Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
A-21114/AICGC 1896 CA 02220269 1997-11-0~
BENZOTRIAZOLE UV ABSORBERS HAVING ENHANCED DURABILITY
Benzotriazole UV absorbers being substituted in the benzo ring by electron withdrawing
moieties exhibit enhanced durability and low loss rates when incorporated into automotive
coatings.
The benzotriazoles have long been an important class of UV absorbers and have gained
wide commercial importance and acceptance for many industrial applications. The prior art
is replete with references to their manufacture and utility. However, as requirements
become ever more stringent and demanding, the search for still more stable and durable
benzotriazoles continues. The gradual phase out of HAPS solvents, such as xylene,
because of environmental concerns and their replacement with non-HAPS solvents, such
as esters, ethers or ketones, and increased durability requirements for automotive coatings
make this search more urgent. Indeed, the automotive industry is most concerned about
UVA losses from automotive paints and coatings as seen in the publication by J. L. Gerlock
et al., Proc. 36th Annual Tech. Sym. (Cleveland ~oating Society), May 18, 1993.
Vysokomol Soedin, Ser. A, 18(3), 553 (1976) describes the linear dependence of hydrogen
bond strength and photostability in benzotriazoles.
J. E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995) describe the
photodegradation of benzotriazole UV absorbers in poly(methyl methacrylate) films.
Structural variation generally caused only small differences in the rates of degradation
unless the substitution disrupted the intramolecular hydrogen bonds which are critical for
stability. Pickett et al. did not test any benzotriazoles containing both electron withdrawing
and electron donating groups as in the instant invention.
The prior art leads one to the conclusion that strengthening the hydrogen bond leads to a
more stable benzotriazole, but does not teach how this can be accomplished. The instant
invention discloses benzotriazoles which exhibit enhanced durability, but surprisingly this
enhanced durability is not always related to greater hydrogen bond strength. Indeed,
compounds with enhanced durability often have weaker, not stronger hydrogen bonds
United States Patent Nos. 4,226,763; 4,278,589; 4,315,848; 4,275,004; 4,347,180;5,554,760; 5,563,242; 5,574,166 and 5,607,987 describe selected benzotriazoles,
substituted in the 3-position of the hydroxyphenyl ring by an a-cumyl group, which show
CA 02220269 1997-11-0~
very good durability in automotive coatings. These benzotriazoles represent the present
state of the art. The instant invention is directed at preparing benzotriazoles which exhibit
still better durability and low loss rates from the prior art benzotriazoles.
United States Patent Nos. 5,278,314; 5,280,124; 5,436,349 and 5,516,914 describe red-
shifted benzotriazoles. These benzotriazoles are substituted in the 5-position of the benzo
ring by thio ethers, alkylsulfonyl or phenylsulfonyl moieties. Red-shifting the benzotriazoles
is desirable for spectral reasons. A group at the 5-position which is also electron
withdrawing provides additional benefits in low loss rates and durability as found in the
instant invention.
The instant invention pertains to benzotriazole UV absorbers having enhanced stability and
durability and a low loss rate when incorporated into automotive coatings.
More particularly, the instant invention pertains to a coating composition, stabilized with a
benzotriazole, which benzotriazole exhibits enhanced durability and a low loss rate when
incorporated in said coating, which composition comprises
(a) a resin selected from the group consisting of a thermoset acrylic melamine
resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine,
an acrylic resin with carbamate pendant groups crosslinked with melamine or an acrylic
polyol resin crosslinked with melamine containing carbamate groups, and
(b) 0.01 to 5% by weight, based on resin solids, of a benzotriazole of formula A, B,
C or D
OH
~---- \ ) =X/Rl
G2--~ -- / ~, ' (A)
CA 02220269 1997-11-05
OH
N ~ (B)
G, OH
~= ~N ~
G ~ N \$/ (C)
CH2CH2CO R5
G, OH OH G,
,j~ ~N--~L~<N~ ~ (D)
R2 R2
wherein
G" G2 or T is an electron withdrawing radical,
G,is hydrogen or halogen,
G2is halogen, nitro, cyano, R3SO-, R3SO2-,-COOG3, CF3-,-P(O)(C6H5)2,-CO-G3,-
CO-N H-G3~-co-N(G3)2~-N(G3)-co-G3~
/C~ -- G3 CO G3
N N
or
CO-- CO--
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G3 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of
branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,
phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted
on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
R1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of
branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,
phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted
on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
R2 is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched
chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7
to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl
ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or R2is hydroxyl or-OR4 where R4 is straight or
branched chain alkyl of 1 to 24 carbon atoms; or said alkyl substituted by one or more -OH,
-OCO-R1~, -OR4,-NCO or -NH2groups or mixtures thereof; or said alkyl or said alkenyl
interrupted by one or more -O-, -NH- or-NR4- groups or mixtures thereof and which can be
unsubstituted or substituted by one or more -OH, -OR4 or -NH2 groups or mixtures thereof;
or R2 is -SR3,-NHR3 or -N(R3)2 or R2 is
~(CH2)m~CO~X~(Z)p~Y~R1s
wherein
X is -O- or-N(R,6)-,
Y is -O- or-N(R,7)-,
Z is C2-C,2-alkylene, C4-C,2-alkylene interrupted by one to three nitrogen atoms,
oxygen atoms or a mixture thereof, or is C3-C,2-alkylene, butenylene, butynylene,
cyclohexylene or phenylene, each substituted by a hydroxyl group,
m is zero, 1 or 2,
p is 1, or p is also zero when X and Y are -N(R16)- and -N(R17)-, respectively,
R1sis a group -CO-C(R~g)=C(H)R~g or, when Y is -N(R17)-, forms together with R17 a
group -CO-CH=CH-CO-, wherein R1gis hydrogen or methyl, and R1gis hydrogen, methyl or -
CaX-R20, wherein R20 is hydrogen, C,-C,2-alkyl or a group of the formula
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OH
G,~ -- ~ ~R
N ~ )
~ N \~(CH2)m CO--X--(Z)--
wherein the symbols R" R3, X, Z, m and p have the meanings defined above, and R16 and
R17 independently of one another are hydrogen, C1-C12-alkyl, C3-C,2-alkyl interrupted by 1 to
3 oxygen atoms, or is cyclohexyl or C7-C,5aralkyl, and R16together with R,7 in the case
where Z is ethylene, also forms ethylene,
n is 1 or 2,
when n is l, R5 is Cl, OR6 or NR7R8, or
R5 is -PO(OR,2)2, -OSi(R")3 or-OCO-R",
or straight or branched chain C,-C24alkyl which is interrupted by -O-, -S- or -NR11 and which
can be unsubstituted or substituted by -OH or-OCO-R", C5-C12 cycloalkyl which isunsubstituted or substituted by -OH, straight chain or branched C2-C,8alkenyl which is
unsubstituted or substituted by -OH, C7-C,5aralkyl, -CH2-CHOH-R,3 or glycidyl,
R6 is hydrogen, straight or branched chain C,-C24alkyl which is unsubstituted orsubstituted by one or more OH, OR4 or NH2 groups, or-OR6 is -(OCH2CH2)wOH or -
(OCH2CH2)wOR2,where w is 1 to 12 and R2, is alkyl of 1 to 12 carbon atoms,
R7 and R8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight orbranched chain C3-C,8alkyl which is interrupted by -O-, -S- or -NR"-, C5-C,2cycloalkyl, C6-
C,4aryl or C1-C3hydroxylalkyl, or R7 and R8 together with the N atom are a pyrrolidine,
piperidine, piperazine or morpholine ring,
when n is 2, R5 is one of divalent radicals -O-Rg-O- or-N(R")-R,0-N(R")-,
Rg is C2-C8alkylene, C4-C8alkenylene, C4alkynylene, cyclohexylene, straight or
branched chain C4-C10alkylene which is interrupted by -O- or by -CH2-CHOH-CH2-O-R14-O-
CH2-CHOH-CH2-.
R10 being straight or branched chain C2-C12alkylene which may be interrupted by -
O-, cyclohexylene, or
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~ r=\
~ CH2~ or
~}CH2~
or R~o and R1,with the two nitrogen atoms form a piperazine ring,
R,4 is straight or branched chain C2-C8alkylene, straight or branched chain C4-
C10alkylene which is interrupted by -O-, cycloalkylene, arylene or
CH3
H~ or
CH3
CH
where R7 and R8 are independently hydrogen, alkyl of 1 to 18 carbon atoms or R7 and R8
together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-
iminopentamethylene or 3-methyliminopentamethylene,
R" is hydrogen, straight or branched chain C,-C,8alkyl, C5-C,2cycloalkyl, straight or
branched chain C3-C8alkenyl, C6-C,4aryl or Crc15aralkyl~
R,2 is straight or branched chain C,-C,8alkyl, straight or branched chain C3-
C,8alkenyl, C5-C,0cycloalkyl, C6-C,6aryl or C7-C,5aralkyl,
R,3 is H, straight chain or branched C,-C,8alkyl which is substituted by -PO(OR,2)2,
phenyl which is unsubstituted or substituted by OH, C7-C,5aralkyl or-CH20R,2,
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R3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of
3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon
atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4
carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to
16 carbon atoms,
L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms,
benzylidene, p-xylylene or cycloalkylidene, and
T is -sa, -so2-, -saE-sa, -so2-E-so2-, -ca, -caE-co-, -coaE-oca, -co-
NG3-E-NG3-Ca or-NG3-caE-caNG3-~
where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon
atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms,
which benzotriazole exhibits enhanced durability and low loss rate values when the coating
is exposed to actinic radiation as witnessed by a loss of less than 0.22 absorbance units
after exposure for 1200 hours, or less than 0.27 absorbance units after 1500 hours
exposure, or less than 0.40 absorbance units after 2500 hours exposure in a Xenon-Arc
Weather-Ometer.
