NL9300634A - NEW PIPERIDINE-TRIAZINE CO-OLIGOMERS FOR USE AS STABILIZERS IN ORGANIC MATERIALS. - Google Patents

Description

New piperidine triazine co-olgomers for use as stabilizers in organic materials.

The present invention relates to novel piperidine triazine co-oligomers, for their use as light stabilizers, heat stabilizers and oxidation stabilizers in organic materials, especially synthetic polymers, and to organic materials thus stabilized.

The stabilization of synthetic polymers by triazine oligomers and co-oligomers with compounds possessing 2,2,6,6-tetramethylpiperidine groups has been described in several patents, in particular in the following patents US-A-4,086,204 , US-A-4,315-859. USrA-4,331,586, US-A-4,335,242, US-A-4,412,020, US-A-4,459,395. US-A-4,477,615, US-A-4,547,548, EP-A-II7,229 and EP-A-0217,149 and JP-A-Sho-63,196,654.

The present invention relates to novel piperidine triazine co-oligomers having the recurring units of formulas (Ia) and (Ib)

with an average molecular weight of 1000 to 20,000 and an (Ia) :( Ib) ratio of 4: 1 to 1: 4, wherein Rx is -0R5, -SR5 or

** group in which R5, R6 and R7 may be the same or different and a hydrogen atom, a C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl which is unsubstituted or 1, 2 or 3 times substituted by a C 1 -C 8 alkyl group ; C 3 -C 18 alkenyl, phenyl which is unsubstituted or 1, 2 or 3 times substituted by a C 1 -C 8 alkyl or alkoxy; C 1 -C 9 phenylalkyl which is unsubstituted or 1, 2 or 3 times substituted on the phenyl group by a C 1 -C 11 alkyl; tetrahydrofurfuryl, 1,2,6,6,6-pentamethyl-4-piperidyl or O 2 -Oή alkyl substituted in the 2, 3 or 4 position by a C 1 -C 8 alkoxy, by a di 1 -C *, alkyl) amino or by a group of formula (II)

(II) wherein A is a direct bond, -0-, -CH2-, -CH2CH2- or> N-CH3, or Rx is a group of formula (II) or one of the groups of formulas (Illa) - (IIIc )

(lilac) (Illb) (IIIC) wherein R 8 is C 1 -C 7 alkyl, cycloalkyl which is unsubstituted or 1, 2 or 3 times substituted by a C 1 -C * alkyl group; C7-C8 phenyl alkyl which is unsubstituted or 1, 2 or three times substituted in the phenyl group by a Οχ-Οή alkyl group; or 1,2,2,6,6-pentamethyl - ^ - pipe-ridyl, m is an integer from 2 to 6, n is zero or 1, X is -0- or> N-CH3 and R? has the same meaning as Rg or a hydrogen atom, R2 has the same meaning as R8 or a hydrogen atom, R3 is a C2-C12 alkylene, ϋή-012 alkylene interrupted by 1, 2 or 3 oxygen atoms or by a group> N-CH3; C5-C7 cycloalkylene, C5-C7 cycloakylene di (C1-C /, alkylene), C 1 -C 3, alkylene di (C5-C 7 cycloalkylene), C2-C 1, alkylene di (C5-C7 cycloalkylene) or phenylene dimethylene and C 2 -C 12 alkylene, C 2 -C 12 alkylene is interrupted by 1, 2 or 3 oxygen atoms; 2-hydroxytrimethylene, phenylene dimethylene, carbonyl, C2-C15 diacyl, C1, -C15 dicarbamoyl, a group - (CH2) p-C0- where p is an integer from 1 to 10, or a group -C00-R10 -00C ~ where R10 has the same meaning as R3.

The co-oligomers of the invention may have different terminal groups depending on the type and molecular proportions of the reagents used in the preparation.

