The invention relates to novel 2,2,6,6-tetramethylpiperidines which are substituted on the ring nitrogen and contain, in the 4-position, a substituent with a polymerizable double bond, to their homopolymers and copolymers, to their use for stabilizing 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 stabilizers; these include

4-substituted derivatives of 1 -propargyl-2,2,6,6-tetramethylpiperidine. By way of example, the following publications may be mentioned in this respect:

US-A-4 472 547 (C.A.l02:46831z); EP-A-11 051 (C.A.94:39518r); DE-A-2 805 838

(C.A.90:22820c). US-A-4 386 127 (C.A.99:89380p) also describes 1-butynyl-2,2,6,6- tetramethyl-4-hydroxypiperidine.

The use of some compounds of the 2,6-diarylpiperidin-1 -yl-substituted 2-butene type as stabilizers has also been disclosed (US-A-5 204 474).

A number of scientific publications describe 1 -butynyl-2,2,6,6-tetramethylpipehdines whose piperidine ring is unsubstituted in the 4-position, and their possible use as medicaments; for example M. E. Zuhair et al., Eur. J. Med. Chem. 27, 93 (1992) (C.A.U7:26405v); 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 unsubstituted 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.

It has now been found that certain compounds of the 2,2,6,6-tetramethylpiperidine type which contain both a triple bond in the β-position on the ring nitrogen atom and a polymerizable double bond in the 4-position on the piperidine ring are surprisingly suitable as stabilizers for organic material. They also have high thermal stability and thus allow higher processing temperatures in the application and consequently a higher throughput on further processing of the products stabilized in this way.

The invention therefore relates firstly to compounds of the formula I

in which

R is H, Cι-C ₁₂ alkyl, phenyl, (C--C ₄ alkyl)phenyl, phenyl-C.-Caalkyl, halogen,

C ₂ -Ci ₂ alkynyl or C--Ci ₂ alkoxy,

X is NR', NCOR' or O, and

Y is R" or R"-CO-, where R" is rCe-alkenyl or C ₃ -C ₆ alkenyl which is interrupted by -O-,

-CO-, -NR'-, -S-, -SO-, -SO ₂ - or phenylene, or (Cι-C ₄ alkenyl)phenyl, and

R' is H or Cι-C ₁₂ -alkyl, or

-X-Y

is a group of the formula —

d-Ci ₂ alkyl 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-tetramethylpentyl, 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. Cι-C ₄ alkylphenyl R is phenyl which is mono- or polysubstituted by alkyl. This group contains, for example, from 1 to 3, in particular 1 or 2, alkyl substituents. C--C ₄ alkylphenyl can be, for example, methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl), ethylphenyl, propylphenyl or butylphenyl.

Phenyl-C--C ₄ alkyl R is, for example, benzyl, phenethyl, 3-phenylpropyl, α-methylbenzyl or α.α'-dimethylbenzyl.

C ₂ -Ci ₂ alkynyl R is, for example, ethynyl, 1 -propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, etc.. These alkynyl groups preferably have 2 to 4 carbon atoms.

d-Cu-alkoxy 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 I, preferably Cl or Br, but in particular Cl.

C ₂ -C ₆ alkenyl 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.

Preference is given to compounds of the formula I in which

R is H, Cι-C ₈ alkyl, phenyl, (C--C ₄ alkyl) phenyl or phenyl-C--C ₄ alkyl, and

R" is C ₂ -C ₄ alkenyl, C ₃ -C ₄ alkenyl which is interrupted by -O-, -CO- or -NR'-, or benzyl or phenyl which is substituted by C ₂ -C ₄ alkenyl.

Of particular interest are compounds of the formula I in which

R is H, d-Cβalkyl or phenyl,

X is NH, N(C--C ₄ alkyl) or O, and

Y is a group of the formula CH ₂ =CH-CO-, CH ₂ =C(CH ₃ )-CO-,

or

-X-Y is the group of the formula

Of very particular importance are compounds of the formula I in which

R is H or methyl,

X is O or NH, and

Y is CO-CH=CH ₂ , CO-C(CH ₃ )=CH ₂ or vinylbenzyl.

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

These novel homopolymers and copolymers preferably conform to the formula II

in which m is 0 or 1 ,

R _2l R ₃ and R ₄ , independently of one another, are H or d-C-oalkyl, C ₃ -C ₁₀ alkyl which is interrupted by -0-, -CO-, -NR'-, -S-, -SO-, -SO ₂ - or phenylene,

Z is a direct bond, phenylene, phenylene(d-C alkylene), d-C ₄ alkylene or

C ₃ -C ₄ alkylene, which is interrupted by -O-, -CO-, -NR'-, -S-, -SO-, -S0 ₂ - or phenylene, with the proviso that the total number of carbon atoms in all four radicals R ₂ , R ₃ , R ₄ and Z does not exceed 10, excluding carbon atoms in optional interruptions, or, if

R ₂ and R ₄ are H and m is 0, R ₃ , 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.

