Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
A-20802/A ,~,
~2V1 l~2
- 1 -
Stabilisation of polyamide, polyester and polyketone
The present invention relates to compositions comprising a polyamide, polyester or polyke-
tone, a specific organic phosphite (Irgafos012, Ciba-Geigy) and a sterically hindered phenol,
to the use thereof for stabilising polyamide, polyester or polyketone against oxidative, ther-
mal and/or light-induced degradation, as well as to a process for stabilising these plastic
materials.
It is known from U.S. patent 4 360 617 that stabiliser mixtures comprising symmetrical tri-
arylphosphites and specific phenolic antioxidants are particularly suitable for protecting spe-
cific organic materials, such as polyurethane, polyacrylonitrile, polyamide 12 or polystyrene,
from oxidative, thermal or light-induced degradation. Tris(2,4-di-tert-butylphenyl)phosphite
(Irgafos~168, Ciba-Geigy) is disclosed as the preferred triaryl phosphite.
In polyamides, polyesters and polyketones, these known stabiliser mixtures cannot meet all
the demands made on them. It is known that such stabiliser mixtures reduce the starting co-
lour as well as the colour development of the polyamide during oven ageing and that they
reduce the decrease of the mechanical properties of the polyamide during oven ageing and
exposure to light. A disadvantage of these stabiliser mixtures is that it is often found that
these phosphites have a tendency to bloom.
U.S. Patents 4 318 845 and 4 374 219 disclose alkanolamine esters of cyclic 1,1'-biphenyl-
2,2'-diyl phosphites and alkylidene-1,1'-biphenyl-2,2'-diyl phosphites as stabilisers for orga-
nic polymers and lubricating oils, especially as processing stabilisers for polyolefins, elasto-
mers, polyesters and polycarbonates.
It has now been found that a stabiliser mixture comprising a very specific phosphite, selec-
ted from the U.S. patents 4 318 845 and 4 374 219, together with a very specific group of
sterically hindered phenols, is particularly suitable as stabiliser for polyamides, polyesters or
polyketones. The polyamides, polyesters or polyketones thus stabilised have enhanced pro-
perties with respect to oxidative, thermal and/or light-induced degradation, and the novel
phosphite does not bloom.
2201 1 82
Accordingly, this invention relates to compositions, comprising
a) a polyamide, polyester or polyketone which is subject to oxidative, thermal or light-
induced degradation,
b) the phosphite of formula I
(CH3)3C ~C(CH3)3
g~_ ,P O CH2CH2 N (1)~
(CH3)3C
C(CH3)3
and
c) at least one compound of formula ll
- H3C
\C~CH3
H3C
~ (Il),
HO ~ X--R2
wherein
R1 is C,-C4alkyl,
nis1,2,30r4,
O o
Il 11
X is methylene, --CH2--CH2--C--Y-- or --CH2--C--0--CH2--CH2
Y is oxygen or-NH-; and,
if n = 1,
3 220 1 1 82
X is --CH2--CH2 C--Y-- , wherein Y is bound to R2, and
R2 is C,-C2salkyl; and,
if n = 2,
X is --CH2--CH2--C--Y-- , wherein Y is bound to R2, and
R2 is C2-C12alkylene, C4-C,2alkylene which is interrupted by oxygen or sulfur; or, if Y is
-NH-, R2 is additionally a direct bond; and,
if n = 3,
o
X is methylene or --CH2--C--O--CH2--CH2 , wherein the ethylene group isbound to R2, and
I
0~,~ N ~0
R2 is I ~ ; and,
/N~N
if n = 4,
o
X is --CH2--CH2--C--Y-- , wherein Y is bound to R2, and
R2 is C4-C,Oalkanetetrayl.
Alkyl of up to 25 carbon atoms is a branched or straight-chain radical, typically methyl, ethyl,
propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-
methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetrame-
thylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-
2201 1 ~2
tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethyl-
hexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.
Preferred meanings of R, are methyl and tert-butyl. R2 is particularly preferably C,-C20alkyl,
especially C,-C,8alkyl, typically C4-C,8alkyl. R2 is particularly preferably C8-C,8alkyl, especial-
ly C,4-C,8alkyl, typically C,8-alkyl.
C2-C,2Alkylene is a branched or straight-chain radical, typically ethylene, propylene, tetra-
methylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethy-
lene or dodecamethylene. R2 is particularly preferably e.g. C2-C,Oalkylene, especially C2-C8-
alkylene. R2 is particularly preferably e.g. C4-C8alkylene, especially C4-C6-alkylene, typically
hexamethylene.
