Note: Descriptions are shown in the official language in which they were submitted.
21 639~6
,
A-20209/A/CHM80
Piperidine triazine compounds con~ining silane ~roups as stabiliærs for or~anic m~ter1~1.c
The present invention relates to novel piperidine triazine compounds containing silane
groups, to their use as light, heat and oxidation stabilizers for organic m~teri~ls, especially
synthetic polymers, and to organic m~teri~ thus stabilized.
The use of derivatives of 2,2,6,6-tetramethylpiperidine con~ining silane groups, such as
those noted in US-A-4 177 186, US-A-4 859 759, US-A-4 895 885, US-A-4 946 880,
US-A-4 948 888, US-A-5 134 233, US-A-5 219 905, US-A-5 321 066, EP-A-162 524,
EP-A-182 415, EP-A-244 026, EP-A-343 717, EP-A-388 321, EP-A-480 466,
DD-A-234 682 and DD-A-234 683, as stabilizers for synthetic polymers, is known.
The present invention relates to novel compounds of formula (I)
CH3 CH3 CH3 ' CH3
H3C--Si o i O ' i O--' i CH3
CH3 (CH2)3 A CH3
/I~N ~\ /m \ l n
RlN N--Rl
CH3I CH3 CH3 1 CCHH33 (I)
R2 R2
in which
m + n is a number from 1 to 100 and n varies from zero to 90~o of the sum of m + n;
X is -O- or -NH-;
Rl is hydrogen, Cl-C~8aLkyl, C2-C4alkyl substituted in position 2, 3 or 4 by Cl-C8aL~oxy
or by di(C~-C4alkyl)amino; Cs-Cl2cycloalkyl unsubstituted or substituted with 1, 2 or 3
Cl-C4alkyls; C7-Cgphenylalkyl unsubstituted or substituted on the phenyl with 1, 2 or 3
2 1 63956
- 2 -
Cl-C4alkyls; or a group of formula (II);
C~CH3
~N R2 (II)
/\
R2 is hydrogen, Cl-C8alkyl, O, OH, NO, CH2CN, Cl-Cl8aLI~oxy, Cs-Cl2cycloalkoxy,
C7-Cgphenylalkyl unsubstituted or substituted on the phenyl with 1, 2 or 3 Cl-C4alkyls;
Cl-C8acyl; and
A is C6-Cl8alkyl.
Examples of alkyl with up to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl,
2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl,
nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Examples of C2-C4alkyl substituted with Cl-C8alkoxy, preferably Cl-C4aL~oxy, in
particular methoxy and ethoxy, are 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl,
3-ethoxypropyl, 3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.
Examples of C2-C4alkyl substituted by di(Cl-C4alkyl)amino, preferably with
dimethylamino or diethylamino, are 2-dimethylaminoethyl, 2-diethylaminoethyl,
3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and
4-diethylaminobutyl.
Examples of Cl-Cl8aLkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy,
hexadecyloxy and octadecyloxy. Preferred examples are C6-Cl2alkoxy, in particular
heptoxy and octoxy.
Examples of Cs-Cl2cycloalkyl unsubstituted or substituted with 1, 2 or 3 Cl-C4aL~yls, are
cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl,
dimethylcyclohexyl, trimethylcyclohexyl, t-butylcyclohexyl, cyclooctyl, cyclodecyl and
cyclododecyl. Cyclohexyl unsubstituted or substituted with Cl-C4alkyl is preferred.
Examples of C7-Cgphenylalkyl unsubstituted or substituted on the phenyl with 1, 2 or 3
Cl-C4alkyls are benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, t-butylbenzyl and
~ 3 21 63956
2-phenylethyl. Benzyl is preferred.
Examples of Cs-Cl2cycloaL~oxy are cyclopentoxy, cyclohexoxy, cycloheptoxy,
cyclooctoxy, cyclodecyloxy and cyclododecyloxy. Cyclopentoxy and cyclohexoxy arepreferred.
Examples of Cl-C8acyl, which can be aliphatic or aromatic, are formyl, acetyl, propionyl,
butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl and benzoyl. Cl-C8aL~anoyl
and benzoyl are preferred. Acetyl is especially preferred.
