CA2232573A1 - Thermally stable hindered amines as stabilizers - Google Patents

Abstract

The invention relates to compounds of formula (I), in which R is H, C1-C12alkyl, phenyl, (C1-C4alkyl)phenyl, phenyl-C1-C4alkyl, halogen, C2-C12alkynyl or C1-C12alkoxy, X is NR', NCOR' or O, and Y is R'' or R''-CO-, where R'' is C2-C6alkenyl or C3-C6 alkenyl which is interrupted by -O-, -CO-, -NR'-, -S-, -SO-, -SO2- or phenylene, or (C1-C4alkenyl)phenyl, and R' is H or C1-C12alkyl, or -X-Y is the group of formula (a) or (b), and homopolymers and copolymers thereof and copolymers with further polymerizable monomers. These compounds and their copolymers are advantageously used, for example, for stabilizing organic material against the damaging effect of light, oxygen and/or heat.

Description

CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 Thermallv stable l.i,~ red amines as .st~hili~rs q The invention relates to novel 2,2,6,6-tetramethylpiperidines which are sl ~hstitl ~ted on the ring nitrogen and contain, in the 4-position, a s-lbstit--ent with a polymerizable double bond, to their homopolymers and copolymers, to their use for st~hili~ing organic material against damage by light, oxygen and/or heat, and to organic material stabilized by means of said compounds or polymers.

A number of hindered amines of the 2,2,6,6-tetramethylpiperidine type have already been disclosed as additives for synthetic polymers, in particular as light st~h~ ers; these include 4-suhstitlIted derivatives of 1-propargyl-2,2,6,6-t~lrd,-,e~hylpi~ueridi,le. By way of example, the following publiG~tions may be mentioned in this respect:
US-A-4 472 547 (C.A.102:46831z); EP-A-11 051 (C.A.94:39518r); DE-A-2 805 838 (C.A.90:22820c). US-A-4 386 127 tC.A.99:89380p) also describes 1-butynyl-2,2,6,6-tetramethyl-4-hydroxypiperidine.

The use of some compounds of the 2~6-diarylpiperidin-l-yl-sllhstitllted 2-butene type as sf~ ers has also been disclosed (US-A-5 204 474).

A number of scienli~ic puhlic~tions describe 1-butynyl-2,2,6,6-tetramethylpiperidines whose piperidine ring is unsllhstitllted in the 4-position, and their possihlE use as medicaments; for e,~d.--,clE M. E. Zuhair et al., Eur. J. Med. Chem. 27, 93 (1992) (C.A.117:26405v); J. M. A.
Al-Rawi et al. in Org. Magn. Reson.19, 91 (1982) (C.A.97:155132w) and Org. Magn.Reson.15, 285 (1981) (C.A.95:60789k); B. Karlen et al., J. Med. Chem.13, 651 (1970) (C.A.73:44857w) .
.

1,6-Bis(2,2,6,6-tetramethylpiperidin-1-yl)hexadiyne, whose piperidine rings are unsl~hstitl,ted in the 4-position, is described in the publications US-A-3 755 586 (C.A.80:19550c); W. B. Lutz et al., J. Org. Chem. 27,1695 (1962) and US-A-3 085 093 (C.A.59:9998e) as a pharmaceutically active compound.

CA 02232~73 1998-03-20 W O 97/13752 PCT/~G/0~264 It has now been found that certain compounds of the 2,2,6,6-tetramethylpiperidine type which contain both a triple bond in the ,~-position on the ring nitrogen atom and a polymerizable double bond in the 4-position on the piperidine ring are surprisingly suitable as st~h~ ers for organic ~-al~rial. They also have high thermal stability and thus allow higher processing lempe~lures in the ~rplic~tion and consequently a higher throughput on further processing of the products st~h~ ed in this way.

The invention therefore relates firstly to compounds of the formula I

H3C~CH3 CH2 (1) R

in which R is H, C1-C12alkyl, phenyl, (C1-C4alkyl)phenyl, phenyl-Cl-C4alkyl, halogen, C2-C12alkynyl or C1-C12alkoxy, X is NR', NCOR' or O, and Y is R" or Rn-CO-, where R" is C2-C6alkenyl or C3-C6alkenyl which is interrupted by -O-, -CO-, -NR'-, -S-, -SO-, -SO2- or phenylene, or (C1-C4alkenyl)phenyl, and R' is H or C1-Cl2-alkyl, or -X-Y

CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 O O
is a group of the formula --N;~ or N
O O

C,-C12alkyl R and R' are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1~1~3~3-L~Lrdlllelllylpentyl~ nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, or 1,1,3,3,5,5-hexamethylhexyl. Alkyl R and R' contain, in particular, from 1 to 6, preferably from 1 to 4, carbon atoms.
C,-C4alkylphenyl R is phenyl which is mono- or polysllhstituted by alkyl. This group contains, for example, from 1 to 3, in particular 1 or 2, alkyl suhstituents.
C,-C4alkylphenyl can be, for example, methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl), ethylphenyl, propylphenyl or butylphenyl.

Phenyl-C,-C4alkyl R is, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl or a,a'-dimethylbenzyl.

C2-C,2alkynyl R is, for exa." 'E, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, etc.. These alkynyl groups preferably have 2 to 4 carbon atoms.

C1-C12alkoxy R is, for example, methoxy, ethoxy, propoxy, butoxy, etc.. These alkoxy groups preferably have 1 to 6, in particular 1 to 4, carbon atoms.

Halogen is F, Cl, Br or 1, prer~rdbly Cl or Br, but in particular Cl.

C2-C6alkenyl is, for example, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl etc.. Preference is given to alkenyl groups having 2 to 4 carbon atoms. Preference is generally given to alkenyl groups containing a C=C double bond in the 1,2-position.

CA 02232~73 1998-03-20 r, ~rt ~nce is given to compounds of the formula I in which R is H, C1-caalkyl~ phenyl, (C,-C4aikyl)phenyl or phenyl-C,-C4alkyl, and R" is C2-C4alkenyl, C3-C4alkenyl which is interrupted by -O-, -CO- or-NR'-, or benzyl or phenyl which is substituted by C2-C4alkenyl.

Of particular il ~lere: il are compounds of the formula I in which R is H, C,-C8alkyl or phenyl, X is NH, N(Ct-C4alkyl) or 0, and Y is a group of the formula CH2=CH-CO-, CH2=C(CH3)-CO-, CH~CH2-- /CH~CO-- or CH~CH2--CO--CH2 , CH2 CH2 or -X-Y is the group of the formula N~ .

Of very particular il"pO~ lance are compounds of the formula I in whichR is H or methyl, X is O or NH, and Y is CO-CH=CH2, CO-C(CH3)=CH2 or vinylbenzyl.

The invention furthermore relates to homopolymers and copolymers obtainable by addition polymerization of one or more compounds of the formula 1.

These novel homopolymers and copolymers preferably conform to the formula 11 c CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 14 12_ n ( l ~)m H3C l H2 in which m is O or 1, R2, R3 and R4, independently of one another, are H or C,-C10alkyl, C3-C,Oalkyl which is interrupted by-O-, -CO-, -NR'-, -S-, -SO-, -SO2- or phenylene, Z is a direct bond, phenylene, phenylene(C,-C4alkylene), C,-C4alkylene or C3-C4alkylene, which is interrupted by -O-, -CO-, -NR'-, -S-, -SO-, -SO2- or phenylene, with the proviso that the total number of carbon atoms in all four radicals R2, R3, R4 and Z
does not exceed 10, excluding carbon atoms in optional interruptions, or, if R2 and R4 are H and m is 0, R3, Z and X together can also be the ~ o~ o t~i unit, and Z and R are as defined under the formula 1, and n is a number from 5 to 10,000, and the general symbols in each recurring unit are identical or different.
-CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 Preference is given to compounds of the formula ll in which Z is a direct bond and R2, R3 and R4, independently of one another, are H or C1-C4alkyl.

n in the compounds of the formula ll is preferably from 2 to 1,000, in particular from 2 to 100.

The invention furthermore relates to copolymers obtainable by addition copolymeri~Lion of compounds of the formula I with at least one comonomer containing a polymeri~ble, ethylenically unsaturated C=C double bond.

r, ~r~rence is given to copolymers in which the comonomer is one or more compounds from the group consisting of a-olefins, styrenes, ~-methylstyrenes, acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, methacryla".:~'Ps, acrylonitrile, vinyl acetate or vinyl chloride.