C4-C,2Alkylene which is interrupted by oxygen or sulfur can be interrupted once or several
times and is typically -CH2-O-CH2CH2-O-CH2-, -CH2-(O-CH2CH2-)2O-CH2-,
-CH2-(O-CH2CH2)3O-CH2-, -CH2-(O-CH2CH2-)4O-CH2-, -CH2CH2-O-CH2CH2-O-CH2CH2- or
-CH2CH2-S-CH2CH2-. R2 is particularly preferably e.g. C4-C,Oalkylene which is interrupted by
oxygen or sulfur, especially C4-C8alkylene which is interrupted by oxygen or sulfur, typically
C4-C6alkylene which is interrupted by oxygen or sulfur. R2 is particularly preferably
-CH2CH2-O-CH2CH2-O-CH2CH2- or -CH2CH2-S-CH2CH2-.
CH2
Alkanetetrayl of 4 to 10 carbon atoms is typically --CH2--IC--CH2-- (pentaerythritol),
CH2
--CH2--CH--CH--CH2-- ' --CH2--CH2 CH--CH-CH2-- '
or
--CH2--CH2 CH--CH-CH2 CH2-- ' --CH2--CH2--CH--CH2 CH-CH2 CH2--
2 2 CH CH2 CH2--CH-CH2 CH2 ~ Pentaerythritol is preferred
Component (c) can also be mixtures of different sterically hindered phenols of formula ll.
~2)1 i~
Interesting compounds are those containing as component (c) at least one compound of
formula ll, wherein, if n = 1, R2 is C,-C20alkyl.
Preferred compositions are those containing as component (c) at least one compound of
formula ll, wherein,
if n = 2,
R2 is C2-C8alkylene, C4-C8alkylene which is interrupted by oxygen or sulfur; or, if Y is -NH-,
R2 is additionally a direct bond and,
if n = 4,
R2 is C4-C8alkanetetrayl.
Preferred compositions are also those containing as component (c) at least one compound
of formula ll, wherein,
R, is methyl or tert-butyl,
n is 1, 2 or 4,
ll
X is --CH2--CH2--C--Y-- ,
Y is oxygen or -NH-; and,
if n = 1,
R2 is C,4-C,8alkyl; and,
if n = 2,
R2 is C4-C6alkylene, or C4-C6alkylene which is interrupted by oxygen; and,
if n = 4,
22~
- 6 -
R2 is C4-C6alkanetetrayl.
Interesting compositions are also those containing as component (c) at least one compound
of formula 1, wherein the compound of formula I is a compound of formula lla to llh
H3C
\ ~CH3
H3C ~ ~
HO~ ~CH2--CH--C--NH (CH )
~ 2 2 3 (lla), Irganox~1098
H3C C/
CH
H3C 3 - 2
& ~CH3
H3C &,=, 1~l
H3C ~CH2--CH2 C--O--C,8H37 (llb), Irganox~1076
CH
H3C 3
& ~ CH3
H3C &, , ~
HO ( ~CH2--CH--C--O--CH C
~ 2 2 (llc), Irganox~1010
H3C C
CH3
H3C _ 4
220 ~ I &2
H C
3 \ ~ CH3
H C~C\
HO~ CH2 CH2--C--O--CH2--CH2--O--CH2 (lld), Irganox~245
H3C - 2
H3C
\C~CH3
H C~
/--~
HO~ CH2--CH2C--O--(CH2)3
y (lle), Irganox~259
H3C
~C~CH
H3C 3 - 2
H3C
\ ~CH3
H C ~ C~ 1~
HO~,~ CH2--CH2C--O--(CH) S
~ 22 (llf), Irganox~1035
H3C C/
~CH
3 2
IR3 H3C ~
0~ N ~0 ~ CH3
R3 ~f R3 ~COH3 (119), Irganox~3114
H C/ \
2201 i~2
- 8 -
R H3C\ /CH3
13 ,~ C~
O~N f~;O _ I /~ CH3
~N~N~ R3 = (CH2)2 ~--~--CH2~0H (llh), Irganox 3125.
H C/ \
Irganox~1098, Irganox~1076, Irganox~1010, Irganox~245, Irganox~259, Irganox~3114, Irga-
nox~1035 and Irganox~3125 are trademarks of Ciba-Geigy.
Preferred compositions are those containing as component (c) at least one compound of
formula 1, wherein the compound der formula I is a compound of formula lla, llb, llc or lld, in
particular a compound of formula lla, llb or llc, typically a compound of formula lla.
Component (b) of the novel composition, or the phosphite of formula 1, is known and its pre-
paration is disclosed in Example 4 of U.S. patents 4 318 845 and 4 374 219 mentioned at
the outset. This phosphite can be obtained in different modifications, as disclosed, inter alia,
in the following U.S. patents. U.S. 5 276 076 discloses a solid amorphous form of the phos-
phite of formula 1. U.S. 5 334 739 discloses the a-crystalline form of the phosphite of formu-
la 1. U.S. 5 326 802 discloses the ,B-crystalline form, and U.S. 5 321 031 discloses the y-cry-
stalline form, of the phosphite of formula 1. The phosphite of formula I is commercially avai-
lable under the trademark Irgafos~12 (Ciba-Geigy).