Those compounds of formula (I) are of interest in which m + n is a number from 1 to 100,
n is e.g. æro or a number from 1 to 50 and can vary from æro to 50% of the sum of m + n
The sum m + n may be, for example, also a number from 2 to 100, 4 to 100, 8 to 100, 2 to
70, 4 to 70 or 8 to 70. The variable n preferably varies from 10 to 50%, e.g. 20 to 50% or
30 to 50%, of the sum m + n. Furthermore, the variable m may be for example a number
from 10 to 50 and the variable n may be for example a number from 0 to 50, 5 to 50 or 10
to 40-
The radical A may be for example Cg-Cl8alkyl, Cl0-Cl8alkyl or Cl2-Cl8alkyL
Preferred meanings of R2 are hydrogen, Cl-C4aLI~yl, OH, C6-Cl2alkoxy,
C5-C8cycloaL~oxy, benzyl or acetyl, in particular hydrogen or methyl.
Preferred compounds of formula (I) are those in which
m + n is a number from 1 to 90 and n varies from æro to 90% of the sum m + n;
X is -O- or -NH-;
Rl is hydrogen, Cl-Cl2aL~yl, Cs-C7cycloaL~yl, C7-Cgphenylalkyl or a group of formula
(II); and
A is C6-Cl2alkyl.
Particularly preferred compounds of formula (I) are those in which
m + n is a number from 1 to 80 and n varies from æro to 90% of the sum m + n;
X is -O- or-NH-;
Rl is hydrogen, Cl-C8alkyl, cyclohexyl, benzyl or a group of formula (II); and
A is C8-Cl2alkyl.
21 63956
Compounds of formula (I) of special interest are those in which
m + n is a number from 1 to 70 and n varies from zero to 50% of the sum m + n;
X is -O- or -NH-;
Rl is hydrogen, Cl-C4aLkyl or a group of formula (II); and
A is C8-Cl2alkyl.
Compounds of formula (I) of particular interest are those in which
m + n is a number from 1 to 60 and n varies from zero to 50% of the sum m + n;
X is -O- or-NH-;
Rl is Cl-C4aLkyl or a group of formula (II); and
A is C8-Cl2aLkyl.
Examples of compounds of formula (I) are
CH3 ICH3 CH3 \ CH3
H3C--Si O--Si O--';i O ~ CH3
CH3 ~ ( ~ H2)3 / 27
N~N
/~ N ~\
Hgc4--N N--C4Hg
CH~CH3 CH~CH3
CH3 N CH3 CH3 Nl CH3
CH3 CH3
CH3 / ~CH3 / CH3 \ CH3
H3~ ~i O--'`i O--"i O--' I--CH3
CH3 \ (8H2)3 \ ~ 17' CH3
N~N
/~ N ~\
Hgc4--N N C4H~
CH3~<CH3 CH3~CH3
CH3 N CH3 CH3 IN CH3
H H
21 63956
CH3 CH3 / CH3 \CH3
H3C- Si 0- Si 0- Si0- Si- CH3
CH3 ~(CH2)3 ~ ~ / 27
N^N
/~N J
HgC4 - N N - C4Hg
CH3~<CH3 CH~CH3
CH3 N CH3 CH3 N CH3
H H
,CH3 / CH3 \ / ,CH3 \Cl H3
H3C- Si 0- Si O - Si- O- Si- CH3
CH3 ~(CH2)3 ~ / 27
N ^N
/~ N !~
HgC4 - N N - C4Hg
CH3~CH3 CH~CH3
CH3 N CH3 CH3 N CH3
CH3 CH3
CH3 ~CH3 CH3 CH3
H3{~ '`i O--Si O-- i O-- ,i--CH3
CH3 ( ~CH2)3 ~ C,2H2s / CH3
N~N 27
/~ N ~J\
Hgc4--N N--C4Ha
CH~CH3 CH~)~CH3
CH3 N CH3 CH3 Nl CH3
CH3 CH3
2 1 63956
