyclic-substituted pyrimidines and
triazines of the present invention are particularly useful as ultraviolet
light absorber agents
for stabilizing a wide variety of materials including, for example, various
polymers (both
crosslinked and thermoplastic), photographic materials and dye solutions for
textile
materials, as well as in ultraviolet light screening agents (such as
sunscreens). The novel
benzocyclic-substituted pyrimidines and triazines of the present invention can
be
incorporated into such material in any one of a variety of conventional
manners, including
for example, physical mixing or blending, optionally, with chemical bonding to
the material
(typically to a polymer), as a component in a light stabilizing composition
such as a coating
or solution, or as a component in a UV screening composition such as a
sunscreen
composition.
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In one embodiment of the present invention, the benzocyclic-substituted
pyrimidines and triazines of the present invention can be employed to
stabilize materials
which are subject to degradation by ultraviolet radiation by incorporating the
presently
claimed compounds into polymeric materials, either chemically or physically.
Non-limiting
examples of polymeric materials that may be so stabilized are polyolefins,
polyesters,
polyethers, polyketones, polyamides, natural and synthetic rubbers,
polyurethanes,
polystyrenes, high-impact polystyrenes, polyacrylates, polymethacrylates,
polyacetals,
polyacryIonitriles, poIybutadienes, polystyrenes, ABS, SAN (styrene
acrylonitrile), ASA
(acrylate styrene acrylonitrile), cellulosic acetate butyrate, cellulosic
polymers, polyimides,
polyamideimides, polyetherimides, polyphenylsulfides, PPO, polysulfones,
polyethersulfones, polyvinylchlorides, polycarbonates, polyketones, aliphatic
polyketones,
thermoplastic TPO's, aminoresin crosslinked polyacrylates and polyesters,
polyisocyanate
crosslinked polyesters and polyacrylates, phenol/formaldehyde,
urea/formaldehyde and
melamine/formaldehyde resins, drying and non-drying alkyd resins, alkyd
resins, polyester
I 5 resins, acrylate resins cross-linked with melamine resins, urea resins,
isocyanates,
isocyanurates, carbamates, and epoxy resins, cross-linked epoxy resins derived
from
aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds, which
are
cross-linked with anhydrides or amines, polysiloxanes, Michael addition
polymers, amines,
blocked amines with activated unsaturated and methylene compounds, ketimines
with
activated unsaturated and methylene compounds, polyketimines in combination
with
unsaturated acrylic polyacetoacetate resins, polyketimines in combination with
unsaturated
acrylic resins, radiation curable compositions, epoxymelamine resins, organic
dyes,
cosmetic products, cellulose-based paper formulations, photographic film
paper, ink, and
blends thereof.
The preferred polymeric material is selected from the group consisting of
polyolefins; copolymers of one or more monoolefins and/or diolefns with carbon
monoxide
and/or with other vinyl monomers; hydrocarbon resins (such as CS-C9) including
hydrogenated modifications thereof and mixtures of polyalkylenes and starch;
polyesters;
copolyethers esters; polyethers; polyketones; polyamides and copolyamides
derived from
diamines, dicarboxylic acids and/or aminocarboxylic acids or the corresponding
Iactams;
natural and synthetic rubbers and elastomers; polyurethanes; polystyrenes,
poly-a-methylstyrenes and copolymers with other vinyl monomers; graft
copolymers of
styrene; high impact polystyrenes; polyacrylic acids, polymethacrylics acids,
palyacrylates,
polymethacrylates, polyacrylamides, polyacrylonitriles; homo- and copolymers
derived from
unsaturated alcohols and amines or the acyl derivatives or acetals thereof
such as polyvinyl
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alcohol, polyvinyl acetate, polyacetals, and polybutyrals; homo- and
copolymers of cyclic
ethers such as alkylene glycols and alkylene oxides, as well as copolymers
with bisglycidyl
ethers; polybutadienes; polystyrenes; ABS (acrylonitrile butadiene styrene);
SAN (styrene
acrylonitrile); ASA (acrylate styrene acrylonitrile); cellulosic acetate
butyrate; cellulosic
polymers; polyureas; polyimides; polyamides-imides; polyester-imides;
polyether-imides;
polyhydantoins; polybenzimidazoles; polyphenylsulfide; PPO (polypropylene
oxide);
polysulfones; polyether sulfones; polyether ketones; halogen-containing
polymers;
polyvinylchlorides; polycarbonates; polyester carbonates; thermoplastic TPO's;
amino resin
cross-linked polyacrylates and polyesters; polyisocyante cross-linked
polyesters and
polyacrylates; phenol/formaldehyde, urea/formaldehyde and
melamine/formaldehyde resins;
saturated and unsaturated polyester resins; cross-linkable acrylic resins
derived from
substituted acrylates such as epoxy acrylates, hydroxy acrylates, isocyanato
acrylates,
urethane acrylates or polyester acrylates; alkyd resins, polyester resins, and
acrylate resins
cross-linked with melamine resins, urea resins, isocyantes, isocyanurates,
carbamates, or
epoxy resins; cross-linked epoxy resins derived from aliphatic cycloaliphatic,
heterocyclic
and/or aromatic glycidyl compounds which are cross-linked with anhydrides or
amines;
polysiloxanes; Michael addition polymers of amines or blocked amines (e.g.,
ketimines)
with activated unsaturated and/or methylene compounds; of ketimines with
activated
unsaturated and/or methylene compounds such as acrylates and methacrylates,
maleates, and
acetoacetates; polyketimines in combination with unsaturated acrylic
polyacetoacetate resins
or with unsaturated acrylic resins; radiation curable compositions;
epoxymelamine resins;
natural polymers such as cellulose, rubber, gelatin, and chemically modified
derivatives
thereof; organic dyes and pigments; any mixture or blends of the above;
cosmetic products;
cellulose-based paper formulations; photographic film; paper; ink; and
intraocular lenses.
Further non-limiting examples of specific polymers which may be stabilized
include:
1. Homo- and copolymers of monoolefins and diolefins including but not limited
to
ethylene, propylene, isobutylene, butenc, methylpentene, hexene, heptene,
octene,
isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene and cycloolefins
such
as cyclopentene and norbornene; for example, polyethylenes (which optionally
can
be crosslinked) such as high density polyethylene (HDPE), high density and
high
molecular weight polyethylene (HDPE-HMVI~, high density and ultrahigh
molecular
weight polyethylene (HDPE-UHMV~, medium density polyethylene (MDPE), low
density polyethylene (LDPE), linear low density polyethylene (LLDPE) and
branched low density polyethylene (BLDPE).
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2. Copolymers of one or more monoolefins and/or diolcfins with carbon monoxide
and/or
with other vinyl monomers, including acrylic and methacrylic acid, acrylates
and
methacrylates, acrylamides, acrylonitriles, styrenes, vinyl acetate (such as
ethylene/vinyl acetate copolymers), vinyl halides, vinylidene halides, malefic
anhydride and allyl monomers such as allyl alcohol, allyl amine ally glycidyl
ether
and derivatives thereof.
3. Hydrocarbon resins (such as CS-C9) including hydrogenated modifications
thereof and
mixtures of polyalkylenes and starch.
4. Homo- and copolymers of styrenes such as styrene, p-methylstyrene and
IO a-methylstyrene.
S. Copolymers of one or more styrenes with other vinyl monomers such as
olefins and
diolefins (e.g., ethylene, isoprene and/or butadiene), acrylic and methacrylic
acid,
acrylates and methacrylates, acrylamides, acrylonitriles, vinyl acetate (such
as
ethylene/vinyl acetate copolymers), vinyl halides, vinylidene halides, malefic
15 anhydride and aliyl compounds such as allyl alcohol, allyl amine allyl
glycidyl ether
and derivatives thereof.
6. Graft copolymers of styrenes on polybutadienes, polybutadiene/styrene
copolymers and
polybutadiene/acrylonitrile copolymers; styrene (or a-methylstyrene) and
acrylonitrile (or methacryIonitrile) on polybutadiene; styrene and malefic
anhydride
20 on polybutadiene; styrene, acrylonitrile and malefic anhydride or maleimide
on
polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene
copolymers;
styrene and acrylonitrile on polyalkyl acrylates or methacrylates; and styrene
and
acrylonitrile on acrylate/butadiene copolymers.
7. Halogen-containing polymers such as polychloroprene; chlorinated rubbers;
chlorinated
25 and brominated isobutylene/isoprene copolymers; chlorinated or
sulf~chlorinated
polyethylene; copolymers of ethylene and chlorinated ethylene; epichlorohydrin
polymers and copolymers; and polymers and copolymers of halogen-containing
vinyl
compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride and/or
vinylidene fluoride and other vinyl monomers.
30 8. Homo- and copolymers derived from a,~i-unsaturated acids and derivatives
thereof such
as acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides and
acrylonitriles.
9. Copolymers of the monomers mentioned in (8) with other unsaturated monomers
such as
olefins and diolefins (e.g., butadiene), styrenes, vinyl halides, maieic
anhydride and
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WO 99/67225 PCTNS99/13708
allyl monomer such as allyl alcohol, allyl amine, allyl glycidyl ether and
derivatives
thereof.
10. Homo- and copolymers derived from unsaturated alcohols and amines or the
acyl
derivatives or acetals thereof, such as vinyl alcohol, vinyl acetate, vinyl
stearate,
vinyl benzoate, vinyl maleate, vinyl butyral, allyl alcohol, allyl amine,
allyl glycidyl
ether, allyl phthalate and allyl melamine; as well as copolymers of such
monomers
with other ethylenically unsaturated monomers mentioned above.
For the preceding groups 1-10 of polymers, the present invention further
encompasses these
polymers as prepared by metallocene catalysts.
11. Homo- and copolymers of cyclic ethers such as aIkylene glycols and
alkylene oxides, as
well as copolymers with bisglycidyl ethers.
12. PoIyacetals such as polyoxymethylene and those polyoxymethylenes which
contain
ethylene oxide as a comonomer; and polyoxymethylenes modified with
thermoplastic polyurethanes, acrylates and/or MBS.
1 S I 3. Polyphenylene oxides and sulfides.
14. Polyurethanes derived from hydroxy-functional components such as
polyhydric
alcohols, polyethers, polyesters, polyacrylics and/or polybutadienes on the
one hand,
and aliphatic and/or aromatic isocyanates on the other, as well as precursors
thereof.
15. Polyamides and copolyamides derived from diamines, dicarboxylic acids
and/or
aminocarboxylic acids or the corresponding lactams, such as polyamide 4,
polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 6/9, polyamide 6/12,
polyamide 4/6, polyamide 12/12, polyamide 11 and polyamide 12; aromatic
polyamides starting from m-xylene diamine and adipic acid; polyamides prepared
from hexamethylene diamine and isophthalic and/or terephthalic acid and with
or
without an elastomer as a modif er, for example, poly-2,4,4-
trimethylhexamethylene
terephthalamide or poly-m-phenylene isophthalamide; block copolymers of the
aforementioned polyamides with polyolefins, olefin capolymer, ionomers,
chemically bonded or grafted elastomers, or polyethers such as pol;~ethylene
glycol,
polypropylene glycol or polytetramethylene glycol; and polyamides condensed
during processing (RIM polyamide systems).
16. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides,
polyhydantoins and polybenzimidazoles.
17. Polyesters derived from dicarboxylic acids, diols and/or hydroxycarboxylic
acids or the
corresponding lactones, such as polyethylene terephthalate, polybutylene
terephthalate, poly-1,4-dimethylcyclohexane terephthalate and
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polyhydroxybenzoates, as well as block conolycthcr cstcrs dcrivcd from
hydroxyl-
tcrminatcd ethers; 1'1:'1'G; 1'L;N; P'1"1'; and also polyesters modified with
polycarbonate or MBS.
18. I'olycarbonates and polyester carbonates.
19. Polysulfoncs, polyethcr sulfones and polycther ketoncs.
20. Crosslinked polymers derived from aldehydes condensation resins such as
phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde
resins.
21. Drying and non-drying alkyd resins.
22. 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.
23. Crosslinkable acrylic resins derived from substituted acrylates such as
epoxy acrylates,
hydroxy acrylates, isocyanato acrylates, urethane acrylates or polyester
acrylates.
24. Alkyd resins, polyester resins and acrylate resins crosslinked with
melamine resins, urea
resins, isocyanates, isocyanurates, carbamates or epoxy resins.
25. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,
heterocyclic and/or
aromatic glycidyl compounds such as bisphenol A and bisphenol F, which are
crosslinked with hardeners such as anhydrides or amines.
26. Natural polymers such as cellulose, rubber, gelatin and chemically
modified
homologous derivatives thereof, including cellulose acetates, cellulose
propionates
and cellulose butyrates, or the cellulose ethers such as methyl cellulose, as
well as
rosins and their derivatives.
27. Polysiloxanes.
28. Michael addition polymers of amines or blocked amines (e.g., ketimines)
with activated
unsaturated and/or methylene compounds such as acrylates and methacrylates,
maleates and acetoacetates.
29. Mixtures or blends of any of the above, such as PP/EPDM, polyamide/EPDM or
ABS,
PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT,
PVC/CPE, PVC/acrylate, POMlthermoplastic PUR, P(:/thermoplastic polyurethane,
POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA6.6 and copolymers,
PATENT/HDPE, PP/HDPE, PP/LDPE, LDPE/HDPE, LDPE/EVA, LDPE/EAA,
PATENT/PP, PATENT/PPO, PBT/PC/ABS, PBT/PET/PC and the like.