Preferably, component (b) is a compound of formula A'
OH
G J~:~ R,
wherein
G2 is fluoro, chloro, cyano, R3SO2-, CF3-, -CO-G3, -COO-G3 or -CO-N(G312
G3 is alkyl of 1 to 12 carbon atoms,
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Rl is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon
atoms or said phenyl or said phenyialkyl substituted on the phenyl ring by 1 or 2 alkyl
groups of 1 to 4 carbon atoms,
R2 is alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or-
CH2CH2COOG4 where G4 is hydrogen, alkyl of 1 to 24 carbon atoms or said alkyl
substituted by OH, interrupted by one to six -O- atoms or both substituted by OH and
interrupted by one to six -O- atoms, and
R3 is alkyl of 1 to 18 carbon atom, aryl of 6 to 10 carbon atoms or said aryl
substituted one or two alkyl of 1 to 4 carbon atoms.
Most preferably, in the compound of formula A',
G2 is fluoro, chloro, cyano, R3S02-, CF3-, -COO-G3 or -CO-N(G3)2,
G3 is alkyl of 1 to 8 carbon atoms,
R1 is hydrogen, phenyl or a-cumyl,
R2 is alkyl of 4 to 12 carbon atoms or phenyl, and
R3 is phenyl or alkyl of 8 to 12 carbon atoms.
Especially preferred are the compounds of formula A' where G2 is phenyl-SO2-, octyl-SO2-,
fluoro or CF3-, R, is a-cumyl or phenyl, and R2 is tert-butyl or tert-octyl.
Preferably, the resin is a thermoset acrylic melamine resin or an acrylic urethane resin.
Examples of these various radicals are as follow:
When any of R, to R2, is alkyl, such groups are, for example, methyl, ethyl, isopropyl, n-
butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, 2-ethylhexyl, tert-octyl, lauryl, tert-dodecyl,
tridecyl, n-hexadecyl, n-octadecyl and eicosyl; when any of said radicals is alkenyl, such
groups are, for example, allyl or oleyl; when any of said radicals is cycloalkyl, such groups
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are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl; when
any of said radicals are phenylalkyl, such groups are, for example, benzyl, phenethyl, a-
methylbenzyl and a,a-dimethylbenzyl; and when any of said radicals is aryl, they are, for
example, phenyl, naphthyl, or when substituted by alkyl are, for example, tolyl and xylyl.
When R6 is alkyl substituted by one or more -O- groups and/or substituted by one or more -
OH, the -OR6 moiety can be -(OCH2CH2)wOH or -(OCH2CH2)wOR21 where w is 1 to 12 and
R21 is alkyl of 1 to 12 carbon atoms, for example.
When E is alkylene, it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-
1,4-tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene;
when E is cycloalkylene, it is, for example, cyclopentylene, cyclohexylene, cycloheptylene,
cyclooctylene and cyclododecylene; and when E is alkylene interrupted or terminated by
cyclohexylene, it is, for example, the saturated diyl radical derived from limonene, herein
called dihydrolimonenediyl.
A further preferred embodiment of the invention is a compound of formula lll in which R, is
tert-butyl, n is 1, R3 is phenyl and R5 is -OR6 where R6 is a straight chain or substituted octyl
group. Yet another preferred embodiment of the instant invention is a compound of formula
C where n is 2, R, is tert-butyl, R3 is phenyl, and R5 is -O-Rg-O- where Rg is C2-C24alkylene
interrupted by -O- or by -CH2-CHOH-CH2-O-R14-O-CH2-CHOH-CH2-.
When E is alkylene, it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-
1,4-tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene;
when E is cycloalkylene, it is, for example, cyclopentylene, cyclohexylene, cycloheptylene,
cyclooctylene and cyclododecylene; and when E is alkylene interrupted or terminated by
cyclohexylene, it is, for example, the saturated diyl radical derived from limonene, herein
called dihydrolimonenediyl.
When the instant compounds contain a free carboxyl moiety where R2 is -CH2CH2COOR6
where R6 is hydrogen, tlle alkali metal or amine salts of said acids are also contemplated as
part of this invention allowing such UV absorbers to be used in aqueous systems due to the
enhanced water solubility of such instant compounds.
R6, R7 and R8 can be the following C3-C,8alkyl radicals which are interrupted by -O-, -S-, or -
NR"- and can be substituted by OH: methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl,
methylthioethyl, CH30CH2CH20CH2CH2-, CH3CH20CH2CH20CH2CH2-,
CA 02220269 1997-11-0~
- 10 -
C4HgOCH2CH20CH2CH2-, ethylthiopropyl, octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl,
2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl,-CH2CH2-NH-C4Hg,-CH2CH2CH2NH-C8H,7
and -CH2CH2CH2-N (CH3)-CH2CH (C2H5)C4Hg,
R6, R7, R8, R11 and R12 can be the following C5-C12cycloalkyl radicals: cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl or cyclodecyl. In the case of R6, the radical can also be
substituted by-OH.
R7, R8 and R11 can be the following alkenyl radicals: allyl, methallyl, 2-n-hexenyl or 4-n-
octenyl.
When R6 is alkenyl, it can have the same meaning as R7, R8and R" as alkenyl radicals, but
it can also be -CH=CH2, n-undec-1 0-enyl or n-octadec-9-enyl, and it is also possible for the
radical R6 to be substituted by -OH.
R7 and R8 can be the following C7-C,5aralkyl radicals: benzyl, a-phenethyl, 2-phenethyl or
4-tert-butylbenzyl .
When R1" R,3 or R12 are aralkyl, they can, independently of one another, have the same
meaning as R7 or R8-
Independently of one another, R7, R8 and R1, can be the following C6-C14 aryl radicals:
phenyl, a-naphthyl or ~-naphthyl.
When R7 and R8 are C1-C3 hydroxyalkyl, they can be the following radicals: hydroxymethyl,
2-hydroxyethyl or 2-hydroxypropyl.
As C2-C8 alkylene, Rg and R14 can be the following radicals: ethylene, propylene, butylene,
hexylene or octylene.
As alkylene, R10 can be the same radicals, but can, in addition, also be higher-molecular
groups such as decylene or dodecylene.
When Rg is a C4-C8alkenylene radical, the following is an example of a suitable group:
butenylene.
CA 02220269 1997-11-0~
In the case of Rg and R14, suitable straight or branched chain C4-C,Oalkylene groups which
are interrupted by -0- are the following groups: -CH2CH20CH2CH2-, -CH(CH3)-CH2-aCH2-
CH(CH3)-CH2CH20CH2CH20CH2CH2- and -CH2CH20CH2CH20CH2CH20CH2CH2-.
When R14 is a cycloalkylene radical, the following groups are embraced: l ,3-cyclohexylene
and 1,4-cyclohexylene.
When R,4 is arylene, this can be, specifically, the following groups: 1 ,3-phenylene or 1,4-
phenylene.
As C2-C12-alkylene, Z is a straight or branched chain. It is for example: ethylene,
propylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, 1,1-
ethylidene, 2,2-propylidene, 2,2-amylidene or 2-ethylhexamethylene. C2-C6-alkylene groups
are preferred.
When Z is C4-C,2-alkylene which is interrupted by oxygen, it is for example: -CH2-CH2-0-
CH-2-CH2-, -CH2-CH2-aCH2-CH2-CH2, CH2-CH2-aCH2-CH2-aCH2-CH2 or -CH2-CH2-aCH2-
CH2-aCH2-CH2-aCH2-CH2-, and, when alkylene is interrupted by nitrogen, a group -N(R,6)-
is meant, where R,6 is as defined in the foregoing, for example-CH2-CH2-NH-CH2-CH2-CH2-
CH2, -CH2-CH2-CH2-NH-(CH2)8- or-CH2CH2-CH2-N(CH3-CH2-CH(C2H5)(CH2)4-.
As C3-C,2-alkylene substituted by a hydroxyl group, Z is 2-hydroxytetramethylene, 2-
hydroxyhexamethylene and, in particular, 2-hydroxytrimethylene.
As cyclohexylene, Z is for example 1,4-cyclohexylene and, in particular, 1,2-cyclohexylene.
As phenylene, Z is for example m-phenylene or p-phenylene.
m can be zero, 1 or 2, but it is preferably 2.
p is preferably 1, but can also be zero if both X and Y are bound by way of nitrogen.
As C,-C8-alkyl, R, is for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-
butyl, n-pentyl, tert-amyl, n-nexyl, n-heptyl, n-octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is
preferred.
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As C1-C,2-alkyl, R16 R17 and R20 can have the same meaning as that given in the foregoing
for R1, and can additionally be straight or branched-chain nonyl, decyl, undecyl, or dodecyl.
When R16 and R,7 are alkyl interrupted by oxygen atoms, the examples which apply are the
same as those described in the foregoing for Z.
Examples for R16 and R,7 as aralkyl are: benzyl, a-methylbenzyl, 1-phenylethyl, a,a-
dimethylbenzyl or 1-phenylpropyl.
If Z is ethylene, R16 and R,7 together can likewise form ethylene, which is equivalent to a
bridging over by way of a piperazine group.
When Y is a group -N(R17)-, R15 and R17 together make up a group -CO-CH=CH-CO-, and
o
)~ '
thus form the substituent N~ on the group -X-(Z)p-.
o
The preferred meaning of R1s is, however, -CO-C(R18)=CHR,4, R,~ and R~g are preferably
methyl and especially hydrogen.
R2 is -CH2-CH2-CO-O-C(G)=CH2 and G is hydrogen or methyl.
The instant invention also pertains to new benzotriazoles of formulas 1, Il, lll or IV
OH
G1 ~ ~N /~=~
G2~ -- / ~E, (I)
CA 02220269 l997-ll-05
- 13-
OH
T -2
- 2
G, OH
, N ~ (III)
CH2CH2CO E5
G, OH OH G,
,~ ,N ~L~ NX~\G
E2 E2
wherein
G, is hydrogen or halogen,
G2 is cyano, E3SO-, E3SO2-, -COOG3, CF3-, -P(O)(C6H5)2, -CO-G3, -CO-NHG3 or-
CO-N(G3)2,
G3 is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched
chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7
to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl
ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
CA 02220269 l997-ll-0
- 14-
E1 is hydrogen, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said
phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,
E2 is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched
chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7
to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl
ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E2 is hydroxyl or-OE4 where E4 is straight or
branched chain alkyl of 1 to 24 carbon atoms; or said alkyl substituted by one or more -OH,
-OCO-E1" -OE4, -NCO or -NH2 groups or mixtures thereof; or said alkyl or said alkenyl
interrupted by one or more -O-, -NH- or -NE4- groups or mixtures thereof and which can be
unsubstituted or substituted by one or more -OH, -OE4 or -NH2groups or mixtures thereof;
or E2 is -SE3, -NHE3 or-N(E3)2; or E2 is
-(CH2)m-CO-X-(Z)p-Y-E,5
wherein
X is -O- or-N(E16)-,
Y is -O- or-N(E,7)-,
Z is C2-C,2-alkylene, C4-C,2-alkylene interrupted by one to three nitrogen atoms,
oxygen atoms or a mixture thereof, or is C3-C,2-alkylene, butenylene, butynylene,
cyclohexylene or phenylene, each substituted by a hydroxyl group,
m is zero, 1 or 2,
p is 1, or p is also zero when X and Y are -N(E,6)- and -N(E,7)-, respectively,
E,s is a group -CO-C(E,8)=C(H)E19 or, when Y is -N(E17)-, forms together with E,7 a
group-CO-CH=CH-CO-, wherein E18 is hydrogen or methyl, and E19 is hydrogen, methyl or -
CO-X-E20, wherein E20 is hydrogen, C,-C,2-alkyl or a group of the formula.