Preference is given to compounds of the formula II in which Z is a direct bond and R ₂ , R ₃ and R ₄ , independently of one another, are H or d-C alkyl.

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

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

Preference is given to copolymers in which the comonomer is one or more compounds from the group consisting of α-olefins, styrenes, α-methylstyrenes, acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, methacrylamides, acrylonitrile, vinyl acetate or vinyl chloride.

These copolymers preferably contain from 1 to 99 mol% of structural units of the formula II and from 99 to 1 mol% of structural units of the formula III

in which

Rs is H, d-doalkyl, phenyl, -COOR ₇ , -CONH ₂ , -C-N or -Cl,

R ₆ is H or Cι-C ₁₀ alkyl and

R ₇ is H or Cι-C ₁₀ alkyl.

Preference is given to copolymers in which, in the formula R ₅ is Cι-C ₂ alkyl, phenyl, -COOR ₇ , -CONH ₂ , -C«N or -Cl,

R ₆ is H or methyl and R ₇ is H or d-C ₂ alkyl.

The copolymers comprising compounds of the formula I with a comonomer containing a C=C double bond preferably have a mean molecular weight M _n of from 500 to1 ,000,000, preferably 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

C 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-substituted 2,2,6,6-tetramethylpiperidines of the formula VI

Y

I

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 preferably carried out by reacting compounds of the formula IV or V in which R is H or CH ₃ and

R' is C C ₄ alkyl or H with, for example, acryloyl chloride, methacryloyi chloride, methacrylic acid, methylmethacrylic acid or vinylbenzyl chloride, or by reacting compounds of the formula VI in which X and Y together are CH ₂ =CHCONH- or CH ₂ =C(CH ₃ )CONH- with propargyl tosylate.

Both compounds of the formula IV and of the formula VI can be prepared in a manner known per se from 4-alkylamino-2,2,6,6-tetramethylpiperidines of the formula Vll or compounds of the formula V or VI can be prepared in a manner known per se from 4- hydroxy-2,2,6,6-tetramethylpiperidine of the formula VIII

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 suitable solvents are toluene, hexane, cyclohexane, ligroin, petroleum ether and other hydrocarbon mixtures, dimethylformamide, tetrahydrofuran, dioxane, chloroform, diethyl ether, dimethyl sulfoxide and acetonitrile; particular preference is given to acetonitrile.

The temperature during the reaction can be in the range from -50 to 200°C, preferably from -25 to 160°C, in particular from -15 to 140°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 suitable condenser and fed back into the reaction mixture.

The reaction can be carried out with exclusion of oxygen, for example by flushing with an inert gas such as argon; however, oxygen does not always interfere, so that it may also be possible to carry out the reaction without this measure.

When the reaction is complete, work-up can be carried out by customary methods; the mixture is expediently first diluted with water, for example by adding the reaction 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 expediently 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, recrystallization and/or distillation.

The homopolymers and copolymers of compounds of the formula I, for example of those of the formula II or III, are prepared by free-radical polymerization.

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

The polymerization is generally initiated by a conventional free-radical polymerization initiator. These include thermal initiators, such as azo compounds, for example azoisobutyronitrile (AIBN), peroxides, for example benzoyl peroxide, redox initiator systems, such as a mixture of iron (111) acetylacetonate, benzoin and benzoyl peroxide, and photochemical free-radical formers, such as benzoin or benzil methyl ketal.

The initiator is expediently 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 transfer compounds can be added, for example in amounts of from 5 to 20 mol%. Examples of such compounds are disulfides, mercaptans, halides, dibutyl sulfide, and others.

The polymerization is preferably carried out in solution. The reaction temperature is generally in the range from 10 to 200°C, preferably from 30 to 150°C, particularly preferably from 40 to 100°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 preference is given to toluene and tetrahydrofuran.

The polymerization is expediently carried out in the absence of oxygen, for example under argon or under nitrogen.

The compounds of the formula I and novel homopolymers and copolymers thereof are particularly suitable for stabilizing organic materials against thermal, oxidative or actinic degradation.

Examples for those materials are:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1 -ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW). high density and ultrahigh molecular 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 paragraph, prefe¬ rably 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, Vlb or VIII 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-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or me¬ tal alkyloxanes, said metals being elements of groups la, lla and/or Ilia of the

Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

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

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propyleπe/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 copolymers, 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 mentioned 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. Hydrocarbon resins (for example C ₅ -C ₉ ) 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-methyistyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maieic anhydride, styrene/acrylo- nitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another

polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene 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 polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl meth¬ acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylo¬ nitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on poly¬ butadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copoly¬ mers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, 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/alkyi acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl

benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.