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30. Polyketimines in combination with unsaturated acrylic polyacetoacetate
resins or with
unsaturated acrylic resins including urethane acrylates, polyether acrylates,
vinyl or
acryl copolymers with pendant unsaturated groups and acrylated melamines.
31. Radiation curable compositions containing ethylenically unsaturated
monomers or
oligomers and a polyunsaturated aliphatic oligomer.
32. Epoxymelamine resins such as light-stable epoxy resins cross-linked by an
epoxy
functional coetherified high solids melamine resin. "
Other materials which can be stabilized include, for example:
33. Naturally occurring and synthetic organic materials which may be mixtures
of
compounds, including mineral oils, animal and vegetable fats, oils and waxes,
or
oils, fats or waxes based on synthetic esters (e.g., phthalates, adipates,
phosphates or
trimellitates) and also mixtures of synthetic esters with mineral oils in any
ratio.
34. Aqueous emulsions of natural or synthetic rubber such as natural latex or
lattices of
carboxylated styrene/butadiene copolymers.
35. Organic dyes such as azo dyes (diazo, triazo and polyazo), anthraquinones,
benzodifuranones, polycyclic aromatic carbonyl dyes, indigoid dyes,
polymethines,
styryl dyes, di- and triaryl carbonium dyes, phthalocyanines, quinophthalones,
sulfur
dyes, nitro and nitroso dyes, stilbene dyes, formazan dyes, quinacri3ones,
carbazoles
and perylene tetracarboxylic diimides.
36. Cosmetic products, such as skin lotions, collagen creams, sunscreen,
facial make-up,
etc., comprising synthetic materials such as antioxidants, preservatives,
lipids,
solvents, surfactants, colorants, antiperspirants, skin conditioners,
moisturizers etc.;
as well as natural products such as collagen, proteins, mink oil, olive oiI,
coconut oil,
carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe, etc.
37. Cellulose-based paper formulations for use, e.g., in newsprint, cardboard,
posters,
packaging, labels, stationery, book and magazine paper, bond typing paper,
multi-
purpose and office paper, computer paper, xerographic paper, laser and ink jet
printer paper, offset paper, currency paper, etc.
38. Photographic film paper.
39. Ink.
ALIPHATIC POLYAMIDE
The novel benzocycIic-substituted pyrimidines and triazines of the present
invention can also be used with aliphatic polyamide polymers. An "Aliphatic
polyamide" is
a polyamide characterized by the presence of recurring carbonamide groups as
an integral
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WO 99/67225 PCT/US99/13708
part of the polymer chain which are separated from one another by at least two
aliphatic
carbon atoms. Illustrative of these polyamides are those having recurring
monomeric units
represented by the general formula:
-NHC(O)RC(O)NHR' - or -NH-R-C(O)-
or a combination hereof in which R and R' are the same or different and are
alkyIene groups ~.
of at least about two carbon atoms, preferably alkylene having from about 2 to
about 12
carbon atoms. Exemplary of such polyamides are polyamides formed by the
reaction of
diamines and diacids such as poly (tetramethylene adipamide)(nylon 4,6);
poly(hexamethylene adipamide) (nylon 6,6); poly (hexamethylene azelamide)
(nylon 6,9);
poly(hexamethylene sebacamide) (nylon 6,10); poly(heptamethylene pimelamide)
(nylon
8,8); poly(nonamethylene azelamide) (nylon 9,9); poly(decamethylene azelamide)
(nylon
10,9); and the like. Also illustrative of useful aliphatic polyamides are
those formed by
polymerization of amino acids and derivatives thereof, as for example lactams.
Illustrative
of these useful polyamides are poly(4-aminobutyric acid) (nylon 4); poly(6-
aminohexanoic
acid) (nylon 6); poly(7-aminoheptanoic acid) (nylon 7); poly(8-aminoocatanoic
acid) (nylon
8); poly(9aminononanoic acid) (nylon 9); poly(10-aminodecanoic acid) (nylon
10); poly(1 I-
aminoundecanoic acid) (nylon 11); poly(12-aminododecanoic acid) (nylon 12);
and the like.
Blends of two or more aliphatic polyamides may also be employed.
Copolymers formed from any combination of the recurring units of the above
referenced aliphatic polyamides can be used. By way of illustration and not
limitation, such
aliphatic polyamide copolymers include caprolactam/hexamethylene adipamide
copolymer
(nylon 6/6,6); hexamethylene adipamide/caprolactam copolymer (nylon 6, 6/6);
hexamethylene adipamide/hexamethylene-azelamide copolymer {nylon 6,6/6,9); and
copolymers formed from recurring units of the above referenced aliphatic
polyamides with
aliphatic/aromatic polyamide recurring units may also be used. Examples of
such
copoiyamides are nylon 6/6T; nylon 6,6/6, T; nylon 6/IOT; nylon 6/12T; nylon
6,10/6,T etc.
Preferred aliphatic polyamides for use in the practice of this invention are
poly(caprolactam); poly(7-aminoheptanic acid); poly(tetramethylene adipamide);
poly(hexamethylene adipamide); and mixtures thereof. The particularly
preferred aliphatic
polyamides are poly(caprolatam); poly(hexamethylene adipamide);
poly(tetramethylene
adipamide); and mixtures thereof.
Aliphatic polyamides useful in the practice of this invention may be obtained
from commercial sources or prepared in accordance with known preparatory
techniques. For
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example, polycaprolactam may be obtained from Allied Signal Inc. and
poly(hexamethylene
adipamide) may be obtained from DuPont Co.
The number average molecular weight of the aliphatic polyamide may vary
widely. Usually, the aliphatic polyamide is of film forming molecular weight
that is
sufficiently high to form a free standing film and sufficiently low to allow
melt processing
of the blend into a film. Such number average molecular weights are well known
to those of
skill in the film art and are usually at least about 5,000 as determined by
the formic acid
viscosity method. In this method, a solution of 9.2 wt. Concentration of
aliphatic polyamide
in 90% formic acid at 25°C is used. In the preferred embodiments of the
invention, the
number average molecular weight of the aliphatic polyamide is from about 5,000
to about
1,000,000 and in the particularly preferred embodiments is from about 10,000
to about
100,000. Amongst the particularly preferred embodiments, most preferred are
those in
which the molecular weight of the aliphatic polyamide is from about 20,000 to
about
40,000.
POLYURETHANE
Polyurethane (PUR) elastomer products ("spandex") can be stabilized against
discoloration and loss of elasticity during UV light exposure with
combinations of UV
absorbers according to the invention and hindered amine light stabilizers.
Spandex fibers is
a PUR elastomer product, which requires very specific UV absorber and hindered
amine
light stabilizers properties in order to achieve optimum performance. UV
absorbers of the
triazine class of this invention can be combined with polymeric hindered amine
light
stabilizers (HALS) to provide outstanding performance in achieving the desired
properties
for the Spandex fiber applications.
The triazine UV absorber of the invention, used alone or in combination with
HALS provides the following properties in the Spandex fiber application: (1)
low color
contribution at typical use levels in the 0.5-2.0% range; (2) sufficient MW,
thermal stability
and low volatility for f ber processing and thermal exposure conditions; (3)
high
compatibility and permanence; (4) prevent discoloration and loss of elasticity
during
exposure to UV light energy; (S) low extraction by water and dry cleaning
solvents; (6) low
color development during exposure to atmospheric pollutants, NOX, SOX,
hydrocarbons, etc.;
(7) low interaction with sea water and pool chemicals; (8) low interaction and
color
development with typical phenolic antioxidants used for the thermal
stabilization of
Spandex fibers; and (9) low interaction with copper based antioxidant systems
used in
Nylon fibers for Nylon/Spandex fabrics.
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The triazine UV absorber with or without the polymeric HALS provides
outstanding stabilization with minimum negative effect on secondary
performance
properties, such as low color development during NOx exposure and low
interaction with
copper based antioxidant systems using in Nylon fibers.
As noted above, any of the triazine compounds disclosed herein can be used
to impart one or more of the properties described above to Spandex fibers when
added
thereto in a stabilization effective amount. '
Preferably, these triazine compounds are added in combination with
polymeric HALS. The polymeric HALS is preferably poly[(6-morpholino-s-triazine-
2,4-
diyl)[2,2,6,6,-tetramethyl-4-piperidyl)imino]-hexamethylene [(2,2,6,6-
tetramethyl-4-
piperidyl)imino]]. Most preferably, the polymeric HALS is the methylated (M)
version of
the above HALS, which is sold by Cytec Industries, Inc. as CYASORB~UV-3529
light
stabilizer. Other polymeric HALS disclosed in US Patent 4,331,586 are also
suitable.
Spandex fibers are made from a polyurethane (PUR) prepolymer prepared
1 S from a diisocyanate and a glycol. There are four basic processes used to
convert the PUR
prepolymer into the fiber product. These processes are Solution Dry Spinning,
Solution
Wet Spinning, Melt Extrusion, and Reaction Spinning. The above UV stabilizer
alone or in
combination with HALS would be suitable for use in any or all four processes.
Spandex fibers may contain a processing antioxidant system, such as a
phenolic antioxidant, or a phenolic/phosphite antioxidant combination. In
addition,
pigments, such as Ti02 are commonly used in the fiber products.
The triazine UV absorber alone or with M-HALS can be dissolved into DMF
or DMAC and added to the PUR prepolymer solution prior to solution fiber
spinning
processes. Also, the combination can be extrusion compounded into the PUR
compound
used in the melt spinning process.
POLYCARBONATES
Among polymeric materials to be stabilized with the novel
benzocycle-substituted pyrimidines and triazines of the present invention,
preference is
given to the polycarbonates, polyesters, polyamides, polyacetals,
polyphenylene oxides and
polyphenylene sulfides, but especially to the polycarbonates. Those compounds
are to be
understood as being especially those polymers the constitutional repeating
unit of which
corresponds to the formula:
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O
O A O C
wherein A is a divalent phenolic radical. Examples of A are given inter alia
in U.S. Pat. No.
4,960,863 and
DE-A-3 922,496. A can be derived, for example, from hydroquinone, resorcinol,
dihydroxybiphenylene or bisphenols in the broadest sense of the term, such as
bis(hydroxyphenyl)alkanes, cycloalkanes; sulfides, ethers, ketones, sulfones,
sulfoxides,
a,a'-bis(hydroxyphenyl)-diisopropylbenzenes, for example the compounds 2,2-
bis(4-
hydroxyphenyl)propane, 2,2-bis(3,S-dimethyl-4-hydroxyphenyl)-propane, 2,2-
bis(3,5-
dichloro-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, or from
the
compounds of the formulae:
HO
CH3
HO OH
CH3
HO
OH
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HO OH
CH3- ~ CH3
CH3
H
25
HO OH
CH3
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CH3-C CH3
CH3-C(CH3)3
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H
v
CHz
OH
CH3
U
In one embodiment, the preferred resins are polycarbonates based on dihydric
phenols such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); 2,4-bis (4-
hydroxyphenyl)-2-methylbutane; 1,1-bis-(4-hydroxyphenyl)-cyclohexane; 2,2-bis-
(3-chloro-
4-hydroxyphenyl)propane; 4,4'-sulfonyldiphenol; and 1,1-bis-(4-hydroxyphenyl)-
3,3,5-
trimethylcyclohexane.
Also preferred are polycarbonate copolymers incorporating two or more
phenols, branched polycarbonates wherein a polyfunctional aromatic compounds
is reacted
with the dihydric phenols) and carbonate precursor, and polymer blends of
which
polycarbonate comprises a significant portion of the blend.
The most preferred resins for both layers are polycarbonates based on
bisphenol A.
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U.S. Patent No. 5,288,788 also describes polycarbonates and polyester
carbonates, especially aromatic polycarbonates, for example those based on 2,2-
bis(4-
hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane.
MULTILAYER SYSTEMS
British Patent Application No. 2,290,745 describes a number of methods
have been developed to concentrate UV absorbers near or at the surface of
polymeric
materials. These include surface impregnation (see U.S. Patent Nos. 3,309,220,
3,043,709,
4,481,664 and 4,937,026) and coating a plastic article with solutions
containing
I O thermoplastic resins and UV absorbers (see U.S. Patent Nos. 4,668,588 and
4,353,965).
Both techniques suffer from drawbacks including requiring additional
processing steps (i.e.
applying, drying or curing), and encounter difficulties associated with the
handling of large
processed articles. An additional drawback, particularly relevant to
polycarbonate sheet
production, is the detrimental effect such post addition treatment would have
on the surface
I 5 of the polymeric substrate.
As described in the U.S. Pat. No. 5,445,872, application of surface layers via
coextrusion takes place in a known manner in known coextrusion equipment as
taught in
U.S. Pat. Nos. 3,487,505 and 3,557,265. Coextrusion is a well recognized
method of
producing laminated thermoplastic materials by simultaneously extruding
various numbers
20 of layers which form a single composite material. U.S. Patent No. 4,540,613
describes
coextruded materials of at least forty layers. Other methods produce as few as
two or three
different layers.
In one embodiment, the invention also relates to thermoplastic articles coated
with a thermoplastic layer 0.1 to 10 mil (0.00254 mm to 0.254 mm), preferable
0.1 to 5 mil
25 (0.00254 mm to 0.127 mm), thick, in which said layer contains 0.1 % to 20%
by weight of
the benzocyclic-substituted pyrimidines and triazines of the present
invention. Preferred
concentrations of are 2% to 15% by weight; most preferred concentrations of 5%
to 10% by
weight.
The benzocycle-substituted pyrimidines and triazines of the present invention
30 may be incorporated into the thermoplastics of the surfaces layer by
standard methods such
as dry mixing the additives with granular resin prior to extruding.
The benzocycle-substituted pyrimidine or triazine layer may be applied to
one or both sides of the thermoplastic article.