OH
,~ N ~R,
~----N \~(CH2)--CO--X--(Z)--
wherein the symbols E" G2, X, Z, m and p have the meanings defined above, and E,6 and
E,7 independently of one another are hydrogen, C,-C,2-alkyl, C3-C,2-alkyl interrupted by 1 to
CA 02220269 l997-ll-0
- 15-
3 oxygen atoms, or is cyclohexyl or C7-C~saralkyl~ and E,6together with E,7 in the case
where Z is ethylene, also forms ethylene,
n is 1 or 2,
when n is l, E5 is Cl, OE6 or NE7E8, or
E5 is -PO(OE,2)2, -OSi(E")3 or -OCO-E",
or straight or branched chain C,-C24alkyl which is interrupted by -O-, -S- or -NE" and which
can be unsubstituted or substituted by -OH or -OCO-E", C5-C,2 cycloalkyl which is
unsubstituted or substituted by -OH, straight chain or branched C2-C,8alkenyl which is
unsubstituted or substituted by -OH, C7-C,5aralkyl, -CH2-CHOH-E,3 or glycidyl,
E6 is hydrogen, straight or branched chain C,-C24alkyl which is unsubstituted orsubstituted by one or more OH, OE4 or NH2 groups, or -OE6 is -(OCH2CH2)wOH or -
(OCH2CH2)wOE2,where w is 1 to 12 and E2, is alkyl of 1 to 12 carbon atoms,
E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight orbranched chain C3-C,8alkyl which is interrupted by -O-, -S- or-NE"-, C5-C,2cycloalkyl, C6-
C,4aryl or C,-C3hydroxylalkyl, or E7 and E8 together with the N atom are a pyrrolidine,
piperidine, piperazine or morpholine ring,
when n is 2, E5 is one of divalent radicals -O-Eg-O- or-N(R")-E,0-N(E")-,
Eg is C2-C8alkylene, C4-C8alkenylene, C4alkynylene, cyclohexylene, straight or
branched chain C4-C,0alkylene which is interrupted by -O- or by -CH2-CHOH-CH2-O-E,4-O-
CH2-CHOH-CH2-,
E10 being straight or branched chain C2-C,2alkylene which may be interrupted by -
O-, cyclohexylene, or
~ ~CH2~ or
~ } C H2~
or E~o and E"with the two nitrogen atoms form a piperazine ring,
E,4 is straight or branched chain C2-C8alkylene, straight or branched chain C4-
C,Oalkylene which is interrupted by -O-, cycloalkylene, arylene or
CA 02220269 1997-11-0~
~CH,
CH3
~1~
where E7 and Ea are independently hydrogen, alkyl of 1 to 18 carbon atoms or E7 and Eg
together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-
iminopentamethylene or 3-methyliminopentamethylene,
E1, is hydrogen, straight or branched chain C1-C18alkyl, C5-C12cycloalkyl, straight or
branched chain C3-C8alkenyl, C6-C14aryl or C7-C15aralkyl,
E12 is straight or branched chain C1-C18alkyl, straight or branched chain C3-
C,Balkenyl, C5-C,0cycloalkyl, C6-C,6aryl or C7-C15aralkyl,
E13 is H, straight chain or branched C1-C18alkyl which is substituted by -PO(OR12)2,
phenyl which is unsubstituted or substituted by OH, C7-C15aralkyl or-CH2OE12,
E3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of
3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon
atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4
carbon atoms or 1,1 ,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to
16 carbon atoms,
L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms,
benzylidene, p-xylylene or cycloalkylidene, and
T is -SO-, -SO2-, -SO-E-SO-, -SO2-E-SO2-, -CO-, -CO-E-CO-, -COO-E-OCO- or-
CO-NGs-E-NGs-CO-,
where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon
atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms;
Gs is G3 or hydrogen, and
CA 02220269 1997-11-0~
with the proviso that E, is not phenylalkyl when G2 is E3SO- or E3S02
Preferably, the new benzotriazole is a compound of formula 1
OH
wherein
G2 is cyano, E3SO2-, CF3-, -COO-G3-CO-NHG3or-CO-N(G3)2,
G3 is alkyl of 1 to 12 carbon atoms,
E, is hydrogen, phenyl, phenylalkyl of 7 to 15 carbon atoms or said phenyl or said
phenylalkyl substituted on the phenyl ring by 1 or 2 alkyl groups of 1 to 4 carbon atoms,
E2 is alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or-
CH2CH2COOG4 where G4 is hydrogen, alkyl of 1 to 24 carbon atoms or said alkyl
substituted by OH, interrupted by one to six -O- atoms or both substituted by OH and
interrupted by one to six -O- atoms,
E3 is alkyl of 8 to 18 carbon atom, aryl of 6 to 10 carbon atoms or said aryl
substituted one or two alkyl of 1 to 4 carbon atoms, and
with the proviso that E1 is not phenylalkyl when G2 is E3SO- or E3S02-.
Most preferably, in the compound of formula 1',
G2 is cyano, E3SO2-, CF3-, -CO-G3 or -CO-N(G3)2,
G3 is alkyl of 1 to 8 carbon atoms,
E, is hydrogen, phenyl or a-cumyl,
E2 is alkyl of 4 to 12 carbon atoms, and
E3 is phenyl or octyl, and
with the proviso that E1 is not a-cumyl when G2 is E3S02-.
Especially preferred are the compounds of formula 1' where G2 is CF3-, E1 is a-cumyl, and
E2 is tert-butyl or tert-octyl.
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The instant invention also pertains to a composition stabilized against thermal, oxidative or
light-induced degradation which comprises,
(a) an organic material subject to thermal, oxidative or light-induced degradation,
and
(b) an effective stabilizing amount of a compound of formula 1, Il, lll or IV.
Preferably, the organic material is a natural, semi-synthetic or synthetic polymer, especially
a thermoplastic polymer.
Most preferably, the polymer is a polyolefin or polycarbonate, especially polyethylene or
polypropylene; most especially polypropylene.
In another preferred embodiment of the present invention the organic material is a resin
selected from the group consisting of a thermoset acrylic melamine resin, an acrylic
urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin
with carbamate pendant groups crosslinked with melamine or an acrylic polyol resin
crosslinked with melamine containing carbamate groups.
Moste preferred the resin is a thermoset acrylic melamine resin or an acrylic urethane resin.
In yet another preferred embodiment of the present invention the organic material is a
recording material.
The recording materials according to the invention are suitable for pressure-sensitive
copying systems, photocopying systems using microcapsules, heat-sensitive copying
systems, photographic materials and ink jet printing.
The recording materials according to the invention are distinguished by an unexpected
improvement in quality, especially with regard to the fastness to light.
The recording materials according to the invention have the construction known for the
particular use. They consist of a customary carrier, for example paper or plastic film, which
has been coated with one or more layers. Depending on the type of the material, these
layers contain the appropriate necessary components, in the case of photographicmaterials, for example, silver halide emulsions, dye couplers, dyes and the like. Material
CA 02220269 1997-11-0~
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particularly suitable for ink jet printing has a layer particularly absorptive for ink on a
customary carrier. Uncoated paper can also be employed for ink jet printing. In this case the
paper acts at the same time as the carrier material and as the ink-absorbent layer. Suitable
material for ink jet printing is, for example, described in U.S. Pat. No. 5,073,448
(incorporated herein by reference).
The recording material can also be transparent, as, for example, in the case of projection
films.
The compounds of the formula 1, Il, lll or IV can be incorporated into the carder material as
early as the production of the latter, in the production of paper, for example, by being added
to the paper pulp. A second method of application is to spray the carder material with an
aqueous solution of compounds of the formula 1, Il, lll or IV or to add the compounds of the
to the coating composition.
Coating compositions intended for transparent recording materials suitable for projection-
cannot contain any particles which scatter light, such as pigments and fillers.
The dye-binding coating composition can contain a number of other additives, for example
antioxidants, light stabilizers (including also UV absorbers which do not belong to the UV
absorbers according to the invention), viscosity improvers, fluorescent brighteners, biocides
and/or antistatic agents.
The coating composition is usually prepared as follows:
the water-soluble components, for example the binder, are dissolved in water and stirred
together. The solid components, for example fillers and other additives already described,
are dispersed in this aqueous medium. Dispersion is advantageously carded out by means
of devices, for example ultrasonic samples, turbine stirrers, homogenizers, colloid mills,
bead mills, sand mills, high-speed stirrers and the like. The compounds of the formula 1, Il,
lll and IV can be incorporated easily into the coating composition.
The recording material according to this invention preferably contains 1 to 5000 mg/m2, in
particular 50-1200 mglm2, of a compound of the formula 1.
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As already mentioned, the recording materials according to the invention embrace a wide
field. The compounds of the formula l, ll, lll or IV can, for example, be employed in
pressure-sensitive copying systems. They can be introduced either into the paper in order
to protect the microencapsulated dye precursors there from light, or into the binder of the
developer layer in order to protect the dyes formed there.