These copolymers pr~:rt:r~bly contain from 1 to 99 mol% of structural units of the formula ll and from 99 to 1 mol% of structural units of the formula lll _ IRs Hl ----C C - (ill) in which R5 is H, C1-C,0alkyl, phenyl, -COOR7, -CONH2, -GN or-CI, R6 is H or Cl-C10alkyl and R7 is H or C,-C10alkyl.

Preference is given to copolymers in which, in the formula lll, Rs is C1-C2alkyl, phenyl, -COOR,, -CONH2, -C=N or-CI, , CA 02232573 l998-03-20 W O 97/13752 PCT~EP96/04264 R6 is H or methyl and R7 is H or C1-C2alkyl.

~ The copolymers co",pris;"g compounds of the formula I with a comonomer conl~i"il,g a C=C double bond pre:r~r~bly have a mean molecular weight Mn of from 500 to1,000,000, plere,dbly from 1,000 to 100,000, in particular from 1,000 to 10,000.

Compounds of the formula I are prepared, for example, by reacting 4-(alkyl)amino- or 4-hydroxy-2,2,6,6-tetramethylpiperidines of the formula IV or V

NHR' OH

H3C ~ CH3 H3C ~ CH3 f H2 (,", f H2 ""
C C

Cl C
R R

in which R and R' are as defined above, with unsaturated, polymerizable carboxylic acids, carboxylic acid chlorides or carboxylic acid ester derivatives in a manner known per se, or by reacting 4-sl Ihstitl It~-l 2,2,6,6-tetramethylpiperidines of the formula Vl CA 02232~73 l998-03-20 W O 97/137S2 PcT/~l9~lo1264 ~_ (Vl) H

in which X and Y are as defined above, with an appropriate alkynyl-p-toluenesulfonic acid compound in a manner known per se.

The preparation is pr~rerably carried out by reacting compounds of the formula IV or V in which R is H or CH3 and R' is C,-C4alkyl or H with, for example, acryloyl chloride, methacryloyl chloride, methacrylic acid, methylmethacrylic acid or vinylbenzyl chloride, or by reacting compounds of the formula Vl in which X and Y together are CH2=CHCONH- or CH2=C(CH3)CONH- with propargyl tosylate.

Both compounds of the formula IV and of the formula Vl can be prepared in a l"anner known per se from 4-alkylamino-2,2,6,6-tetramethylpiperidines of the formula Vll or compounds of the formula V or Vl can be prepared in a manner known per se from 4-hydroxy-2,2,6,6-tetramethylpiperidine of the formula Vlll NHR' OH

H3C ~ CH (Vl 1) H3C ~CH (Vl 11) H H

CA 02232~73 l998-03-20 W O 97/13752 PCT~EP96/04264 which are commercially available or can easily be prepared by known processes, and the appropriate reagents mentioned above.

The reaction is preferably carried out in an inert solvent. The solvents which can be employed are polar or nonpolar organic solvents, for example hydrocarbons, halogenated hydrocarbons, esters, ethers, ketones, amides, nitriles, tertiary amines or sulfoxides;
examples of 5Uit~h'e solvents are toluene, hexane, cyclohexane, ligroin, petroleum ether and other hydrocarbon mixtures, dimethylformamide, tetrahydrofuran, dioxane, chlo~urur,,,.
diethyl ether, dimethyl sulfoxide and acetonitrile; particular preference is given to ac~lul liLI ile.

The Len"~er~lure during the reaction can be in the range from -5û to 200~C, preferably from -25 to 1 6û~C, in particular from -15 to 1 40~C.

The temperature of the reaction mixture can be kept in the boiling range (reflux) for the duration of the reaction. To this end, a solvent-containing reaction mixture is warmed to the boiling point, generally under atmospheric pressure, and the evaporated solvent is condensed with the aid of a suit~lE condenser and fed back into the reaction mixture.

The (ea~;lion can be carried out with exclusion of oxygen, for example by flushing with an inert gas such as argon; however, oxygen does not always i"l~, rt:re, so that it may also be poss~ lc to carry out the reaction without this measure.

When the ,eaclion is complete, work-up can be carried out by customary methods; the mixture is eYrediently first diluted with water, for example by adding the, t:a~lion mixture to from 1 to 4 times the volume of (ice) water; the product can subsequently be separated off directly or extracted, expediently using, for example, ethyl acetate or toluene. In the case of extraction, the product can be isolated in a conventional manner by removing the solvent;
~ this is Yxred Qntly carried out after drying of the organic phase. It is also possible to insert further purification steps, for example washing with aqueous sodium bicarbonate solution, dispersion of activated charcoal, chromatography by means of silica gel, filtration, recry~ lion and/or distillation.

CA 02232~73 l998-03-20 W O 97/13752 PCT/~l~/o~26 The homopolymers and copolymers of compounds of the formula 1, for example of those of the formula ll or lll, are prepared by free-radical polyme,i~dlion.

The free-radical polymerization can be carried out using various methods. These are described, for example by S. Sandler and W. Karo in Polymer Synthesis, Vol. 1-3,Academic Press, New York 1968. Examples of conventional polymerization p,ocesses are bulk, solvent, emulsion, suspension and preciri~tion polymerization.

The polymerization is generally i"ilidled by a conventional free-radical polyme~ lion initiator. These include thermal irlilialur:j~ such as azo compounds, for example azoisobutyronitrile (AIBN), pe,uxides, for example benzoyl peroxide, redox initiator systems, such as a mixture of iron(lll) acetylacetonate, benzoin and benzoyl peroxide, and phuluchemical free-radical ~unller:j~ such as benzoin or benzil methyl ketal.

The initiator is expe~liently added to the reaction solution in an amount of from 0.1 to 5 mol%, preferably from 0.5 to 3 mol%, based on the amount of ethylenically unsaturated monomers.

In order to control the molecular weight, chain l~ansrer compounds can be added, for example in amounts of from 5 to 20 mol%. Examples of such compounds are disulfides, mercaplans, halides, dibutyl sulfide, and others.

The polyl"e,i~alio" is prer~,ably carried out in solution. The reaction le",perdlure is generally in the range from 10 to 200~C, preferably from 30 to 1 50~C, particularly preferably from 40 to 1 00~C.

Any solvent present must be inert under the reaction conditions. Suitable solvents include aromatic hydrocarbons, ketones and ethers. Examples thereof are benzene, toluene, xylene ethylbenzene, isopropylbenzene, methyl ethyl ketone, acetone, cyclohexanone, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane. Particular prt~ nce is given to toluene and tetrahydrofuran.

-CA 02232~73 l998-03-20 W O 97/13752 PCT~EP96/04264 The polymeri~dlion is expediently carried out in the absence of oxygen, for exa",ple under argon or under nitrogen.

The compounds of the formula I and novel homopolymers and copolymers thereof areparticularly suitable for st~hi~ ng organic n~dl~rials against thermal, oxidative or actinic degradation.

Examples for those mdL~rials are:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, poly;soprel-e or polybllt~ ne, as well as polymers of cycloolefins, for i"~ance of cyclopentene om~or~o,~ene, polyethylene (which opliollally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh " -'ec-~l~r weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethy-lene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding pardy,dph, prefe-rably polyethylene and polypropylene, can be prepared by dirr~,enl, and especially by the following, methods:

a) radical pol~",erisdlion (normally under high pressure and at elevated temperature).

b) catalytic poly" ,erisdlion using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or Vlll of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coorcJi, ,clled.
These metal complexes may be in the free form or fixed on suL,~IIdles, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insolut'~ in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or me-tal alkyloxanes, said metals being elements of groups la, lla and/or Illa of the CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Slandard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo-lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/oc-tene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copo!ymers, ethy-lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers " ~e~ ~Lioned in 1 ) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alter-nating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrucalbon resins (for example C5-Cg) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch 5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).

6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/rr aieic anhydride, styrene/acrylo-nitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another ~ == :
CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpo-lymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/iso-prene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.

7. Graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybl ~t~iene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl meth-acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylo-nitrile and maleic anhydride or malei.~ de on polybutadiene; styrene and maleimide on poly-butadiene; styrene and alkyl acrylates or methacrylates on polybuPdiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/but~iiene copoly-mers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinaled and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chloril,~L~d or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl ch~oride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluo-ride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chlo-ride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from a,b-unsaturated acids and derivatives thereof such as polyacry-lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni-triles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu-rated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl CA 02232~73 l998-03-20 W O 97/13752 PCT~EP96/04264 benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phLhalale or polyallyl r"ela",i,le; as well as their copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethy-Iene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comono",er; polyacetals modified with ther."opl~slic polyl"~li,anes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyan,ides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybuta-dienes on the one hand and aliphatic or aromatic polyiso.;yanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from a" li. ,oca,l-oxylic acids or the cor,esponding lactams, for example polyamide 4, poly-amide 6, polyamide 6/6,6/10,6/9,6/12,4/6, 12/12, polyamide 1 1, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephLl,alic acid and with or without an elc.~ er as modifier, for example poly-2,4,4,-trimethylhexamethylene tert:phll,alamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned poly-amides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or poly-tetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS;
and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, pol~a~" ~e imides, polyetherimids, polye:jLt:,i"i'-, polyhydanto-ins and polybenzimid~.,les.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene -CA 02232~73 1998-03-20 W O 97/13752 PCT/~r5/01264 terephlhalate, poly-1,4-dimethylolcyelohe,~dne LerephLl,aldl~7 and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-te", li. ,aled polyethers; and also poly-esters modified with poly~;~,bonales or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Cn~ssli. ,ked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/~r"~aldehyde resins, urea/formaldehyde resins and " ,ela" ,ine/~r, . ,aldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyestcr resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as cluss!;nhi-lg agents, and also halogen-cor,l~in;"g ~~lud;ric~lions thereof of low flammability.

24. Crossli.~ ''e acrylic resins derived from suhstitllted acrylates, for ~ mple epoxy acry-lates, u, ~lhane acrylates or polyester acrylates 25. Alkyd resins, polyester resins and acrylate resins crossliliked with ",elar":ne resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from ali~ hdLic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenolF, 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 propion~l~s and cellu-lose butyrates, orthe Ics'l(l'cse ethers such as methyl cellulose; as well as rosins and their derivatives.

_ CA 02232~73 1998-03-20 O 97113752 PCTrEP96/04264 28. Blends of the aforementioned polymers (polyblends), for ex~n,ple 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/ther",opl~f~lic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA~PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

The invention therefore furthermore relates to compositions co""~risi"g a) an organic material which is sensitive to oxidative, thermal and/or actinic degradation/build-up and b) at least one compound of the formula I and/or a homopolymer and/or copolymer thereof, and to the use of compounds of the formula I and/or homopolymers and/or copolymers thereof for ~i~hil;,; lg organic material against oxidative, thermal or actinic degradation/build-up.
The invention also relates to a process for st~h ~ 7ing organic material against thermal, oxidative and/or actinic degradation/build-up which comprises adding at least one compound of the formula I and/or a homopolymer and/or copolymer thereof to this material.

Of particular interest is the use of compounds of the formula I as 5t~hjii~er5 in synthetic organic polymers and co"~spo"ding composilions.

The organic materials to be protecLed are preferably natural, semisynthetic or preferably synthetic organic materials. Particular pr~f~rence is given to synthetic organic polymers or mixtures of such polymers, in particular thermoplastic polymers, such as polyolefins, especially polyethylene (PE) and polypropylene (PP). Other particularly pr~:fe"~d organic materials are coating compositions. Coating compositions which can advantageously be 5t~hjii~ed in accordance with the invention are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th. Edn., Vol. A18, pp. 359-464, VCH
Verlagsgesellschaft, Weinheim 1991.
Other materials which can be stabilized by means of the novel compounds are photographic materials. These are taken to mean, in particular, those described in Research Disclosure 1990, 31429 (pages 474-480) for photographic reproduction and other reproductionmethods.

In general, the compounds of the formula I are added to the material to be st~hili~ed in amounts of from 0.01 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2%, --CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 based on the total weight of the '~ ed col"posilion. The novel compounds are particularly pfert:rdbly used in amounts of from 0.0~ to 1 .~i%, especis'ly from 0.1 to 0.5%.

The incGr~uolalion into the ~I~aL~:lials can be carried out, for exd,- ,~!e, by i,.co.~.or~ling or applying the compounds of the formula I and, if desired, further additives by the usual ods in industry. If the ",alelials are polymers, in particular synthetic polymers, the i"cor~.ordlion can be carried out before or during shaping or by apply;"g the dissolved or dlspe,~ed compound to the polymer, if necessary with s~bse-lllent evdporalion of the solvent. In the case of elastomers, these can also be SIA~ ed as lattices. Another way of i"col~,ordli"g compounds of the formula I into polymers cG",prises adding them before, during or immediately after poly.neri~dlion of the co..t:sponding l--onome~ or before clossli~ .lg. The compounds of the formula I can be added as such, or allt:r"dli-/ely in enc~ps~ t~d form (for exa...ple in waxes, oils or polymers). In the case of addition before or during the polymeri,dlion, the compounds of the formula I can also act as regl~'~rs for the chain length of the polymers (chain terminators).

The compounds of the formula I can also be added to the plastics to be ~ hil;~ed in the form of a ma~terL,alcl . which co. Ildil Is these compounds, for example, in a concenlrdlion of 2.5 to 25% by weight.

The compounds of the formula I can expediently be incorporated by the r~,llo~ ;ng methods:
- as an emulsion or dispersion (for e~xdl I Ir !e to lattices or emulsion polymers), - as a dry mix during mixing of adcJilional components or polymer mixtures, - by direct addition into the p-ocessing equipment (for ~,cd---ple extruder, internal mixer, etc.), - as a solution or melt.

Novel polymer co..~posilions can be used in various forms or converted into various products, for example as or into films, fibres, tapes, moulding co",posilions, profiles, or as binders for paints, adhesives or adhesive cements.

CA 02232~73 1998-03-20 ln addition to the compounds of the formula I or homopolymers and/or copolymers thereof, the novel coi"posilions can contain, as additional component (c), one or more conventional additives, such as, for example, the following:

1. Antioxidants 1.1. Alkylated monoDhenols, 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-methylcyclohexyl)-4,6-di-methylphenol, 2,6-~1io~t~decyl-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. AlkylthiomethylDhenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthio-methyl-4-nonylphenol .

1.3. Hydroquinones and alkylated hydroquinones, for exdr"ple 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa-decyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl? adipate.

1.4. Tocopherols, for example a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol and mixtures thereof (\/itamin E).

1.5. Hydroxvlated thiodiDhenyl 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.

CA 02232573 l998-03-20 WO 97/13752 PcT/~ r f.'C1264 - 1g-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-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a-methylbenzyl)-4-nonylphenol3, 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-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-dodecylmerc~ptobllt~ne, ethylene ~Iycol 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-benzvl comPounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi-benzyl ether, ocl;1decyl-4-hydroxy-3,5-dimethylbenzyll,,er~,-aplu~cet~te, tridecyl-4-hydroxy-3,6-di-tert-butylbenzyl" ,e. captoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)di~l,iuterephll)alate, bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercapto~cet~te.

1.8. Hvdroxvbenzylated 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)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl). . .alondLe, 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-hydroxy-benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetra-methylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.1û. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercaptû-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, CA 02232~73 l998-03-20 W O 97/13752 PCT/~l~G~I~1264 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-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpr~F ~nyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)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-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-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)ca, bar"ate.

1.13. Esters of b-(3,5-di-tert-butvl-4-hydroxvPhenyl)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.

1.14. Esters of b-(5-tert-butyl-4-hydroxv-3-methylphenvl)proPionic acid with mono- or poly-hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, oct~lec~nol, 1,6-hexane-diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo~2.2.2~octane.

1.15. Esters of b-(3,5-dicyclohexyl-4-hydroxYPhenvl)Propionic acid with mono- or polyhydric alcohois, 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-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo~2.2.2]octane.