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Laminated thermoplastic articles which contain additional layers such as a
water resistant layer as found in U.S. Pat. No. 4,992,322 are also part of the
present
invention.
The core layer and the coating layer may be the same or different
thermoplastic resin including polyesters, polyester carbonates, polyphenylene
oxide,
polyvinyl chloride, polypropylene, polypropylene, polyethylene, polyacrylates,
polymethacrylates and copolymers and blends such as styrene and acrylonitrile
on
polybutadiene and styrene with malefic anhydride, and mixtures (polyblends) of
such
polymers with one another or with other polymers, for example with
polyolefins,
polyacrylates, polydienes or other elastomers in the form of impact strength
modifiers.
BONDABLE STABILIZERS
The benzocycle-substituted pyrimidines and triazines of the present invention
can also be chemically bonded to substrates, such as polymers, thereby greatly
reducing the
migration of such UV absorbers, e.g., out of the substrate or away from the
substrate
surface. The bonding mechanism of the triazines of the present invention
involves the
formation of a bond (chemical and/or co-valent) between a functionality
attached to the
amido or carbamate group, e.g., by a pendant vinyl or hydroxyl group, and the
"host"
substrate, such as a polymer.
Incorporation of the benzocycle-substituted pyrimidines and triazines of the
invention can be brought about by copolymerization, copolyaddition,
copolycondensation,
by reaction with a polymer which carries suitable functional groups, or by
grafting, in a
manner as disclosed in United States Patent Nos. 3,423,360 and 5,189,084 which
are
incorporated herein by reference as if fully set forth.
Bonding of the benzocycle-substituted pyrimidines and triazines of the
invention can occur by polymerization or copolymerization. In the case of the
novel
triazines of the present invention comprising pendant vinyl groups,
polymerization or
copolymerization with at least one vinyl monomer, e.g., (meth)acrylic acid,
esters of
(meth)acrylic acid such as methyl acrylate, amides of (meth)acrylic acid,
hydroxyethylacrylate, olefins, vinyl chloride, styrene, butadiene, isoprene
and acrylonitrile
can be carried out to form homopolymers or copolymers in which the vinyl group
is
incorporated into the backbone of the polymer. Polymerization or
copolymerization can be
initiated by initiators, such as free radical, anionic and cationic types, or
by actinic radiation,
such as UV, electron beam, x-rays and gamma irradiation from a Cob°
source, as is well
3 S known to those in the polymerization art. Polymerization or
copolymerization can be
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carried out in solution, in an emulsion, in a dispersion, in the melt, or in
the solid state as is
well known to those in the polymerization art.
Also, bonding of the presently claimed benzocycle-substituted pyrimidines
and triazines compounds of the present invention can be brought about by
copoIyaddition or
S copolycondensation. Such incorporation can be made by addition during the
synthesis of an
addition polymer or copolymer or by condensation during the synthesis of a
condensation
polymer or copolymer by methods known to those skilled in the art. For
example,
compounds of the formula (I}, (II), or (IV)-(IX} containing the appropriate
functional groups
can be incorporated into polyesters, polyamides, polyurethanes, epoxy resins,
melamine
resins, alkyd resins, phenolic resins, polyurethanes, polycarbonates,
polysiloxanes,
polyacetals and polyanhydrides, to name but a few.
In addition, compounds of the formula (I), (II), or (IV)-(IX) can be bonded to
a monomeric component which is then incorporated into a polymer or copolymer,
e.g., by
the free radical initiated addition or copolycondensation methods described
above.
1 S Analogous methods are disclosed in, for example, United States Patent No.
5,459,222
(incorporated by reference herein for alt purposes as if fully set forth) for
the bonding of
benzotriazole and benzophenone stabilizers to diol precursors which are then
incorporated
by condensation polymerization into polyurethanes and polyesters to impart UV
stabilizing
properties to said polymers.
Alternately, the benzocycle-substituted pyrimidines and triazines of the
invention may also be bonded to polymers by reaction with an oligomer and/or
polymer
which carries suitable functional groups. For example, at least one triazine
compound
comprising a vinyl pendant group can be added, optionally with at least one
other vinyl
monomer or compound comprising a vinyl group, to unsaturated polyester resins,
unsaturated polybutadiene oligomers or unsaturated rubbers and then cured by
actinic
radiation or by a free radical catalyst. Or, at least one triazine compound
comprising a
terminal functional group, such as hydroxyl or amido, may be reacted with a
polymer and/or
oligomer such as polyesters, polyurethanes and polydiols with reactive end-
groups, partially
hydrolyzed polyvinylacetate, epoxy resins, polysiloxanes and polymers
comprising malefic
anhydride, either in the main chain or as a side-chain, by methods analogous
to those well
known to those of ordinary skill in the art.
Grafting is yet another way of bonding of the presently claimed benzocycle-
substituted pyrimidines and triazines to polymers and/or oIigomers. Grafting
may be carried
out in solution, in the melt, or in the solid state with the initiators or
actinic radiation types
discussed above for polymerization when, for example, the novel triazines of
the present
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WO 99/6?225 PCT/US99/13?08
invention comprising pendant vinyl groups are used. Such benzocycle-
substituted
pyrimidines and triazines may be grafted to saturated polymers, e.g.,
polyolefins and their
copolymers such as polyethylene, polypropylene and polyethylene-vinyl
acetate), or to
polymers comprising unsaturated moieties, e.g., polybutadiene, polyisoprene,
ethylene-
S propylene-(diene monomer) terpolymers and polystyrene and its copolymers.
The benzocycle-substituted pyrimidines and triazines of the present invention
may be used in widely varying amounts in such applications depending upon such
things as ~I
the material to be stabilized and the particular application. However, when
employed as a
stabilizing additive for materials such as organic polymers, the benzocycle-
substituted
pyrimidines and triazines of the present invention are typically employed in
amounts from
about 0.01 to about 20% by weight, preferably from about 0.1 to about 10% by
weight, and
most preferably from about 0.1 to about 5% by weight, based on the weight of
the material
to be stabilized. In screening applications such as sunscreening compositions,
the triazines
are utilized in the same relative amounts but based on the total weight of the
screening
agent.
The novel stabilizers of the present invention may also be employed in a non-
bondable capacity, for example, in the stabilization of thermoplastic polymers
as set forth in
the many of the previously incorporated references. Examples of preferred
thermoplastic
polymers are polyolefins and polymers comprising heteroatoms in the main
chain. Preferred
polymers are also thermoplastic polymers comprising nitrogen, oxygen and/or
sulphur,
especially nitrogen or oxygen, in the main chain. Also of interest are
compositions in which
the polymer is a polyolefin, for example polyethylene or polypropylene.
Incorporation into the thermoplastic polymers can be carried out by addition
of the novel benzocycle-substituted triazine or pyrimidine compound and any
further
additives by the methods conventional in the art. The incorporation can
expediently be
made before or during shaping, for example by mixing the pulverulent
components or by
adding the stabilizer to the melt or solution of the polymer, or by applying
the dissolved or
dispersed compounds to the polymer, with or without subsequent evaporation of
the solvent.
Elastomers can also be stabilized as lattices.
The novel mixtures can also be added to the polymers to be stabilized in the
form of a masterbatch which comprises these compounds, for example, in a
concentration of
from about 2.5 to about 25%, preferably from about 5 to about 20% by weight of
the
polymer.
The novel mixtures can expediently be incorporated into the polymeric
material by any number of methods, including those conventionally employed in
the art,
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including by, for cxamplc: a) as an emulsion or dispersion (for example to
lattices or
emulsion polymers); (b) as a dry mix during mixing of additional components or
polymer
mixtures; (c) by direct addition to the processing equipment (for example
extruders, internal
mixers, etc.); or (d) as a solution or melt.
The stabilized polymer compositions obtained in this way can be converted
into shaped articles, for example fibers, films, tapes, sheets, sandwich
boards, containers,
pipes and other profiles, by any number of conventional methods, for example
hot pressing,
spinning, extrusion, roto-molding or injection molding. Therefore, the present
invention
additionally relates to the use of the polymer composition according to the
invention for the
production of a shaped article.
Depending upon their ultimate end use, the benzocycle-substituted
pyrimidines and triazines of the present invention may be combined with a
variety of
additives conventionally employed in the UV stabilizing art, Examples of such
additives
include but are not limited to:
a. Antioxidants
(i) Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol; 2-tert-
butyl-4,6-
dimethylphenol; 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-dimethylphenol; 2,6-dioctadecyl-4-methylphenol; 2,4,6-
tricyclohexylphenol; 2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols
which
are liner or branched in the side chains such as 2,6-di-nonyl-4-methylphenol;
2,4-
dimethyl-6-(I-methylundec-I-yl)phenol; 2,4-dimethyl-6-(1-methylheptadec-I-
yl)phenol; 2,4-dimethyl-6-(1-methyltridec-1-yl)phenol; and mixtures thereof.
(ii) Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tent-butylphenol;
2,4-
dioctylthiomethyl-6-methylphenol; 2,4-dioctylthiomethyl-6-ethylphenol; and 2,6-
di-
dodecylthiomethyl-4-nonylphenol.
(iii) Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-
methoxyphenol; 2,5-di-tert-butylhydroquinone; 2,5-di-tert-amylhydroquinone;
2,6-
diphenyl-4-octadecyloxyphenol; 2,6-di-tert-butylhydroquinone; 2,5-di-tert-
butyl-4-
hydroxyanisole; 3,5-di-tert-butyl-4-hydroxyanisole; 3,5-di-tert-butyl-. 4-
hydroxyphenyl stearate; and bis(3,S-di-tert-butyl-4-hydroxyphenyl)adipate.
(iv) Tocopherols such as a-tocopherol, (3-tocopherol, y-tocopherol, b-
tocopherol, and
mixtures thereof (vitamin E).
(v) Hydroxylated thiodiphenyl ethers such as 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-
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tert-butyl-2-methylphenol); 4,4'-thiobis(3,6-di-sec-amylphenol); and 4,4'-
bis(2,C-
dimethyl-4-hydroxyphenyl)disulfide.
(vi) Alkylidenebisphenols such as 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-methylphenol); 2,2'-methylenebis(4,6-di-tert-
butylphenol);
2,2'-ethylidenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(6-tert-butyl-4-
isobutylphenol); 2,2'-methylenebis[6-(a-methylbenzyl)-4-nonylphenol]; 2,2'-
methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenolj; 4,4'-methylenebis(2,6-di-
tert-
butylphenol); 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-hydroxylbenzyl)-
4-
methylphenol; 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl}butane; 1,1-
bis(5-
tert-butyl-4-hydroxy-2-methylphenyl}-3-n-dodecylmercaptobutane; ethylene
glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrateJ, bis(3-tert-butyl-4-
hydroxy-5-
methylphenyl)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-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane; and 1,1,5,5-
tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
(vii) O-, N- and S-benzyl compounds such as 3,5,3',5'-tetra-tert-butyl-4,4'-
dihydroxydibenzyl ether; octadecyl-4-hydroxy-3,S-
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;
and isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
(viii) Hydroxybenzylate malonates such as dioctadecyl-2,2-bis(3,5-di-tert-
butyl-2-
hydroxybenzyl)malonate; dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-
methylbenzyl)malonate; didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-
hydroxybenzyl)malonate; and bis[4-(1,1,3,3-tetramethylbutyl)phenyl)-2,2-
bis(3,5-di-
tert-butyl-4-hydroxybenzyl)malonate.
(ix) Aromatic hydroxybenzyl compounds such as 1,3,5-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)-2,4,6-trimethylbenzene; 1,4-bis(3,5-di-tert-butyl-4-
hydroxybenzyl)-
2,3,5,6-tetramethylbenzene; and 2,4,6-tris(3,5-di-tert-butyl-4-
hydroxybenzyl)phenol.
(x) Triazine compounds such as 2,4-bis(octylmercapto-6-(3,5-di-tert-butyl-4-
hydroxyanilino)-1,3,5-triazine; 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-
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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)-
I,3,5-triazine; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)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-
hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine; and 1,3,5-tris(3,5-
dicyclohexyl-
4-hydroxybenzyl)isocyanurate. "
(xi) Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-
hydroxybenzylphosphonate; diethyl-3,S-di-tert-butyl-4-
hydroxybenzylphosphonate;
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-5-tert-
butyl-
4-hydroxy-3-methylbenzylphosphonate; and the calcium salt of the monoethyl
ester
of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
(xii) Acylaminophenols such as 4-hydroxylauranilide; 4-hydroxystearanilide;
and octyl N-
(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
(xiii) Esters of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with
mono- or
polyhydric alcohols such as 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(hydroxyethyl)oxamide, 3-
thiaundecanol, 3-
thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-
1-
phospha-2,6,7-trioxabicyclo[2.2.2]octane.
(xiv) Esters of [3-(S-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or
polyhydric alcohols such as 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(hydroxyethyl)oxamide, 3-
thiaundecanol, 3-
thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-
I-
phospha-2,6,7-trioxabicyclo[2.2.2Joctane.
(xv) Esters of [3-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or
polyhydric alcohols such as 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 and 4-hydroxymethyl-I-phospha-2,6,7-
trioxabicyclo[2.2.2]octane.
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(xvi) Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or
polyhydric
alcohols such as 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-1-phospha-2,6,7-
trioxabicyclo[2.2.2]octane. '
(xvii) Amides of ~i-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid such as
N,N'-bis(3,5
di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine; N,N'-bis(3,5-di-
tert
butyl-4-hydroxyphenylpropionyl)trimethylenediamine; and N,N'-bis(3,5-di-tert
butyl-4-hydroxyphenylpropionyl)hydrazine.