Photocopying systems using light-sensitive microcapsules which are developed by means
of pressure are described in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050;
4,5365,463; 4,551,407; 4,562,137 and 4,608,330, also in EP-A 139,479; EP-A 162,664;
EP-A 164,931; EP-A 237,024; EP-A 237,025 or EP-A 260,129. In all these systems the
compounds can be put into the dye-receiving layer. The compounds can, however, also be
put into the donor layer in order to protect the colour formers from light.
Photographic materials which can be stabilized are photographic dyes and layers containing
such dyes or precursors thereof, for example photographic paper and films. Suitable
materials are, for example, described in U.S. Pat. No.5,364,749 (incorporated therein by
reference). The compounds of the formula l, ll, lll or IV act here as a UV filter against
electrostatic flashes. In colour photographic materials couplers and dyes are also protected
against photochemical decomposition.
The instant compounds can be used for all types of colour photographic materials. For
example, they can be employed for colour paper, colour reversal paper, direct-positive
colour material, colour negative film, colour positive film, colour reversal film, etc. They are
preferably used, inter alia, for photographic colour material which contains a reversal
substrate or forms positives.
Colour-photographic recording materials usually contain, on a support, a blue-senitive
and/or a green-sensitive and/or a red-sensitive silver-halide emulsion layer and, if desired, a
protection layer, the compounds being, preferably, either in the green-sensitive or the red-
sensitive layer or in a layer between the green-sensitive and the red-sensitive layer or in a
layer on top of the silver-halide emulsion layers.
The compounds of the formula l, ll, lll or IV can also be employed in recording materials
based on the principles of photopolymerization, photoplasticization or the rupture of
CA 02220269 1997-11-0~
microcapsules, or in cases where heat-sensitive and light-sensitive diazonium salts, leuko
dyes having an oxidizing agent or dye lactones having Lewis acids are used.
Furthermore, they can be employed in recording materials for dye diffusion transfer printing,
thermal wax transfer printing and not matrix printing and for use with electrostatic,
electrographic, electrophoretic, magnetographic and laser-electrophotographic printers and
pen-plotters. Of the above, recording materials for dye diffusion transfer printing are
preferred as, for example described in EP-A-507,734.
They can also be employed in inks, preferably for ink jet printing, as, for example, further
described in U.S. Pat. No. 5,098,477 (incorporated herein by reference).
The compounds of this invention exhibit superior hydrolytic stability, handling and storage
stability as well as good resistance to extractability when present in a stabilized
composition.
The methodology to make the instant compounds is described in the prior art. Theintermediates needed to make the instant compounds are largely items of commerce.
Preferred compounds are those in which one of X and Y is -O-; and particularly those in
which both X and Y are -~.
In general polymers which can be stabilized include
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene,
polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers
of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally
can be crosslinked), for example high density polyethylene (HDPE), low density
polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density
polyethylene (BLDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph,
preferably polyethylene and polypropylene, can be prepared by different, and especially by
the following, methods:
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a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one
metal of groups IVb, Vb, Vlb or Vlll of the Periodic Table. These metals usually have one or
more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls,
alkenyls and/or aryls that may be either 1l- or ~-coordinated. These metal complexes may
be in the free form or fixed on substrates, typically on activated magnesium chloride,
titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in
the polymerisation medium. The catalysts can be used by themselves in the polymerisation
or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides,
metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla and/or
Illa of the Periodic Table. The activators may be modified conveniently with further ester,
ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts
(SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene
with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE)
and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers,
for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and
mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers,
propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexenecopolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers,
ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprenecopolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers,
ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or
ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of
ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-
norbornene; and mixtures of such copolymers with one another and with polymers men-
tioned in 1 ) above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers
(EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide
copolymers and mixtures thereof with other polymers, for example polyamides.
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4. Hydrocarbon resins (for example C5-Cg) including hydrogenated modifications thereof
(e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).
6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example
styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl
acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/-
acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and
another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/-
diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene,
styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/
styrene.
7. Graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene,
styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and
acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl meth-
acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylo-
nitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on poly-
butadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and
acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl
acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copoly-
mers, as well as mixtures thereof with the copolymers listed under 6), for example the
copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated
or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epi-
chlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl com-
pounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyviny-
lidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride,
vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from a"~-unsaturated acids and derivatives thereof such as polyacry-
lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni-
triles, impact-modified with butyl acrylate.
CA 02220269 1997-11-0
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10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu-
rated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or
acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or
acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl
benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as
well as their copolymers with olefins mentioned in 1 ) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethy-
lene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain
ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes,
acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene
polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybuta-
dienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as
precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or
from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, poly-
amide 6, polyamide 6/6j 6/10, 619, 6/12, 416, 12/12, polyamide 1 1, polyamide 12, aromatic
polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from
hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an
elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or
poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned poly-
amides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or poly-
tetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS;
and polyamides condensed during processing (RIM polyamide systems).
CA 02220269 1997-11-0
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17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic
acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene
terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as
well as block copolyether esters derived from hydroxyl-terminated polyethers; and also poly-
esters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and
melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde
resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated
dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and
also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry-
lates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins,
urea resins, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl
ethers or from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homolo-
gous derivatives thereof, for example cellulose acetates, cellulose propionates and cellu-
lose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their
derivatives.
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28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly-
amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA,
PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,
POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP,
PA/PPO.
29. Naturally occurring and synthetic organic materials which are pure monomeric com-
pounds or mixtures of such compounds, for example mineral oils, animal and vegetable
fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adi-
pates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in
any weight ratios, typically those used as spinning compositions, as well as aqueous emul-
sions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of
carboxylated styrene/butadiene copolymers.
31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in
U.S. Patent No. 4,259,467; and the hard polyorganosiloxanes described, for example, in
U.S. Patent No. 4,355,147.
32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with
unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates,
polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the
acrylated melamines. The polyketimines are prepared from polyamines and ketones in the
presence of an acid catalyst.
33. Radiation curable compositions containing ethylenically unsaturated monomers or
oligomers and a polyunsaturated aliphatic oligomer.
34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy
functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).
In general, the compounds of the present invention are employed in from about 0.01 to
about 5% by weight of the stabilized composition, although this will vary with the particular
substrate and application. An advantageous range is from about 0.05 to about 3%, and
especially 0.05 to about 1 %.
CA 02220269 1997-11-0~
The stabilizers of the instant invention may readily be incorporated into the organic
polymers by conventional techniques, at any convenient stage prior to the manufacture of
shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry
powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution,
suspension, or emulsion of the polymer. The resulting stabilized polymer compositions of
the invention may optionally also contain from about 0.01 to about 5%, preferably from
about 0.025 to about 2%, and especially from about 0.1 to about 1% by weight of various
conventional additives, such as the materials listed below, or mixtures thereof.
1. Antioxidants
1.1. Alkylated monophenols, for example.
2,6-di-tert-butyl-4-methy Iphenol
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-i-butylphenol
2,6-di-cyclopentyl-4-methylphenol
2-(a-methylcyclohexyl)-4 ,6-dimethylphenol
2,6-di-octadecyl-4-methylphenol
2,4,6-tri-cyclohexylphenol
2,6-di-tert-butyl-4-methoxymethylphenol
1.2. Alkylated hydroquinones, for example.
2,6-di-tert-butyl-4-methoxyphenol
2,5-di-tert-butyl-hydroquinone
2,5-di-tert-amyl-hydroquinone
2,6-diphenyl-4-octadecyloxyphenol
1.3. Hydroxylated thiodiphenyl ethers. for example.
2,2'-thio-bis-(6-tert-butyl-4-methylphenol)
2,2'-thio-bis-(4-octylphenol)
4,4'-thio-bis-(6-tert-butyl-3-methylphenol)
CA 02220269 1997-11-0~
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4,4'-thio-bis-(6-tert-butyl-2-methylphenol)
1.4. Alkylidene-bisphenols, for example,
2,2'-methylene-bis-t6-tert-butyl-4-methylphenol)
2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)
2,2'-methylene-bis-[4-methyl-6-(a-methylcyclohexyl)-phenol]
2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)
2,2'-methylene-bis-(6-nonyl-4-methylphenol)
2,2'-methylene-bis-[6-(a-methylbenzyl)-4-nonylphenol]
2,2'-methylene-bis-[6-(a,a-dimethylbenzyl)-4-nonylphenol]
2 ,2 '-methylene-bis-(4 ,6-di-tert-butylphenol)
2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)
2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)
4 ,4'-methylene-bis-(2 ,6-di-tert-butylphenol)
4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)
1 ,1 -bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol
1 ,1 ,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
1 ,1 -bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane
ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]
di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene
di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl] terephthalate.
1.5. Benzyl compounds. for example.
1 ,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene
di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide
3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate
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
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt
1.6. Acylaminophenols. for example,
CA 02220269 1997-11-0~
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4-hydroxy-lauric acid anilide
4-hydroxy-stearic acid anilide
2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine
octyl-N-(3,5-di-tert-butyl -4-hydroxyphenyl)-carbamate
1.7. Esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or
polyhydric alcohols, for example,
methanol diethylene glycol
octadecanol triethylene glycol
1,6-hexanediol pentaerythritol
neopentyl glycol tris-hydroxyethyl isocyanurate
thiodiethylene glycol di-hydroxyethyl oxalic acid diamide
triethanolamine triisopropanolamine
1.8. Esters of ,B-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or
polyhydric alcohols, for example,
methanol diethylene glycol
octadecanol triethylene glycol
1,~hexanediol pentaerythritol
neopentyl glycol tris-hydroxyethyl isocyanurate
thiodiethylene glycol di-hydroxyethyl oxalic acid diamide
triethanolamine triisopropanolamine
1.9. Amides of ,B-(3.5-di-tert-butyl-4-hydroxyphenyl)-propionic acid for example,
N ,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine
N ,N'-di-(3,5-di-tert-butyl- 4-hydroxyphenylpropionyl)-trimethylenediamine
N ,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine
1.10 Diarylamines, forexample,
diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, 4,4'-di-
tert-octyl-diphenylamine, reaction product of N-phenylbenzylamine and 2,4,4-
CA 02220269 1997-11-OS
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trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction
product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.