CA 02232~73 l998-03-20 W O 97/13752 PCT/~,'/C1264 - 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenvl 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)-O~dll d~, 3-thiaundecanol, 3-thiapent~dec~nol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of b-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert--butyl-4-hydroxyphenylprop.anyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

1.18. Ascorbic acid (vitamin C) 1.19. Aminic antioxidants, for 6','CdlllplE: N,N'-di-isopropyl-p-phenylenedia".i.le, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediar"i,le, 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-thyl)-p-phenylenedid~ le, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenedidn,i"e, N-cyclo-hexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-aliyldiphenylamine, 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-nonanoylamino-phenol, 4-dodecanoyl-aminophenol, 4-octadecanoylal"i"ophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 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, CA 02232~73 l998-03-20 W O 97/13752 PCTrEP96/04264 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- und dial-kylated tert-butyl/tert-octylpher,ull ,i~i"es, a mixture of mono- und dialkylated tert-octyl-phe-noLl,ia~ es, N-allylphenothid~il" 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)seb~c~te, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and liqht stabilisers 2.1. 2-(2'-Hydroxv~henYl)ben~ulli~ùles~ for example 2-(2'-hydroxy-5'-methylphenyl)-benzo-triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)be-,~ul.ia~ùle, 2-(5'-tert-butyl-2'-hydroxyphe-nyl)be, l~ul- i~ole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)be, ,~ul, ia~ùle, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-bel ,~ul, ia~ole, 2-(3'-tert-butyl- 2'-hydroxy-5'-methyl-phenyl)-5-chloro-bel l~ulr i~ole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)ben~ul~ ule, 2-(2'-hydroxy-4'-octyloxyphenyl)ben~ul,i~ùle, 2-t3',5'-di-tert-amy,-2'-hydroxyphenyl)benzo-triazole, 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)ben~ul,ia~ùle, mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-ben~ul,id~ole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-ben~ulrid~ole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxyl;arbonylethyl)phenyl)-5-chloro-ben~ulrid~ole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)ben~ul~ia~ùle, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)ben ,ull ia~ole, 2-(3'-tert-butyl-5'-~2-(2-ethylhexyl-oxy)carbonylethyl]-2'-hydroxyphenyl)ber,~ulri~,ule, 2-(3'-dodecyl-2'-hydroxy-5'-methylphe-nyl)bel,~ulric~ule, and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarlJo"ylethyl)phenylben-~ulri~ùle~ 2,2'-methylene-bisi-4-(1,1,3,3-tetramethylbutyl)-6-ben~ul,i~ole-2-ylphenol]; the transe:jleriric~lion product of 2-i3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-ben~ul,i~ùle with polyethylene glycol3ûO;, where R = 3'-tert-butyl-4'-hydroxy-5'-2H-ben-~ul~i~ù1-2-ylphenyl.

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-phenyi salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben-zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzo-CA 02232~73 l998-03-20 W O 97/13752 PCT/~l~/0l264 ate, hexadecyl 3,5-di-tert-butyl-4-hydroxyberl~oale, 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-b,b-di-phenylacrylate, methyl a-carbomethoxycil~nal"dle, methyl a-cyano-b-methyl-p-methoxy-~i. ,na~ le, butyl a-cyano-b-methyl-p-methoxy-ci. ~nal "aLe, methyl a-car60, l I~Ll ,~x~-p-methoxyci- ~na"~le and N-(b-ca, l.on It:Lh~xy-b-cyanovinyl)-2-methylindol;i)e.

2.5. Nickel comoounds, for ~,~d",ple nickel complexes of 2,2'-thio-bis-[4-(1,1 ,3,3-tetra-methylbutyl)phenoq, such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, I,i~Ll,anolamine or N-cyclohexyl~i~ ',anola",i"e, nickel dibutyldiLl.iocar-ba,ndle, nickel salts of the ",onoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel con,r'sx~s of keluxi",es, e.g. of 2-hydroxy-4-methylphenyl undecylkt:luxi",e, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

2.6. Stericallv hi.,deled amines, for exdr, FIE bis(2,2,6,6-tetramethyl-4-piperidyl)seb~le, bis(2,2,6,6-tetramethyl-4-piperidyl)succ;..dle, bis(1,2,2,6,6-pentamethyl-4-piperidyl)seba-cate, bis(1 -octyloxy-2,2,6,6-l~lr~ Lhyl-4-piperidyl)seh~o~te, 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, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-1 ,3,5-tri~ine, tris(2,2,6,6-t~ll dm~l hyl-4-piperidyl)nitrilotri~cePte, 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-tetramethyl,uiperidine, 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-t~ dl l leLl lyl-1 ,3,8-LI i~spil ~[4.5]decan-2~4-dion~
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)seb~c~te, bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl)succinate, the condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethy-lenediamine and 4-morpholino-2,6-dicllloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-t~rd",~ll,ylpiperidyl )-1,3,5-triazine and 1,2-bis(3-aminopropyl-amino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethyl-piperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-CA 02232~73 1998-03-20 O 97113752 PCT/~i5./01264 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)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-tri~ine, a condensation product of 1,2-bis(3-amino-propylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetra-methylpiperidine (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-di~a-4-oxo-spiror4,51decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-di~a-4-oxospiro [4,5]decane und epichlorohydrin.

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-dimethyla",inopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para-methoxy-rlisubstituted oxanilides and mixtures of o- and p-ethoxy-disllhstitllted oxanilides.

2.8. 2-t2-HvdroxyPhenyi)-1 .3,5-tri~ines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tri~ine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tri~ine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tri~ine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyll-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 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-phenyll-4,6-bis(2,4-dimethylphe-nyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-di-methylphenyl)-1,3,5-tri~ine, 2-(2-hydroxy-4-hexyioxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-trisl2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-tri~ine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1 ,3,5-tri~ine.

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 CA 02232~73 l998-03-20 W O 97/13752 PCT~EP96/04264 dihydrazide, sebacoyl bisphenylhydr~ide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl-oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. PhosPhites and phosphoniles. for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosplliles, tris(nonylphenyl) phosphite, trilauryl phospl~ile, trioctadecyl phos-phite, distearyl pentaerythritol cli~.hosphiLe, tris(2,4-di-tert-butylphenyl) phosph;le, ~iiisodecyl pentaerythritol di,~llos~llile, bis(2,4-di-tert-butylphenyl3 pentaerythritol di,uhosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol di~hospl ,iLe, diisodecyloxypentaerythritol di-phospllilt:, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol di~)hosphiLe, tristearyl sorbitol L~iphosphiLe, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benz[d,g~-1 ,3,2-dioAdphospl)oci, 1, 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)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyllJhosphite.

5. Hydrox~lamines. for eAdlllple, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl-hydroxylamine, N-hepl;l-le~;yl-N-oct~decylhydroxylamine, 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-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heplddecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-oc~t~-lecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-hep-tadecyl-nitrone, N-oct~-~ecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkyl-hydroxylamine derived from hydrogendled tallow amine.

7. Thiosvnerqists, for example, dilauryl thiodipropionate or distearyl Ihiodi~ ,upionate.

8. Peroxide scavenqers. for example esters of b-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptoben,i",idazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(b-dodecylmercapto)propionate.

CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 9. Polyamide st~ sers, for example, copper salts in cornbi"dliorl with iodides and/or phos-phorus compounds and salts of divalent manganese.

10. Basic co- ~ ~ " ,e. ~. for example, melamine, polyvinylpy" olidone, dicyan~lia" ,;de, triallyl cyanurate, urea derivatives, hydr~i"e derivatives, amines, poly~n ~!es, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for e~dr"ple calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and pot~sciurn palmitate, antimony pyrocatecholate or tin pyrocatecholate.

11. Nuclealillg agents. for example, inorganic sul,~L~nces such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphdl~s, carbonates or sulfates of, prefe-rably, alkaline earth metals; organic compounds such as mono- or polycalbokylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium suc-cinate or sodium ber,~o~le; polymeric compounds such as ionic copolymers ("ionomers").

12. Fillers and le;"rurei"~ agents. for example, calcium carbonate, 5jli~ 5, glass fibres, glass bulbs, ~-~bestos, 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, p!-slioi~ers, lubricanL~, emulsfflers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, anli~l~lic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, 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)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-but-yl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

CA 02232~73 l998-03-20 W O 97/13752 PCT~EP96/04264 These additional additives are expediently employed in amounts of from 0.1 to 10% by weight, for example from 0.2 to 5% by weight, based on the polymer to be st~hili~ed The examples below illustrate the invention in greater detail. All parts and percentages, in the examples, in the remainder of the description and in the claims, are by weight, unless stated otherwise. The following abbreviations are used in the examples:

GPC: Gel permeation chromatography;
'H-NMR: Magnetic nuclear resonance of the nuclide 1H;
Mn Number average molar mass (unit g/mol);
Mw: Number average molar mass (unit g/mol);
TGA: Thermogravimetric analysis;
THF: Tetrahydrofuran.