(xviii) Ascorbic acid (Vitamin C).
(xix) Aminic antioxidants such as N,N'-diisopropyl-p-phenylenediamine; N,N'-di-
sec-
butyl-p-phenylenediamine; N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine;
N,N'-
IS bis(1-ethyl-3-methylpentyl)-p-phenylenediamine; N,N'-bis(I-methylheptyl)-p-
phenylenediamine; N,N'-dicyclohexyl-p-phenylenediamine; N,N'-diphenyl-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'-phenyl-p-
phenylenediamine; 4-(p-toluenesulfonamoyl)diphenylamine; N,N'-dimethyl-N,N'-di-
sec-butyl-p-phenylenediamine; diphenylamine; allyldiphenylamine; 4-
isopropoxydiphenylamine; -phenyl-1-naphthylamine; N-(4-tent-octylphenyl)-1-
naphthylamine; N-phenyl-2-naphthylamine; octylated diphenylamine such as p,p'-
di-
tert-octyldiphenyIamine; 4-n-butylaminophenol; 4-butyrylaminophenol; 4-
nonanoylaminophenol; 4-dodecanoylaminophenol; 4-octadecanoylaminophenol;
bis(4-methoxyphenyl)amine; 2,6-di-tert-butyl-4-dimethylaminomethylphenol; 2,4'-
diaminophenylmethane; 4,4'-diaminodiphenylmethane; N,N,N',N'-tetramethyl-4,4'-
diaminodiphenylmethane; 1,2-bis[(2-methylphenyl)amino]ethane; I,2-
bis(phenylamino)propane; (o-tolyl)biguanide; bis[4-(I',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
isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-
butyldiphenylamines; 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine;
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phenothiazine; a mixture of mono- and dialkylated tert-butyl/tert-o;,tyl
phenothiazines; a mixture of mono- and dialkylated tent-octylphenothiazines; N-
allylphenothiazine; N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene; N,N-
bis(2,2,6,6-
tetramethylpiperid-4-yl)hexamethylenediamine; bis(2,2,6,6-tetramethylpiperid-4-
yl)sebacate; 2,2,6,6-tetramethylpiperidin-4-one; and 2,2,6,6-
tetramethylpiperidin-4-
ol.
b. UV-absorbers and light stabilizers
(i) 2-(2'-Hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-S'-methylphenyl)-
benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2-(5'-
tent-butyl-
2'-hydroxyphenyl)benzotriazole; 2-(2'-hydroxy-5'-(1,1,3,3-
tetramethylbutyl)phenyI)benzotriazole; 2-(3',5'-di-tert-butyl-2'-
hydroxyphenyl)-5-
chlorobenzotriazole; 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'-octoxyphenyl)benzotriazole; 2-(3',5'-di-tert-amyl-2'-
hydroxphenyl)benzotriazole; 2-(3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl)-
benzotriazole; a mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-
(2-
ethylhexyloxy)-carbonylethyl]-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-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-
tert-
butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl}benzotriazole, 2-(3'-tert-
butyl-
S'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-
dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(3'-tert-butyl-2'-
hydroxy-S'-
(2-isooctyloxycarbonylethyl)phenylbenzotriazole; 2,2-methylenebis[4-(1,1,3,3-
tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product
of 2-[3'-
tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with
polyethylene glycol 300; and [R-CHZCH-COO(CHZ)3]z B where R = 3'-tert-butyl-4'-
hydroxy-S'-2H-benzotriazol-2-ylphenyl.
(ii) 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-
decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-
dimethoxy derivative.
(iii) Esters of substituted and unsubstituted benzoic acids such as 4-tert-
butyl-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,S-di-tert-butyl-4-hydroxybenzoate;
octadecyl
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3,5-di-tert-butyl-4-hydroxybenzoate; and 2-methyl-4,6-di-tert-butylphenyl 3,5-
di-
tert-butyl-4-hydroxybenzoate.
(iv) Acrylates such as ethyl a-cyano-(3,~3-diphenylacrylate; isooctyl a-cyano-
~3,(3-
diphenylacrylate; methyl a-carbomethoxycinnamate; methyl a-cyano-(i-methyl-p-
methoxycinnamate; butyl a-cyano-~i-methyl-p-methoxycinnamate; methyl a-
carbomethoxy-p-methoxycinnamate; and N-((3-carbomethoxy-~i-cyanovinyl)-2-
methylindoline. "
(v) Nickel compounds such as nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-
tetramethylbutyl)phenol], including 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
monoalkyl
esters including the methyl or ethyl ester of 4-hydroxy-3,5-di-tert-
butylbenzylphosphonic acid; nickel complexes of ketoximes including 2-hydroxy-
4-
methylphenyl undecyl ketoxime; and nickel complexes of 1-phenyl-4-lauroyl-5-
1 S hydroxypyrazole, with or without additional ligands.
(vi) Sterically hindered amines as well as the N derivatives thereof (e.g., N-
alkyl, N-
hydroxy, N-alkoxy and N-acyl), such as bis(2,2,6,6-tetramethylpiperidin-4-yl)
sebacate; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate; bis(1,2,2,6,6-
pentamethylpiperidin-4-yl)sebacate; bis( 1-octyloxy-2,2,6,6-
tetramethylpiperidin-4-
yl)sebacate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 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; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-
dichloro-1,3,5-triazine; tris(2,2,6,6-tetramethylpiperidin-4-yl)
nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)- 1,2,3,4-butanetetracarboxylate;
1,1'-(1,2-
ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4-benzoyl-2,2,6,6-
tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine;
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; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)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-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-
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1,3,5-triazine and l,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-
tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-1-(I-ethanoyl-
2,2,6,6-
tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-1-(1,2,2,6,6-
pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; a mixture of 4-hexadecyloxy-
and
4-stearyloxy-2,2,6,6-tetramethylpiperidine; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-
dichloro-1,3,5-triazine; the condensate of 1,2-bis(3-aminopropylamino)ethane,
2,4,6-
trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS
Reg.
No. [136504-96-6]); 2-undecyl-7,7,9,9-tetramethyl-I-oxa-3,8-diaza-4-
oxospiro[4.5]decane; oxo-piperanzinyl-triazines or so-called PIP-T HALS, e.g.,
GOODRITE~ 3034, 3150 and 3159 and similar materials disclosed in US5071981;
photobondable HALS such as SANDUVOR~ PR-31 and PR-32 (Clariant Corp.)
and similar materials disclosed in GB-A-2269819; and the reaction product of
IS 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]deeane
and
epichlorohydrin. See also generally US4619956, US5106891, GB-A-2269819, EP-
A-0309400, EP-A-0309401, EP-A-0309402 and EP-A-0434608.
{vii) Oxamides such as 4,4'-dioctyloxyoxanilide; 2,2'-diethoxyoxanilide; 2,2'-
dioctyloxy
5,5'-di-tert-butoxanilide; 2,2'-didodecyloxy-5,5'-di-tert-butyloxaniIide; 2-
ethoxy-2'
ethyloxanilide; N,N'-bis(3-dimethylaminopropyl)oxamide; 2-ethoxy-5-tert-butyl-
2'
ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-
butoxanilide; and
mixtures of o- and p-methoxy disubstituted oxanilides and mixtures of o- and p-
ethoxy disubstituted oxanilides.
(viii) 2-(2-Hydroxyphenyl)-1,3,5-triazines disclosed in the previously
incorporated
references, such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine; 2-
(2-
hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2-
hydroxy-4-(mixed iso-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-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2-hydroxy-
4-
octyloxyphenyl)-4,6-his(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-butyloxypropyloxy)phenylJ-4,6-bis(2,4-dimethylphenyl)-1,3,5-
triazine; 2-
[2-hydroxy-4-{2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine; 2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-
2-
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hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-[2-hydroxy-4-(2-
hydroxy-3-dodecyloxypropoxy)phenyl J-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-iris[2-hydroxy-4-(3-butoxy-2-
hydroxypropoxy)phenylJ-1,3,5-triazine; and 2-(2-hydroxyphenyl)-4-(4-
methoxyphenyl)-6-phenyl-1,3,5-triazine.
(c) Metal deactivators such as 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(salicyloyl)oxalyl dihydrazide; and N,N'-
bis(salicyIoyl)thiopropionyl dihydrazide.
(d) Phosphites and phosphonites, such as triphenyl phosphite; diphenyl alkyl
phosphites;
phenyl dialkyl phosphites; tris(nonylphenyl) phosphite; trilauryl phosphite;
trioctadecyl
1 S phosphitc; distcuryl pcntacrythritol diphosphitc; iris(2,4-di-tcrt-
butylphcnyl)phosphitc;
diisodecyl pentaerythritol diphosphite; bis(2,4,-di-tert-
butylphenyl)pentaerythritol
diphosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite;
bis(isodecyloxy}pentaerythritol diphosphite; bis(2,4-di-tert-butyl-6-
methylphenyl)pentaerythritol diphosphite; bis(2,4,6-iris(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-
dibenzo[d,gJ-1,3,2-
dioxaphosphocin; 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,gJ-
1,3,2-
dioxaphosphocin; bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite; and
bis(2,4-di-tert-
butyl-6-methylphenyl)ethylphosphite.
(e) Hydroxylamines such as N,N-dibenzylhydroxylamine; N,N-
diethylhydroxylamine; N,N-
dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-
ditetradecylhydrcxylamine; N,N-
dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine; N-hexadecyl-N-
octadecyl-
hydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N-
dialkylhydroxylamine
derived from hydrogenated tallow fatty amines.
(f) Nitrones such as N-benzyl-alpha-phenyl nitrone; N-ethyl-alpha-methyl
nitrone; N-octyl-
alpha-heptyl nitrone; N-lauryl-alpha-undecyl nitrone; N-tetradecyl-alpha-
tridecyl nitrone; N-
hexadecyl-alpha-pentadecyl nitrone; N-octadecyl-alpha-heptadecyl nitrone; N-
hexadecyl-
alpha-heptadecyl nitrone; N-octadeeyl-alpha-pentadecyl nitrone; N-heptadecyl-
alpha-
heptadecyl nitrone; N-octadecyl-alpha-hexadecyl nitrone; and nitrones derived
from N,N-
dialkylhydroxylamines prepared from hydrogenated tallow fatty amines.
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(g) T1110SynCr~IStS S11C11 as dilauryl thiodipropionatc and distcary)
thiodipropionatc.
(h) Peroxide scavengers such as esters of [3-thiodipropionic acid, for example
the lauryl,
stearyl, myristyl or tridecyl esters; mercaptobenzimidazole or the zinc salt
of 2-
mercaptobenzimidazole; zinc dibutyldithiocarbamate; dioctadecyl disulfide; and
pentacrythritol tetrakis((3-dodecylmercapto)propionate.
(i) Polyamide stabilizers such as copper salts in combination with iodides
and/or
phosphorus compounds and salts of divalent manganese.
(j) Basic co-stabilizers such as 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 palmitate; antimony pyrocatecholate; and tin pyrocatecholate.
{k) Nucleating agents including inorganic substances such as talc and metal
oxides (e.g.
titanium oxide or magnesium oxide) and phosphates, carbonates and sulfates of,
preferably,
1 S alkaline earth metals; organic compounds such as mono- or polycarboxylic
acids and salts
thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic
acid; sodium
succinate and sodium benzoate; and polymeric compounds such as ionic
copolymers
{e.g., ionomers).
(1) Fillers and reinforcing agents such as calcium carbonate; silicates; glass
fibers; asbestos;
talc; kaolin; mica; barium sulfate; metal oxides and hydroxides; carbon black;
graphite;
wood flour and flours or fibers from other natural products; and synthetic
fibers.
(m) Other additives such as plasticizers, lubricants, emulsifiers, pigments,
rheological
additives, catalysts, levelling assistants, optical brighteners, flameproofing
agents, antistatic
agents and blowing agents.
(n) Benzofuranones and indolinones such as those disclosed in US 4,325,863, US
4,338,244, US 5,175,312, US 5,216,052, US 5,252,643, DE-A-4316611, DE-A-
4316622,
DE-A-4316876, EP-A-0589839 and EP-A-0591102; 3-[4-(2-acetoxy-ethoxy)phenyl]-
5,7-di-
tert-butyl-benzofuran-2-one; 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)-
phenyl]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; and 5,7-di-
tert-butyl-3-
(3,4-dimethylphenyl)-3 H-benzofuran-2-one.
The novel benzocycle-substituted pyrimidines and triazines of the present
invention can also be employed in multilayer systems. In such systems, a
polymer
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WO 99/67225 PCT/US99/13708
composition having from about 0.1 to about 20% by weight and preferably a
relatively hil;h
cuntcnt ol'novcl stabilixcr, Ibr cxuntplc, about 5-IS'%. by weight, is applied
in a thin lilm
(e.g., about 5 - 500 p.m thick and, preferably, about 10 - I 00 pm thick) to a
shaped article
made from a polymer containing little or no ultraviolet stabilizers. Such
composition may
be applied at the same time as the shaping of the base structure, for example
by coextrusion
in a manner analogous to that described in United States Patent No. 4,948,666
(incorporated
by reference herein for all purposes as if fully set forth). Alternatively,
application can also ~r
be made to the ready-formed base structure, for example by lamination with a
film or by
coating with a solution. The outer layer or layers of the finished article
have the function of
a UV filter, which protects the interior of the article from UV light. The
outer layer
preferably contains about 0.1 to about 20%, preferably about 1 to about 1 S%,
and most
preferably about 2 to about 10% by weight of the outer layer composition, of
at least one of
the benzocycle-substituted pyrimidine or triazine compounds of the present
invention.