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

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

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

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

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, poly¬ amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xyiene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned poly¬ amides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or poly- tetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydanto- ins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene

terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also poly¬ esters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry¬ lates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, 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 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, PCΛhermoplastic 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 comprising 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 stabilizing organic material against oxidative, thermal or actinic degradation/build-up. The invention also relates to a process for stabilizing 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 stabilizers in synthetic organic polymers and corresponding compositions.

The organic materials to be protected are preferably natural, semisynthetic or preferably synthetic organic materials. Particular preference 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 preferred organic materials are coating compositions. Coating compositions which can advantageously be stabilized 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 reproduction methods.

In general, the compounds of the formula I are added to the material to be stabilized in amounts of from 0.01 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2%,

based on the total weight of the stabilized composition. The novel compounds are particularly preferably used in amounts of from 0.05 to 1.5%, especially from 0.1 to 0.5%.

The incorporation into the materials can be carried out, for example, by incorporating or applying the compounds of the formula I and, if desired, further additives by the usual methods in industry. If the materials are polymers, in particular synthetic polymers, the incorporation can be carried out before or during shaping or by applying the dissolved or dispersed compound to the polymer, if necessary with subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as lattices. Another way of incorporating compounds of the formula I into polymers comprises adding them before, during or immediately after polymerization of the corresponding monomers or before crosslinking. The compounds of the formula I can be added as such, or alternatively in encapsulated form (for example in waxes, oils or polymers). In the case of addition before or during the polymerization, the compounds of the formula I can also act as regulators for the chain length of the polymers (chain terminators).

The compounds of the formula I can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example, in a concentration of 2.5 to 25% by weight.

The compounds of the formula I can expediently be incorporated by the following methods: as an emulsion or dispersion (for example to lattices or emulsion polymers), as a dry mix during mixing of additional components or polymer mixtures, by direct addition into the processing equipment (for example extruder, internal mixer, etc.), as a solution or melt.

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

ln addition to the compounds of the formula I or homopolymers and/or copolymers thereof, the novel compositions can contain, as additional component (c), one or more conventional additives, such as, for example, the following:

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-methylcyclohexyl)-4,6-di- methylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 ^, -methylundec-1'-yl)phenol, 2,4-di- methyl-6-(1 '-methylheptadec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '-methyltridec-1 '-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di- octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthio- methyl-4-nonylphenol.

1.3. Hvdroquinones and alkylated hydroquinones. for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-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 (Vitamin E).

.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl- 2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis-(2,6-dimethyl-4-hydroxyphe- nyl) disulfide.

1.6. Alkylidenebisphenols. for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert- butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a- methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-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 aptobutane, ethylene glycol bis[3,3-bis(3'-teιt-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-buty l-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'-tet.ra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hvdroxybenzylated malonates. for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2- hydroxybenzy -malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malon ate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxy benzyl) malonate, bis[4-(1 ,1 ,3,3- tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxy benzyl)malonate.

1.9. Aromatic hvdroxybenzyl 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.

1.10. 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-hydroxyanilino)- 1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1 ,3,5-triazine,

2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)- isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1 ,3,5-triazine, 1 ,3,5-tris(3,5- di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1 ,3,5-triazine, 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)carbamate.

1.13. Esters of b-(3.5-di-tert-butyl-4-hvdroχyphenyl) 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-hvdroxy-3-methyl phenyl) propionic acid with mono- or poly¬ hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexane- diol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene 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-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3.5-di-tert-butyl-4-hvdroxyphenyl 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)- oxamide, 3-thiaundecanol, 3-thiapentadecanol, 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-hydroxyphenylpropionyl)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 example N.N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec- butyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1- ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N.N'-dicyclohexyl-p-phenylenediamine, N.N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naph- thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)- N'-phenyl-p-phenylenediamine, N-(1 -methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclo- hexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N.N'-dimethyl- N.N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy- diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phe- nyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoyl- aminophenol, 4-octadecanoylaminophenol, 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-pheπyl-1 -naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert- octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopro- pyl/isohexyldiphenylamines, a mixture of mono- und dialkylated tert-butyldiphenylamines,

2,3-dihydro-3,3-dimethyl-4H-1 ,4-benzothiazine, phenothiazine, a mixture of mono- und dial¬ kylated tert-butylΛert-octylphenothiazines, a mixture of mono- und dialkylated tert-octyl-phe- nothiazines, N-allylphenothiazin, N,N,N',N'-tetraphenyl-1 ,4-diaminobut-2-ene, N,N-bis- (2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4- yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilisers

2.1. 2-(2'-Hvdroxyphenyl)benzotriazoles. for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5 ^, -di-tert-butyl-2 ^, -hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-methyl- phenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5 ^, -tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzo- triazole, 2-(3 ^, ,5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotri azole, mixture of 2-(3'- tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5- chloro-benzotriazole, 2-(3'-tert- butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxypheny l)-5-chloro-benzotriazole, 2-(3'- tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-c hloro-benzotriazole, 2-(3'-tert- butyl-2 ^, -hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazo le, 2-(3'-tert-butyl-2'- hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl- oxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphe- nyl)benzotriazole, and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)p henylben- zotriazole, 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'-hydroxypheny l]- 2H-benzotriazole with polyethylene glycol300;, where R = 3'-tert-butyl-4'-hydroxy-5'-2H-ben- zotriazol-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-phenyl 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-

ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxy- benzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates. for example ethyl a-cyano-b,b-diphenylacrylate, isooctyl a-cyano-b,b-di- phenylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-b-methyl-p-methoxy- cinnamate, butyl a-cyano-b-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p- methoxycinnamate and N-(b-carbomethoxy-b-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 dibutyldithiocar- bamate, 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(1 ,2,2,6,6-pentamethyl-4-piperidyl)seba- cate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-pi- peridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxy- ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, 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-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6- tetramethyl-4-piperidyl)-1 ,2,3,4-butane-tetracarboxylate, 1 ,1 '-(1 ,2-ethanediyl)bis(3,3,5,5- tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6- tetramethylpiperidine, bis(1 ,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di -tert- butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decan-2,4-dion, bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, 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-dichloro-1 ,3,5-triazine, the condensate of 2-chloro-4,6- bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl )-1 ,3,5-triazine and 1 ,2-bis(3-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-aminopropyiamino)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)hexamethylenediamin e and 4-cyclohexylamino-2,6-dichloro-1 ,3,5-triazine, 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-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9- tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin.

2.7. Oxamides. for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani- lide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para- methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hvdroxyphenyl)-1 ,3.5-triazines. for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- (2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl- oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-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)phenyl]-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-(dodecyloxyΛridecyloxy-2-hydroxypropoxy)-2-hydroxy-pheny l]-4,6-bis(2,4-dimethylphe- nyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-b is(2,4-di- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2- hydroxy-propoxy)phenyl]-1 ,3,5-thazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-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-hydroxyphenylpropionyl) hydrazine , 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl

dihydrazide, sebacoyi bisphenylhydrazide, N.N'-diacetyladipoyl dihydrazide, N,N'-bis(saiicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites. for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylpheπyl) phosphite, trilauryl phosphite, trioctadecyl phos¬ phite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6- di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol di¬ phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert- butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert- butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di- benz[d,g]-1 ,3,2-dioxaphosphocin, 6-fluoro-2 ,4,8,10-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. Hydroxylamines. for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N.N-dioctylhydroxylamine, N.N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N.N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl- hydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

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-heptadecyl-nitrone, N-hexadecyl- alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-hep- tadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkyl- hydroxylamine derived from hydrogenated tallow amine.

7. Thiosvnerqists. for example, 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-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(b- dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phos¬ phorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, prefe¬ rably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium suc¬ cinate or sodium benzoate; polymeric compounds such as ionic copolymers ("ionomers").

12. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car¬ bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fi¬ bers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones. for example those disclosed in 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]benzofura n- 2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benz ofuran-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-butyi-benzo furan-2- one.

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 stabilized.

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 foliowing abbreviations are used in the examples:

GPC: Gel permeation chromatography;

¹ H-NMR: Magnetic nuclear resonance of the nuclide ¹ H;

M _n : Number average molar mass (unit g/mol);

M _w : Number average molar mass (unit g/mol);

TGA: Thermogravimetric analysis;

THF: Tetrahydrofuran.

Example 1 : Propargyl tosylate

381 g (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 g (2 mol) of propargyl alcohol in 160 ml of water is poured in. 88 g (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 temperature 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 evaporator. The residue is distilled via a Vigreux column.

Yield: 325 g (77 %) of a liquid of boiling point 102°C / 0.008 mbar.