- 6 -
~CH3 ~CH3 / CH3 \ CH3
H3C--Si O--Si O---`i O--.';i--CH3
CH3 ( ~ H2)3 ~ ~ / 27
N N
/~ N ~\
Hgc4--N N--C4Hg
CH~CCH3 CH~cCH3
CH3 IN CH3 CH3 IN CH3
CH3 / ~CH3 / CH3 \ CH3
H3C--Si O--Si O-- 'i O--';i--CH3,
CH3 ( ~ H2)3 ~ 14
N N
/l` N ~J\
HgC4--N N--C4Hg
CH~CH3 CH3~CH3
CH3 N CH3 CH3 Nl CH3
CH3 CH3
CH3 ~CH3 CH3 \ CH3
H3C--Si O--Si O-- `J O--';i--CH3
CH3 ~ ( ~CH2)3 ~ ~ C8H17/ CH3
NH 39 14
N~N
/~ N ~\
HgC4--N N--C4Hg
CH~cCH3 CH~CH3
CH3 N CH3 CH3 IN CH3
H H
2 1 63956
- 7 -
CH3 / ~CH3 \ / CH3 \ CH3
H3C--'`i O--Si o _ r j O ~ ''i--CH3
CH3 (~CH2)3 ~ \ C,2H2s / CH3
39 14
N~N
/~N~
Hgc4--N N--C4Hg
CH~CH3 CH~CH3
CH3 N CH3 CH3 Nl CH3
CH3 CH3
~CH3 ~ C~ H3 \ ~ CH3 \ CH3
H3C--Si O--Si O-- `iO--!;j--CH3
CH3 ~ (C~ H2)3 ~ ~ C,2H2s~ CH3
N~N
/~ N ~J\
HgC4--N N--C4Hg
CH~CH3 CH3~CH3
CH3 N CH3 CH3 I CH3
H H
CH3 / CH3 CH3 CH3
H3C--';i -- 'i O~ CH3
CH3 ( ~CH2)3 ~ C,2H2s ~ CH3
N~N
/1` N ~\
CH3 CH3 / ~ CH~CH3
H3C--N~ N N ~N--CH3
CH3 CH3 l l CH3 CH3
CH~CH3 CH,~)~CH3
CH3 IN CH3 CH3 Nl CH3
CH3 CH3
and
2 1 6395G
- 8 -
CH3 / CH3 CH3 \ CH3
H3C--Si O--~:j O-- i--CH3
CH3 ( IcH2)3 ~ Cl2H25 / CH3
NH 26 27
N~N
CH3 CH3 /~N ~\ CH3 CH3
HN~} N N ~NH
CH3 CH3 l l CH3 CH3
CH:~3~CH3 CH ~CH
H H
The compounds of the present invention can be prepared, for example, by reacting a
compound of formula (III)
CIH3 / CH3 \ CIH3
H3C--Si --Si O--Si--CH3 (III)
CH3 \ H / m+n CH3
where m and n are as defined above, with the appropriate amounts of alkene capable of
- forming a group
(CH2)3
NlN
/~N J\
R~ R
CH3`~ k CH3 CH3 ~ ,1< CH3
CH3--I CH3 CH3--N CH3
R2 R2
21 63956
and a group A- where Rl, R2, X and A are as defined above, effecting the reaction of
hydrosilylation in the presence of catalytic amounts of complex of Pt or Rh as described in
EP-A-343 717 and EP-A-388 321 (Chemical Abstracts 115: 160 562f; Derwent
90-284499/38) and by Speier (J.A.C.S. 79, 974, 1957).
The compounds of formula (III) are commercially available or they can be prepared
according to known methods.
The alkenes capable of forming a group
(CH2~3
NlN
/J`ON J\
R1--N N--R1
CH3~1<CH3 CH3~h~CH3
CH3 Nl CH3 CH3 Nl CH3
R2 R2
are prepared, for example, as described in US-A-4 731 393 or according to known
methods, whereas the alkenes capable of forming a group A are commercially available.
The compounds of the present invention are very effective in improving the light, heat and
oxidation resistance of organic materials, in particular synthetic polymers and copolymers,
and are particularly suitable for stabilizing polypropylene fibres on account of their
increased resistance to volAtili7Atinn.