The polymers stabilized in this way are notable for high weathering
resistance, especially for high resistance to UV light. This enables them to
retain their
mechanical properties, and their color surface properties such as gloss and
distinctness of
image, for a long time even when used outside. Moreover, due to the bondable
nature of the
presently claimed triazine compounds, migration of these UV absorbers between
the layers
of the multi-layer coatings can, under the appropriate circumstances, be
minimized.
In another embodiment of the present invention, the novel mixtures
comprising compounds of the formula (I), (II), or (IV)-(IX) can be used as
stabilizers for
coatings, for example for paints such as disclosed in numerous references
(see, e.g., US
4,619,956, US 4,740,542, US 4,826,978, US 4,962,142, US 5,106,891, US
5,198,498, US
5,298,067, US 5,322,868, US 5,354,794, US 5,369,140, US 5,420,204, US
5,461,151, US
5,476,937, EP-0434608 and EP-A-0444323). Of particular interest are coatings
and paints
for the automobile industry. The invention therefore also relates to those
compositions
which are film-forming binders for coatings.
Such novel coating compositions comprise about 0.01 to about 20%,
preferably about 0.01 to about 10%, and more preferably about 0.02 to about S%
by weight
of the binder of the coating composition of the presently claimed benzocycle-
substituted
pyrimidines and triazines of the present invention.
Multilayer systems are possible here as well (such as
electrocoat/basecoat/clearcoat systems), where the concentration of the novel
stabilizer in
one or more of the layers, and typically the outer layer such as the
clearcoat, can be
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relatively high, for example from about 0.01 to about 20%, preferably about
0.01 to about
10%, and more preferably about 0.02 to about 5% by weight of binder.
The use of the novel stabilizer in coatings is accompanied by the additional
advantage that it prevents delamination, i.e. the flaking-off of the coating
from the substrate.
This advantage is particularly important in the case of metallic substrates,
including
multilayer systems on metallic substrates, and particularly epoxy e-coated
metallic
substrates.
The binder can in principle be any binder which is customary in industry, for
example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th
Edition,
Vol. A18, pp. 368-426, VCH, Weinheim 1991 which is incorporated herein by
reference. In
general, it is a film-forming binder based on a thermoplastic or curable
resin, predominantly
on a curable resin. Examples of thermoplastic binders include acrylics,
polyesters,
polyurethanes and PVC plastisols. Examples of curable binders include
functional alkyd,
acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and
mixtures thereof.
I S Such curable binders can be an ambient curable or a thermosetting binder.
Further, in some systems it may be advantageous to add a curing catalyst to
such systems.
Suitable catalysts which accelerate curing of the binder are described, for
example, in
Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, p. 469, VCH
Verlagsgesellschaft, Weinheim 1991. Preferred binders include those which
comprise a
functional acrylate resin and a crosslinking agent.
A wide variety of binders may be employed in such coating systems.
Examples of suitable coating compositions containing specific binders include
but are not
limited to:
1. paints based on ambient curable or thermosetting alkyd, acrylate,
polyester, epoxy or
melamine resins or mixtures of such resins, if desired with addition of a
curing catalyst;
2. two-component polyurethane paints based on hydroxyl-containing acrylate,
polyester
or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
3. one-component polyurethane paints based on blocked isocyanates,
isocyanurates or
polyisocyanates which are deblocked during baking;
4, two-component paints based on (poly)ketimines and aliphatic or aromatic
isocyanales, isocyanurates or poIyisocyanates;
5. two-component paints based on (poly)ketimines and an unsaturated acrylate
resin or
a polyacetoacetate resin or a methacrylamidoglycolate methyl ester;
6. two-component paints based on carboxyl- or amino-containing polyacrylates
and
polyepoxides;
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7. two-component paints based on acrylate resins containing anhydride groups
and on a
polyhydroxy or pUIya111111U COlllpOnellt;
8. two-component paints based on (poly)oxazolines and acrylate resins
containing
anhydride groups, or unsaturated acrylate resins, or aliphatic or aromatic
isocyanates,
.isocyanurates or polyisocyanates;
9. two-component paints based on unsaturated polyacrylates and polymalonates;
10. thermoplastic polyacrylate paints based on thermoplastic acrylate resins
or externally ~.
crosslinking acrylate resins in combination with etherified melamine resins;
1 I . paint systems based on siloxane-modified or fluorine-modified acrylate
resins.
In addition to the binder and novel benzocycle-substituted pyrimidines and
triazines of the present invention, the coating composition according to the
invention
preferably further comprise one or more additional ultraviolet light
absorbers, including but
not limited to those specifically listed above in section b. The additional UV
absorbers may
be, for example, another tris-aryl-1,3,5-triazine, a 2-hydroxyphenyl-2H-
benzotriazole, a
2-hydroxybenzophenone, an ester of an unsubstituted benzoic acid, an acrylate,
an oxamide
(oxanilide), or any combination of the above. Preferably, the additional UV
absorber is a
2-hydroxyphenyl-2H-benzotriazole and the weight ratio of benzotriazole to
triazine is 4:1 to
1:4. More preferably, the weight ratio is 2:1 to 1:2.
To achieve maximum light stability, it is of particular interest to add
sterically hindered amines, examples of which are set out in the above-
mentioned section
b(vi). The invention therefore also relates to a coating composition which, in
addition to the
binder, the novel benzocycle-substituted pyrimidines and triazines and,
optionally,
additional UV absorbers, comprises a light stabilizer of the sterically
hindered amine type.
The sterically hindered amine is employed in an amount of about 0.01 to S% by
weight
based on the weight of the solid binder, preferably about 0.02 to 2% by
weight.
One specific example of such a sterically hindered amine is a 2,2,6,6-
tetramethyl piperazinone containing at least one group of the formula:
O
-T1 N-J
in which J is, for example, hydrogen, hydroxyl, alkyl (such as methyl), alkoxy
(such as
methoxy) or acyl.
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More preferably the stabilizer is a 2,2,6,6-tetraalkylpiperidine derivative
containing at least one group of the formula:
S N-J
in which J is, for example, hydrogen, hydroxyl, alkyl (such as methyl), alkoxy
(such as
methoxy) or acyl.
Examples of tetraalkylpiperidine derivatives which can be used in
combination with the present trisaryl-1,3,5-triazine compounds are given in
United States
Patent Nos. 4,314,933, 4,344,876, 4,426,471, 4,426,472, 4,619,956, 5,004,770,
5,006,577,
5,064,883, 5,112,890, 5,124,378, 5,106,891, 5,204,473, and 5,461,1 S 1, which
are
incorporated by reference herein for all purposes as if fully set forth. It is
particularly
1 S expedient to employ the following tetraalkylpiperidine derivatives, as
well as their N-alkyl,
N-acyl, N-hydroxyl and N-alkoxy analogs (where not already included in the
following list):
bis(2,2,6,6-tetramethylpiperid-4-yl) succinate,
bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,
bis(1,2,2,6,6-pentamethylpiperid-4-y1) sebacate,
di(1,2,2,6,6-pentamethylpiperid-4-yl) butyl-(3,S-di-tert-butyl-4-
hydroxybenzyl)malonate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate, tetra(2,2,6,6-
tetramethylpiperid-4-
yl) butane-1,2,3,4-tetracarboxylate, tetra(1,2,2,6,6-pentamethylpiperid-4-yl)
butane-1,2,3,4-
tetracarboxylate, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.1
l.2Jheneicosane,
and 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.SJdecane-2,4-
dione.
2S Commercially available examples of these and other tetraalkylpipieridine
derivatives
include SANDUVOR~ 3050, 3052, 3055, 3056, 3058, PR-31 and PR-32 (Clariant
Corp.);
TINUVIN~ 079L, 123, 144, 292, 440L and 622LD (Ciba Specialty Chemicals);
CHIMASORB~ 119 and 944 (Ciba Specialty Chemicals); and CYASORB~ UV-3346, UV
3529, UV-3853, UV-500 and UV-516 (Cytec Industries Inc.).
Apart from the binder, the benzocycle-substituted pyrimidine or triazine, and,
if used, the additional ultraviolet light absorber or stabilizer, the coating
composition can
also comprise further components, examples being solvents, pigments, dyes,
plasticizers,
stabilizers, thixotropic agents, drying catalysts and/or leveling agents.
Examples of possible
components are those described in many of the previously incorporated
references as well as
3S Ullmann's Encyclopedia of Industrial Chemistry, Sth Edition, Vol. A18, pp.
429-471, VCH,
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WO 99/67225 PCT/US99/13708 '
Weinheim 1991; and Calbo, Leonard J., ed., Handbook of Coatings Additives, New
York:Marccl I~ckkcr (1987).
Possible drying catalysts or curing catalysts are, for example, organometallic
compounds, amines, acids, amino-containing resins and/or phosphines.
Examples of acid catalysts are mineral acids, aliphatic and aromatic sulfonic
acids (e.g. p-toluene sulfonic acid, dinonylnaphthalene disulfonic acid,
dodecylbenzene
sulfonic acid), oxalic acid, malefic acid, hexamic acid, phosphoric acid,
alkyl phosphate
esters, phthalic acid and acrylic acid copolymers.
Examples of organometallic compounds are metal carboxylates, especially
those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, especially
those of the metal
Al, It or Zr, or organometallic compounds such as organotin compounds, for
example.
Examples of metal carboxylates are the stearates of Pb, Mn or Zn, the octoates
of Co, Zn or
Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates
or tallates.
Examples of metal chelates are the aluminum, titanium or zirconium chelates of
acetylacetone, ethyl acetylacetate, salicylaldehyde, salicylaldoxime, o-
hydroxyacetophenone
or ethyl trifluoroacetylacetate and the alkoxides of these metals. Examples of
organotin
compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.
Examples of amine drying or curing catalysts are, in particular, tertiary
amines, for example tributylamine, triethanolamine, N-methyldiethanolamine, N-
dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or
diazabicyclooctane
(triethylenediamine) and salts thereof. Further examples are quaternary
ammonium salts, for
example trimethylbenzylammonium chloride. Amino-containing resins are
simultaneously
binder and curing catalyst. Examples thereof are amino-containing acrylate
copolymers.
The curing catalyst used can also be a phosphine, for example
triphenylphosphine.
Another type of curing catalyst is a peroxide which can be used, for example,
to cure a gel coating for a fiberglass article.
The novel coating compositions can also be radiation-curable coating
compositions. In this case, the binder essentially comprises monomeric or
oligomeric
compounds containing ethylenically unsaturated bonds, which after application
are cured by
actinic radiation, i.e. converted into a crosslinked, high molecular weight
form. Where the
system is UV-curing, it generally contains a photoinitiator as well.
Corresponding systems
are described in the above-mentioned publication Ullmann's Encyclopedia of
Industrial
Chemistry, 5th Edition, Vol. A18, pages 451-453. In radiation-curable coating
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WO 99/67225 PCT/US99113~08
compositions, the novel stabilizers can also be employed without the addition
of sterically
hindered amines.
The novel coating compositions according to the invention can be applied to
any desired substrates, for example to metal, wood, plastic, fiberglass or
ceramic materials.
The coating compositions can be pigmented mono-coats or mufti-layer
(primer/basecoat/clearcoat) systems typical of automotive finishes. In the
latter case, the
novel coating composition can be used for either the base coat, or clear coat,
or for both
layers. If the topcoat of an automotive finish comprises twa layers, of which
the lower layer
is pigmented and the upper layer is not pigmented, the nwcl coating
composition can he
used for either the upper or the lower layer or for both layers, but
preferably for the upper
topcoat layer.
The novel coating compositions can be applied to the substrates by the
customary methods, for example by brushing, spraying, pouring, dipping or
electrophoresis;
see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol.
A18, pp. 491-
500.
Depending on the binder system, the coatings can be cured at room
temperature or by heating. Thermosetting coatings are preferably cured at 50 -
150°C and,
in the case of powder coatings, even at higher temperatures.
The coatings obtained in accordance with the invention have excellent
resistance to the damaging effects of light, oxygen and heat; particular
mention should be
made of the good light stability and weathering resistance of the coatings
tins obtained, for
example paints.
The invention therefore also relates to a coating, in particular a paint,
which
has been stabilized against the damaging effects of light, oxygen and heat by
a content of the
compound of the formula (I), (II), or (IV)-(IX), according to the invention.
The paint can be
a pigmented mono-coat which comprises a film-forming binder and an organic
pigment or
dye, an inorganic pigment, a metallic pigment, or a mixture thereof. The paint
may also be a
composition which comprises a primer in adhesion to a metal or plastic
substrate; a
pigmented basecoat that is in adhesion to the primer and which comprises a
film-forming
binder and an organic pigment or dye, an inorganic pigment, a metallic
pigment, or a
mixture thereof; and a clear coat that is in adhesion to the base coat and
which comprises a
film-forming binder and optionally a transparent pigment. One especially
preferred use is a
paint which is a clear topcoat for automobile original equipment manufacture
(OEM) and/or
refinish applications.
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The invention furthermore relates to a process for stabilizing a coating based
on polymers against damage by light, oxygen and/or heat, which comprises
mixing with the
coating composition a mixture comprising a compound of a benzocycle-
substituted
pyrimidine or triazine and to the use of mixtures comprising benzocycle-
substituted
pyrimidine or triazine compound in coating compositions as stabilizers against
damage by
light, oxygen and/or heat.
The coating compositions can comprise an organic solvent or solvent mixture~~
in which the binder is soluble. The coating composition can otherwise be an
aqueous
solution or dispersion. The vehicle can also be a mixture of organic solvent
and water. The
I 0 coating composition maybe a high-solids paint or can be solvent-free (e.g.
a powder coating
material).