For example, the terminal group bound to the triazine ring of formula (Ia) - consequently referred to as Xx - is in particular Cl, OH, ONa, OK or a group Rx or a group

and the terminal group bonded to the nitrogen atom of formula (Ia) or (Ib) is, for example, a methyl group or a group

which has the same meaning as above, or a group -R ^ OH.

The different groups R1, R2, R3 and R4 of the formulas (Ia) and (Ib) can in any case be the same or different.

Examples of alkyl groups with no more than 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Examples of O 2 -O 4 alkyl substituted by C 1 -C 6 alkoxy, preferably by C 1 -C 6 alkoxy, especially oethoxy or ethoxy, are 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-buoxy toxypropyl, 3-octoxypropyl and 4-methoxybutyl.

Examples of C 2 -C 6 alkyl substituted by d ± (0Χ-C /, alkyl) amino, preferably by dimethylamino or diethylamino, are 2-dimethylaminoethyl, 2-diethylaminoethyl, 3 "dimethylaminoproyl, 3" diethylamino-propyl, 3- dibutylaminopropyl and 4-diethylamino butyl.

A representative example of C 2 -C 7 alkyl group substituted by a group of formula (II) is the group of formula

is preferred.

Examples of unsubstituted or substituted C5 -C12 cycloalkyl are cyclopentyl, methylcyclopentyl, dimethylcyclpentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexylcycloecyl, cyclodecyl, cyclodecyl. Unsubstituted or O 1 -alkyl substituted cyclohexyl is preferred.

Examples of alkenyl are allyl, 2-methylallyl, butenyl, hexenyl, decenyl, undecenyl or oleyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.

Examples of substituted phenyl groups are methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl, di-tert-butylphenyl, 3,5-di-tert-butyl-4-methylphenyl, methoxyphenyl and ethoxyphenyl.

Examples of phenylalkyl groups which are unsubstituted or substituted on the phenyl group are benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl and 2-phenylethyl. Benzyl is preferred.

Examples of C 2 -C 12 alkylene groups are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene, decamethylene and dodecamethylene. '

Examples of C 1 -C 12 alkylene group interrupted by 1, 2 or 3 oxygen atoms are 3 ° x x & pentane-1,5-diyl, 4-oxaheptane-1,7-diyl, 3,6-dioxaoctane-1,8-diyl, 4.7 -dioxadecane-1,110-diyl, 4,9-dioxadodecane-1,12-diyl and 3,6,9 "trioxaundecane-1,11-diyl.

A representative example of a C / (- C12 alkylene group and R3 and R10 interrupted by a group> N-CH3 is the group

Representative examples of groups with 1 or 2 C5-C7 cycloalkylene groups are cyclohexylene, methylcyclohexylene, cyclohexylene dimethylene, methylene dicyclohexylene and isopropylidene dicyclohexylene.

Representative examples of C 2 -C 15 diacyl R 4 are oxalyl, malonyl, ethylmalonyl, butylmalonyl, benzylmalonyl, succinyl, glutaryl, adi-poyl, trimethyladipoyl, sebacoyl, oxydiacetyl, cyclohexanediocyl, isophthaloyl, C2-isophthaloyl, C2-isophthaloyl C2 or substituted by benzyl; C 1 -C 15 alkanedioyl in which the alkane group is interrupted by an oxygen atom; (C5-C7 cycloalkane) dicarbonyl, phthaloyl, isophthaloyl and terephthaloyl are preferred.

, (C2-C13alkylene) dicarbamoyl,

Representative examples of C 1 -C 15 dicarbamoyl R * are hexamethylenedicarbamoyl, trimethylhexamethylenedicarbamoyl, cyclohexylene dicarbamoyl, phenylenedicarbamoyl, toluylenedicarbamoyl or a group or

C5-C7 cycloalkylene) dicarbamoyl, phenylenedicarbamoyl, toluylenedicarbamoyl and the groups are preferred.