2. UV absorbers and light stabilizers
2.1. 2-(2'-Hydroxyphenyl~-benzotriazoles, for example, the 5'-methyl-, 3',5'-di-tert-butyl-, 5'-
tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-
methyl-, 3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-, 3',5'-bis-(a,a-dimethylbenzyl),
3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-, 3'-dodecyl-5'-methyl-,
and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-, and dodecylated-5'-methyl derivatives.
2.2. 2-Hydroxy-benzophenones, 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
derivatives.
2.3. Esters of optionally substituted benzoic acids for example, phenyl salicylate, 4-tert-
butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-
resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl
ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.
2.4. Acrvlates, for example, a-cyano-,B"13-diphenylacrylic acid ethyl ester or isooctyl ester, a-
carbomethoxy-cinnamic acid methyl ester, a-cyano-~-methyl-p-methoxy-cinnamic acid
methyl ester or butyl ester, a-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(,B-
carbomethoxy-~-cyanovinyl)-2-methyl-indoline.
2.5. Nickel compounds. for example, nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-
tetramethylbutyl)-phenoll, such as the 1:1 or 1:2 complex, optionally with additional ligands
such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel
dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid
monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes
such as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-
lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
2.6. Sterically hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate,
bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl
malonic acid bis-(1 ,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of 1-
CA 02220269 l997-ll-0
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hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation
product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-
2,6-dichloro-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-
tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1'(1,2-ethanediyl)-bis-(3,3,5,5-
tetramethylpiperazinone), bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
2.7. Oxalic acid diamides. for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di--
tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide,
N,N'-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its
mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-
methoxy- as well as of o- and ~ethoxy-disubstituted oxanilides.
2.8. Hydroxyphenyl-s-triazines, for example 2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-
octyloxyphenyl)-s-triazine; 2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;
2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bisl2-hydroxy-4-(2-hydroxy-
ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-
ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-
phenyl]-6-(4-bromophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4
chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.
3. Metal deactivators. for example, N,N'-diphenyloxalic acid diamide, N-salicylal-N'-
salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenyl-
propionyl)-hydrazine, 3-salicyloylamino-1,2,4-triazole, bis- benzylidene-oxalic acid
dihydrazide.
4. Phosphites and phosphonites, for example, triphenyl phosphite, diphenylalkyl
phosphites, phenyldialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite,
trioctadecyl phosphite, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)
phosphite, di-isodecylpentaerythritol diphosphite, di-(2,4,6-tri-tert-butylphenyl)-
pentaerythritol diphosphite, di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,
di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis-
(2,4-di-tert-butylphenyl) 4,4'-diphenylylenediphosphonite.
5. Compounds which destroy peroxide. for example, esters of ~-thiodipropionic acid, for
example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc
CA 02220269 1997-11-0
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salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide,
pentaerythritol tetrakis-(,~-dodecylmercapto)-propionate.
6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,
N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-
dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl-hydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived
from hydrogenated tallow amine.
7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-
octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl
nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-
hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-
alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone derived from N,N-
dialkylhydroxylamine derived from hydrogenated tallow amine.
8. Polyamide stabilizers, for example copper salts in combination with iodides and/or
phosphorus compounds and salts of divalent manganese.
9. Basic co-stabilizers. for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl
cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes,
alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca
stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony
pyrocatecholate or zinc pyrocatecholate.
10. Nucleating agents. for example, 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic
acid.
11. Fillers and reinforcing agents. for example, calcium carbonate, silicates, glass fibers,
asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black,
graphite.
12. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical
brighteners, flameproofing agents, anti-static agents, blowing agents and thiosynergists
such as dilauryl thiodipropionate or distearyl thiodipropionate.
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13. Benzofuranones and indolinones, for example those disclosed in US-A-4325863, US-A-
4338244 or US-A-5175312, or 3-[4-(2-acetoxyethoxy)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.
The co-stabilizers, with the exception of the benzofuranones listed under 13, are added for
example in concentrations of 0.01 to 10%, relative to the total weight of the material to be
stabilized.
Further preferred compositions comprise, in addition to components (a) and (b) further addi-
tives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.
Particularly preferred additives are phenolic antioxidants (item 1 of the list), sterically hin-
dered amines (item 2.6 of the list), phosphites and phosphonites (item 4 of the list) and per-
oxide-destroying compounds (item 5.) of the list.
Additional additives (stabilizers) which are also particularly preferred are benzofuran-2--
ones, such as described, for example, in US-A-4 325 863, US-A-4,338 244 or US-A-5175312.
The phenolic antioxidant of particular interest is selected from the group consisting of n-
octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert--
butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphos-
phonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-
tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy-
benzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydro-cinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-
tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-
tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]-
isocyanur ate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-
tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-
triazine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium
bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tert-butyl-4-
hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-
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tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,N'-bis[2-(3,5-di-tert-butyl-4-
hydroxyhydrocinnamoyloxy)-eth yl]-oxamide.
A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-tri-
methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4--
hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert-
butylphenol).
The hindered amine compound of particular interest is selected from the group consisting of
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) seb~c~te,
di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,
4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-
octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dio ne,
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,
1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-
diaza-21-oxodispiro[5.1 11.2] heneicosane, polycondensation product of 2,4-dichloro-6-tert-
octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, polycondensation product of 4,4'-hexamethylenebis-(amino-2,2,6,6-tetra-
methylpiperidine) and 1,2-dibromoethane,
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate,
tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate,
polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-
hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N',N",N"'-tetrakis[(4,6-bis(butyl-
1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-y 1]-1,10-diamino-4,7-diazadecane,
mixed [2,2,6,6-tetramethylpiperidin-4-yl/,B"B"B',~'-tetramethyl-3,9-(2,4,8 ,10-
tetraoxaspiro[5.5]-undecane) diethyl] 1,2,3,4-butanetetracarboxylate,
mixed [1,2,2,6,6-pentamethylpiperidin-4-yl/~"B"B',~'-tetramethyl-3,9-(2,4 ,8,10-tetraoxaspiro[5.5]undecane)diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene
bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),
4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n-
dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, N-1-
acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide, 1-acetyl3-dodecyl-7,7,9,9-
tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, di-(1-octyloxy-2,2,6,6-tetramethyl-
CA 02220269 1997-11-0~
piperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-
octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly~[6-tert-octylamino-s-triazin-2,4-
diyl][2-(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1
cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], and 2,4,6-tris[N-(1-cyclohexyloxy--
2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.
A most preferred hindered amine compound is bis(2,2,6,6-tetramethylpiperidin-4-yl)
sebacate, bis(l,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-
pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, thepolycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N',N",N"'-tetrakis[(4,6-
bis(butyl-(1 ,2,2,6,6-pentamethylpiperidin-4-yl)amino)- s-triazine-2-yl]-1,10-diamino-4,7-
diazadecane. di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di-(1-cyclohexyloxy-
2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-
piperidine, poly~[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethyl-
piperidin-4-yl)imino-hexamethylene-[4-(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-
yl)imino], or 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-
triazine.
The instant composition can additionally contain another UV absorber selected from the
group consisting of the s-triazines, the oxanilides, the hydroxybenzophenones, benzoates
and the a-cyanoacrylates.
Particularly, the instant composition may additionally contain an effective stabilizing amount
of at least one other 2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or
hindered amine or mixtures thereof.
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Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
2-[2-hydroxy-3,5-di(a,a-dimethylbenzyl)phenyl]-2H-benzotriazole;
2-[2-hydroxy-3-(a,a-dimethylbenzyl)-5-octylphenyl]-2H-benzotriazole;
2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl~2H-
benzotriazole; and
2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl~2H- benzotriazole.
Preferably, the other tris-aryl-s-triazine is selected from the group consisting of
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;
2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; 2,4-bis(2,4-dimethylphenyl)-6-[2-
hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine; and
2-(2-hydroxyethylamino)-4,~bis[N-butyl-N-(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-
yl)amino]-s-triazine.
The alkyd resin lacquers which can be stabilized against the action of light and moisture in
accordance with the instant invention are the conventional stoving lacquers which are used
in particular for coating automobiles (automobile finishing lacquers), for example lacquers
based on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and H.
F. Sarx, "Lackkunstharze" (1977), pages 99-123). Other crosslinking agents include
glycouril resins, blocked isocyanates or epoxy resins.
The lacquers stabilized in accordance with the invention are suitable both for metal finish
coatings and solid shade finishes, especially in the case of retouching finishes, as well as
various coil coating applications. The lacquers stabilized in accordance with the invention
are preferably applied in the conventional manner by two methods, either by the single-coat
method or by the two-coat method. In the latter method, the pigment-containing base coat is
applied first and then a covering coat of clear lacquer over it.
It is also to be noted that the compounds of the present invention are applicable for use in
non-acid catalyzed thermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic
and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. The
epoxy and epoxy-polyester resins are crosslinked with conventional crosslinkers such as
acids, acid anhydrides, amines and the like. Correspondingly, the epoxide may be utilized
as the crosslinking agent for various acrylic or polyester resin systems that have been
modified by the presence of reactive groups on the backbone structure.
CA 02220269 1997-11-0
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When used in two-coat finishes, the compounds of the instant invention can be
incorporated in the clear coat or both in the clear coat and in the pigmented base coat.
When water-soluble, water miscible or water dispersible coating are desired ammonium
salts of acid groups present in the resin are formed. Powder coating composition can be
prepared by reacting glycidyl methacrylate with selected alcohol components.
The instant benzotriazoles are made by conventional methods for preparing such
compounds. The usual procedure involves the diazotization of a substituted o-nitroaniline
followed by coupling the resultant diazonium salt with a substituted phenol and reduction of
the azobenzene intermediate to the corresponding desired benzotriazole. The starting
materials for these benzotriazoles are largely items of commerce or can be prepared by
normal methods of organic synthesis.
While the instant benzotriazoles with their enhanced durability are particularly suited for
automotive coating applications, it is contemplated that they will also be espeically useful in
other applications where their enhanced durability is required such as in solar films and the
like.
The following examples are for illustrative purposes only.