The pigments can be inorganic, organic or metallic pigments. The novel
coating compositions preferably contain no pigments and are used as a
clearcoat.
Likewise preferred is the use of the coating composition as a topcoat for
15 applications in the automobile industry, especially as a pigmented or
unpigmented topcoat
of the paint finish. Its use for underlying coats, however, is also possible.
The benzocycle-substituted pyrimidine or triazines of this invention may be
applied topically by polishing a surface with a composition comprising the
benzocycle-
substituted pyrimidine or triazines and an inert carrier such as solvent,
petroleum jelly,
20 silicone oil in water emulsions, or automotive paint wax, e.g. Carnauba
wax. These topical
treatment compositions may be used to stabilize coating films, fabrics,
leather, vinyl and
other plastics and wood.
Preference is also given to the use of the novel benzocycle-substituted
pyrimidine or triazine compounds in photographic materials as stabilizer
against damage by
25 light, especially by UV Iight. The invention therefore also relates to a
photographic material
comprising an benzocycle-substituted pyrimidine or triazine compound.
The compounds according to the invention can be used for photosensitive
materials of all kinds. For example, they can be employed for color paper,
color reversal
paper, direct-positive color material, color negative film, color positive
film, color reversal
30 film and other materials. They are preferably used, inter alia, for
photosensitive color
material which comprises a reversal substrate or which forms positives.
Furthermore, the novel compounds can be combined with other UV
absorbers, especially those which are dispersible in aqueous gelatin, for
example with
hydroxyphenylbenzotriazoles (cf. for example United States Patent Nos.
4,853,471,
35 4,973,702, 4,921,966 and 4,973,701), benzophenones, oxanilides,
cyanoacrylates,
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WO 99/67225 PCT/US99/13708
salicylates, or acrylonitriIes or thiazolines. In this context it is
advantageous to employ these
further, oil-dissolved UV absorbers in the photographic material in layers
other than those
comprising the novel UV absorbers.
The present invention also encompasses compositions containing one or
more binders. In particular, the binder may comprise an alkyd, acrylic,
polyester, phenolic,
melamine, epoxy or polyurethane resin, or blends thereof. Examples of such
binders
include, but are not limited to:
(a) cold- or hot-crosslinkable alkyd, acrylate, polyester, epoxy or melamine
resins or mixtures of such resins;
(b) a two-component polyurethane system comprising hydroxyl-containing
acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates,
isocyanurates or polyisocyanates;
(c) a one-component polyurethane system comprising blocked isocyanates,
isocyanurates or polyisocyanates which are deblocked during baking;
1 S (d) a two-component system comprising (poly)ketimines and aliphatic or
aromatic isocyanates, isocyanurates or polyisocyanates;
(e) a two-component system comprising (poly)ketimines and an unsaturated
acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate
methyl ester;
(f) a two-component system comprising carboxyl- or amino-containing
polyacrylates and polyepoxides;
(g) a two-component system comprising acrylate resins containing anhydride
groups and on a polyhydroxy or polyamino component;
(h) a two-component system comprising (poly)oxazolines and acrylate resins
containing anhydride groups, or unsaturated acrylate resins, or aliphatic or
aromatic isocyanates, isocyanurates or polyisocyanates;
(i) a two-component system comprising unsaturated polyacrylates and
polymalonates;
(j) a thermoplastic polyacrylate system comprising thermoplastic acrylate
resins
or externally crosslinking acrylate resins in combination with etherified
melamine resins; and
(k) a system comprising siloxane-modified or fluorine-modified acrylate
resins.
Such binder-containing compositions may further comprise a curing catalyst, or
an organic
solvent, and may be radiation-curable. In particular, such compositions may
serve as coating
compositions.
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In particular, it is possible successfully to stabilize photographic materials
similar to those described in United States Patent No. 4,S 18,686.
The invention therefore additionally relates to a photographic material
comprising, on support, a blue-sensitive, a green-sensitive and/or a red-
sensitive silver-
s halide emulsion layer and, if desired, a protective layer, with a layer
comprising a UV
absorber being arranged above the uppermost silver-halide emulsion layer,
wherein the UV
absorber is a benzocycle-substituted pyrimidine or triazine compound.
Preference is additionally given to photographic materials which have a layer
comprising a compound of the formula (I), (II), or (IV)-(IX) above the
uppermost silver-
halide emulsion layer and/or between the 'green- and red-sensitive silver-
halide emulsion
layers.
Furthermore, it may be advantageous for all or some of the said layers which
can comprise a UV absorber to have a UV absorber mixture and/or a further UV
absorber
which is dispersible in aqueous gelatin, but a compound of the formula (I),
(II), or (IV)-(IX)
1 S must be present at least in one layer.
The novel material preferably has gelatin interlayers between the silver-
halide emulsion layers.
Preference is given to photographic materials in which the silver halide in
the
blue-sensitive, green-sensitive and/or red-sensitive layer is silver chloride
bromide
comprising at least 90 mot % of silver chloride.
The compounds of the formula (I), (II), or (IV)-(IX), which are used in
accordance with the invention, can be incorporated, alone or together with the
color coupler
and, if used, further additives, into the color photographic materials by
dissolving the
compounds beforehand in high-boiling organic solvents. It is preferred to use
solvents
which boil at higher than 160°C. Typical examples of such solvents are
the esters of
phthalic acid, phosphoric acid, citric acid, benzoic acid or of fatty acids,
or alkylamides and
phenols.
Preferred color couplers for use in the compositions of the invention,
examples of such compounds, further additives such as color cast inhibitors,
DIR couplers
and further light stabilizers, such as UV absorbers, phenols, phosphorus (III)
compounds,
organometallic complexes, hydroquinones and hydroquinone ethers, and more
precise
details on the structure of various photographic materials, can be found, for
example, in the
publications EP-A-OS312S8 and EP-A-OS20938 and in the literature cited
therein.
3 S FILM
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The invention also relates to a process for the stabilization of polyolefin or
polyolefm copolymer films for agricultural applications, especially greenhouse
applications,
this polyolefin or polyolefin copolymer film having improved light stability
and pesticide
resistance, comprising incorporation of at least one benzocycle-substituted
pyrimidine or
triazine UV absorbers of the present invention, sterically hindered amines and
metal oxides
of hydroxides selected from the oxides of zinc, aluminum, calcium, and
magnesium and
hydroxides of zinc, aluminum, and calcium into the polyolefin or polyolefin
copolymer.
A further subject of the invention is a greenhouse, characterized in that it
is
covered by a polyolefin or polyolefin copolymer film having improved light
stability and
pesticide resistance and stabilized with a: at least one benzocycle-
substituted pyrimidine or
triazine UV absorbers of the present invention, sterically hindered amines and
metal oxides
of hydroxides selected from the oxides of zinc, aluminum, calcium, and
magnesium and
hydroxides of zinc, aluminum, and calcium.
Another subject of the invention is a process for stabilizing a polyolefin or
I 5 polyolefin copolymer greenhouse film against detrimental effects of
pesticides and light,
oxygen and/or heat, which process comprises incorporation of at least one
benzocycle-substituted pyrimidine or triazine UV absorbers of the present
invention,
sterically hindered amines and metal oxides of hydroxides selected from the
oxides of zinc,
aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, and calcium
into
said greenhouse film.
Further subjects of the invention are the use of a polyolefin copolymer film
stabilized with at least one benzocycle-substituted pyrimidine or triazine UV
absorbers of
the present invention, sterically hindered amines and metal axides of
hydroxides selected
from the oxides of zinc, aluminum, calcium, and magnesium and hydroxides of
zinc,
~5 aluminum, and calcium for the stabilization of polyolefin or polyolefin
copolymer films in
contact with pesticides against photodegradation and damage by pesticides.
To form a film, forcing a quantity of the said melted composition through a
film die, such as a flat film die or a circular blown film die, and forming a
film therefrom. In
the case where the composition is used to form a film therefrom, it is
contemplated that the
f lms may be unoriented, or may be subjected to a conventional operation to
impart a degree
of orientation on the film. Such a film may be oriented in one direction, such
as in the
machine direction, such as in the "machine direction" and/or the "transverse
direction", or
may be oriented in both directions, or "biaxially" oriented.
The present invention is also suitable for sheet applications.
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The benzocycle-substituted pyrimidine or triazine compounds of the formula
(I), (II), or (IV)-(IX) are suitable for the photochemical stabilization of
undyed, dyed or
printed fiber materials comprising for example, silk, leather, wool, polyamide
or
polyurethanes and especially cellulose-containing fiber materials of all
kinds. Examples of
such fiber materials are the natural cellulose fibers, such as cotton, linen,
jute and hemp and
also viscose staple fiber and regenerated cellulose. Preferred textile fiber
materials are those
of cotton. The triazine and pyrimidine compounds of the present invention are
also suitable "
for the photochemical stabilization of hydroxyl-containing fibers in blend
fabrics, for
example blends of cotton with polyester Iibcrs or polyamidc fibers. A further
preferred area
I 0 of application relates to the blocking or reduction of the UV radiation
which passes through
the above-mentioned textile materials (UV cutting) and the heightened sun
protection which
textile materials finished with a novel compound offer to the human skin.
To this end, one or a number of different compounds of the formula (I), (II),
or (IV)-(IX) are applied to the textile fiber material by one of the customary
dyeing methods,
1 S advantageously in a quantity of 0.01 to 5% by weight, preferably 0.1 to 3%
by weight and,
in particular, from 0.25 to 2% by weight, based on the weight of the fiber
material.
The benzocycle-substituted pyrimidine or triazine compounds can be applied
to the fiber material in various ways and fixed on the fiber, especially in
the form of aqueous
dispersions or printing pastes.
20 The textile fiber materials finished with the novel compounds of the
formula
(I), (II), or (IV)-(IX) possess improved protection against photochemical
breakdown of the
fiber and yellowing phenomena and, in the case of dyed fibre material, are of
enhanced (hot)
light fastness. Particular emphasis should be drawn to the greatly improved
photoprotective
effect of the treated textile fiber material and, in particular, the good
protective effect with
25 respect to short-wave UV-B rays. This is manifested by the fact that the
textile fiber
material finished with an benzocycle-substituted pyrimidine or triazine
compound has,
relative to untreated fabric, a greatly increased sun protection factor
(SPF)..
The sun protection factor is defined as the quotient of the dose of UV
radiation which damages protected skin to that which damages unprotected skin.
30 Accordingly, a sun protection factor is also a measure of the extent to
which untreated fiber
materials and fiber materials treated with a novel compound of the formula
(I), (II), or
(IV)-(IX) are permeable to UV radiation. The determination of the sun
protection factor of
textile fiber materials is explained, for example, in W094/04515 or in J. Soc.
Cosmet.
Chem. 40, 127-133 (1989) and can be carried out analogously thereto.
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Yet another use of the UV absorbers according to the invention is in the
stabilization of intra-ocular and contact lenses.
The inventive UV absorbers are suitable as photoprotective agents in
cosmetic preparations. The invention additionally relates, therefore, to a
cosmetic
preparation comprising at least one benzocycle-substituted pyrimidine or
triazine compound
and cosmetically acceptable carriers or auxiliaries.
The novel cosmetic composition contains from 0.1 to 15% by weight,
preferably from 0.5 to 10% by weight, based on the overall weight of the
composition, of a
benzocycle-substituted pyrimidine or triazine UV absorber and a cosmetically
acceptable
auxiliary.
The cosmetic composition can be prepared by physically mixing the novel
UV absorber with the auxiliary by means of customary methods, for example by
simply
stirring together the two materials.
The cosmetic preparation according to the invention can be formulated as a
water-in-oil or oil-in-water emulsion, as an oil-in-oil alcohol lotion, as a
vesicular dispersion
of an ionic or nonionic amphiphilic lipid, as a gel, solid stick or as an
aerosol formulation:
As a water-in-oil or oil-in-water emulsion, the cosmetically acceptable
auxiliary preferably contains from 5 to 50% of an oily phase, from 5 to 20% of
an emulsifier
and from 30 to 90% water. The oil phase can comprise any oil which is suitable
for
cosmetic formulations, e.g., one or more hydrocarbon oils, a wax, a natural
oil, a silicone
oil, a fatty acid ester or a fatty alcohol. Preferred mono- or polyols are
ethanol, isopropanol,
propylene glycol, hexylene glycol, glycerol and sorbitol.
For these cosmetic formulations, it is possible to use any conventionally
employed emulsifier, e.g., one or more ethoxylated esters of naturally
occurring derivatives,
i.e., polyethoxylated esters of hydrogenated castor oil; or a silicone oil
emulsifier such as
silicone polyol; an unmodified or ethoxylated fatty acid soap; an ethoxylated
fatty alcohol;
an unmodif ed or ethoxylated sorbitan ester; an ethoxylated fatty acid; or an
ethoxylated
glyceride.
The cosmetic formulation can also comprise further components, for example
emollients, emulsion stabilizers, skin moisteners, tanning accelerators,
thickeners such as
xanthan, moisture retention agents such as glycerol, preservatives, or li-
agrances and
colorants.
The novel cosmetic formulations are notable for good protection of human
skin against the damaging effect of sunlight while at the same time providing
for reliable
tanning of the skin.
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The invention will now be illustrated by the following examples. The
examples arc not intcnclcd to be limiting oflhe scope ol'thc present
invention. In
conjunction with the general and detailed descriptions above, the examples
provide further
understanding of the present invention.
EXAMPLES
Examples and reaction schemes for producing specific examples of
benzocycle substituted triazines in accordance with the invention are provided
below.