Component (c) of the novel composition, or the compounds of formula ll, are known and
some are commercially available. Possible processes for the preparation of the compounds
of formula ll may be found, inter alia, in U.S. patents 3 330 859 and 3 960 928.
Polyamides will be understood as meaning aliphatic and aromatic polyamides or copoly-
amides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic
acids or their corresponding lactams. Suitable polyamides are, for example: PA 6, PA 11,
PA 12, PA 46, PA 6.6, PA 6.9, PA 6.10 or PA 6.12, PA 10.12, PA 12.12 and also amor-
22~J1 1 82
phous polyamides of the Trogamid PA 6-3-T and Grilamid TR 55 type. Polyamides of the
cited type are commonly known and are commercially available.
Interesting compositions are those containing as component (a) polyamide 6, polyamide
6.6, polyamide 11 or polyamide 12 or copolymers thereof, in particular polyamide 6 or poly-
amide 6.6, or elastomer-modified polyamide 6 or polyamide 6.6 blended with polypropylene.
Polyesters may be homopolyesters or mixed polyesters which are composed of aliphatic,
cycloaliphatic or aromatic dicarboxylic acids and diols or hydroxycarboxylic acids.
The aliphatic dicarboxylic acids may contain 2 to 40 carbon atoms, the cycloaliphatic dicar-
boxylic acids may contain 6 to 10 carbon atoms, the aromatic dicarboxylic acids may con-
tain 8 to 14 carbon atoms, the aliphatic hydroxycarboxylic acids may contain 2 to 12 carbon
atoms, and the aromatic as well as the cycloaliphatic hydroxycarboxylic acids may contain 7
to 14 carbon atoms.
The aliphatic diols may contain 2 to 12 carbon atoms, the cycloaliphatic diols may contain 5
to 8 carbon atoms, and the aromatic diols can contain 6 to 16 carbon atoms.
Aromatic diols are those, wherein two hydroxyl groups are bound to one or different aroma-
tic hydrocarbon radicals.
It is also possible that the polyesters are branched with small amounts, e.g. from 0.1 to
3 mol%, based on the dicarboxylic acids present, of more than difunctional monomers (e.g.
pentaerythritol, trimellitic acid, 1,3,5-tri(hydroxyphenyl)benzene, 2,4-dihydroxybenzoic acid
or 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane).
In polyesters consisting of at least 2 monomers, these can be randomly distributed or may
be block copolymers.
Suitable dicarboxylic acids are linear and branched saturated aliphatic dicarboxylic acids,
aromatic dicarboxylic acids, and cycloaliphatic dicarboxylic acids.
220 I 7 82
10 -
Aliphatic dicarboxylic acids are suitably those containing 2 to 40 carbon atoms, typically
oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, pimelic acid, adipic acid, tri-
methyladipic acid, sebacic acid, azelaic acid and dimeric acids (dimerisation products of un-
saturated aliphatic carboxylic acids such as oleic acid), alkylated malonic and succinic acids
such as octadecylsuccinic acid.
Suitable cycloaliphatic dicarboxylic acids are: 1,3-cyclobutanedicarboxylic acid, 1,3-cyclo-
pentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-(dicarbo-
xylmethyl)cyclohexane, 4,4'-dicyclohexyldicarboxylic acid.
Suitable aromatic dicarboxylic acids are: Preferably terephthalic acid, isophthalic acid, o-
phthalic acid as well as 1,3-, 1,4-, 2,6- or 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldi-
carboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid,
1,1,3-trimethyl-5-carboxyl-3-(p-carboxylphenyl)indane, 4,4'-diphenyl ether dicarboxylic acid,
bis-p(carboxylphenyl)methane, or bis-p(carboxylphenyl)ethane.
The aromatic dicarboxylic acids are preferred and of these, in particular, terephthalic acid,
isophthalic acid and 2,6-naphthalenedicarboxylic acid.
Further suitable dicarboxylic acids are those containing -CO-NH groups; they are disclosed
in DE-A-2 414 349. I:~icarboxylic acids containing N-heterocyclic rings are also suitable, for
example those which are derived from carboxylalkylated, carboxylphenylated or carboxy-
benzylated monoamine-s-triazinedicarboxylic acids (see DE-A-2 121 184 and 2 533 675),
mono- or bishydantoins, benzimidazoles which may be halogenated, or parabanic acid. The
carboxyalkyl groups can in this case contain 3 to 20 carbon atoms.
Suitable aliphatic diols are the linear and branched aliphatic glycols, preferably those of 2 to
12, preferably 2 to 6, carbon atoms in the molecule, for example: ethylene glycol, 1,2- and
1,3-propylene glycol, 1,2-, 1,3-, 2,3- or 1,4-butanediol, pentyl glycol, neopentyl glycol, 1,6-
hexanediol, 1,12-dodecanediol. A suitable cycloaliphatic diol is, for example, 1,4-dihydroxy-
cyclohexane. Further suitable aliphatic diols are typically 1,4-bis(hydroxymethyl)cyclo-
hexane, aromatic-aliphatic diols, such as p-xylylene glycol or 2,5-dichloro-p-xylylene glycol,
2,2-(,~-hydroxyethoxyphenyl)propane as well as polyoxyalkylene glycols, such as diethylene
-11 220 1 1 82
glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alkylenediols are
preferably linear and preferably contain 2 to 4 carbon atoms.