Example 1: Propargvl tosvlate 381 9 (2 mol) of toluenesulfonyl chloride are dissolved in 400 ml of methylene chloride in a 2.5 I sulfonation flask fitted with a mechanical stirrer, thermometer and dropping funnel. A
solution of 112 9 (2 mol) of propargyl alcohol in 160 ml of water is poured in. 88 9 (2.2 mol) of sodium hydroxide, dissolved in 132 ml of water, are added dropwise at such a rate that the temperature of the emulsion does not exceed 25~C. The mixture is then stirred overnight at room ter"per~ re and then diluted with 400 ml of water and 200 ml of methylene chloride. The organic phase is separated off and washed twice with water. The solvent is removed on a rotary evapora~ur. The residue is distilled via a Vigreux column.

Yield: 325 9 (77 %) of a liquid of boiling point 1 02~C / 0.008 mbar.

CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 Microanalysis:
C~IGI ~ted Found C 57.13 57.07 H 4.79 4.80 S 15.25 15.24 1H-NMR (CDC13):

2.45 ppm (3H, s) : CH3 2.47 - 2.53 ppm (1 H, m) : ~C-H
4.69- 4.70 ppm (2H, m) :.C-CH2-O
7.34 - 7.37 ppm ' (4H, m) : H-Ar 7.80 - 7.83 ppm FxamPle 2: P~ epardlion of 1 -proParqyl-4-hydroxv-2,2~6,6-tetramethylpiperidine 197 g (1.25 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine, 105 9 (0.5 mol) of the compound from F~ample 1 and 1.81 of aceLunilr:!e are introduced into a 2.51 sulrurl~lion flaskfitted with precision glass stirrer, ll,er,non,eL~r and condenser. The suspension is warmed to the boil, a clear solution initially being obtained above 70~C. After half an hour, a slight suspension is formed. The mixture is refluxed for 18 hours, cooled to room temperature, diluted with 51 of water and extracted three times with ethyl acetate, and the combined organic phases are dried and evaporated. The solid residue is recrystallized from ethyl acetate.

Yield: 72.2 9 (74%) Melting Point: 151 ~C

CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96rO4~64 Microanalysis:
C~ t~d Found C 73.80 73.78 H 10.84 10.83 N 7.17 7.21 H-NMR (CDC13):

1.07 ppm and 1.26 ppm (12H, s) : CH3 1.38 - 1.45 ppm (2H, m) : CH2 (pi~.ed~' ~e) 1.54- 1.~6 ppm (1H, d) : OH
1.79- 1.84 ppm (2H, m) : CH2 (piperidine) 2.11 - 2.12 ppm (lH, t) : H-C~C
3.32 - 3.33 ppm (2H, d) : ~C-CH2-N
X~
3.91 - 3.96 ppm (1H, m) ExamPle 3: ~\ epardlion of 1 -(but-2-ynyl)-4-hvdroxy-2,2,6,6-tetramethylPiperidine 27.2 9 (0.12 mol) of 2-butynyl p-toluenesulfonate [Lancaster Synthesis Ltd., Lancashire LA 30Y, England], 47.7 9 (0.3 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine and 0.6 1 of ac~:lonil,ile are introduced into a 1 I round-bottom flask fitted with magnetic stirrer and condenser. The mixture is warmed to reflux. After 19 hours, the solution is poured onto ice and extracted three times with ethyl acetate. The organic phases are dried and evaporated.
The crude product is recry~ Hd from n-hexane.

Yield: 20 9 (80%) Melting point: 106~C

W O 97/137S2 PCT~EP96/04264 Microanalysis:
C~ICUi-~PCI Found C74.59 74.47 H11.08 11.04 N6.69 6.80 'H-NMR (CDCI3):

1.07- 1.25 ppm (12H, s) : CH3 (piperidine) 1.16-1.19ppm (1H d) : OH
1.38 - 1.46 ppm (2H, m) : CH2 (piperidi"e) 1.78 - 1.95 ppm (5H m) : CH2 (piperidine) and CH3-C~
3.29 ppm (2H, m) : ~C-CH2-N
\ o 3.91 - 3.99 ppm (1 H m) : X

ExamDle 4: PreParation of N-(2 2.6 6-tetramethylpi~eridin-4-yl)acrylamide 469 9 (3 mol) of 4-amino-2 2 6 6-tetramethylpipe, idil ,e are dissolved in 500 ml of diethyl ether in a 1.51 sulroncllion flask fitted with precision glass stirrer Ll,e""o",eter d,opping funnel and condenser. 90.5 g (1 mol) of acryloyl chloride are slowly added dropwise at -15~C. ~f~er the dropwise addition the mixture is allowed to warm to room temperature and is poured into ice-water and the solid is separated off and recrystallized from acetonitrile.

Yield: 67 g (32%)Meltinq Point: 122~C

CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 Microanaiysis:
C~lc~ ~'~ed Found C 68.53 68.65 H 10.54 10.61 N 13.32 13.22 1H NMR (CDCb):

0.69 ppm (1H, s) : NH (piperidine) 0.91 - 0.99 ppm (2H, t) : CH2 (piperidine) 1.13 ppm and 1.27 ppm (12H, s) : CH3 (piperidine) 1.91 - 1.96 ppm (2H, m) : CH2 (pipe,idi"e) N
4.29 - 4.40 ppm (1H, m) : ~

5.46 ppm (1 H, m) : -NH-CO-5.61 - 5.65 ppm (1 H, m) : CO-CH=C
6.02- 6.32 ppm (2H, m) : C=CH2 Example 5: P~e~a,dlion of N-(2,2,6,6-tetramethyl"iperidi,--4-vl)methacrylamide 344 9 (2.2 mol) of 4-amino-2,2,6,6-lelr~",e:ll,ylpiperidine are dissolved in 1.51 Of methylene chloride in a 2.51 sulfonation flask fitted with precision glass stirrer, thermometer and d~upp;. ,g funnel. The mixture is cooled to -10~C, and 104.5 g (1 mol) of methacryloyl chloride are added dropwise with stirring. The mixture is then stirred for a further 3 hours at room te""~e,dlure and poured into 21 Of 0.5 N sodium hydroxide solution, the organic phase is separdled off, washed with water and dried, and the volatile constituents are removed by evaporation. The residue is recryst~lli7ed from n-hexane.

Yield: 87 9 (39%) Meltinq Point: 119~C

CA 02232~73 1998-03-20 O 97/13752 PCT~EP96/04264 Microanalysis:
C~lcu'-ted Found C 69.60 69.52 H 10.78 10.79 N 12.49 12.42 1H-NMR (CDCI3):

0.6g ppm (1H, s) : NH (piperidine) 0.91 - 0.99 ppm (2H, t) : CH2 (piperidine) 1.13 ppm and 1.27 ppm (12H, s) : CH3 (piperidine) 1.91 -1.95 ppm (2H, m) : CH2 (piperidine) 1.96 ppm (3H, s) : CH3 (methacrylate) N
4.25 - 4.36 ppm (1 H, m) : ~,~

5.31 ppm and 5.65 ppm (2H, s) : CH2 =C
5.55 pm (1H, d) : -NH-CO-Example 6: rlel~ar~Lion of 4-acrylolyloxy-1-proParayl-2,2,6,6-tetramethylPiPeridine 290 9 (1.48 mol) of the compound prepared in Example 2, 195 9 (1.9 mol) of triethylamine and 2.71 of diethyl ether are introduced under argon into a 51 flask with plane ground joints fitted with pl ecision glass stirrer, thermometer and dropping funnel. This mixture is cooled to 5~C, and 161 9 (1.8 mol) of acryloyl chloride are then slowly added dropwise with stirring.
The mixture is then stirred at room temperature for about 18 hours. The reaction solution is poured into sodium bicarbonate solution, and the organic phase is separated off. The water phase is extracted once with ethyl acetate. The combined organic phases are dried and evaporated. The residue is recrystallized from n-hexane.

Yield: 206.5 g (56%) Meltinq Point: 48~C

CA 02232~73 1998-03-20 W O 97/13752 PCT/~l~c~1264 Microanalysis:
C~lc~ ted Found ~ C72.25 72.40 H9.30 9.34 I r N5.62 5.64 'H-NMR (CDCI3):

1.14 ppm and 1.27 ppm (12H, s) : CH3 (piperidine) 1.54- 1.62 ppm (2H, m) : CH2 (piperidine) 1.83- 1.89 ppm (2H, m) : CH2 (piperidine) 2.11 - 2.13 ppm (lH, t) : H-C~C
3.33 - 3.34 ppm (2H, d) : N-CH2-\ o 5.10-5.21 ppm (lH,m) : ~,<

5.78 - 5.82 ppm (1 H, d) : C0-CH=C
6.05 - 6.14 and 6.3~ - 6.41 ppm (2H, m) : C=CH2 Example 7: r~epardlion of 4-methacryloxy-1-ProPargvl-2.2,6.6-tetramethvlPiperidine 240 9 (1.25 mol) of the compound described in Example 2, 177 9 (1.75 mol) of triethylamine and 1.7 1 of diethyl ether are introduced under argon into a 2.5 I sulfonation flask fitted with preci~ion glass stirrer, thermometer and dropping funnel. The suspension is cooled to 5~C, and 1 56 9 (1.5 mol) of methacryloyl chloride are then added dropwise. The mixture is allowed to warm to room temperature, stirred for a further 20 hours and poured into aqueous sodium bicarbonate solution, and the organic phase is separated off, dried and evaporated. The residue is recryst~ 7ed from n-hexane.