Examples of organic materials that can be stabiliæd are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene,
polybut- l-ene, poly-4-methylpent- l-ene, polyisoprene or polybutadiene, as well as poly-
mers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which
optionally can be crosslinked), for example high density polyethylene (HDPE), high den-
21 63956
- 10-
sity and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh
molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE),
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:
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, VIb or VIII of the Periodic Table. These
metals usually have one or more than one ligand, typically oxides, halides,
alcoholates, esters, ethers, ~min~s, aL~yls, aL~enyls and/or aryls that may be
either ~- or ~-coordinated. These-metal complexes may be in the free form or
fixed on substrates, typically on activated m;~gnesium chloride, titanium(III)
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 aL~yls, metal
hydrides, metal aL~yl h~ es, metal aL~yl oxides or metal aL~yloxanes, said
metals being elements of groups Ia, IIa and/or IIIa 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 mono-
mers, for example ethylene/propylene copolymers, linear low density polyethylene(LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-
l-ene copolymers, propylene/isobutylene copolymers, ethylene/but-l-ene copolymers,
ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene
21 63956
11 -
copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/-
isoprene copolymers, ethylene/aLkyl acrylate copolymers, ethylene/alkyl methacrylate
copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon mon-
oxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpoly-
mers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethy-
lidene-norbornene; and mixtures of such copolymers with one another and with polymers
mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers,
LDPl~/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers
(EAA), LLDPEIEVA, LLDP~/EAA and alternating or random polyaLkylene/carbon mon-
oxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example Cs-Cg) including hydrogenated modifications thereof
(e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(o~-methylstyrene).
6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for
example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/buta-
diene/alkyl acrylate, styrene/butadiene/aLkyl methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/met'nyl acrylate; mixtures of high impact strength of styrene copoly-
mers and another polymer, for example a polyacrylate, a diene polymer or an ethylenél-
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 polybut~içne,
styrene on polybutadiene-styrene or polybut~ .ne-acrylonitrile copolymers; styrene and
acrylonitrile (or methacrylonitrile) on polybut~ nf~.; styrene, acrylonitrile and methyl
methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene,
acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide
on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene
and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on
polyaL~yl acrylates or polyaLkyl methacrylates, styrene and acrylonitrile on acrylate/buta-
diene copolymers, as well as mixtures thereof with the copolymers listed under 6), for
example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated
21 63956
and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or
sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlo-
rohydrin homo- and copolymers, especially polymers of halogen-cont~ining vinyl com-
pounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, poly-
vinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chlo-
ride, 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 polyacrylo-
nitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other
unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/-
aL~yl acrylate copolymers, acrylonitrile/aL~coxyaL~yl acrylate or acrylonitrile/vinyl halide
copolymers or acrylonitrile/ aL~yl 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, poly-
vinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl ph~h~l~te or polyallyl
melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyaL~ylene glycols, poly-
ethylene 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 sty-
rene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-termin~e~ 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-
2 1 63956
- 13-
amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic
polyamides st~rting from m-xylene diAminP and adipic acid; polyamides prepared from
hexamethylene~iAmin~ and isophthalic or/and terephthalic acid and with or without an
elastomer as modifier, for example poly-2,4,4,-trimethylhP~r~methylene terephthAlAmide
or poly-m-phenylene isophthAlAmide; and also block copolymers of the aforementioned
polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or graf-
ted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or
polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM
or ABS; and polyamides condensed during proces~ing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydan-
toins 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-tPrmin:~ted polyethers; and also
polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and
melAminPs on the other hand, such as phenol/formaldehyde resins, urealformaldehyde
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 cro.s.clinking agents,
and also halogen-containing modifications thereof of low flAmmAbility.
24. Cro.~slinkAble acrylic resins derived from substituted acrylates, for example epoxy
acrylates, urethane acrylates or polyester acrylates.
25. ALkyd resins, polyester resins and acrylate resins crosslinked with melamine resins,
21 63956
- 14-
urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aro-
matic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphe-
nol F, which are crosslinked with customary hardeners such as anhydrides or amines, with
or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified 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.
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, PAIPPO, PBT/PC/ABS or PBT/PET/PC.
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. phth~ es, 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.
The compounds of the formula (I) are particularly suitable for improving the light
stability, heat stability and oxidation stability of polyolefins, especially polyethylene and
polypropylene.