Preferred diols are the alkylenediols,1,4-dihydroxycyclohexane and 1,4-bis(hydroxymethyl)-
cyclohexane. Ethylene glycol,1,4-butanediol as well as 1,2- and 1,3-propylene glycol are
particularly preferred.
Further suitable aliphatic diols are the ,B-hydroxyalkylated, preferably ,~-hydroxyethylated,
bisphenols such as 2,2-bis[4'-(~-hydroxyethoxy)phenyl]propane. Further bisphenols as in-
dicated later.
Another group of suitable aliphatic diols are the heterocyclic diols disclosed in the German
specifications 1 812 003, 2 342 432, 2 342 372 and 2 453 326.111ustrative examples are:
N,N'-bis(~-hydroxyethyl)-5,5-dimethylhydantoin, N,N'-bis(,B-hydroxypropyl)-5,5-dimethyl-hyd-
antoin, methylenebis[N-(~-hydroxyethyl)-5-methyl-5-ethylhydantoin], methylenebis[N-(,~-hy-
droxyethyl)-5,5-dimethylhydantoin], N,N'-bis(,~-hydroxyethyl)benzimidazolone, N,N'-bis(~-hy-
droxyethyl)-(tetrachloro)benzimidazolone, or N,N'-bis(,B-hydroxyethyl)-(tetrabromo)benzimi-
dazolone.
Suitable aromatic diols are mononuclear diphenols and, preferably, binuclear diphenols,
which carry a hydroxyl group at each aromatic nucleus. Aromatic will preferably be under-
stood as meaning aromatic hydrocarbon radicals such as phenylene or naphthylene. In
addition to, for example, hydroquinone, resorcinol or 1,5-, 2,6- and 2,7-dihydroxynaphtha-
lene, those bisphenols merit particular mention which can be illustrated by the following
formulae:
R~ R~ R~ R~
~A~ HO~
R" R" R" R"
2 2 ~ I l 8 L
- 12-
R" R"
R' R'
~,A~OH
R" R"
R' R'
~A ~3A~A~
R" R"
R' R'
~OH,
R" R"
The hydroxyl groups can be in m-position, preferably in p-position, R' and R" in these for-
mulae may be alkyl of 1 to 6 carbon atoms, halogen such as chloro or bromo and, prefe-
rably, hydrogen atoms. A can be a direct bond, or oxygen, sulfur, -SO-, -SO2-, ~C=O,
-P(O)(C1-C20alkyl)-, unsubstituted or substituted alkylidene, cycloalkylidene or alkylene.
Typical examples of unsubstituted or substituted alkylidene are ethylidene, 1,1- or 2,2-pro-
pylidene, 2,2-butylidene, 1,1-isobutylidene, pentylidene, hexylidene, heptylidene, octyli-
dene, dichloroethylidene, trichloroethylidene.
2201 18~
- 13-
Typical examples of unsubstituted or substituted alkylene are methylene, ethylene, phenyl-
methylene, diphenylmethylene, methylphenylmethylene.Typical examples of cycloalkylidene
are cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.
Illustrative examples of bisphenols are: bis(p-hydroxyphenyl)ether or bis(p-hydroxyphenyl)-
thioether, bis(p-hydroxyphenyl)sulfone, bis(p-hydroxyphenyl)methane, bis(4-hydroxyphe-
nyl)-2,2'-biphenyl, phenylhydroquinone, 1,2-bis(p-hydroxyphenyl)ethane, 1-phenyl-bis(p-
hydroxyphenyl)methane, diphenyl-bis(p-hydroxyphenyl)methane, diphenyl-bis(p-hydroxy-
phenyl)ethane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3,5-dimethyl-4-hydroxyphe-
nyl)-p-diisopropylbenzene, bis(3,5-dimethyl-4-hydroxyphenyl)-m-diisopropylbenzene, 2,2-
bis(3',5'-dimethyl-4'-hydroxyphenyl)propane, 1,1- or 2,2-bis(p-hydroxyphenyl)butane, 2,2-
bis(p-hydroxyphenyl)hexafluoropropane, 1,1-dichloro- or 1,1,1-trichloro-2,2-bis(p-hydroxy-
phenyl)ethane, 1,1-bis(p-hydroxyphenyl)cyclopentane and, preferably, 2,2-bis(p-hydroxy-
phenyl)propane (bisphenol A) and 1,1-bis(p-hydroxyphenyl)cyclohexane (bisphenol C).
Suitable polyesters of hydroxycarboxylic acids are typically polycaprolactone, polypivalo-
lactone or the polyesters of 4-hydroxycyclohexanecarboxylic acid or 4-hydroxybenzoic acid.