While the following examples illustrate preparations with one or more tetralin
benzocylcs,
one of ordinary skill will understand that these reactions may also be carried
out with any of
a variety of other benzocycles, where when necessary, reactive substituents on
such other
benzocycles are protected in accordance with procedures and reagents well
known and
understood by those of ordinary skill.
PREPARATIVE EXAMPLES
Example 1: Reaction of Cvanuric Chloride with Tetralim Use of Tetralin as
Solvent
CI
N'~N ; o
~o~
cl N cl
AICI3
NO~N
CI"N' 'CI
C
To a reaction flask equipped with a reflux condenser, an argon inlet, a
magnetic stirring bar and a glass stopper was added 100 mL of tetralin and 9.2
g of cyanuric
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chloride. To the resulting solution was added 10 g of anhydrous AIC13 over a
period of 10
minuies at 0°C. After the addition was over, the reaction mixture was
heated in an oil bath
at 40°C for 16 hours. The heating was discontinued and the reaction
mixture was cooled in
an ice bath and treated with ice-cold water. The reaction mixture was then
extracted with
methylene chloride and the organic layer dried over anhydrous sodium sulfate
and
concentrated to remove volatiles. The residue was treated with methanol
affording a
precipitate which was filtered, washed with methanol and dried to give 12.4 g
of the
product. The NMR and mass analysis of the product showed it to consist of a
mixture of
monotetralin-bischloro-triazine (Compound A), bistetralin-monochloro-triazine
(Compound
B) and tristetralin-triazine (Compound C).
Exam le 1 Alternate Procedure: Use of Monochlorobenzene as Solvent
A mixture of 47.7 g (0.256 mole) of cyanuric chloride and 67.6 g (0.507 mot}
of aluminum chloride in 360 mL of chlorobenzene under nitrogen was heated to
40°C.
Tetralin (68 mL, 0.500 mole) was added over the course of two hr. During this
time the
temperature increased to 50°C. The temperature was maintained at
50°C until an exotherm
occurred.
After the exotherm had subsided, 200 mL of 10% aqueous HCI was added
drop-wise such that the temperature was maintained below SO°C. The
resulting mixture was
filtered. The aqueous layer from the filtrate was extracted with methylene
chloride. The
combined organic layers were washed with water, dried over anhydrous magnesium
sulfate,
and treated with activated carbon. After filtration, the filtrate was
concentrated in vacuo.
The residue was taken up in 300 mL of tetrahydrofuran, and cooled to
0°C. The precipitate
was removed by filtration. The f Itrate was concentrated in vacuo to give an
oil which
slowly crystallized to a dark yellow to brown solid, which cantained P-4036
(50 - 70 area
by HPLC) plus tris-tetralin triazine and unreacted cyanuric chloride.
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Example 2: Bistetralin-monoresorcinol triazine (Compound D)
O
Exam le AICI3
p ~ product mixture
Chlorobenzene NO OH
'N \~~ H
O
A mixture of 132.3 g of the product of Example 1 Alternate Procedure
(Compound B) and 38.7 g of resorcinol in 300 mL of chlorobenzene was heated to
60°C.
Aluminum chloride (61.0 g) was added over a 2 hr. during which time the
temperature
increased to 80°C. The mixture has held at 80°C for an
additional 2 hr.
After cooling to 60°C, the reaction mixture was poured into 400 mL
of ice
water. The mixture was concentrated in vacuo. The residue was triturated with
400 mL of
water, and the resulting slurry was filtered. The solid was air-dried and then
dried in vacuo.
A SoxhIet extraction of the solid was done with refluxing chloroform. A solid
precipitated
from the chloroform extract. The solid was filtered, washed with cold
chloroform, and dried
to give Compound D as a light yellow powder in >92% purity by HPLC.
Example 3 ~ Bistetralin-(monoresorcinol-4-O-octyl) triazine derivative
(Compound E)
lodooctane
K2C03; acetone
reflux; a hr.
E
A mixture of 400 mg of the product of Example 2 (Compound D), 1.38 g of
anhydrous potassium carbonate, 0.2 mL of 1-iodooctane and 10 mL of acetone was
heated
to reflux for 24 hours. The reaction mixture was then cooled to room
temperature and
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diluted with methylene chloride. The resulting mixture was filtered through
Celite, and /
concentrated to dryness to give 422 mg of a crude product. The crude product
was purified
by column chromatography over silica gel to give a pure compound which was
identified to
be the bistetralin-(monoresorcinol-4-O-octyl)-triazine derivative (Compound E)
by NMR
and mass spectra.
Example 4: Monotetralin-bisresorcinol-triazine Com ound G .
O OH
AICI3
NON O Chlorobenzene~ OH N N OH
~ ~ OH
CI"N' \CI
HO
G
To a 3-necked 250-mL round bottomed flask was charged with 14.0 g of
monotetralin-bischloro-triazine (Compound F), I 1.56 g of resorcinol, and 130
mL of
chlorobenzene and then purged with nitrogen. Into the solids addition funnel
was placed
I 8.76 g of anhydrous aluminum chloride. The solution was heated to
49°C and addition of
aluminum chloride was begun in portions. The aluminum chloride was added over
the
course of two hours and the temperature allowed to slowly climb to 65
°C. The reaction
mixture was then heated to 90-95 °C and held in that range for 3 hours.
The mixture was a
dark red slurry at this point.
At the end of the reaction period, the heat was removed and the temperature
allowed to fall to about 60°C. The attachments were then removed from
the reaction flask
and the mixture was poured into 200 mL of cold water. The mixture was shaken,
discharging the red color and leaving a yellow emulsion. When this had cooled
completely,
it was transferred to a round bottomed task and the chlorobenzene-water
azeotrope was
removed on a rotary evaporator until no further chlorobenzene was observed in
the
condensate. The resultant light yellow slurry was filtered, washed with water
and dried in
vacuo to give the desired product (Compound G).
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Example 5: Preparation of Compounds H and 1
OH NON OH ,
'N
HO ~ '~~nN
15
C8Hi71: KZC03;
Acetone; reflux
CBH»O
CBH»(
I
A mixture of 4.27 g of Compound G, 5.28 g of 1-iodooctane, 6.9 g of
anhydrous potassium carbonate, 0.5 g of Aliquat 336 and 50 mL of acetone was
heated to
reflux for 20 hr. At this stage additional 1 mL of 1-iodooctane and 3.5 g of
anhydrous
potassium carbonate were added and the refluxing was continued for an
additional 8 hr. A
TLC analysis at this stage showed almost complete disappearance of Compound G
and
formation of two new products. The reaction mixture was allowed to cool to
room
temperature, diluted with methylene chloride and filtered through Celite. The
filtrate was
concentrated under reduced pressure to give a crude product which consisted of
compounds
H and 1 as analyzed by NMR and mass spectra. The mixture is separable by
column
chromatography over silica gel.
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Exam le 6: Pre aration of 4- 2-h dox eth I ether of Bis-Tetralin-mono-
Resorcinol
Triazine ~Comnound J)
OH , CICH2CHZOH ~ NON OH
0 ~N O
H CH~ZOH
A mixture of 10.0 g of bis-tetralin-mono-resorcinol triazine (Compound D),
130 mL of DMF, 2.6 g of anhydrous sodium carbonate, 0.25 g of potassium
iodide, 0.88 g
of PEG-400 (polyethylene glycol), and 7.5 g of 2-chloroethanol was heated to
120 °C for 1 S
hr. After the f rst 9 hr, an additional 2.5 g of 2-chloroethanol was added and
heating was
continued. After completion of the reaction, the mixture was poured into 300
mL of ice
water. The precipitated solids were filtered, washed with water, and dried.
HPLC and
NMR analyses indicated that Compound J was obtained in >90% purity.
Triazine ~Comnound Kl
D
. CI(CHy)gOH ----w
K
A mixture of 10 g of bis-tetralin-mono-resorcinol triazine (Compound D,
0.02 mole) and 80 mL of MIBK was heated to 90°C. Sodium hydroxide 1.0 g
(0.031 mole)
was slowly added, resulting in a nearly clear solution. Then 0.25 g (0.0015
mole) of
potassium iodide and 0.88 g of PEG-400 (polyethylene glycol, approx. 0.0022
mole) were
added. After the solution again became clear, 5.7 g (0.031 mole) of 6-
chlorohexanol were
added. The mixture was heated at 107-11 I °C for 18 hr. The mixture was
then washed
3~ with 1 N HCl and with water. The resulting solution was dried over
magnesium sulfate,
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filtered and cooled to O°C. The resulting pale yellow solid was
fltered, dried. HPLC and
NMR analyses indicated that the Compound K was obtained in >90% purity.
Exam le 8: Pre aration of 4-L.auro 1 Ester Derivative of Bis-Tetralin-mono-
Resorcinol
Triazine lCom~pou_nd Ll
. CH3(CH?yoCOG --.
lU
D L
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene
were added I I .0 mL of lauroyl chloride (Aldrich) and 10 mL of ortho-
dichlorobenzene. The
15 stirred mixture was heated at 150°C for 9 hr . The mixture was then
cooled to 100°C and
200 mL of ethanol were added. The resulting precipitate was filtered, washed
with ethanol,
and allowed to air affording 21.3 g of Compound L as a pale yellow solid.
The solid was dissolved in 50 mL of hot toluene. The slurry was warmed in
a water bath until all of the solid dissolved. Methanol (300 mL) was added to
the mixture
20 maintained at reflux temperature. The solution was then cooled to room
temperature. The
resulting solid was filtered, washed with several portions of methanol, and
dried in vacuo to
give 20.25 g of the title compound as a pale yellow solid.
25 Triazine (Compound M)
30 ~ CH3(CHy)4COCI s
D
M
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene were
added 8 mL of hexanoyl chloride (Aldrich) and 10 mL of ortho-dichlorobenzene.
The
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stirred mixture was heated at 150°C for 12.5 hr. The product was
isolated by the procedure
of Example 9 to give 14.1 g of the Compound M as a pale yellow solid.
Example 10: Preparation of 4-Octanovl Fster Derivative of Bis Tetralin mono
Resorcinol
Tnaztne (Compound Nl
. CH3(CH2)sCOCI --
N
To a mixture of 20 g of Compound D and 80 mL of artho-dichlorobenzene
were added 8 mL of octanoyl chloride (Aldrich) and 10 mL of ortho-
dichlorobenzene. The
stirred mixture was heated at 150°C for 23.5 hr. The product was
isolated by the procedure
of Example 2 to give 17.8 g of the Compound N as a pale yellow solid.
Example 11: 4-(2-Ethylhexanoyl) Ester Derivative of Bis Tetralin mono
~tesorcmol
Triazme (Compound 07
Et
CH3(CHz)3~HCOCi -----.
D
O
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene
were added 8 mL of 2-ethylhexanoyl chloride (Aldrich) and 10 mL of ortho-
dichlorobenzene. The stirred mixture was heated at 150°C for 20 hr. The
mixture was then
cooled to 100°C and 200 mL of ethanol was added. Upon cooling to
0°C overnight an oil
precipitated. The supernatant was decanted off. The oil was dissolved in a
refluxing
hexanes-toluene mixture, and then cooled to 0°C. The resulting solid
was filtered, washed
with methanol, and air dried to give 21.4 g of a pale yellow solid. The solid
was
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Example 12: 4-(3 S S-trimethvlhexanovl) Ester Derivative of Bis Tetralir mono
Resorcinol
S Tr~azme (Compound P)
D
To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzene
were added 9 mL of 3,S,S-trimethylhexanoyl chloride (Aldrich) and 10 mL of
ortho-
1 S dichlorobenzene. The stirred mixture was heated at 1 SO °C for 7
hr. The mixture was then
cooled to 100°C and 200 mL of ethanol was added. Upon cooling to
0°C overnight, an oil
precipitated. The supernatant was decanted off. The oil was washed with five 1
SO mL
portions of methanol and dried in vacuo. The resulting glass was
recrystallized twice from
hexanes to give 13.1 g of the Compound P as a pale yellow solid.
Exam le 13: Pre aration of 2- 2-h drox -4-ethox carbon lmethox hen 1 -4 6-
bis(tretralin)-1 3 S-triazine (Compound O)
2S
WO 99/67225 PCT/US99/13708
recrystallized from hexanes-toluene, filtered, washed with methanol, and dried
in vacuo to
givc 15.8 g of Compound O as a pale yellow solid.
O
Me
NO
OH . (CH~)~CCH~CHCHZCOCI
OH
P
CICHyCOzCZHS
3a
D
Q
To a mixture of 9 g of Compound D, 6.9 g of anhydrous potassium
carbonate, 0.3 g of potassium iodide and SO mL of acetone was added 2.4 mL
(2.7 g) of
ethyl chloroacetate. The mixture was stirred at reflux for six hours. HPLC
analysis
indicated full conversion of Compound D. After cooling, the mixture was
diluted with 100
3S mL of methylene chloride and filtered through a bed of diatomaceous earth,
which was
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washed with an additional SO mL of methylene chloride. The combined filtrates
were
concentrated in vacuo. The product was recrystallized from ethyl acetate and
dried in vacuo
to give 8.4 g of Compound Q as a near white solid in 94% purity (HPLC area %
at 290 nm).
The structure was verified by'3C and'H-NMR spectroscopy.