The compounds of the formula (I) can be used in mixtures with organic materials in
various proportions depending on the nature of the material to be stabilized, on the end use
and on the presence of other additives.
In general, it is appropriate to use, for example, 0.01 to 5 Yo by weight of the compounds
2 1 63956
of the formula (I), relative to the weight of the material to be stabilized, preferably
between 0.05 and 1 %.
In general, the compounds of the formula (I) can be added to the polymeric materials
before, during or after the polymeri7~tion or cro.c.clinking of the said m~tP.ri~
The compounds of the formula (I) can be incorporated in the polymeric m~teri~ls in the
pure form or encapsulated in waxes, oils or polymers.
The compounds of the formula (I) can be incorporated in the polymeric m~te.ri~l.c by
various processes, such as dry mixing in the form of powder, or wet mixing in the form of
solutions or suspensions or also in the form of a masterbatch; in such operations, the
polymer can be used in the form of powder, granules, solutions, suspensions or in the form
of latices.
The materials stabilized with the products of the formula (I) can be used for the production
of mouldings, films, tapes, monofilaments, fibres, surface coatings and the like.
If desired, other conventional additives for synthetic polymers, such as antioxidants, UV
absorbers, nickel stabilizers, pigme.nt~, fillers, plasticizers, corrosion inhibitors and metal
deactivators, can be added to the mixtures of the compounds of the formula (I) with the
organic m~te.ri~
Particular examples of additives which can be used in admixture with the compounds of
the formula (I) are:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-
4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclo-
hexyl)-4,6-dimethylphenol, 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'-methyl-
undec- 1 '-yl)phenol, 2,4-dimethyl-6-( 1 '-methylheptadec- 1 '-yl)phenol, 2,4-dimethyl-6-( 1'-
methyltridec- l'-yl)phenol and mixtures thereof.
21 639~6
-
- 16-
1.2. AL~ylthiomèthylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-do-
decylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and aL~ylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di-
phenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxy-
anisole, 3,5-di-tert-butyl4-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, ~-tocopherol, ~-tocopherol and
mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methyl-
phenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thio-
bis(6-tert-butyl-2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis-(2,6-dim-
ethyl-4-hydroxyphenyl) 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-methyl-
cyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-
bis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidene-
bis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methy-
lenebis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-
4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-
butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-
tert-butyl-5-methyl-2-hydro~ybenzyl)-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-dodecylmer-
captobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-
tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-
5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-
hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-
tert-butyl-4-hydroxy2-methylphenyl)4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-
butyl-4-hydroxy2-methylphenyl)pentane.
1.7. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxy-
dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-
21 63956
hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)-
amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephth~l~te, bis(3,5-di-tert-
butyl- 4-hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-
hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malo-
nate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis-
[4-(1, 1 ,3,3-tetramethylbutyl)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-hy-
droxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydlo~yl,ellzyl)-2,3,5,6-
tetramethylbenzene, 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-
hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-
anilino)-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-tri~7ine, 1,3,5-tris-
(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di-
methylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-tri-
azine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tri~7ine,
1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphos-
phonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-
butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzyl-
phosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzyl-
phosphonic 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 poly-
hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane-
diol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanu-
rate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl-
hexanediol, trimethylolpropane, 4-hydroxymethyl- 1 -phospha-2,6,7-trioxabicyclo[2.2.2]-
21 63956
- 18-
octane.
1.14. Esters of ,~-(S-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or
polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-
hexanediol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodi-
ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapent~dec~nol, tri-
methylhexanediol, 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 poly-
hydric alcohols, e.g. with methanol, ethanol, octanol, oc~(lecanol, 1,6-hexanediol, 1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, di-
ethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-
bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri-
methylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric
alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, l,9-nonane-
diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene
glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis-
(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri-
methylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of ,B-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-
tert-butyl-4-hydroxyphenylpropionyl)hexamethylene(li~mine, N,N'-bis(3,5-di-tert-butyl-
4-hydroxyphenylpropionyl)trimethylene~i~min~, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-
phenylpropionyl)hydrazine .