Polymers which are also suitable are those predominantly containing ester bonds, but which
can also contain other bonds, e.g. polyester amides or polyester imides.
Polyesters containing aromatic dicarboxylic acids have become of the greatest importance,
especially the polyalkylene terephthalates. Those novel moulding compounds are therefore
preferred, wherein the polyester is composed of at least 30 mol%, preferably of at least 40
mol%, of aromatic dicarboxylic acids, and of at least 30 mol%, preferably of at least 40
mol%, of alkylenediols which preferably contain 2 to 12 carbon atoms, based on the poly-
ester.
In this case the alkylenediol is preferably linear and contains 2 to 6 carbon atoms, typically
ethylene-, tri-, tetra- or hexamethylene glycol, and the aromatic dicarboxylic acid terephtha-
lic acid and/or isophthalic acid.
Particularly suitable polyesters are PET, PETG (glycol-modified polyethylene terephthalate)
or PBT and corresponding copolymers. PET and its copolymers are particularly preferred.
22 0 1 i 8 2
- 14-
Polyketones will be understood as meaning plastic materials which are prepared by polyme-
rising carbon monoxide with unsaturated hydrocarbons, such as dislosed, inter alia, in
EP-A-0 222 454 or EP-A-0 685 517.
Convenient compositions, as described above, are those wherein components (b) and (c)
are present together in an amount of 0.05 to 5 %, preferably of 0.1 to 5 %, typically of 0.1 to
2 %, based on the weight of component (a).
Also preferred are those compositions, wherein the weight ratio of the components (b):(c) is
from 10:1 to 1:10, preferablyfrom 5:1 to 1:5, typicallyfrom 4:1 to 1:2.
In addition to the components (b) and (c), the novel compositions can contain additional
additives or costabilisers, such as the following:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-
methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu-
tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethyl-
phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-
methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for
example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-di-
methyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and
mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioc-
tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-
4-nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxy-
phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-
cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-
-15- 22fJ~ i 1 b2
butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-
hydroxyphenyl) adipate.
1.4. Tocopherols, for example a-tocopherol, ~-tocopherol, y-tocopherol, ~-tocopherol and
mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-
2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphe-
nyl)disulfide.
1.6. Alkylidenebisphenols. for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-
methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)-
phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-me-
thylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl-
phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a-methylben-
zyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methy-
lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-
tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-
4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-
4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-
butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadi-
ene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha-
late, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphe-
nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,
1 ,1 ,5 ,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane .
1.7. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi-
benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-
3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-
tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy-
benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
220, 182
- 16-
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hy-
droxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-
dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-te-
tramethylbutyl)phenyl]-2,2-bis(3 ,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-
benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame-
thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hy-
droxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-
triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-
tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-
benzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxyben-
zyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho-
nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy-
droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate,
the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-
(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric
alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy-
lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy-
droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-
propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
-17- 220 1 1 -~
1.14. Esters of ,B-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-
hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane-
diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene gly-
col, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,
N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of ~-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric
alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox-
amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-
droxymethyl-1 -phospha-2,6,7-trioxabicyclol2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alco-
hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox-
amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-
droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-
butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis( 3,5-di-tert-butyl-4-hydroxy-
phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-
hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide
(Naugard~XL-1 supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-
butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-
ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naph-
220 1 i 82
- 18 -
thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-
N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclo-
hexyl-N'-phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-
N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-
diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phe-
nyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine,
4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylamino-
phenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dime-
thylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane,
1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-
octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of
mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopro-
pyl/isohexyldiphenylamines, a mixture of mono- und dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- und dial-
kylated tert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylated tert-octyl-phe-
nothiazines, N-allylphenothiazin, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis-
(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)-
sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV absorbers and light stabilisers
2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzo-
triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe-
nyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-
tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-methylphe-
nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-
(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotri-
azole, 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hy-
droxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hy-
droxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-
5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-
220 1 1 8~
- 19-
carbonylethyi)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-
hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-
tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis-
[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-
[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethy-
lene glycol 300; [R--CH2CH2--COO-CH2CH2~ where R = 3'-tert-butyl-4'-hydroxy-5'-2H-
benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-
phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)-
phenyl]benzotriazole .
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl-
oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl
salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben-
zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo-
ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxy-
benzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl a-cyano-,B"B-diphenylacrylate, isooctyl a-cyano-,~,~-diphe-
nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-~-methyl-p-methoxy-cinna-
mate, butyl a-cyano-~-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxycin-
namate and N-(~-carbomethoxy-,~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetrame-
thylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate,
nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-
butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe-
nyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands.