Yield: 163 9 (50%) Melting point: 49~C

CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 Microanalysis:
C~lc~ d Found C 72.97 72.28 H 9.57 9.80 N 5.32 5.22 -NMR (CDCI3):

1.13 ppm and 1.27 ppm (12H, s) : CH3 (piperidine) 1.48- 1.68 ppm (2H, m) : CH2 (piperidine) 1.84- 1.90 ppm (2H, m) : CH2 (piperidine) 1.93 ppm (3H, s) : Clt3 (methacrylate) 2.11 - 2.13 ppm (1 H, t) : H-C-C
3.34- 3.35 ppm (2H, d) : N-CH2 \ o 5.08 - 5.18 ppm (1 H, m) : ~
H

5.53 ppm and 6.07 ppm (2H, s) : CH2=C

Example 8: P,ePar~lion of 4-acryloyloxy-1-but-2-ynyl-2.2.6.6-tetramethylpi~eridine 10.5 9 (50 mmol) of the compound prepared in Example 3, 5.6 9 (55 mmol) of triethylamine and 65 ml of diethyl ether are introduced under argon into a 250 ml sulfonation flask fitted with precision glass stirrer, thermometer and dropping funnel. 4.5 g (50 mmol) of acrylic acid are added dropwise at 5~C. The mixture is then stirred at roorn temperature for a further 24 hours and washed twice with sodium bicarbonate solution, and the organic phase is dried using sodium sulfate and evaporated. The residue is chromatographed on silica gel 60 [Merck, Darmstadt] using n-hexane/ethyl acetate = 3: 1, giving 10.3 g (78%) of a colourless liquid.

CA 02232~73 l998-03-20 O 97/13752 PCT~EP96/04264 Microanalysis:
C~lcul~t~sd Found C72.97 72.77 H9.57 9.63 N5.32 5.11 H NMR (CDCI3):

1.06 ppm and 1.18 ppm (12H, s) : CH3 (pi~.eridi.,e) 1.46 - 1.54 ppm (2H, t) : CH2 (pi~,eri.Jil,e) 1.69 - 1.70 ppm (3H, m) : CH3 (butyne) 1.74- 1.80 ppm (2H, m) : CH2 (piperidine) 3.21 - 3.22 ppm (2H, m) : CGC CH2 N
\ o 5.02 - 5.12 ppm (1H, m) :

5.70 - 5.74 ppm ~
5.97-6.06 ppm ~ (3H, m) : CH2=CH-CO
6.26 - 6.32 ppm J

ExamDle 9: r~epar~lion of 4-(4-vinvlbenzyloxv)-1-proPa,u~/1-2,2~6~6-tetramethylPiPeridine 30 9 (154 mmol) of the compound prepared in Example 2, 1 50 ml of toluene, 7.7 g(7.7 mmol) of polyethylene glycol 1000 and 43.1 g (770 mol) of powdered pot~ssi~hydroxide are introduced under argon into a 350 ml sulfonation flask fitted with precision glass stirrer, thermometer and dropping funnel. This suspension is warmed to 80~C, and 25.9 g (170 mmol) of vinylbenzyl chloride [Fluka AG, Buchs] are then added dropwise. The mixture is stirred at 80~C for a further 4 hours, then cooled to room temperature and poured into water. The organic phase is separated off and extracted with 2N HCI solution. This aqueous phase is washed with toluene and then rendered basic by means of 1 N sodium hydroxide solution. The water phase is extracted with toluene, and the organic phase is W O 97/13752 PCT~EP96/04264 dried using sodium sulfate and the solvent is evaporated co,~ tely. Bulb-tube distillation at 150~C/0.02 mbar gives a colourless liquid.

Yield: 23.5 g ( 51 %) Microanalvsis:
C~ fed Found C80.98 80.89 H9.38 9.39 N4.50 4.47 'H-NMR (CDCI3):

1.05 ppm and 1.26 ppm (12H s) : CH3 (piperidine) 1.46 - 1.54 ppm (2H t) : CH2 (piperidine) 1.86 - 1.92 ppm (2H, m) : CH2 (piperidine) 2.10-2.11 ppm (1H t) : H-C~C
3.31 - 3.32 ppm (2H, d) : C~C-CH2-N
\ o 3.64 - 3.75 ppm (1 H m) : ~<

4.52 ppm (2H s) : Ar-CH2-O-5.19 - 5.25 ppm l 5.69 - 5.77 ppm ~ (3H, m) : CH2=CH-6.65 - 6.75 ppm J
7.21 - 7.38 ppm (4H m) : H-Ar CA 02232573 l998-03-20 ExamPle 10: Preparation of N-(1-Proparqyl-2.2.6.6-tetramethylpiperdin-4-vl)acrvlamide 66.6 g (0.31 mol) of the compound from Example 1,131 9 (0.62 mol) of the compound described in Example 4 and 940 ml of acetonitrile are introduced into a 21 round-bottomed flask fitted with magnetic stirrer and condenser. The mixture is warmed to reflux, a clear solution forming. The mixture is refluxed for 6 hours, giving a suspension again. The solid is filtered off, and the solution is evaporated to dryness. The residue is purified on silica gel 60 [Merck] by means of ethyl acetEe and recryst~lli7~d from xylene.

Yield: 47 9 (61 %) Melting point: 125.3~C

Microanalysis:
C~lcul~ted Found C72.54 72.39 H9.74 9.71 N11.28 11.30 CA 02232~73 l998-03-20 W O 97/13752 PCT~EP96/04264 1H-NMR (CDC13):

1.13 ppm and 1.22 ppm (12H, s) : CH3 (p;~ elidine) 1.30 - 1.38 ppm (2H, t) : CH2 (piperidine) 1.79- 1.84 ppm (2H, m) : CH2 (piperidine) 2.11 - 2.12 ppm (1 H, t) : H-C~C-3.32 - 3.33 ppm (2H, d) : C-=C-CH2-N
N
4.20 - 4.32 ppm (1 H, m) : ~
H

5.50 ppm (lH, d) :-NH-C0-5.60 - 5.64 ppm ~
6.03 - 6.12 ppm ~ (3H, m) :CH~=CH-6.24 - 6.31 ppm J

ExamPle 11: r~epardlion of N-(1-ProDar~lvl-2~6~6-tetramethylPiperidin-4-yl)methacrylamide 40.2 g (0.19 mol) of the compound from Example 1,85.8 9 (0.38 mol) of the compound described in Example 5 and 600 ml of acetonitrile are introduced into a 1 I round-bottomed flask fitted with magnetic stirrer and condenser. The solution is warmed to reflux, stirred for 6 hours, cooled to room tei"pe~dlure and separated from the solid. The solvent is evaporated. The residue is purified on silica gel 60 [Merck] using ethyl acetate and sl lhsequently recryst~ d from cyclohexane.

Yield: 25.4 9 (51 %)Meltinq point: 117.4~C

Microanalysis:
C~lcul~ted Found C 73.2¢ 73.21 H 9.99 9.98 N 10.68 10.65 CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 lH-NMR (CDCI3):

1.13 ppm and 1.25 ppm (12H, s) : CH3 (piperidine) 1.29-1.37 ppm (2H,t) : CH2 (piperidine) 1.80 -1.86 ppm (2H, m) : CH2 (piperidine) 1.95 ppm (3H, s) : CH3 (methacrylate) 2.11-2.12ppm (1H,t) : H-C-C-3.32-3.33 ppm (2H, d) : C=C-CH2-N
N
4.17 - 4.28 ppm (1H, m) :

5.31 ppm and 5.64 ppm (2H, s) : CH2=
5.52 ppm (1 H, m) : -NH-C0-ExamPle 12: P~ePardlion of Poly(4-acryloyloxv-1-ProPa,~/1-2,2,6,6-tetramethvlpiperidine) 90 g (0.36 mol) of the monomer from Example 6, 1.19 9 (7.2 mmol) of ~,o~isic017lltyronitrile (AIBN), 3.2 g (36 mmol) of butyl ")er.;aptan and 270 9 of tetrahydrofuran (THF) are introduced under argon into a 500 ml round-bottom flask fitted with magnetic stirrer. The solution is freed from oxygen and polymerized overnight at 70~C under argon. The reaction solution is precipil;.l~d in ",~ll,anol, and the solid is re-dissolved in THF and preci~ led in methanol. The white polymer powder is dried under a high vacuum, giving 33.1 9 (37%) of polymer.