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenedi~mine, N,N'-di-
sec-butyl-p-phenylene~ mine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenedi~mine, N,N'-
bis(l-ethyl-3-methylpentyl)-p-phenylene~i~mine, N,N'-bis(l-methylheptyl)-p-phenylene-
mine, N,N'-dicyclohexyl-p-phenylene~ mine~ N,N'-diphenyl-p-phenylenetii~mine~
N,N'-bis(2-naphthyl)-p-phenylene(iiamine, N-isopropyl-N'-phenyl-p-phenylene(li~min~,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylene(li~min(~, N-(l-methylheptyl)-N'-phenyl-p-
21 63956
- 19-
phenylenedi~mine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)-
diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenerli~min~, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine,
for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophe-
nol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol,bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-di-
aminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-di-
aminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)pro-
pane, (o-tolyl)biguanide, Bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phe-
nyl- 1-naphthylamine, a mixture of mono- and diaL~ylated tert-butyl/tert-octyldiphenyl-
amines, a mixture of mono- and diaL~ylated nonyldiphenyl~minçs, a mixture of mono- and
diaL~ylated dodecyldiphenylamines, a mixture of mono- and diaL~ylated isopropyl/isohex-
yldiphenylamines, a mixture of mono- und diaLkylated tert-butyldiphenyl;~minçs, 2,3-di-
hydro-3,3-dimethyl-4H-1,4-benzothi~7.inç, phenothi~7.inç, a mixture of mono- und dialky-
lated tert-butyVtert-octylphenothi~7.inçs, a mixture of mono- und diaL~ylated tert-octyl-
phenothiazines, N-allylphenothiazin, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-
bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenedi~min~., bis(2,2,6,6-tetramethylpipe-
rid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV absorbers and li~ht stabilisers
2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-S'-methylphenyl)-
benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-27-
hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzo-
triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-
2'-hydroxy-5'-methylphenyl)-S-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-
hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-
di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3'757-bis-(a,oc-dimethylbenzyl)-2'-
hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycar-
bonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-car-
bonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyl-
oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonyl-
ethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzo-
triazole, and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
2 1 ~ 95~
- 20 -
azole, 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'-hydroxy-
phenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3~,
where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-de-
cyloxy, 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-tellbulyl-
phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-
tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-
4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-
butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxy-
benzoate.
2.4. Acrylates, for example ethyl oc-cyano-~"~-diphenylacrylate, isooctyl o~-cyano-,~"3-di-
phenylacrylate, methyl a-carbometho~ycinn~ln~te, methyl a-cyano-,B-methyl-p-methoxy-
cinnamate, butyl a-cyano-~-methyl-p-methoxy-cinn~m~te, methyl a-carbomethoxy-p-
methoxycinn~m~te and N-(,3-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetra-
methylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands
such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldi-
thiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-
hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of
2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-
hydroxypyrazole, with or without additional ligands.
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(l,2,2,6,6-pentamethyl-4-piperidyl)seba-
cate, bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(l,2,2,6,6-pentamethyl-
4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-
hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate
of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene~ mine and 4-tert-octyl-
amino-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-ethane-
21 63956
- 21 -
diyl)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-triaza-
spiro[4.5] decan-2,4-dion, bis( 1 -octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis( 1-
octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N,N'-bis-(2,2,6,6-tetra-
methyl-4-piperidyl)hexamethylene~ min~ 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-tri-
azine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-
butylamino- 1 ,2,2,6,6-pentamethylpiperidyl)- 1 ,3,5-triazine and 1 ,2-bis-(3-aminopropyl-
amino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-
dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-
( 1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy-
and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,N'-bis-
(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene~liamine and 4-cyclohexylamino-2,6-di-
chloro- 1 ,3,5-tria7in~, a condensation product of 1 ,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro- 1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS
Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N-
(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-
1-oxa-3,8-diaza-4-oxo-spiro~4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cyclo-
undecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin.