220 1 i ~2
- 20 -
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)seba-
cate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-pi-
peridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxy-
ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic conden-
sates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylami-
no-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis-
(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis-
(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-
2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-
di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-
dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetrame-
thylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis-(2,2,6,6-tetramethyl-4-piperi-
dyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl )-1,3,5-triazine and 1,2-bis(3-
aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pen-
tamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dode-
cyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetrame-
thyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrroli-
dine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine,
a condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine
and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-ami-
nopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-te-
tramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-do-
decylsuccinimid, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-
7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-
tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-
formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxy-
methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-
3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction product of maleic acid anhydride-
a-olefin-copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-
amlnoplpendlne.
2~0 1 i 82
- 21 -
2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-
5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani-
lide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its
mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disub-
stituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1.3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-
(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-pro-
pyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-
(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphe-
nyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tri-
azine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-tri-
azine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-
triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-di-
methylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-
triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-
(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphe-
nyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phe-
nyl}-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine,
N,N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl
dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl-
oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites,
phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos-
phite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl
pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-
di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol di-
- 22 - 2 2 ~ 2
phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-
butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-bu-
tylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-
benz[d,g~-1 ,3,2-dioxaphosphocin, 6-fluoro-2,4,8,1 0-tetra-tert-butyl-1 2-methyl-dibenz[d,g]-
1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-
tert-butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-
1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-di-
yl)phosphite.
5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,
N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-
dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhy-
droxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived
from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-oc-
tyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone, N-
hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-
alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-hep-
tadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhy-
droxylamine derived from hydrogenated tallow amine.
7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of ~-thiodipropionic acid, for example the lauryl,
stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-
benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(~-
dodecylmercapto)propionate.
9. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phos-
phorus compounds and salts of divalent manganese.
22QI i82
- 23 -
10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl
cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, al-
kali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stea-
rate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and po-
tassium palmitate, antimony pyrocatecholate or zink pyrocatecholate.
11. Nucleating agents, for example, inorganic substances such as talcum, metal oxides
such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, pre-
ferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids
and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium
succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
12. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres,
glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car-
bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fi-
bers.
13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology
additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863;
U.S.4,338,244; U.S. 5,175,312; U.S.5,216,052; U.S. 5,252,643; DE-A-4316611;
DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)-
phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phe-
nyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-
one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphe-
nyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-bu-
tyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-di-
methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
With the exception of the benzofuranones listed under item 14, the costabilisers are added
typically in concentrations of 0.01 to 10 %, based on the total weight of the stabilising poly-
amide, polyester or polyketone.
220 i 1 ~2
- 24 -
Further preferred compositions comprise, besides the components (a), (b) and (c), further
additives, preferably antioxidants, light stabilisers and/or processing stabilisers.
Particularly preferred additives are phenolic antioxidants (item 1 in the list), sterically hin-
dered amines (item 2.6 in the list), phosphites and phosphonites (item 4 in the list) and
peroxide scavengers (item 8 in the list).
Further additional additives (stabilisers) which are also particularly preferred are benzo-
furan-2-ones, such as those disclosed, inter alia, in US-A-4 325 863, US-A-4 338 244,
US-A-5 175 312, US-A-5 216 052, US-A-5 252 643, DE-A-4 316 611, DE-A-4 316 622,
DE-A-4 316 876, EP-A-0 589 839 and EP-A-0 591 102.
Illustrative examples of such benzofuran-2-ones are compounds of formula
R ~CIC~
R'.2 H "
wherein
R'" is an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system;
R'12 is hydrogen;
R',4 is hydrogen, alkyl of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, or chloro;
o
R',3 has the meaning of R',2 or R',4, or is a radical of formula --(CH2)s C--OR',
O O O
Il 11 11
--(CH2)s C--N(R ,7)2 ~ --(CH2)s C--O--A--O--C--(CH2)s E ,
O O O O
Il 11 11 11
--(CH2)s C--NR',8 A--NR',8 C--(CH2)s E, --(CH2)s C--NR',8 A--o--C--(CH2)s E,
~2C17 ~
- 25 -
O ~ o o
--(CH2)s C--N N--C--(CH2)s E . -CH2-S-R ~9, --CH(C6Hs)--C--OR~,6 or -D-E,
wherein
R'16 is hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of 2 to 18 carbon atoms which is inter-
rupted by oxygen or sulfur, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclo-
pentyl, cyclohexyl, phenyl, or phenyl which is substituted by 1 to 3 alkyl radicals having a
total of at most 18 carbon atoms;
sis0, 1 or2;
substituents R',7 are each independently of one another hydrogen, alkyl of 1 to 18 carbon
atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals
having a total of at most 16 carbon atoms, a radical of formula -C2H40H, -C2H4-O-CtH2t+, or
o
--C2H4 o--C--R'20 , or, together with the linking nitrogen atom, form a piperidine or
morpholine radical;
tis 1 to 18;
R'20 is hydrogen, alkyl of 1 to 22 carbon atoms, or cycloalkyl of 5 to 12 carbon atoms;
A is alkylene of 2 to 22 carbon atoms which may be interrupted by nitrogen, oxygen or sul-
fur;
R'18 is hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl; phenyl
which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, or
benzyl;
R',g is alkyl of 1 to 18 carbon atoms;
D is -O-, -S-, -SO-, -SO2- or -C(R'2,)2-;
substituents R'21 are each independently of the other hydrogen or C,-C16alkyl, the two R'
together containing 1 to 16 carbon atoms, or R'2, is phenyl or a radical of formula
O O
Il 11
(CH2)s C OR 16 or --(CH2)s C--N(R'17)2 , wherein s, R'16 and R',7 are as defined
above;
E is a radical of formula
-26- 220~
R 14~_,0
~C~O
R'-2 H R"
wherein R'", R',2 and R',4 are as defined above; and
R'1s is hydrogen, alkyl of 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chloro, or a radical
O O
of formula --CH2--C--OR',6 or --CH2--C--N(R'~7)2 , wherein R'16 and R',7 are as de-
fined above, or R',5, together with R',4, forms a tetramethylene radical.