The preferred co-oligomers have the recurring units of formulas * (Ia) and (Ib) with an average molecular weight of 1000 to 10,000 and a (Ia) :( Ib) ratio of 3: 1 to 1 : 3, where R1 is a group -0R5 ,. -SR5 or

wherein r5, R6, and R7 may be the same or different and a hydrogen atom, Oχ-O6 alkyl, C5-C8 cycloalkyl which is unsubstituted or 1, 2 or 3 times substituted by alkyl; C 3 -C 12 alkenyl, phenyl which is unsubstituted or substituted 1 or 2 or 3 times by C 1 -C 3 alkyl or C 1 -C 3 alkoxy; benzyl which is unsubstituted or mono-, substituted two or three times on the phenyl group by a C 1 -C 18 alkyl; tetrahydrofurfuryl, 1,2,2,6,6-pentamethyl-4-piperidyl or C 2 -C 3 alkyl substituted at the 2- or 3 ”position by C 1 -C 1, alkoxy, by di-C 1 -alkyl amino or group of formula (II) in which A is a direct bond, -0-, -CH2- or -CH2CH2-, or Rx is the group of formula (II) or one of the groups of formulas (IlIa) - (IIIc) wherein R8 is C1 -C12 alkyl, C5 -C8 cycloalkyl which is unsubstituted or 1, 2 or 3 times substituted by alkyl; benzyl which is unsubstituted or substituted 1, 2 or 3 times on the phenyl by C 1 -C 6 alkyl; or 1,2,2,6,6-pentamethyl-4-piperidyl, m is 2, 3 or k, n is zero or 1, X is -0- or> N-CH3 and R9 has the same meaning as Rg or hydrogen atom R 2 has the same meaning as R 8 or hydrogen atom, R 3 is C 2 -C 10 alkylene, C 1 -C 10 alkylene interrupted by 1, 2, or 3 oxygen atoms or a> N-CH 3 group; cyclohexylene, cyclohexylene dimethylene, methylene dicyclohexylene, isopropylidene diyclohexylene or phenylene dimethylene and R4 is C2-C10 alkylene, O-010 alkylene interrupted by 1, 2 or 3 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C 2 -C 10 diacyl, C /, - C 12 dicarbamoyl, a group - (CH 2) pCO - where p is an integer from 1 to 5. or a group -C00-R 10 -00C- where R10 has the above-mentioned meaning of R3.

Particularly preferred eol oligomers include recurring units of formulas (Ia) and (Ib) with an average molecular weight of 1000 to 8000 and a (Ia): (Ib) ratio of 2: 1 to 1; 3. where Rx is a group -0R5, -SR5 or

wherein R5 is Cx-C12 alkyl, cyclohexyl which is unsubstituted or 1, 2 or 3 times substituted by CX-CA alkyl; allyl, undecenyl, phenyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6-pentamethyl-4-piperidyl, R 6 and R 6 which may be the same or different have the above meaning for R 5 or its hydrogen atom or C 2 -C 3 alkyl substituted in the 2 or 3 position by C 1 -C 1, alkoxy, by dimethylamino, by diethylamino or by a 4-morpholinyl group, or Rx is 4 morpholinyl or one of the groups of the formulas (IIIa) - (IIIc) wherein R 8 is 0χ-08 alkyl, cyclohexyl which is unsubstituted or 1, 2 or 3 times substituted by CX-CA alkyl; benzyl or 1,2,2,6,6-pentamethyl-4-piperidyl, m is 2 or 3 »n is zero or 1, X is -0- or> N-CH3 and R9 has the same meaning as R8 or hydrogen, R2 has the same meaning as Rg or hydrogen, R3 is C2-C8 alkylene, C8-C10 alkylene interrupted by 2 or 3 oxygen atoms; cyclohexylene dimethylene, methylene dicyclohexylene or phenylene dimethylene and R 1, C 2 -C 8 alkylene, C 1 -C 8 alkylene is interrupted by 1 or 2 oxygen atoms; 2-hydroxy-trimethylene, phenylenedimethylene, carbonyl, C 2 -C 6 diacyl, C 1 -C 10 dicarbamoyl, a group - (CH 2) pCO- where p is 1, 2 or 3. or a group -COO-R10-00C- wherein R10 has the above-mentioned meaning of R3.