Microanalvsis:

Calculated Found

C 57.13 57.07

H 4.79 4.80

S 15.25 15.24

¹ H-NMR (CDCI,):

2.45 ppm (3H, s) CH ₃

2.47 - 2.53 ppm (1H, m) -C-H

4.69 - 4.70 ppm (2H, m) -C-CH ₂ -O

7.34 - 7.37 ppm } r (4H, m) H-Ar 7.80 - 7.83 ppm J

Example 2: Preparation of 1-propargyl-4-hvdroxy-2.2.6,6-tetramethylpiperidine

197 g (1.25 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine, 105 g (0.5 mol) of the compound from Example 1 and 1.8 I of acetonitrile are introduced into a 2.5 1 sulfonation flask fitted with precision glass stirrer, thermometer 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 5 I 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 g (74%) Melting point: 151 °C

Microanalvsis:

Calculated Found

C 73.80 73.78

H 10.84 10.83

N 7.17 7.21

¹ H-NMR (CDCW:

1.07 ppm and 1.26 ppm (12H. S) CH ₃

1.38 - 1.45 ppm (2H, m) CH ₂ (piperidine)

1.54 - 1.56 ppm (1 H, d) OH

1.79 - 1.84 ppm (2H, m) CH ₂ (piperidine)

2.11 - 2.12 ppm (1 H, t) H-C-C

3.32 - 3.33 ppm (2H, d) «C-CH ₂ -N

3.91 - 3.96 ppm (1 H, m)

H

Example 3: Preparation of 1-(but-2-vnvD-4-hvdroxy-2.2.6.6-tetramethylpiperidine

27.2 g (0.12 mol) of 2-butynyl p-toluenesulfonate [Lancaster Synthesis Ltd., Lancashire LA 3OY, England], 47.7 g (0.3 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine and 0.5 I of acetonitrile 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 recrystallized from n-hexane.

Yield: 20 g (80%) Melting point: 106°C

Microanalvsis:

Calculated Found

C 74.59 74.47

H 11.08 11.04

N 6.69 6.80

1.07 - 1.25 ppm (12H. S) CH ₃ (piperidine) 1.16 - 1.19 ppm (1H, d) OH 1.38 - 1.46 ppm (2H, m) CH (piperidine) 1.78 - 1.95 ppm (5H, m) CH ₂ (piperidine) and CH ₃ -C» 3.29 ppm (2H, m) -C-CH ₂ -N

3.91 - 3.99 ppm (1 H, m)

H

Example 4: Preparation of N-(2.2.6.6-tetramethylpiperidin-4-yl)acrylamide

469 g (3 mol) of 4-amino-2,2,6,6-tetramethylpiperidine are dissolved in 500 ml of diethyl ether in a 1.5 I sulfonation flask fitted with precision glass stirrer, thermometer, dropping funnel and condenser. 90.5 g (1 mol) of acryloyl chloride are slowly added dropwise at -15 ^C C. After 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%) Melting point: 122°C

Microanalvsis:

Calculated Found

C 68.53 68.65

H 10.54 10.61

N 13.32 13.22

¹ H-NMR (CDCIa):

0.69 ppm (1 H, s) NH (piperidine) 0.91 - 0.99 ppm (2H, t) CH ₂ (piperidine) 1.13 ppm and 1.27 ppm (12H. S) CH ₃ (piperidine) 1.91 - 1.96 ppm (2H, m) CH ₂ (piperidine)

4.29 - 4.40 ppm (1 H, m)

H ^N

5.46 ppm (1 H, m) -NH-CO-

5.61 - 5.65 ppm (l H, m) CO-CH=C

6.02 - 6.32 ppm (2H, m) C=CH ₂

Example 5: Preparation of N-(2.2.6.6-tetramethylpiperidin-4-yl)methacrylamide

344 g (2.2 mol) of 4-amino-2,2,6,6-tetramethylpiperidine are dissolved in 1.5 I of methylene chloride in a 2.5 I sulfonation flask fitted with precision glass stirrer, thermometer and dropping funnel. The mixture is cooled to -10 ^C C, and 104.5 g (1 mol) of methacryloyi chloride are added dropwise with stirring. The mixture is then stirred for a further 3 hours at room temperature and poured into 2 I of 0.5 N sodium hydroxide solution, the organic phase is separated off, washed with water and dried, and the volatile constituents are removed by evaporation. The residue is recrystallized from n-hexane.