2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyox~nilide, 2,2'-dioc-
tyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-
ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethox-
anilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of
ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disub-
stituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxy-
phenyl)-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-propyloxyphenyl)-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-dodecyloxy-
phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-
4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-pro-
poxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyl-
oxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyl-
21 63956
-
- 22 -
oxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-
[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl] -4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-
hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-bu-
toxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphe-
nyl)-6-phenyl- 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-hydroxyphenyl-
propionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl di-
hydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-di-
acetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)-
thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phos-
phites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, triocta-
decyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phos-
phite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol
diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyl-
oxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol di-
phosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol tri-
phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyl-
oxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-
tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-
methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.
5. Hydroxyl~mines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxyl-
amine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhy-
droxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexa-decyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkyl-
hydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone,
N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tride-
cyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone,
N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-hepta-
decyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived
21 63956
from N,N-diaLkylhydroxylamine derived from hydrogenated tallow amine.
7. Thiosynergists, for ex~mple, dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of ,B-thiodipropionic acid, for example the
lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of
2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, penta-
erythritol tetrakis(,3-dodecylmercapto)propionate.
9. Polyamide stabilisers, for example, copper salts in combination with iodides and/or
phosphorus compounds and salts of divalent m~ng~nP.se.
10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyan~ mi~e, tri-
allyl cyanurate, urea deflvalives, hydrazine derivatives, amines, polyamides, polyure-
thanes, alkali metal salts and ~lk~line earth metal salts of higher fatty acids for example
calcium stearate, zinc stearate, m~gnP.sium behenate, m~gnP.sium stearate, sodium rici-
noleate and potassium p~lmit~te, antimony pyrocatecholate or tin pyrocatecholate.
11. Nucleatin~ agents, for example, inorganic substances such as talcum, metal oxides
such as tit~ni-lm dioxide or m~nPsillm oxide, phosphates, carbonates or sulfates of, prefe-
rably, ~lk~line earth metals; organic compounds such as mono- or polycarboxylic acids
and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, so-
dium 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, antista-
tic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed 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 or EP-A-0 591 102 or 3-[4-(2-acet-
21 b3956
- 24 -
oxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyl-
oxyethoxy)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-piva-
loyloxyphenyl)-5,7 -di-tert-butyl-benzofuran-2-one.
The compounds of the invention can also be used as stabilizers, especially as light
stabilizers, for almost all m~tPri~ls known in the art of photographic reproduction and
other reproduction techniques as e.g. described in Research Disclosure 1990, 31429 (pages
474 to 480).
Several examples of the preparation and use of the compounds of formula (I) are given in
order to give a more detailed illustration of the present invention-, these examples are
given solely for illustrative purposes and do not imply any restriction.
Example 1: Preparation of a polysiloxane of the formula
,CH3 C, H3 ,CH3 C~ H3
H3C-Si O-Si O-SiO-Si--CH3
CH3 (CH2)3 ~ ~ / 27
N^N
~N~
HgC4 - N N - C4Hg
CH~<CH3 CH3~CH3
CH3 N CH3 CH3 N CH3
CH3 CH3
44.5 g (77.8 mmol) of 2-allyloxy-4,6-bis[N-(1,2,2,6,6-pentamethyl-4-piperidyl)butyl-
amino]- l ,3,5-triazine are dissolved in 50 ml of xylene and 2 mg of PtCl2(styrene)2 are
added.
The solution is heated to 140C and to it is slowly added, while stirring, a solution of 10 g
(3 mmol) of trimethyl-silyl terminated polymethylhydrosiloxane (possessing 53 Si-H
units) in 150 ml of xylene. The reaction is m;lin~ined at 140C for 3 hours. It is cooled to
70C and, while still stirring, 15 g (133.9 mmol) of l-octene and a further 2 mg of
PtCl2(styrene)2 are added.
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- 25 -
The mixture is heated for 6 hours while stirring at 100C and the solvent and the excess of
l-octene are removed by vacuum distillation (140C/0.1 mbar).
A white solid with m.p. 75-79C is obtained.
NMR and IR analysis confirms the expected structure.
Example 2: Preparation of a polymethylsiloxane of the formula
/
,CH3 C, H3 C, H3 C~ H3
H3C-Si O-Si O-Si o-Si-CH3.