The co-oligomers of particular interest are those with the recurring units of formulas (Ia) and (Ib) with an average molecular weight of 1500 to 6000 and a (Ia) :( Ib) ratio of 2: 1 to 1: 2, where Rx is a group -0R5 or

wherein R 5 is C 1 -C 8 alkyl, cyclohexyl, allyl, benzyl, tetrahydrofurfuryl or 1, -6-pentamethyl-1-piperidyl, R 6 and R 7 which may be the same or different have the meaning of R 5 or hydrogen, or R 2 4-morpholynyl or one of the groups of formulas (lilac) - (IIIc) wherein Rg is 1,2,6,6,6-pentamethyl-4-piperidyl, m is 2, n is zero or 1, X is - O- or> N-CH3 and Rg is hydrogen or 1,2,6,6,6-pentamethyl-4-piperidyl, R2 is hydrogen, methyl or GG-pentamethyl-1-piperidyl, R3 is C2- C6 alkylene, C6-C10 alkylene interrupted by 2 or 3 oxygen atoms; cyclohexylenedimethylene, methylenedicyclohexylene or phenylene dimethylene, and R 1 is C 2 -C 6 alkylene, 2-hydroxy trimethylene, phenylenedimethylene, C 2 -C 8 diacyl, -CH 2 CO 3 - or a group -C00-R 10 O-00C- where R 10 is C 2 -C 6 alkylene.

Those co-oligomers of particular interest are those with recurring units of formulas (Ia) and (Ib) with an average molecular weight of 2000 to 5000 and a (Ia): (Ib) ratio of 1: 1 to 1: 2, where Rx is the group -0R5 or

wherein R5 is C1 -C1 alkyl or tetrahydrofurfuryl, R8 and R7 which may be the same or different are C1 -C8 alkyl, cyclohexyl or 1,2,2,6,6-penta-methyl-4-piperidyl or R6 may also be hydrogen or Rx is 4-morpholinyl or a group of formula (lilac) wherein n is zero, R2 is 1,2,2,6,6-pentamethyl-4-piperidyl, R3 is a group - (CH2) 2 -6 'or - (CH2) 3 -O- (CH2) 2. -O- (CH2) 3 - and R4 is 2-hydroxy trimethylene.

The compounds of the present invention can be prepared by well-known methods, for example, by N-methylation of the corresponding co-oligomeric compounds containing 2,2,6,6-tetramethyl-piperidine groups with one of the well-known N-methyl- ringing processes, for example by reacting the 2,2,6,6-tetramethylpiperidine compounds with formaldehyde and formic acid, the conversion taking place in water or in an aromatic hydrocarbon solvent, or by reacting them with formaldehyde and hydrogen in the presence of a hydrogenation catalyst such as Pt, Pd or Ni, as described in US-A-4,459,395, EP-A-319.48O and EP-A-365,469.

The co-oligomers that are not methylated in the 1-position of the 2,2,6,6-tetramethylpiperidine groups can be prepared in a well known manner, for example as described in US-A-4,547,548 ·

The co-oligomers of the present invention are very efficient in improving the light stability, heat stability and oxidation stability of organic compounds, especially synthetic polymers, for example polyolefins.

The remarkable light stabilizing action in polypropylene, especially in the form of fibers, is particularly surprising.

Examples of organic compounds that can be stabilized are: 1. Polymers of mono-olefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example of cyclopentene or norbornene, polyethylene (which may optionally be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), low linear density polyethylene (LLDPE), polyethylene (BLDPE) with branched low density.