GPC (THF): Mn = 6700 Mw = 10600 TGA (Heating rate 2~C / min., air) : 10% weight loss at 303~C

CA 02232~73 l998-03-20 ExamPle13:PreParation ofpoly(4-methacryloxy-1-proparqyl-2,2.6.6-tetramethylpiPeridine) 70 g (0.27 mol) of the monomer from Example 7 are polymerized with 0.87 g (5.3 mmol) of AIBN and 3.6 g (40 mmol) of butyl mercaptan in 210 9 of THF as described in Example 12.

Yield: 40.3 g (58%) of a white polymer powder.

GPC (THF): Mn = 6100 Mw = 9900 TGA (Heating rate 2~C / min., air) : 10% weight loss at 298~C

ExamPle 14: PreParation of Poly(4-acryloyloxy-1-but-2-ynvl-2.2.6,6-tetramethvlpi,.eri.li"e) 20 g (76 mmol) of the monomer from Example 8 are polymerized with 0.12 g (0.76 mmol) of AIBN and 0.68 g (7.5 mmol) of butyl mercaptan in 63 9 of toluene as described inExample 1 2.

Yield: 7 g (35%) of polymer.

GPC (THF): Mn = 4400 Mw = 5600 TGA (Heating rate 2~C / min., air) : 10% weight loss at 278~C

W O 97/13752 PCT~EP96/04264 ExamPle 15: PreParation of Poly~N-t1-proparqvl-2~2~6~6-tetramethylpiperidin-4-yl)acrvlamide 42 g (169 mmol) of the monomer from Example 10 are polymerized with 280 mg (1.7 mmol) of AIBN and 3.05 g (33.8 mmol) of butyl mercaptan in 120 g of THF as described in Example 1 2.
The polymer is precil-iL~ied in n-hexane.

Yield: 32.5 g (77%) of white polymer.

GPC (THF): Mn = 1500 Mw = 41 00 TGA (Heating rate 2~C / min., air) : 10% weight loss at 31 5~C

Example 16: P~ePardLion of poly~N-(1-Proparqyl-2~2~6~6-tetramethvlpiperidin-4-yl) methacrvlamidel 25 g (95 mmol) of the monomer from Example 1 1 are polymerized with 156 mg (0.95 mmol) of AIBN and 1.71 9 (19 mmol) of butyl mercaptan in 75 9 of THF as described in Example 12.
The polymer is precirit~ted in n-hexane.

Yield: 14 g (56%) of white polymer.

GPC (THF): Mn = 1500 Mw = 4000 TGA (Heating rate 2~C / min., air) : 10% weight loss at 321 ~C

, CA 02232~73 l998-03-20 Determination of the PKa of the substance Titration in acetonitrile/chloroform = 1: 1 using 0.1 N HCI04 in dioxane. The half neulrdli~lion point (HNP) is relative to 2-ai,.;nopyridine (= 0 m\/):

HNP (m\/) pKa 2- 0 6.86 Aminopyridine Polymer + 75 6.45 ExamPle 1 7: PreParation of poly(4-vinvlbenzyloxy-1 -proPargvl-2,2,6.6-tetramethylpiperidine) 29 9 (97 mmol) of the monomer from Example 9, 0.64 9 (3.9 mmol) of azobisisobutyronitrile (AIBN) and 11 6 g of toluene are introduced into a 250 ml round-bottom flask fitted with magnetic stirrer and reflux condenser. The solution is freed from oxygen and stirred overnight at 70~C under argon.
The viscous solution is poured into methanol. The preci~iL~Le is taken up in toluene and re-precipit~tPd in methanol. The polymer is dried under a high vacuum.

Yield: 24 g (83%) MALDI-MS (~aatrix_ssisted Laser Desorption/~onization-Mass Spectrometry):

Mn = 6000 Mw = 8500 TGA (Heating rate 2~C / min., air) : 10% weight loss at 316~C

CA 02232~73 l998-03-20 O 97/13752 PCT~EP96/04264 ExamPle 18: Liqht st~hi~ qtion of PolyProPylene fibres 2.5 9 of each of the novel stfih~ erS from Exal"ples 12 to 14 together with 1 9 of tris(2,4-di-tert-butylphenyl) phosphite, 1 9 of calcium monoethyl 3,5-di-tert-butyl-4-hydroxyben~yl-phosphonate, 1 9 of calcium stearate and 2.5 9 of TiO2 (Kronos RN 57) are mixed with 1000 9 of polypropylene powder (melt flow index 12 g/10 min, measured at 230~C/2.16 kg) in a turbomixer. The mixtures are extruded at 200-230~C to give pellets, which are sl Ihsec-lently converted into fibres with the aid of a pilot plant (Leonard; Sumirago/VA, Italy) under the following conditions:

Extruder temperature: 1 90-230~C
Head temperature: 255-260~C
SLI~lchillg ratio: 1:3.5 Sl.~lchi, ,9 temperature: 1 00~C
Fibres: 12 den The fibres produced in this way are exposed against a white background in a type 65 WR
Weather-O-Meter~ (Atlas Corp.) at a black panel temperature of 63~C in accordance with ASTM D 2565-85. After various exposure times, the residual tensile strength of the samples is measured. The measurements are used to cfllc,J'qte the exposure time Tso after which the tensile strength of the samples has halved.

For comparative purposes, fibres are produced without novel st~qhi'i~er under oll,er~ise identical conditions and are tested. The test results are shown in Table 1.

Table 1:
Exposure time for the initial tensile strength to halve .SPhiii7erExposure time None 300 h from Example 122270 h from Example 132470 h from Example 1431 10 h CA 02232~73 l998-03-20 W O 97/13752 PCT~EP96/04264 The fibres sl;-hil;~ed in accordallce with the invention have excellent ~lrenyLll retention.

Example 19: Stabilization of a two-coat Paint The light sPhili7er from Example 10 is incorporated into 5-10 g of xylene and tested in a varnish of the following co,llposilion:

SynthacrylD SC 303 l) 27.51 9 Synthacryl~ SC 370 2) 23.34 9 Maplenal~ MF 650 3) 27.29 9 Butyl acetate/butanol (37/8) 4.33 9 Isobutanol 4.87 9 Solvessoe 150 4) 2.72 9 Crystal Oil K-30 5) 8.74 9 Flow-control agent Baysil~ MA6) 1.20 9 100.00 9 1) Acrylate resin, Hoechst AG; 65% solution in xylene/butanol 26:9 2) Acrylate resin, Hoechst AG~ 75% solution in Solvessoe 1004) 3) Melamine resin, Hoechst AG; 55% solution in isobutanol 4) Manufacturer: ESSO
5) Manufacturer: Shell 6) 1% in Solvesso~ 150; manufacturer: Bayer AG

The varnish is mixed with 1 % of the stabilizer from Example 10, based on the solids content of the varnish. The control is a varnish containing no light st~bili7er.

The varnish is diluted to spray consi~Lency with Solvesso~100 and sprayed onto a prepared aluminium sheet (coil coat, filler, silver-metallic base coat) and baked for 30 minutes at 130~C, giving a dry film thickness of 40-50 ~Lm.

W ~ 97113752 PCT~EP96/04264 The samples are then weathered in a UVCON~weathering unit from Atlas Corp.
(UVB-313 Lamps) with a cycle of 4 hours' UV irradiation at 60~C and 4 hours' condensation at 50~C.

The samples are regularly assessed for cracks.

The samples co,~Lhi.,;ny the novel .~l~h~ er have high cracking ,~sisl~nce.