Exam le 14: Pre aration of 2- 2-h drox -4- - n-bu 1 -N- 2-h drox eth 1 -
methanamidoox hen 1 -4 6-bis tetralin -1 3 5-triazine 'Com ound R
~CONHC2H,,OH
C~Ha
4 CZH~OH
R
A mixture of S g of Compound Q, 1.66 g of butyl ethanolamine, 0.12 g of
4-dimethylaminopyridine, and 30 mL of xylenes was stirred at reflux. After 26
hr, 2 g of
butyl ethanolamine was added. After 48 hr, HPLC analysis showed 99.5%
conversion of
Compound P (area % at 290 nm). The mixture was allowed to cool. The
precipitated solids
were diluted with 175 mL of hexanes and stirred for 3 hr. The mixture was f
ltered and the
collected solid was air dried. The solid was stirred with 150 mL of methanol
for several
hours, filtered, washed with methanol, and dried in vacuo to give 5 g of
Compound R as a
white solid in 96% purity (HPLC area % at 290 nm). The structure was verified
by '3C and
'H-NMR spectroscopy.
ester tCompound S)
C3H~SOpCI
-~~---i~
H
p 02CaH~
S
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To a stirred mixture of I 1.6 g of Compound D, 9 g of anhydrous potassium
carbonate, and 100 mL o!'tetrahydrofuran ('f1-IF), cooled to 4°C was
added a solution of
3. I 5 mL of propanesulfonyl chloride in 30 mL of THF over 22 min. The
resulting mixture
was stirred for 40 hr at room temperature. An additional 1 mL of
propanesulfonyl chloride
was added, and the mixture was stirred for 24 hr. HPLC analysis showed
complete
conversion of starting material. The solids were removed by filtration and the
product was
crystallized from the filtrate. The filtered solids were extracted with
chloroform, and the '
chloroform was removed in vacuo to afford additional product. The combined
yield was
8.5 g. Recrystallization from ethyl acetate afforded Compound S in 99% purity
as
I 0 determined by HPLC (area % at 290 nm). The structure was verified by IR,
'3C, and
'H-NMR spectroscopy.
Exam le I 6: Pre aration of bis-tetralin-mono-resorcinol triazine 4-O- hen
lsulfonate ester
(Compound T~
IS
( ( ) }-so2ci
20 °s°2 0
D
T
To a mixture of 15 g of Compound D, 13.8 g of anhydrous potassium
carbonate and 100 mL of tetrahydrofuran, cooled to 4 °C, was added a
solution of 5.2 mL
25 (7, I g) of benzenesulfonyl chloride in 30 mL of THF over 37 minutes. The
resulting
mixture was allowed to warm to room temperature and stirred for 19 hr. An
additional 1
mL of benzenesuIfonyl chloride was added, and the mixture was stirred for 3
hr. Methanol
(5 mL) was added. The mixture was filtered, and the solids washed with THF.
The product was crystallized from the combined filtrates, filtered, and dried.
30 Compound T (11.3 g) was obtained as a white solid by recrystallization from
chlorofomz/hexanes (1:3 v/v). HPLC analysis showed 99% purity (area at 290
nm). The
structure was verified by'3C and'H-NMR spectroscopy.
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Exam le 17: Pre aration of monotetralin-monoresorcinol-monochlor~-1 3 5-
tria~ine
lCompound Ul
S
OH
AIC13
1 1 Chlorobenzene
N N
CI~~~ + ~ OH ,.
CI
°~ CI
F
U
To a stirring mixture of 2.8 g of monotetralin-bischloro-I,3,5-triazine
(Compound F), 1 g of resorcinol, and 25 mL of chlorobenzene was added 1.34 g
of
aluminum chloride at ice-bath temperature. The reaction mixture was allowed to
warm to
1 S °C and stirred for 3 hr. The reaction mixture was then allowed to
warm to room
temperature and stirred for 20 hr. The reaction mixture was quenched with ice-
cold 2%
aqueous hydrochloric acid. A precipitate formed, whcih was collected by
filtration, washed
with water, and dried. The precipitate was analyzed by thin layer
chromatography (TLC),
HPLC, and mass spectroscopy, which identified Compound U as the major product.
Example 18: Preparation of a hindered phenol adduct of
bistetralin-monoresorcinol-I 3 S-triazine Com ound V
off
K2C1
ClCHz
~ I
V CHz
'OH
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To a stirnng mixture of 2.25 g of compound D, 2.76 g of anhydrous
potassium carbonate, and SO mL ofacctonc was added 1.24 g ol'3-chloromcthyl-
2,4-
dimethyl-6-tert-butylphenol, 1 SO mg of sodium iodide and 250 mg of Aliquat~
336
(triscaprylmethylarrimonium chloride). The reaction mixture was heated to
reflux for 3 hr.
No starting material and only one major product was detec#ed using ThC and I-
IPLC
analysis. The reaction mixture was allowed to cool to room temperature,
diluted with 50
mL of methylene chloride, and filtered through Celite~ brand filter agent. The
filtrate was "
concentrated under reduced pressure. The residue was dissolve in 100 mL of
methylene
chloride, washed with water, dried over anhydrous sodium sulfate, and
concentrated to
dryness to give Compound V, which was analyzed by mass spectroscopy.
Example 19' Preparation of hindered phenol adducts of
monotetralin-bisresorcinol-1 3 5-triazine Com ounds W and X
OH
K2C03 ; MlBK
CICHy ~ ~OR~
G ..~ ~ ~OR
W and X
OH
R~=H;R=
~-c~h
OH
R=Rt=
CHZ
To a stirring mixture of 2.14 g of Compound ti, 5.5 g of anhydrous
potassium carbonate, and 40 mL of MIBK was added 2.49 g of 3-chloromethyl-2,4-
dimethyl-6-tert-butylphenol, 150 mg of sodium iodide, and 250 mg of Aliquat~
336. The
reaction mixture was heated to reflux for 8 hr. After 8 hr, TLC analysis
showed almost no
starting material. The reaction mixture was allowed to cool to room
temperature, diluted
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with methylene chloride, and filtered through Celite~ brand filter agent. The
filtrate was
concentrated under reduce pressure, to give a mixture of C'.ompounds W and X
as
determined by TLC.
Exam le 20: Pre aration of 2 4-bistetralin-6- 2 4-dih drox -3-diall laminometh
1 -l 3 5-
triazine (Compound Yl
HN + HCHO -
CHz-N
OH
D
Y
1 S To a stirring suspension of 2.2.5 g of Compound D in 50 mL of toluene was
added 3 mL of diallylamine and S mL of aqueous formaldehyde. The reaction
mixture was
heated to reflux for 4 hr. After 4 hr, TLC analysis detected almost no
starting material and
the formation of one major product. The reaction mixture was allowed to cool
to room
temperature and concentrated under reduced pressure. The residue was dissolved
in 100 mL
of methylene chloride, washed with water, dried over anhydrous sodium sulfate,
and
concentrated under reduce pressure to give Compound X, which was analyzed by
mass
spectroscopy.
Exam le 21: Pre aration of bis-tetralin-mono-resorcinol-1 3 5-triazine dimes
~omno.Tun
I(CHz),
D
Z
To a mixture of 10 g of Compound D, 12.2 g of anhydrous potassium
carbonate, 3.9 g of 1,5-diiodopentane, a catalytic amount of Aliquat~ 336, and
60 mL of
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dioxane was stirred at reflux for 24 hr. HPLC analysis indicated full
conversion of
compound D. After cooling, the mixture was diluted with I 50 mL of methylene
chloride
and filtered through a bed of diatomaceous earth. The f ltrate was
concentrated under
reduced pressure to give compound U.
PERFORMANCE TESTING EXAMPLES
Example 22'
3% Toluene solutions of the stabilizers were prepared. The colors of these
solutions were measured in a 1-cm cell using a Byk-Gardner Liquid Color
Spectrophotometer. As can be seen from Table I, tetralin triazine UV absorbers
Compound E and Compound J have lower color than Tinuvin I 577, a current art
triazine
UV absorber.
Table I. Color Values Of 3% Toluene Solutions Of Stabilizers
Stabilizer APHA Color Gardner Color CIE b value
Tinuvin 1577 485 3 17.1
Compound E 364 2 13.2
Compound O 218
1 7.9
Example 23
Thermogravimetric analysis was carried out. Duplicate specimens were
heated in a Perkin-Elmer 7 Series thermobalance from 30 - 500°C at
10°C/ min in both air.
The purge gas flow rate was ~25 mL/min. Compound E was com aced a ai
p g nst the mayor
current art stabilizers for polycarbonate. As can be seen from Table II,
Compound E is
significantly less volatile than Tinuvin 1577, a current art stabilizer. (T-
10% and T-20% are
the temperatures at which 10% and 20%, respectively, of weight loss occurs
during the
above heating protocol.)
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TABLE II. Thermogravimetric Data
Stabilizer T-10% (C) 'f-20% (C)
Tinuvin 1577 346 363
Tinuvin 234 310 331
Mixxim BB/100 359 382 .
Compound E 419 440
Example 24:
Polycarbonate plaques were prepared as follows. GE Lexan 105 barefoot
natural flake polycarbonate resin (melt temperature 310 - 333 °C) was
dry blended with
0.35% stabilizer plus 0.10 wt% Mark~ 2112 phosphite. The blended compositions
were
1 S melt-mixed and extruded in a Haake torque rheometer equipped with a a 0.75-
inch 25 : 1
single mixing screw extruder. The zone temperatures were 246, 265, 295, and
304°C. The
extruded polycarbonate was pulled through a water bath, dried, pelletized, and
redried at
120°C for 4 - 48 hr in a forced air oven. The pellets were injection
molded at 340°C with
a 40 second dwell time using an Arburg "Allrounder" hydraulic injection molder
to form 2 x
2.5 x 0.100-inch plaques. The mold temperature was 100°C., The
injection barrel
temperature of 340°C was selected to simulate extremely harsh
conditions. Yellow indices
and delta E data were obtained using a Macbeth Color Eye Colorimeter wi~h
illuminate C,
2 ° observer, specular component excluded, and UV component included.
As can be seen
from Table III, Compound E is more resistant to thermal yellowing than Tinuvin
1577, a
current art triazine UV absorber.
TABLE III: Color Of Stabilized Polycarbonate Plaques Injection Molded At
340°C
I Stabilizer I Yellow Index l
I Tinuvin 1577 I 14.5
Compound E I 1 I .9
Example 25
Stabilized polycarbonate plaques were prepared as in Example 3 with the
exception that the injection molding temperatures were lower. The temperatures
were:
nozzle - 305°C; nozzle side - 310°C; middle - 300°C; and
feed - 290°C. The plaques
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were subjected to 18 days of oven aging at 100°C. As can be seen from
Table IV,
Compound E inhibits thermal yellowing of polycarbonate and has performance
equal or
better than current art triazine UV absorbers Tinuvin 1577 and UV-1164.
Table IV. Oven Aging of Stabilized Potycarbonate Compositions at
100°C
Stabilizer Delta E, 7 days Delta E, 18 days ,
None I 0.4 I .1
Compound E 0.5 0.4
I0 Tinuvin 1577 0.5 0 S
UV-1 I 64 0.4 0.6
Example 26:
I 5 Stabilized polycarbonate plaques were prepared as in Example 4. They were
exposed in a xenon-arc WeatherOmeter following ASTM G-26 using; Test Method B
(Miami, Fla. conditions). The conditions were an irradiance of 0.35 W/m2 at
340 nm,
alternating cycles of light and darkness, intermittent water spray, and a
black panel
temperature of 63 ~ 3 °C. Delta E (total color change) was measured
after 400 hr. of
20 exposure. The results, summarized in Table V show that Compound E is more
effective in
reducing total color change than current art stabilizers Tinuvin I 577 and
Tinuvin 234.
Table V. Accelerated Weathering of Stabilized Polycarbonate Compositions
Stabilizer Delta E
25 None
5.3
Compound E I 0.6
Tinuvin 234 I 0.9
I Tinuvin 1577 ' 1.0
Example 27: Stabilized Coatin ~''~mposition~
Stabilized clear acrylic melamine compositions were prepared and coated
onto steel panels for accelerated weathering testing as follows. Compound E
(2% based on
total resin solids) was pre-dissolved in xylenes, alone and in combination
with Sanduvor~
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WO 99/67225 PCT/US99/13708
3058 HALS (0.67% or 1.0% based on total resin solids), and added to the clear
acrylic
melamine formulation given in Table VI. Steel panels pre-coated with EDSOSOA E-
coat,
764204 primer, and 542DF716 white base-coat and measuring 4" x 12" were
obtained from
ACT Laboratories, Inc. (Hillsdale, Michigan). The panels were coated with the
clear coat
formulations using the draw-down technique (WC-52 Wire-CatorsTM obtained from
Leneta
Co., Ho-Ho-Kus, N.J.). The clear coats were allowed to flash for 10 min. at
ambient
temperature and cured for 30 min. at 135°C.
Table VI. Acrylic Melamine Clear Coat Formulation
Material Amount
Doresco~ TA 39-14 acrylic resin 81.25 g
Cymel~ 303 cross-linker 35.0 g
Cycat~ 4040 catalyst 1.0 g
n-Butanol 20.0 g
Xylene 16.0 g
UV Absorber 0.364 ga
Sanduvor~ 3058b 0.182 gh
a) Amount for 2% based on total resin solids
b) Amount for 1 % based on total resin solids
Accelerated weathering is carried out with a QUV following ASTM G53
(GM cycle), which is weathering under alternate cycles of (i) UV light at 70 C
for 8 hours
and (ii) condensation with no UV light at 50 C for 4 hr. Specular properties
(gloss and
distinctness of image, or DOI) are measured as a function of weathering time.
Compositions
containing either Compound E or Compound J both have improved gloss and DOI
retention
relative to the unstabilized control. Compositions containing HALS S-3058 in
addition to
Compound E or Compound J also exhibit improved gloss and DOI retention.
Although the present invention is described with reference to certain
preferred
embodiments, it is apparent that modifications and variations thereof may be
made by those
skilled in the art without departing from the scope and spirit of this
invention as defined by the
appended claims.
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