Yield: 87 g (39%) Melting point: 119°C

Microanalvsis:

Calculated Found

C 69.60 69.52

H 10.78 10.79

N 12.49 12.42

¹ H-NMR (CDCIa):

0.69 ppm (1 H, s) NH (piperidine)

0.91 - 0.99 ppm (2H, t) CH (piperidine)

1.13 ppm and 1.27 ppm (12H, s) CH ₃ (piperidine)

1.91 - 1.95 ppm (2H, m) CH ₂ (piperidine)

1.96 ppm (3H, s) CH ₃ (methacrylate)

5.31 ppm and 5.65 ppm (2H, s) CH ₂ =C 5.55 pm (1 H, d) -NH-CO-

Example 6: Preparation of 4-acrylolyloxy-1 -propargyl-2.2.6.6-tetramethylpiperidine

290 g (1.48 mol) of the compound prepared in Example 2, 195 g (1.9 mol) of triethylamine and 2.7 I of diethyl ether are introduced under argon into a 5 1 flask with plane ground joints fitted with precision glass stirrer, thermometer and dropping funnel. This mixture is cooled to 5°C, and 161 g (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%) Melting point: 48°C

Microanalvsis:

Calculated Found

C 72.25 72.40

H 9.30 9.34

N 5.62 5.64

H-NMR (CDC ):

1.14 ppm and 1.27 ppm (12H, s) CH ₃ (piperidine)

1.54 - 1.62 ppm (2H, m) CH ₂ (piperidine)

1.83 - 1.89 ppm (2H, m) CH ₂ (piperidine)

2.11 - 2.13 ppm (1H, t) H-C-C

3.33 - 3.34 ppm (2H, d) N-CH ₂ -

5.10 - 5.21 ppm (1 H, m)

H°

5.78 - 5.82 ppm (1 H, d) CO-CH=C

6.05 - 6.14 and 6.34 - 6.41 ppm (2H, m) C=CH ₂

Example 7: Preparation of 4-methacryloxy-1-proparoyl-2.2.6.6-tetramethylpiperidine

240 g (1.25 mol) of the compound described in Example 2, 177 g (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 precision glass stirrer, thermometer and dropping funnel. The suspension is cooled to 5°C, and 156 g (1.5 mol) of methacryloyi 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 recrystallized from n-hexane.

Yield: 163 g (50%) Melting point: 49°C

Microanalvsis:

Calculated Found

C 72.97 72.28

H 9.57 9.80

N 5.32 5.22

¹ H-NMR (CDCIa):

1.13 ppm and 1.27 ppm (12H, s) CH ₃ (piperidine)

1.48 - 1.68 ppm (2H, m) CH ₂ (piperidine)

1.84 - 1.90 ppm (2H, m) CH ₂ (piperidine)

1.93 ppm (3H, s) CH ₃ (methacrylate)

2.11 - 2.13 ppm (1H, t) H-C-C

3.34 - 3.35 ppm (2H, d) N-CH ₂

5.08 - 5.18 ppm (1 H, m)

H

5.53 ppm and 6.07 ppm (2H, s) CH ₂ =C

Example 8: Preparation of 4-acryloyloxy-1 -but-2-ynyl-2,2.6.6-tetramethylpiperidine

10.5 g (50 mmol) of the compound prepared in Example 3, 5.6 g (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 room 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.

Microanalvsis:

Calculated Found

C 72.97 72.77

H 9.57 9.63

N 5.32 5.11

¹ H-NMR (CDCI.,):

1.06 ppm and 1.18 ppm (12H, s) CH ₃ (piperidine)

1.46 - 1.54 ppm (2H, t) CH ₂ (piperidine)

1.69 - 1.70 ppm (3H, m) CH ₃ (butyne)

1.74 - 1.80 ppm (2H, m) CH ₂ (piperidine)

3.21 - 3.22 ppm (2H, m) C=C-CH ₂ -N

5.70 - 5.74 ppm ]

5.97 - 6.06 ppm \ (3H, m) CH ₂ =CH-CO

6.26 - 6.32 ppm J

Example 9: Preparation of 4-(4-vinylbenzyloxy)-1-proparqyl-2.2.6.6-tetramethylpiperidi ne

30 g (154 mmol) of the compound prepared in Example 2, 150 ml of toluene, 7.7 g (7.7 mmol) of polyethylene glycol 1000 and 43.1 g (770 mol) of powdered potassium 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 HCl 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

dried using sodium sulfate and the solvent is evaporated completely. Bulb-tube distillation at 150°C/0.02 mbar gives a colourless liquid.

Yield: 23.5 g ( 51%)

Microanalysis:

Calculated Found

C 80.98 80.89

H 9.38 9.39

N 4.50 4.47

¹ H-NMR (CDCI,):

1.05 ppm and 1.26 ppm (12H, s) CH ₃ (piperidine)

1.46 - 1.54 ppm (2H, t) CH ₂ (piperidine)

1.86 - 1.92 ppm (2H, m) CH ₂ (piperidine)

2.10 - 2.11 ppm (1 H, t) H-C-C

3.31 - 3.32 ppm (2H, d) C«C-CH ₂ -N

4.52 ppm (2H, s) Ar-CH ₂ -O-

5.19 - 5.25 ppm ]

5.69 - 5.77 ppm \ (3H, m) CH ₂ =CH-

6.65 - 6.75 ppm J

7.21 - 7.38 ppm (4H, m) H-Ar

Example 10: Preparation of N-(1-propargyl-2.2.6.6-tetramethylpiperdin-4-yl)acrylamide

65.5 g (0.31 mol) of the compound from Example 1 , 131 g (0.62 mol) of the compound described in Example 4 and 940 ml of acetonitrile are introduced into a 2 I 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 acetate and recrystallized from xylene.