CH3 ~ (CH2)3 ~ 8 17' CH3
N^N
HgC4 - N /~ N - C4Hg
CH3~CH3 CH~CH3
CH3 N CH3 CH3 N CH3
H H
Using a procedure analogous to that described in Example 1, 43.2 g (77.7 mmol) of
2-allylamino-4,6-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)butylamino]-1,3,5-triazine are
reacted with 10 g of trimethylsilyl tennin~ted polymethylhydrosiloxane (posses.~ing 53
Si-H units) and with 15 g (133.9 mmol) of 1-octene in the presence of 4 mg of
PtCl2(styrene)2 in xylene.
After removing the solvent and the excess of 1-octene by vacuum distillation (140C/
1 mbar), a solid with m.p. 110-115C is obtained.
NMR and IR analysis confirms the expected structure.
Example 3: Preparation of a polymethylsiloxane of the formula
2 1 63956
- 26 -
CH3 C, H3 C, H3 \ CH3
H3C- Si O - Si O - Si--O - Si- CH3 .
CH3 ~ (CH2)3 ~ ~/ 27
N ^N
HgC4 - N /~ N - C4Hg
CH3~CH3 CH~CH3
CH3 N CH3 CH3 N CH3
H H
Using a procedure analogous to that described in Example 1, 43.4 g (77.8 mmol) of
2-allyloxy-4,6-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)butylamino]-1,3,5-triazine are
reacted with 10 g (3mmol) of t;imethylsilyl terminated polymethylhydrosiloxane
(possessing 53 Si-H units) and with 15 g (133.9 mmol) of 1-octene in the presence of 4 mg
of PtCl2(styrene)2 in xylene.
After removing the solvent and the excess of 1-octene by vacuum distillation (140C/1
mbar), a solid witn m.p. 90-95C is obtained.
NMR and IR analysis confirms the expected structure.
Example 4: Preparation of a polymethylsiloxane of the formula
CH3 / CH3 CH3 \C~ H3
H3C- Si O - Si 0--Si0- Si- CH3
CH3~ (CH2)3 \ C8H,7~ CH3
N ^N
HgC4 - N /~N - C4Hg
CH3~CH3 CH~CH3
CH3 N CH3 CH3 N CH3
CH3 CH3
Using a procedure analogous to that described in Example 1, 45.5 g (77.8 mmol) of
2-allylamino-4,6-bis[N-(1,2,2,6,6-pentamethyl-4-piperidyl)butylamino]-1,3,5-triazine are
reacted with 10 g (3 mmol) of trimethylsilyl terminated polymethylhydrosiloxane
21 63956
(possessing 53 Si-H units) and with 15 g (133.9 mmol) of l-octene in the presence of 4 mg
of PtCl2(styrene)2 in xylene.
After removing the solvent and the excess of l-octene by vacuum distillation (140C/l
mbar), a solid with m.p. 94-98C is obtained.
NMR and IR analysis confirms the expected structure.
Example 5: Light-stabilizing action in polypropylene fibres.
2.5 g of each of the compounds given in Table 1, 1 g of tris(2,4-di-t-butylphenyl)
phosphite, 0.5 g of calcium monoethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, 1 g of
calcium stearate and 2.5 g of titanium dioxide are mixed in a slow mixer with 1000 g of
polypropylene powder possessing a melt index = 12 g/10 min (measured at 230C and
2.16kg).
The mixtures are extruded at 200-230C to give polymer granules which are then
converted into fibres using a pilot-type apparatus ((~Leonard-Sumirago (VA) Italy) and
operating under the following conditions:
extruder temperature : 200-230C
head temperature : 255-260C
draw ratio : 1:3.5
linear density : 11 dtex per filament
The fibres thus prepared are exposed, after mounting on white cardboard, in a model
65WR Weather-O-Meter (ASTM D2565-85) with a black panel temperature of 63C.
The residual tenacity is measured on samples taken after various times of exposure to light
by means of a constant-speed tensometer, and the exposure time in hours (Tso) needed to
halve the initial tenacity is then calculated.
For comparison, fibres prepared under the same conditions as stated above, but without
addition of the stabilizers according to the present invention, are also exposed.
Table 1 shows the results obtained.
Table 1:
21 63956
- 28 -
Stabilizer ~Eso (hours)
without stabilizer 150
Compound of Example 1 2540
Compound of Example 2 2680