Example l
Preparation of 5-Trifluoromethyl-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzo-
triazole
a) Diazotization of 4-amino-3-nitro-benzotrifluoride
To a 500 ml 3-necked flask, equipped with a mechanical stirrer, are added 41.2 9 of 4-
amino-3-nitro-benzotrifluoride, 52 ml of concentrated hydrochloride acid and 100 ml of
distilled water. The stirred solution is cooled to 5~C and 17.3 9 of sodium nitrite dissolved in
50 ml of water are added. The solution is stirred at O to 5~C for two hours, then filtered and
stored at -1 0~C.
b) Monoazo adduct
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To a 1000 ml flask, fitted with a mechanical stirrer, are added 40 9 of sodium hydroxide
dissolved in 200 mi of methanol and 32.4 g of 2-a-cumyl-4-tert-octylphenol in 50 ml of
xylene. The solution is cooled to 5~C and the diazo solution of 4-amino-nitro-benzotrifluoride
prepared in part a. is added at 0 to 5~C over a two-hour period. Then 100 ml of xylene are
added and the organic layer is washed with water, aqueous hydrochloride acid, water,
aqueous sodium bicarbonate solution and finally water. The solvent is removed under
reduced pressure and the residue is purified by chromatography (silica gel, heptane:ethyl
acetate 95:5) to yield 42.1 9 of the adduct product as a dark red paste.
c) Reduction of the monoazo adduct
A 1000 ml flask is charged with 20 g of sodium hydroxide, 40 ml of water, 42.1 9 of the
monoazo adduct prepared in part b. and 400 ml of ethanol. The mixture is warmed to 80~C
and 27 9 of formamidine sulfinic acid is added in portions with stirring. After 1.5 hours, the
solution is cooled to room temperature and 100 ml of water are added. The pH is adjusted
to pH 7 with concentrated hydrochloric acid. The ethanol is removed under vacuum and the
water layer is extracted with methylene chloride. The solvent is then evaporated in vacuo
and the residue is purified by chromatography (silica gel, heptane:tolunen 9:1) and
crystallized from ethanol. The title compound is obtained in a yield of 5.6 g as a pale yellow
solid melting at 1 19-121~C.
Example 2
Preparation of 5-Fluoro-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
The title compound is prepared according to the general procedure of Example 1 using 31.2
g of 4-fluoro-2-nitroaniline. In part c of the procedure, an additional 9 g of formamidine
sulfinic acid is required to complete the reduction. Purification of the crude product on silica
gel (heptane:toluene, 1:1) yields 4.5 9 of the title compound as a off-white solid. Further
purification by recrystallization from acetonitrile:toluene provides 1.1 9 of the title compound
melting at 93-96~C.
Example 3
Preparation of 5-Chloro-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
CA 02220269 1997-11-0
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The general procedure of Example 1 parts a and b is followed to prepare the monoazo
intermediate of making the title compound from 339.3 9 of 4-chloro-2-nitroaniline. The crude
product is purified by recrystallization from methanol to yield 70.9 g of deep red monoazo
adduct.
c) Reduction of the Monoazo Adduct
A mixture of 11.8 9 of sodium hydroxide and 138 g of 2-butanol is heated to 95~C. A
solution of 60.1 9 of the above monoazo adduct and 1.3 g of 2,3-dichloro-1,4-naphtho-
quinone in 90 9 of 2-butanol is added over a 90 minute period with stirring. The reaction
mixture is heated to rernove the 2-butanone byproduct with additional 2-butanol added to
replace the distillate. The reaction mixture is cooled to 85~C, washed with 2.5 N sulfuric acid
and brine and then concentrated. The residue is recrystallized from methanol:xylene to yield
45.6 9 of the title compound as a light yellow solid melting at 104-105~C.
Example 4
Preparation of 5-Phenylthio-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
To a stirred mixture of 75 g of 5-chloro-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-
benzotriazole and 105 g of N-methylpyrrolidone heated at 90~C is added first 44.3 9 of 45%
aqueous potassium hydroxide solution over a 15-minute period then 20.4 9 of thiophenol
over another 15 minutes. The reaction mixture is then heated at 170-175~C for four hours
with water being removed by distillation. After cooling to 100~C, xylene and water are added
and the resultant mixture is made acidic with 15% aqueous hydrogen chloride solution. The
organic layer is separated and washed with water and then concentrated. The crude
product residue is recrystallized from methanol to yield 82 g of the title compound as a pale
yellow solid melting at 124-125~C.
Example 5
Preparation of 5-Benzenesulfonyl-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-
benzotriazole
A 1000 mL flask is charged with 75.2 g of 5-phenylthio-2-(2-hydroxy-3-a-cumyl-5-tert-octyl-
phenyl)-2H-benzotriazole, prepared in Example 4,102 g of xylene, 0.9 g of sodium
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tungstate dihydrate and 18.4 9 of formic acid. The mixture is heated to 50~C. To this stirred
mixture is slowly added 36.3 g of 50% hydrogen peroxide so that the temperature does not
exceed 85~C. Additional xylene and water are then added. The organic layer is separated,
washed with aqueous sodium sulfite, then twice with water and concentrated. The crude
product residue is recrystallized from methanol to yield 75.2 9 of the title compound as a
light yellow solid melting at 170-171~C.
Example 6
Preparation of 5-Nonylthio-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
Using the procedure of Example 4 with 30 9 of 5-chloro-2-(2-hydroxy-3-a-cumyl-5-tert-octyl-
phenyl)-2H-benzotriazole and 17.6 9 of nonyl mercaptan, the title compound is prepared.
Example 7
Preparation of 5-Nonylsulfonyl-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
5-Nonylthio-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, prepared in
Example 6, is oxidized to the sulfone without purification of the thio intermediate using 8.7 9
of formic acid, 0.7 9 of sodium tungstate dihydrate and 17.6 9 of 50% hydrogen peroxide to
yield the title compound as a yellow resin exhibiting a molecular ion of m/e 631.
Example 8
Preparation of 5-Chloro-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole
The general procedure of Example 1 parts a and b are used to prepare the monoazointermediate for the title compound from 4-chloro-2-nitroaniline and 2-phenyl-4-tert-
octylphenol. The crude product is purified by recystallization from methanol to yield a deep
red monoazo adduct.
The title compound is prepared according to the reduction procedure of Example 3 from 65
g of the monoazo adduct prepared above, 19.9 9 of sodium hydroxide and 2.4 9 of 2,3-
dichloro-1 ,4-naphthoquinone. The crude product is purified by chromatography on silica gel
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(hexane:ethyl acetate,5:1) yielding a fraction which is predominantly the title compound
exhibiting a molecular ion of m/e 433.
Example 9
Preparation of 5-Phenylthio-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole
The title compound is prepared according to the procedure of Example 4 from 20 9 of the
compound of Example 8,20.4 9 of 45% aqueous potassium hydroxide,10.3 9 of thiophenol
and 100 9 of N-methylpyrrolidone. The title compound is an oil purified by chromatography
on silica gel using toluene as eluent.
Example 10
Preparation of 5-Benzenesulfonyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-
benzotriazole
The title compound is prepared according to the procedure of Example 5 from 20 9 of the
thio compound of Example 9, 6.4 9 of formic acid,15.0 9 of 50% hydrogen peroxide and
0.6 9 of sodium tungstate dihydrate. Recrystallization of 2.5 9 of crude material from
xylene/methanol yields 2.0 9 of the purified title compound as a light yellow powder melting
at 204-206~C.
Example 11
Preparation of a mixture of 5-Chloro-2-(2-hydroxy-3.5-dialkylphenyl)-2H-benzotriazole (alkyl
being independently C4, C8, C,~ and C,6~
A mixture of 65.4 9 of 5-chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole,45 mL of
dodecene and 13 mL of methane sulfonic acid is heated to 170~C under nitrogen. An
additional 135 mL of dodecene is added over a 4.5 hour period. The reaction mixture is
allowed to cool to 100~C and then quenched with 400 9 of crushed ice and extracted thrice
with ethyl acetate. The organic layers are combined, washed with water, aqueous sodium
bicarbonate, water again and brine, dried over anhydrous magnesium sulfate and finally
concentrated. The polymeric residue is removed by bulb to bulb distillation under vacuum at
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0.2 mm and up to 210~C. Unreacted starting material is then removed by distillation (at 0.01
mm,160~C) to give 45 9 of the title mixture as a yellow oil.
Example 12
Preparation of a mixture of 5-Phenylthio-2-(2-hydroxy-3.5-dialkylphenyl)-2H-benzotriazole
(alkyl being independently C4, C~. C1~ and C,6,l
The title mixture is prepared according to the procedure of Example 4 using 40 g the
mixture of Example 11,11.2 g of potassium hydroxide and 12.3 mL of thiophenol.
Example 13
Preparation of a mixture of 5-Benzenesulfonyl-2-(2-hydroxy-3,5-dialkylphenyl)-2H-
benzotriazole (alkyl being independently C4, C8, C1~ and C~fi)
A mixture of the crude product of Example 12, 350 mL of isopropanol, l 4.7 mL of formic
acid and 1.8 mL of concentrated sulfuric acid are heated to reflux and 30 mL of 50%
hydrogen peroxide is added dropwise over a two-hour period. After an additional three
hours at reflux, the reaction mixture is cooled and 10% aqueous sodium sulfite and
aqueous sodium bicarbonate are added. The isopropanol is evaporated and the residue is
extracted with methylene chloride. The organic layer is washed with water and then dried
over anhydrous magnesium sulfate. The solution is concentrated to leave 45 9 of crude
product as a viscous prange oil. Some 30 9 of this crude product is purified by
chromatography on silica gel (heptane:ethyl acetate,4:1) to yield 28.9 9 of the title mixture
as a yellow oil.
Example 14
5-Diphenylphosphinyl-2-(2-hydroxy-3,5-tert-butylphenyl)-2H-benzotriazole
To a flame-dried 500 mL three-necked round-bottomed flask equipped with a condenser,
magnetic stirrer and thermometer are charged 100 mL of dimethyl sulfcxide, 7.41 9 (0.066
mol) of potassium tert-butoxide and 11.17 g (0.060 mol) of diphenylphosphine via a syringe.