Preferred benzofuran-2-ones are those, wherein R',3 is hydrogen, alkyl of 1 to 12 carbon
o
atoms, cyclopentyl, cyclohexyl, chloro or a radical of formula --(CH2)s C--OR',6 ~
--(CH2)s C--N(R',7)2 or -D-E, wherein s, R',6, R',7, D and E are as defined above, R',6 is
preferably hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.
Preferred benzofuran-2-ones are also those, wherein R'" is phenyl or phenyl which is sub-
stituted by 1 or 2 alkyl radicals having a total of at most 12 carbon atoms; R',2 is hydrogen;
R',4 is hydrogen or alkyl of 1 to 12 carbon atoms;
o
R',3 is hydrogen, alkyl of 1 to 12 carbon atoms, --(CH2)s C--OR',6 ~
--(CH2)s C--N(R',7)2 or -D-E; R',5 is hydrogen, alkyl of 1 to 20 carbon atoms,
O O
Il 11
--CH2--C--OR',6 or --CH2--C--N(R'~7)2 , or R',5, together with R'14, forms a
tetramethylene radical, wherein s, R',6, R',7, D and E are as defined at the outset.
-27- 220~ 2
Particularly interesting benzofuran-2-ones are also those, wherein R'13 is hydrogen, alkyl
containing 1 to 12 carbon atoms or -D-E; R'12 and R'14 are each independently of the other
hydrogen or alkyl of 1 to 4 carbon atoms; and R'1s is alkyl of 1 to 20 carbon atoms, wherein
D and E are as defined at the outset.
Of particular interest are also those benzofuran-2-ones, wherein R'13 is alkyl of 1 to 4 car-
bon atoms or -D-E; R',2 and R',4 are hydrogen; and R'15 is alkyl of 1 to 4 carbon atoms, cy-
clopentyl or cyclohexyl, D is a -C(R'21)2- group and E is a radical of formula
R',5
~C ~ Il~
n12 n
the substituents R'21 being identical or different from each other and are each alkyl of 1 to 4
carbon atoms, and R'11, R'12, R'14 and R'1s are as defined above.
The amount of benzofuran-2-ones additionally employed can vary within wide limits. They
can be present in the novel compositions typically in amounts of 0.0001 to 5 by weight, pre-
ferably of 0.001 to 2 by weight, most preferably of 0.01 to 2 % by weight.
The components (b) and (c) and any further additives are incorporated into component (a)
[polyamide, polyester or polyketone] by known methods, typically before or during shaping,
or alternatively by applying the dissolved or dispersed components (a) and (b) to the com-
ponent (a), with subsequent evaporation of the solvent, when used. The components (b)
and (c) can also be added to the materials to be stabilised [component (a)] in the form of a
masterbatch which contains these components in a concentration of 2.5 to 25 % by weight.
The components (b) and (c) can also be added before or during polymerisation or before
crosslinking.
The components (b) and (c) can be incorporated into the component (a) to be stabilised in
pure form or encapsulated in waxes, oils or polymers.
2201 182
Components (b) and (c) can also be sprayed onto the component (a) to be stabilised. They
are able to dilute other additives (e.g. the standard additives cited above) or their melts, so
that that they can also be sprayed onto the component (a) to be stabilised together with
these additives. Application by spraying during deactivation of the polymerisation catalysts
is particularly advantageous, in which case the steam used for the deactivation may be
used for spraying.
The polyamides, polyesters and polyketones stabilised in this manner can be used a wide
range of forms, typically including films, fibres, filaments, moulded articles, profiles or bin-
ders for paints, adhesives or putties.
The components (b) and (c) are particularly suitable as processing stabilisers (heat stabili-
sers). To this end they are preferably added to component (a) before or during processing.
A preferred embodiment of this invention is therefore the use of the phosphite of formula I
and at least one compound of formula ll as stabilisers, preferably as processing stabilisers
(heat stabilisers), for polyamides, polyesters or polyketones against oxidative, thermal or
light-induced degradation.