Polyolefins, that is, the polymers of mono-olefins referred to in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by various, and in particular by, the following methods; a) radical polymerization (under normal and high pressure and at elevated temperatures).

b) catalytic polymerization with a catalyst normally containing one or more of the metals of groups IVb, Vb, VIb or VIII of the periodic table. These metals usually have one or more than one ligand, especially oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl groups and / or aryl groups which can be either it or σ 'coordinated. These metal complexes can be in free form or bonded to substrates, in particular to activated magnesium chloride, titanium (III) chloride, aluminum or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used as such or in combination with other activators in the polymerization. Examples of other activators are metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, said metals may be elements of groups Ia, Ha and / or lilac of the periodic table. The activators can be easily modified with ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Philips, 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 mono-olefins and diolefins with each other or with other vinyl monomers, for example ethylene / propylene copolymers, low linear density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-one copolymers, propylene / isobutylene copolymers, ethylene / but-1-one copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / buta-diene copolymers, isobutylene / isopropene copolymers / 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 norbornene; and mixtures of such copolymers with each other and with polymers mentioned in 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

Hydrocarbon resins (e.g. C5-C9) comprising hydrogen modifications thereof (e.g. adhesives) and mixtures of polyalkylene and starch.

5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes of acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene-maleic anhydride, styrene / acrylonitrile / methyl acrylates; high impact blends of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and styrene block polymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on butadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers mentioned under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, poly vinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

9. Polymers derived from α, β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, internally modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example, acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkylmethyl-thacrylate polymers.

11. Polymers derived from unsaturated alcohols and amines of the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyrate, 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, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and dipolyoxymethylenes containing 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 polyethers, polyesters or polybutadienes having terminal hydroxyl groups 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 amino carboxylic acids of the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9. 6/12. 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or / and terephthalic acid and with or without an elastomer as a modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides of copolyamides modified with EPDM or ABS; and polyamides condensed during the conversion (RIM polyamide systems).

17. Polyureas, polyimides, polyamideimides and polybenzimidazoles, 18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids of 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 polyesters modified with polycarbonates or MBS.

19. Polycarbonates and Polyester Carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Cross-linked polymers derived from aldehydes on the one hand and phenols, urea and melamines on the other, 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 crosslinked agents, and also halogen-containing modifications thereof with low flammability.

2k. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

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

26. Cross-linked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic dipoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the above mentioned polymers (polyblends), for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT , PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylic, POM / MBS, PPO / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.

29. Natural and synthetic organics which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oils and fats, or oils, fats and waxes based on synthetic esters (for example phthalates, adipates, phosphates or trimellitates ) and also mixtures of synthetic esters with mineral oils in any weight ratio, typically those used as lubricating compositions, as well as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, for example natural latex or latices of carboxylated styrene / butadiene copolymers.

The compounds of the present invention can be mixed with the organics in different proportions depending on the nature of the compound to be stabilized, the use and the presence of other additives.

In general, it is suitable to use, for example, 0.01 to 5 wt. 2 of the compounds of the invention, based on the weight of the compound to be stabilized, preferably between 0.05 and 1%.

The compounds of the present invention can generally be added to the polymeric substances before, during or after the polymerization or cross-linking of said substances.

The compounds of the present invention can be incorporated into the polymeric materials, for example, in pure form or encapsulated in waxes, oils or polymers.

The compounds of the present invention can be incorporated into the polymeric substances in various ways, such as by dry powder mixing or wet mixing in the form of solutions or suspensions as well as in the form of a master batch; in such processes, the polymer can be used in powder form, granules, solutions, suspensions or in the form of latices.

The materials stabilized with the products of the present invention can be used to make molds, films, magnetic tapes, monofilaments, fibers, surface coatings and the like.

If desired, other conventional synthetic polymer additives such as antioxidants, UV absorbers, nickel stabilizers, pigments, fillers, plasticizers, anti-static agents, flame retardants, lubricants, corrosion inhibitors and metal deactivators can be added to the mixtures of the compounds of the present invention with the organic materials.