A slurry of 10.56 9 (0.030 mol) of 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzo-
triazole in 50 mL of dimethyl sulfoxide is added all at once to the red mixture. The resultant
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brown solution is stirred at 1 35~C for 3.5 hours and then cooled to room temperature. The
mixture is quenched with a portion of saturated ammonium chloride solution and ethyl
acetate is then added. The organic layer is separated and washed thrice with water, once
with brine and then dried over anhydrous magnesium sulfate. To the solution is added 50%
hydrogen peroxide resulting in an exotherm. The mixture is allowed to sit for 30 minutes,
then washed once with 10% sodium metabisulfite solution thrice with saturated sodium
bicarbonate solution once with brine and finally dried over anhydrous magnesium sulfate.
The mixture is filtered with a plug of silica gel and the solvent is removed under reduced
pressure to yield 8.0 9 of a crude yellow solid. The crude product is treated with medium
pressure chromatography using heptane:ethyl acetate, 1:1 to afford 4.2 9 (27% yield) of the
title compound as a yellow solid melting at 98-1 00~C.
Example 15
5-Diphenylphosphinyl-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
Following the procedure of Example 14, the title compound is prepared when 5-chloro-2-(2-
hydroxy-3-a~umyl-5-tert-octylphenyl)-2H-benzotriazole is used as the starting benzotriazole
intermediate.
Examples 1 6-26
Following the general procedure of Example 1, the following additional 2H-benzotriazoles of
formula 1' are preparec.
Example i G2 E1 E2
16 CF3 phenyl tert-octyl
17 CF3 a-cumyl tert-butyl
18 CN a-cumyl tert-octyl
19 CN a-cumyl nonyl
CN a-cumyl tert-butyl
21 COOCH3 a-cumyl dodecyl
22 F phenyl tert-octyl
23 CF3 a-cumyl nonyl
24 CF3 a-cumyl dodecyl
CON(Bu)2 a-cumyl tert-octyl
26 COOCH3 phenyl tert-octyl
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Example 27
Preparation of 5-Octylthio-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
Using the procedure of Example 6 with 5-chloro-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-
2H-benzotriazole and octyl mercaptan, the title compound is prepared.
Example 28
Preparation of 5-Octylsulfonyl-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
5-Octylthio-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole, prepared in
Example 27, is oxidized to the sulfone without purification of the thio intermediate using the
general method of Example 7.
Example 29
Preparation of 5-Chloro-2-(2.4-dihydroxyphenyl)-2H-benzotriazole
Following the general procedure of Example 1, parts a & b, the monoazo intermediate of
the title compound is prepared from 17.3 g of 4-chloro-2-nitroaniline to yield 34.7 g of a
deep red monoazo adduct wetcake.
Reduction of the monoazo adduct
A mixture of 20 g of sodium hydroxide, 500 mL of water and 26.3 of the monoazo adduct
wetcake prepared above is heated to 30~C. Zinc powder (33.0 g) is added incrementally
over two hours. At the end of this addition,180 g of 40% aqueous sodium hydroxide
solution is added dropwise over one hour. The mixture is stirred at ambient temperature for
96 hours. The zinc residue is removed by filtration. The aqueous solution is neutralized to
pH 5-6 and the resulting slurry is filtered. The resulting filter case is washed well with water
and dried to yield 22.5 g of crude product. The crude product is purified by Soxhlet
extraction with acetone to give 9.6 g of the title compound.
Example 30
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Preparation of 5-Chloro-2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole
A mixture of 6.5 g of 5-chloro-2-(2,4-dihydroxyphenyl)-2H-benzotriazole, 7.1 g of 1-
bromooctane, 5.2 9 of anhydrous potassium carbonate and 100 mL of acetone is refluxed
for 24 hours. To the resulting mixture, about 100 mL of water and ethyl acetate are added,
and 10.6 g of crude product is isolated. Column chromatography using petroleum ether
yields 0.9 g of the title compound whose structure is confirmed by Hnmr and massspectrometry.
Example 31
Preparation of 5-Trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-benzotriazole
Following the general procedure of Example 29, the title compound is prepared from 10.3 g
of 4-amino-3-nitrobenzotrifluoride to give 6.4 9 of the title compound whose structure is
confirmed by H nmr.
Example 32
Preparation of 5-Trifluoromethyl-2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole
The title compound is prepared following the general procedure of Example 30 from 5.6 9 of
5-trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-benzotriazole. The crude product is purified by
column chromatography to yield 1.1 9 of the title compound as a white solid melting at 79-
81~C. The structure is confirmed by Hnmr and mass spectrometry.
Example 33
Preparation of 5-Trifluoromethyl-2-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-2H-
benzotriazole
A mixture of 2.3 g of 5-trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-benzotriazole prepared in
Example 31, 1.3 mL of butyl glycidyl ether and 100 mg of ethyl triphenylphosphonium
bromide in 50 mL of xylene is heated to reflux under nitrogen for 14 hours. Water (25 mL)
and 25 mL of ethyl acetate are added and 3 9 of the crude product is isolated.
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Recrystallization from heptane give 2.1 9 of the title compound whose structure is confirmed
by nmr.
Example 34
Preparation of 5-Trifluoromethyl-2-(2-hydroxy-4-aminophenyl)-2H-benzotriazole
The title compound is prepared following the general procedures of Example 1 andExample 29 starting with 4-amino-3-nitrobenzotrifluoride and 3-aminophenol. The structure
of the product is confirmed by nmr.
Example 35
Preparation of 5-Trifluoromethyl-2-[2-hydroxy-4-(2-ethylhexanoylamino)phenyll-2H-
benzotriazole
To a mixture of 4 9 of 5-trifluoromethyl-2-(2-hydroxy-4-aminophenyl)-2H-benzotriazole and
1.4 g of triethylamine in 75 mL of toluene is added dropwise a mixture of 2-ethylhexanoyl
chloride in 125 mL of toluene. The resulting mixture is treated with 100 mL of water and the
crude product formed is purified by column chromatography to give 1.9 9 of the title
compound melting at 179-181 ~C. The structure is confirmed by nmr.
Example 36
Preparation of 5-Carbomethoxy-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-
benzotriazole
a) Esterification of 4-amino-3-nitrobenzoic Acid
To a 2 L 3-necked flask fitted with a mechanical stirrer are added 700 mL of methanol, 20 9
of xylene, 14 9 concentrated sulfuric acid and 100 9 of 4-amino-3-nitrobenzoic acid. The
solution is heated to reflux for 33 hours. The mixture is cooled to 35~C and neutralized to pH
7.8. Water (1 L) is added, the solid collected and washed with 500 ml to give after drying
overnight 100.9 9 of methyl 4-amino-3-nitrobenzoate.
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b) Diazotization of methyl 4-amino-3-nitrobenzoate
To a 1 L 3-necked flask fitted with a mechanical stirrer is added 177 g of 96% sulfuric acid
and then slowly over 90 minutes 11 g of sodium nitrite. The mixture is warmed to 30~C to
initiate the reaction. The temperature is kept below 70~C. The mixture is then cooled to 15~C
and 30 9 of methyl 4-amino-3-nitrobenzoate is added over two hours keeping the
temperature between 15-20~C. The mixture is cooled to 0~c and 200 9 of ice is added to
make the solution suitable for the coupling reaction to form a monoazo compound.
c~ Monoazo adduct
To a 2 L 3-necked flask fitted with a mechanical stirrer and addition funnel are added 52 9
of 2-a-cumyl-4-tert-octylphenol,20 9 of water, 315 9 of methanol, 7 9 of xylene and 150 9
of sodium hydroxide. The mixture is cooled to -5~C and the diazonium salt solution prepared
is step b. is added over a two hour period with cooling to keep the temperature below 3~C.
After the diazonium salt solution is added, the pH is adjusted to 6.5-7Ø The mixture is
poured into 500 mL of xylene and washed thrice with 500 mL of water at 60~C. The xylene
is removed by distillation to give 186 g of the monoazo adduct containing residual xylene.
d) Reduction of the monoazo adduct
To a 500 mL flask fitted with a mechanical stirrer is added the 186 9 of monoadduct
prepared in step c.,125 9 of 2-butanol and 1.7 9 of 2,3-dichloro-1,4-naphthoquinone. The
mixture is heated to 90~C and the resulting solution is then charged to the addition funnel
on a separate flask. In ~aid second flask are added 175 g of 2-butanol and 18.6 9 of sodium
hydroxide, The flask is heated to 95~C and the monoazo solution is added over two hours
while distilling off methyl ethyl ketone and 2-butanol.2-Butanol (100 9) is added and an
azeotrope is distilled off. The mixture is then cooled and 300 9 of xylene and 200 mL of
water are added. The pH is adjusted to 7-7.5 with 20% sulfuric acid. At 60~C, the aqueous
phase is separated and the organic phase washed twice with 200 mL of water. The xylene
is removed by distillation and the residue formed is crystallized from methanol to give 8.8 9
of the title compound melting at 141-143~C.
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Example 37
Preparation of 5-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-a-cumyl-
5-tert-octyl)phenyl]-2H-benzotriazole
a) Saponification of 5-Carbomethoxy-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-
benzotriazole
To a 250 mL 3-necked flask equipped with a mechanical stirrer, thermometer, condenser
and nitrogen inlet is added 1.8 9 of potassium hydroxide and 40 mL of methanol. The
mixture is warmed to 40~C to dissolve the potassium hydroxide. To this solution is added
2.7 9 of 5-carbomethoxy-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole,
prepared in Example 36, in 40 mL of methanol. The reaction mixture is refluxed for six
hours. The mixture is then cooled and acidified with hydrochloric acid. Ether and ethyl
acetate are added, and the organic layer is separated and dried over anhydrous sodium
sulfate. After vacuum stripping of the solvent, 2.5 9 of 5-carboxy-2-(2-hydroxy-3-a-cumyl-5-
tert-octylphenyl)-2H-benzotriazole is isolated.
b) 5-Chlorocarbonyl-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole
The 2.5 g of 5-carboxy-2-(2-hydroxy-3-a~umyl-5-tert-octylphenyl)-2H-benzotriazole,
prepared in step a., are placed in a 250 mL flask equipped with a stirrer, thermometer,
reflux condenser, Dean-Stark trap and nitrogen inlet. Toluene (100 mL) is added and the
mixture is reflux to remove any traces of water. The mixture is then cooled and 0.76 9 of
oxalyl chloride in 15 mL of toluene is added. The reaction mixture is heated slowly to 60~C
and held at 60-65~C for eight hours till all the hydrogen chloride is expelled to give the acid
chloride title compound.
c) 5-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-a-cumyl-5-tert-octyl)phenyl]-2H-benzotriazole
To a 500 mL flask equipped with a mechanical stirrer, drying tube, thermometer and
dropping funnel are added 0.8 g of di-n-butylamine, 6 mL of pyridine and 25 mL of toluene.