Yield: 47 g (61 %) Melting point: 125.3°C

Microanalysis:

Calculated Found

C 72.54 72.39

H 9.74 9.71

N 1 1.28 11.30

Η-NMR (CDCI,):

1.13 ppm and 1.22 ppm (12H, s) CH ₃ (piperidine)

1.30 - 1.38 ppm (2H, t) CH ₂ (piperidine)

1.79 - 1.84 ppm (2H, m) CH ₂ (piperidine)

2.11 - 2.12 ppm (1H, t) H-C-C-

3.32 - 3.33 ppm (2H, d) CBC-CH ₂ -N

4.20 - 4.32 ppm (1 H, m)

H

5.50 ppm (1 H, d) -NH-CO-

5.60 - 5.64 ppm

6.03 - 6.12 ppm } (3H, m) CH ₂ =CH-

6.24 - 6.31 ppm J

Example 11 : Preparation of N-(1-proparoyl-2.2.6,6-tetramethylpiperidin-4-yl)methacrylam ide

40.2 g (0.19 mol) of the compound from Example 1 , 85.8 g (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 temperature and separated from the solid. The solvent is evaporated. The residue is purified on silica gel 60 [Merck] using ethyl acetate and subsequently recrystallized from cyclohexane.

Yield: 25.4 g (51%) Melting point: 117.4°C

Microanalvsis:

Calculated Found

C 73.24 73.21

H 9.99 9.98

N 10.68 10.65

¹ H-NMR (CDCI,):

1.13 ppm and 1.25 ppm (12H. S) CH ₃ (piperidine)

1.29 - 1.37 ppm (2H, t) CH ₂ (piperidine)

1.80 - 1.85 ppm (2H, m) CH ₂ (piperidine)

1.95 ppm (3H, s) CH ₃ (methacrylate)

2.11 - 2.12 ppm (1H, t) H-C-C-

3.32 - 3.33 ppm (2H, d) C-C-CHrN

5.31 ppm and 5.64 ppm (2H, s) CH ₂ =

5.52 ppm (1 H, m) -NH-CO-

Example 12: Preparation of polv(4-acryloyloxy-1-propargyl-2.2.6.6-tetramethylpiperidine )

90 g (0.36 mol) of the monomer from Example 6, 1.19 g (7.2 mmol) of azobisisobutyronitrile (AIBN), 3.2 g (36 mmol) of butyl mercaptan and 270 g 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 C under argon. The reaction solution is precipitated in methanol, and the solid is re-dissolved in THF and precipitated in methanol. The white polymer powder is dried under a high vacuum, giving 33.1 g (37%) of polymer.

GPC (THF): M _n = 6700 M _w = 10600

TGA (Heating rate 2°C / min., air) 10% weight loss at 303°C

Example 13: Preparation of polv(4-methacryloxy-1-proparoyl-2.2.6.6-tetramethylpiperidin e)

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 g of THF as described in Example 12.

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

GPC (THF): M _n = 6100 M _w = 9900

TGA (Heating rate 2°C / min., air) 10% weight loss at 298°C

Example 14: Preparation of polv(4-acryloyloxy-1 -but-2-ynyl-2.2.6,6-tetramethylpiperidine)

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 g of toluene as described in Example 12.

Yield: 7 g (35%) of polymer.

GPC (THF): M _n = 4400 M _w = 5600

TGA (Heating rate 2°C / min., air) 10% weight loss at 278°C

Example 15: Preparation of polvfN-(1 -propargyl-2.2.6.6-tetramethylpiperidin-4-yl)acrylamide1

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 12. The polymer is precipitated in n-hexane.

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

GPC (THF): M _n = 1500 M _w = 4100

TGA (Heating rate 2°C / min., air) 10% weight loss at 315°C

Example 16: Preparation of polyrN-(1-proparoyl-2.2.6.6-tetramethylpiperidin-4-yl)- methacrylamide]

25 g (95 mmol) of the monomer from Example 11 are polymerized with 156 mg (0.95 mmol) of AIBN and 1.71 g (19 mmol) of butyl mercaptan in 75 g of THF as described in Example 12. The polymer is precipitated in n-hexane.