E~xamPle 20: Sl~ lion of a Dhotoqraphic material 0.087 9 of the yellow coupler of the formula (CH3)3 C--C--fH--C NH~ I H2 CH3 ~ NH-C--(CHz)3 O~L ICHH' CHzCH, is dissolved in 2.0 ml of a solution of the novel 5t~hjli7er from Example 6 in ethyl acetate (2.25 9/100 ml). 9.0 ml of a 2.3% aqueous gelatin solution which has been ~just~cl to a pH
of 6.5 and 1.744 g/l of the wetting agent of the formula CA 02232~73 1998-03-20 W O 97/13752 PCT~EP96/04264 CH3cHcH2cHs ~SO3Na are added to 1.0 ml of this solution.

2 ml of a silver bto", de emulsion having a silver content of 6.0 9/l and 1.0 ml of a 0.7%
aqueous solution of the curing agent of the formula Cl >=N
N /~OH
~N
Ci are added to 6.0 ml of the resultant coupler emulsion, and the mixture is cast onto a 13 x 18 cm resin-coated paper. After a curing time of 7 days, the samples are exposed to 125 lux-s behind a silver step wedge and subsequently processed by the Kodak Ektaprint 2~ ,c r~cess.

The yellow wedges obtained are irradiated with a total of 60 kJ/cm2 behind a UV filter (Kodak 2C) in an Atlas Weather-O-Meter~ using a 2500 W xenon lamp.

A sample without ~ hili~er is processed in the same way as standard.

The drop in colour density at the absorption maximum of the yellow dye that occurs on irradiation is measured using a Macbeth TR 924 A densitometer.

The light sPhi~ tion effect is evident from the drop in colour density. The smaller the drop in density, the greater the light Sphili~tion effectiveness.

The novel st~hili~er has a good light st~hi~ tiQn action.

CA 02232~73 l998-03-20 W O 97/13752 PCT~EP96/0426 Exam~le 21: SPhili7~tion of Polypropylene ta~es 1.0 9 of the novel 5t~hili'er from Example 9 together with 1 9 of tris(2,4-di-tert-butylphenyl)-pl ~osphile, 0.5 g of pentaerythrityl tetrakis(3-[3',5'-di-tert-butyl-4'-hydroxyphenyqpropionate) and 1 9 of calcium ~lear~L~ are mixed with 1000 9 of polypropylene powder (STATOILMF;
melt flow index 4.0 g/10 min, measured at 230~C/2.16 kg) in a turbo mixer.

The mixtures are extruded at 200-230~C to give pellets, which are converted into stretch tapes 2.5 mm wide and 50,um thick with the aid of a pilot plant (Leonard; Sumirago/VA, Italy) under the following condilions;

Extruder temperature: 210-230~C
Head temperature: 240-260~C
Slr~l~;hing ratio: 1 :6 SLr eL~,-hil lg temperature: 110~C

The tapes produced in this way are exposed against a white background in a type 65 WR
Weather-O-Meter~ (Atlas Corp.) at a black panel temperature of 63~C in accordance with ASTM D 2565-85. After various exposure times, the residual tensile strength of the samples is measured. The measurements are used to c~icul~te the exposure time T50 after which the tensile strength of the samples has halved.

For comparative purposes, tapes are produced without novel st~hili~er under otherwise identical conditions and are tested.

The sample 5t~hi~i~ed in accordance with the invention has excellent strength retention.

Claims (23)

WHAT IS CLAIMED IS:

1. A compound of the formula I

, in which R is H, C1-C12alkyl, phenyl, (C1-C4alkyl)phenyl, phenyl-C1-C4alkyl, halogen, C2-C12alkynyl or C1-C12alkoxy, X is NR', NCOR' or O, and Y Is R" or R"-CO-, where R" is C2-C6alkenyl or C3-C6alkenyl which is interrupted by -O-, -CO-, -NR'-, -S-, -SO-, -SO2- or phenylene, or (C2-C6alkenyl)phenyl, and R' is H or C1-C12alkyl, or -X-Y

is the group of the formula or .

2. A compound according to claim 1, in which R is H, C1-C8alkyl, phenyl, (C1-C4alkyl)phenyl or phenyl-C1-C4alkyl, and R" is C2-C4alkenyl, C3-C4alkenyl which is interrupted by -O-, -CO- or -NR'-, or benzyl or phenyl which is substituted by C2-C4alkenyl.

3. A compound according to claim 1, in which R is H, C1-C8alkyl or phenyl, X is NH, N(C1-C4alkyl) or O, and Y is a group of the formula CH2=CH-CO-, CH2=C(CH3)-CO-, , or or -X-Y is the group of the formula .

4. A compound according to claim 1, in which R is H or CH3, X is -NH- or -O-, and Y is a group of the formula CH2=CH-CO- or CH2=C(CH3)-CO- or vinylbenzyl.

5. A homopolymer or copolymer obtainable by addition polymerization of one or more compounds of the formula I.

6. A polymer according to claim 5, which conforms to the general formula II

in which m is 0 or 1, R2, R3 and R4, independently of one another, are H or C1-C10alkyl, C3-C10alkyl which is interrupted by -O-, -CO-, -NR'-, -S-, -SO-, -SO2- or phenylene, Z is a direct bond, phenylene, phenylene(C1-C4alkylene), C1-C4alkylene or C3-C4alkylene, which is interrupted by -O-, -CO-, -NR'-, -S-, -SO-, -SO2- or phenylene, with the proviso that the total number of carbon atoms in all four radicals R2, R3, R4 and Z
does not exceed 10, excluding carbon atoms in optional interruptions, or, if R2 and R4 are H and m is 0, R3, Z and X together can also be the unit, and Z and R are as defined under the formula I, and n is a number from 5 to 10,000, and the general symbols in each recurring unit are identical or different.

7. A polymer according to claim 6, where Z is a direct bond, and R2, R3 and R4, independently of one another, are H or C1-C4alkyl.

8. A copolymer obtainable by addition copolymerization of compounds of the formula I
with at least one comonomer containing a polymerizable, ethylenically unsaturated C=C
double bond.

9. A copolymer according to claim 8, in which the comonomer comprises one or more compounds from the group consisting of .alpha.-olefins, styrenes, .alpha.-methylstyrenes, acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, methacrylamides, acrylonitrile, vinyl acetate and vinyl chloride.

10. A copolymer according to claim 8, comprising from 1 to 99 mol% of structural units of the formula II according to claim 6 and from 99 to 1 mol% of structural units of the formula III

(III) , in which R5 is H, C1-C10alkyl, phenyl, -COOR7, -CONH2, -C=N or -Cl, R6 is H or C1-C10alkyl and R7 is H or C1-C10alkyl.

11. A copolymer according to claim 10, in which, in the formula III, R5 is C1-C2alkyl, phenyl, -COOR7, -CONH2, -C=N or -Cl, R6 is H or methyl and R7 is H or C1-C2alkyl.

12. A composition comprising a) an organic material which is sensitive to damage by light, oxygen and/or heat, and b) as stabilizer, at least one compound of the formula I according to claim 1 and/or a polymer according to claim 5 and/or claim 8.

13. A composition according to claim 12, in which component a) is an organic polymer.

14. A composition according to claim 12, in which component a) is a synthetic polymer.

15. A composition according to claim 12, in which component a) is a polyolefin or a paint binder based on acrylic, alkyd, polyurethane, polyester or polyamide resin or correspondingly modified resins.

16. A composition according to claim 12, comprising further conventional additives in addition to components a) and b).

17. A composition according to claim 12, comprising from 0.01 to 10% by weight of component b), based on the weight of the composition.

18. A process for stabilizing organic material against damage by light, oxygen and/or heat, which comprises admixing a compound of the formula I according to claim 1 and/or a polymer according to claim 5 and/or claim 8 with this material.

19. The use of a compound of the formula I according to claim 1 and/or a polymeraccording to claim 5 and/or claim 8 for stabilizing organic material against damage by light, oxygen and/or heat.

20. A process for stabilizing organic polymers produced by addition polymerization against damage by light, oxygen and/or heat, which comprises adding at least onecompound of the formula I to the corresponding monomers before polymerization or to the reaction mixture during polymerization, and incorporating this compound into the polymer structure by copolymerization.

21. A process according to claim 20, in which the monomer is an .alpha.-olefin, a styrene, an a-methylstyrene, acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, methacrylamide, acrylonitrile, vinyl acetate or vinyl chloride, or a mixture of such monomers.

22. A process according to claim 20, in which the compound of the formula I is added in an amount of from 0.01 to 5 mol%, based on the monomer content.

23. A polymer protected against damage by light, oxygen and/or heat by the process according to claim 20.