The mixture is cooled to 0~C. and the acid chloride solution prepared in step b. is placed in
the dropping funnel and added to the reaction mixture over a 30-minute period at -5~C to -
1 0~C. The reaction mixture is stirred at that temperature for 1.5 hours and then held at
ambient temperature overnight. The mixture was filtered and then vacuum stripped to give
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3.0 9 of crude solids. The solid product is chromatographed to provide 1.2 9 of the title
compound as a tan solid melting at 131 -133~C. The structure is confirmed by nmr and mass
spectrometry m/z 596.
Example 38
5-Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole
The title compound is prepared according to general procedure of Example 1 the diazo
compound of 4-amino-3-nitrobenzotrifluoride and 4-tert-octylphenol, and which is purified by
chromatography on silica gel. Recrystallization of the product from either heptane or
methanol yields the title compound as a near white solid melting at 80-81 ~C.
Use Example 39
To ascertain the effect on thermal durability and loss rate from a high solids thermoset
acrylic coating of various 2H-benzotriazole UV absorbers substituted by a variety of electron
withdrawing and electron donating groups, the following tests are carried out.
A high solids thermoset acrylic clear coat is prepared by mixing an experimental acrylic
polyol resin and hexamethoxymethylmelamine (Resimene~ 747, Monsanto) at a solids ratio
of 60/40. The dodecylbenzene sulfonic acid catalyst (Nacure~ 5225; King Industries) is
added at 0.70% by weight. A flow aid Modaflow~ (Monsanto) is added at 0.25% by weight
to form a model acrylic melamine resin system.
The model clear coat is reduced with xylene to a viscosity of 26-27 second using a Zahn #2
cup and applied via a conventional air spray at 50 psi (3.5 Kg/cm2) over a 1 " x 3'1 (2.54 cm x
7.62 cm) quartz slide. Cure is achieved by baking the slide for 30 minutes at 260~F (127~C).
The clear coat is stabilized with 1 % by weight of a hindered amine light stabilizer, bis-(1 -
octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (TINUVIN~ 123, Ciba-Geigy). The
various test benzotriazole UV absorbers are incorporated at the 5 mmol % by weight in the
clear coat. The film thickness on the quartz slides range from 1.15 to 1.41 mils (0.029 to
0.036 mm).
The films on the quartz slides are weathered according to the following conditions in Xenon
Arc Weather-Ometer with a controlled irradiance at 6500 W, using inner quartz and outer
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borosilicate S-type filter. The irradiation cycle is as follows: 40 minutes of straight irradiation
with no water spray, followed by 20 minutes of light plus front spray, followed by 60 minutes
of light irradiation and finally by 60 minutes dart plus rear spray (condensation). The setting
is at 0.55 W/M2 at 340 nm,1.98 kJ/hour. In the light cycle the black panel temperature is
controlled at 70+2~C. The relative humidity in the light cycle is in the range of 50-55% and in
the dark cycle 100%. The absorbance of the long wavelength UV band as a function of
Xenon arc weathering hours are recorded in the table below.
To follow the loss of UV absorbers from the clear coats, UV spectra are measured initially
and after weathering at regular time intervals. The UV spectrophotometer measures
absorbance linearly up to 5.5 absorbance units using a reference beam attenuation
technique.
It is assumed that the degradation products from the UV absorber do not contribute to the
UV spectrum. This is tested by following the ratio of absorbance of the band at about 300
nm and the band at about 340 nm. The ratio does not change upon weathering the sample,
This suggests that the UV spectrum of the weathered films correspond to the amount of UV
absorber remaining in the film with very little if any contribution to the spectrum by photo
degradants.
The data in the table below are based on structural formula A after 1211 hours of exposure
of the clear coats containing the test benzotriazole UV absorbers.
Compound Units Absorbance G2 R, R2
loss
A 1.7982 hydrogen -PO(OEt)2 tert.-octyl
B 1.6300 hydrogen nitro tert.-octyl
C 1.4863 phenyl-S- tert.-butyl -CH2-CH2COOC8H17
D 1.4002 hydrogen hydrogen -CH2-CH2COOCH3
E 1.1872 methoxy tert.-butyl methyl
F 0.5259 hydrogen tert.-butyl -CH2-CH2COOCH3
G 0.4527 hydrogen hydrogen a-cumyl
H 0.4420 hydrogen tert.-butyl -CH2-CH2COOC8Hl7
0.4299 hydrogen tert.-octyl a-cumyl
J 0.4134 hydrogen hydrogen tert.-octyl
K 0.3777 hydrogen tert.-octyl tert.-octyl
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L 0.3712 hydrogen tert.-butyl -CH2CH2CH20H
M 0.3433 hydrogen a-cumyl -CH2-CH2COOCH3
N 0.3098 cyano tert.-butyl tert.-butyl
O 0.2689 phenyl-SO2- tert.-butyl -CH2-CH2COOC8H,7
P 0.2576 hydrogen a-cumyl a-cumyl
Q 0.2492 hydrogen a-cumyl tert.-octyl
Inspection of these data leads to some clear conclusions about the photostability of 2H-
benzotriazole UV absorbers and about the nature of the substitution which will affect that
photostability.
Increased photostability occurs when Rjis a-cumyl or phenyl and when G2is an electron
withdrawing group such as phenyl-sulfonyl or cyano.
The nature of the R2 group has less influence on the photostability of the benzotriazole UV
absorbers.
From these observations, then an idealized benzotriazole UV absorber might theoretically
be designed where G2is an electron withdrawing group, R1 is an effective bulky group, and
R2 is a thermally stable moiety. One such idealized compound might be a benzotriazole
where G2is phenylsulfonyl, R,is a-cumyl and R2is tert-octyl. This benzotriazole is
generically claimed in United States Patent No. 5,280,124. The data given in Example 40
below confirms this prediction and this ~idealized~ compound does indeed exhibit a very low
loss rate well below the present state of the art.
Example 40
Following the general procedure of Example 39, a number of additional benzotriazole test
compounds are incorporated into a high solids thermoset acrylic melamine resin at such
concentrations between 1.93 and 3 % by weight to give equal molar concentrations of test
benzotriazole in equal film thickness, and sufficient to give a starting absorbance of
approximately 2.0 absorbance units.
The test discs are exposed in a Xenon-Arc Weather-Ometer at X180 cycle (0.45 Watts/M2).
The initial UV absorbance is measured followed by measurements at roughly 250 hour
intervals for the first 2000 hours and every 500 hours thereafter. Each clear coat also
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contains 1 % by weight of a hindered amine light stabilizer, bis-(1-octyloxy-2,2,6,~tetra-
methylpiperidin-4-yl) sebacate, as well.
The data in the table below are based on compounds of formula A after 1253 hours of
exposure of the clear coats containing the test benzotriazole UV absorbers.
Compound Units Absorbance G2 R1 R2
loss
R 0.2424 hydrogen phenyl a-cumyl
Q 0.2351 hydrogen a-cumyl tert.-octyl
S 0.1271 CF3 a-cumyl tert-octyl
T 0.1827 phenyl-SO2 tert-butyl tert-butyl
The data in the table below are based on compounds of formula A after 1489 hours of
exposure of t1e clear coats containin~ the test benzotriazole UV absorbers.
Compound Units Absorbance G2 R, R2
loss
R 0.3724 hydrogen phenyl a-cumyl
Q 0.287 hydrogen a-cumyl tert.-octyl
S 0.1547 CF3 a-cumyl tert-octyl
T 0.2654 phenyl-SO2 tert-butyl tert-butyl
The data in the table below are based on compounds of formula A after 2521 hours of
exposure of the clear coats containing the test benzotriazole UV absorbers.
Compound Units Absorbance G2 R1 R2
loss
R 0.4824 hydrogen phenyl a-cumyl
Q 0.4054 hydrogen a-cumyl tert.-octyl
S 0.2192 CF3 a-cumyl tert-octyl
T 0.3570 phenyl-SO2 tert-butyl tert-butyl
It is clear from the three tables above that Compounds S and especially T which have an
electron withdrawing group at the 5-position of the benzo ring are significantly more durable
than benzotriazoles which do not have such a group on the benzo ring.
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The data in the table below are based on compounds of formula A after 1264 hours of
exposure of the clear coats containing the test benzotriazole UV absorbers.
Compound Units Absorbance G2 R, R2
loss
Q 0.2293 hydrogen a-cumyl tert.-octyl
S 0.0921 CF3 a-cumyl tert-octyl
T 0.1965 phenyl-SO2 tert-butyl tert-butyl
U 0.0944 phenyl-SO2 a-cumyl tert-octyl
V 0.1719 chloro a-cumyl tert-octyl
W 0.1655 fluoro a-cumyl tert-octyl
X 0.1796 hydrogen phenyl tert-octyl
The data in the table below are based on compounds of formula A after 1518 hours of
exposure of the clear coats containing the test benzotriazole UV absorbers.
Compound Units Absorbance G2 R1 R2
loss
Q 0.2662 hydrogen a-cumyl tert.-octyl
S 0.1116 CF3 a-cumyl tert-octyl
T 0.2423 phenyl-SO2 tert-butyl tert-butyl
U 0.1114 phenyl-SO2 a-cumyl tert-octyl
V 0.1955 chloro a-cumyl tert-octyl
W 0.1668 fluoro a-cumyl tert-octyl
X 0.2220 hydrogen phenyl tert-octyl
The data in these tables clearly show that benzotriazoles substituted by an electron
withdrawing group on the benzo ring, particularly a group such as trifluoromethyl or phenyl-
sulfonyl, are especially durable as measured by low loss rate absorbance values after
exposure to actinic radiation. Compounds S, U, V and W are especially durable and fit the
profile proposed above. Indeed, the prediction that Compound U would be particularly
durable is borne out by the data above. Inspection of the data for compounds T and U
shows the added beneficial effect of having an effective bulky group such as a-cumyl at the
R, position compared to a mere alkyl moiety such as tert-butyl at that position.