The components (b) and (c) are distinguished by their advantageous colour behaviour, i.e.
minor discoloration of the polyamides, polyesters and polyketones during processing.
This invention also relates to a process for stabilising a polyamide, polyester or polyketone
against oxidative, thermal and/or light-induced degradation, which comprises incorporating
therein, or applying thereto, the phosphite of formula I and at least one compound of for-
mula ll.
This invention also relates to a stabiliser mixture comprising (i) the phosphite of formula I
and (ii) at least one compound of formula ll.
Preferred stabiliser mixtures are also those, wherein the weight ratio of components (i):(ii) is
from 10:1 to 1 :10, preferably from 5:1 to 1:5, typically from 4:1 to 1:2.
~2~ 3 1 82
The preferred compounds of formula ll for use as stabilisers, the process for stabilising, and
the stabiliser mixture are the same as those described for the compositions with a poly-
amide, polyester or polyketone.
The stabiliser mixtures of components (i) and (ii) are called LC blends (low color blends).
They are distinguished by excellent storage stability, low volatility and superb free flowing
properties. The LC blends cited in Table 1 are particularly preferred.
Table 1:
Weight ratio
LC Blend Component(i) Component(ii)(j) (ii)
A Irgafos~12a) Irganox~1010b)1: 1
B Irgafos 12a) IrganOxlD1o1ob) 2: 1
C Irgafos'912a) Irganox~1010b)1: 2
D Irgafos012a) Irganox~1010b)4: 1
E Irgafos~12a) Irganox~3114C)1: 1
F Irgafos'D12a) Irganox~1098d)1: 1
G Irgafos~12a) Irganox~1098d)1: 2
H Irgafos~12a) Irganox~1076e)4: 1
Irgafos~12a) Irganox~1076e)2: 1
a) Irgafos~12 conforms to the compound of formula 1.
b) Irganox~1010 conforms to the compound of formula llc.
c) Irganox~3114 conforms to the compound of formula llg.
d) Irganox~1098 conforms to the compound of formula lla.
e) Irganox~1076 conforms to the compound of formula llb.
.)20 1 1 ~2
- 30 -
The invention is further illustrated by the following Examples in which parts and percentages
are by weight.
Example 1: Stabilisation of polyamide 6.
100 parts of unstabilised polyamide 6 granulate (Ultramide~B3, supplied by BASF) are pow-
dered by cryogenic grinding and the stabilisers of Table 2 are added. The mixture is mixed
with a Henschel mixer for 2 minutes. The powder so obtained is dried at 80~C for 6 hours,
extruded in an extruder (type Berstorff) at a maximum of 240~C and then granulated. The
granulate so obtained is moulded on an injection moulding machine at a maximum of 240~C
to dumbbells 1.0 mm thick and to plates 2.0 mm thick.
The dumbbells are aged in a circulating air oven at 1 40~C. The continuation of the ageing is
observed at intervals of 1-3 days by determining the force-elongation diagrams. The end
point is defined as the time after which the residual strain has fallen to 50 % of its starting
value. The greater the time, the better the stabilisation. The results are summarised in
Table 2.
The plates are aged in a circulating air oven at 80~C over 1500 hours. The yellowness index
(Yl) of these plates is determined in accordance with ASTM D 1925-70. Low Yl values de-
note minor discoloration, high Yl values denote strong discoloration of the samples. The
less discoloration, the more effective the stabiliser mixture. The results are summarised in
Table 2.
22û1 182
- 31 -
Table 2:
Time in hours to 50 %Yellowness Index
ExampleStabiliser after 1500 hours
residual strain at 140~C at 80~C
(dumbbells) (plates)
1a 12 51.5
0.2 % Irgafos~168a)
1 b 282 50.0
0.2 % Irganox~1098
0.2 % Irgafos012C~
1 c 369 42.0
0.2 % Irganox'D1098b)
a) Irgafos~168 (Ciba-Geigy) is tris(2,4-di-tert-butylphenyl)phosphite.
b) Irganox~1098 (Ciba-Geigy) is N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexa-
methylenediamine (compound of formula lla).
C
H3C ~'~ 1~
HO~CH2--CH2--C--NH (CH2)3 (lla)
H3C C
CH3
H3C - 2
c) Irgafos~12 (Ciba-Geigy) is 2,2',2"-nitrilo[triethyl-tris(3,3'5,5'-tetra-tert-butyl-1,1'-biphenyl-
2,2'-diyl)phosphite]; Chemical Abstract "Registry" number: 80410-33-9 and is the com-
pound of formula 1.
220 1 1 82
- 32 -
(CH3)3C ~C(CH3)3
~ 0,
,P--O--CH2CH2 N (I)
(CH3)3C--~
C(CH3)3
The results of Table 2 show that the novel stabiliser mixture (Example 1 c) is markedly more
effective than the known stabiliser mixture (Example 1 b).