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

GPC (THF): M _n = 1500

M _w = 4000

TGA (Heating rate 2°C / min.. air) 10% weight loss at 321 °C

Determination of the pK*, of the substance

Titration in acetonitrile/chloroform = 1 : 1 using 0.1 N HCIO in dioxane. The half neutralization point (HNP) is relative to 2-aminopyridine (= 0 mV):

Example 17: Preparation of polv(4-vinylbenzyloxy-1-propargyl-2.2.6.6-tetramethylpiperid ine)

29 g (97 mmol) of the monomer from Example 9, 0.64 g (3.9 mmol) of azobisisobutyronitrile (AIBN) and 116 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 ovemight at 70°C under argon.

The viscous solution is poured into methanol. The precipitate is taken up in toluene and re- precipitated in methanol. The polymer is dried under a high vacuum.

Yield: 24 g (83%)

MALDI-MS (Matrix Assisted Laser Desorption/lonization-Mass Spectrometry):

M _n = 6000 M _w = 8500

TGA (Heating rate 2°C / min., air) 10% weight loss at 316°C

Example 18: Light stabilization of polypropylene fibres

2.5 g of each of the novel stabilizers from Examples 12 to 14 together with 1 g of tris(2,4-di- tert-butylphenyl) phosphite, 1 g of calcium monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl- phosphonate, 1 g of calcium stearate and 2.5 g of TiO ₂ (Kronos RN 57) are mixed with 1000 g 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 subsequently converted into fibres with the aid of a pilot plant (Leonard; Sumirago/VA, Italy) under the following conditions:

Extruder temperature: 190-230°C

Head temperature: 255-260°C

Stretching ratio: 1 :3.5

Stretching temperature: 100°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 calculate the exposure time T∞ after which the tensile strength of the samples has halved.

For comparative purposes, fibres are produced without novel stabilizer under otherwise identical conditions and are tested. The test results are shown in Table 1.

Table 1 :

Exposure time for the initial tensile strength to halve

Stabilizer Exposure time

None 300 h from Example 12 2270 h from Example 13 2470 h from Example 14 31 10 h

The fibres stabilized in accordance with the invention have excellent strength retention.

Example 19: Stabilization of a two-coat paint

The light stabilizer from Example 10 is incorporated into 5-10 g of xylene and tested in a varnish of the following composition:

Synthacryl* SC 303 27.51 g

Synthacryl* SC 370 ²⁾ 23.34 g

Maprenal* MF 650 ³⁾ 27.29 g

Butyl acetate/butanol (37/8) 4.33 g

Isobutanol 4.87 g

Solvesso* 150 ⁾ 2.72 g

Crystal Oil K-30 ⁵⁾ 8.74 g Flow-control agent Baysil* MA ⁶⁾ 1.20 g

100.00 g

1) Acrylate resin, Hoechst AG; 65% solution in xylene/butanol 26:9

2) Acrylate resin, Hoechst AG; 75% solution in Solvesso' 100 ⁾

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 stabilizer.

The varnish is diluted to spray consistency 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 μm.

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 containing the novel stabilizer have high cracking resistance.

Example 20: Stabilization of a photographic material

0.087 g of the yellow coupler of the formula

is dissolved in 2.0 ml of a solution of the novel stabilizer from Example 6 in ethyl acetate (2.25 g/100 ml). 9.0 ml of a 2.3% aqueous gelatin solution which has been adjusted to a pH of 6.5 and 1.744 g/I of the wetting agent of the formula

are added to 1.0 ml of this solution.

2 ml of a silver bromide emulsion having a silver content of 6.0 g/I and 1.0 ml of a 0.7% aqueous solution of the curing agent of the formula

are added to 5.0 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* process.

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

A sample without stabilizer 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 stabilization effect is evident from the drop in colour density. The smaller the drop in density, the greater the light stabilization effectiveness.

The novel stabilizer has a good light stabilization action.

Example 21 : Stabilization of polypropylene tapes

1.0 g of the novel stabilizer from Example 9 together with 1 g of tris(2,4-di-tert-butylphenyl)- phosphite, 0.5 g of pentaerythrityl tetrakis(3-[3',5'-di-tert-butyl-4'-hydroxyphenyl]propionate) and 1 g of calcium stearate are mixed with 1000 g 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 μm thick with the aid of a pilot plant (Leonard; Sumirago/VA, Italy) under the following conditions:

Extruder temperature: 210-230 ^c C

Head temperature: 240-260°C

Stretching ratio: 1 :6

Stretching 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 calculate the exposure time Tso after which the tensile strength of the samples has halved.

For comparative purposes, tapes are produced without novel stabilizer under otherwise identical conditions and are tested.

The sample stabilized in accordance with the invention has excellent strength retention.