Specific examples of additives which can be used in admixture with the compounds of formula (I) are: 1. Antioxidants 1.1 Alkylated monophenols. for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert -butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2.6 -dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- ( 1'-methylundec-1'-yl) phenol, 2,4-dimethyl-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-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3 Hydroquinones and alkrohydroquinones. for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di -tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3.5 "di-tert-butyl-4-hydroxy-anisole, 3 * 5-di-tert-butyl-4-hydroxyphenyl stearate, bis - (3.5 "di-tert-butyl-4-hydroxyphenyl) adipate.

1.4 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-hydroxyphenyl) disulfide.

1.5 Alkylidene bisphenols. for example 2,2'-methylene bis (6-tert-butyl-4-methylphenol), 2,2'-methylene bis (6-tert-butyl-4-ethylphenol), 2,2'-methylene bis [4-methyl- 6- (α-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'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (6-tert-butyl-4-isobutylphenol), 2, 2'-methylene bis [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-hydroxy-benzyl) -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-dodecyl-mercaptobutane, ethylene glycol bis [3,3 "bis (3'-tert-butyl-4) 1-hydroxyphenyl) butyrate], bis {3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-h ydroxy-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-dodecyl mercaptobutane, 1,1,5,5 "tetra- (5" tert -butyl-4-hydroxy2-methylphenyl) pentane.

Onion 0-. N- and S-benzyl compounds, for example 3'5'3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, 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-hydroxybenzyl) sulfide, iso-octyl-3,5 "di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.7 Hvdroxv benzylated 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 dodecyl mercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis- [4- {1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3 .5-di-tert-buyl-4-hydroxybenzyl) malonate.

1.8 Aromatic hydrogen compounds. for example 1,3,5-tris- (3,5 "di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3.5-di-tert-butyl-4-hydroxybenzyl) -2, 3,5,6-tetramethylbenzene, 2,4,6-tris (3,5 "di-tert-butyl-4-hydroxybenzyl) phenol.

1.9 Triazine compounds. for example 2,4-bis (octyl mercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5 "triazine, 2-octyl mercapto-4,6-bis (3,5" di- tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-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-bu -tyl-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-hydroxyphenyl-propionyl) -hexahydro-1,3, 5 "triazine, 1,3,5" tris (3.5 "dicylohexyl-4-hydroxy-benzyl) isocyanurate.

1.10 Benzyl phosphonates. for example dimethyl-2,5-di-tert-butyl-4-hydroxy-benzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxy3 -methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3.5 "di" tert-butyl-4-hydroxybenzylphosphonic acid.

1.11 Acvlaminophenols. for example, 4-hydroxylaurinilide, 4-hydroxystearanilide, octyl N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.12 Esters of B- (3.S-di-tert-butyl-4-hydroxylphenyl) oronionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonaadiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-tbiaundecanol, 3 "thiapentadecanol, trimethylhexanediol, trimethylhexanediol, trimethylethylane -1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.1S Esters of β-tert-butyl - - - - hydroxyl - - - methylphenyl, propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonaadiol, ethylene glycol, 1,2-propane diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentheanediol, 3-thiapentheanediol trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.14 Esters of β- (λ.5-dicvclohexvl-4-hvdroxvfenvl) -propionic acid with mono or polyhydric alcohols, for example with methanol, 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 -2,6,7-trioxabicyclo [2.2.2] octane.

1.15 Esters of 5.5-di-tert-butyl-4-hydroxylphenyllazic acid with mono- or polyhydric alcohols, for example with methanol, 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, trimethylpropane, 4-hydroxymethyl-1-phospha-2,6 .7_trioxabicyclo [2.2.2] octane.

1.16 Amides of β-Π. 5-di-tert-butyl-4-hydroxylphenyl) propionic acid e.g. N, N'-bis (3,5 "di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5- di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine, N, N'-bis (3 * 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

2. UV absorbers and light stabilizers 2.1 2- (2 * -Hydroxyphenyl) -benzotriazoles. for example, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3'5'-di-tert-butyl-2'-hydroxyphenyl) benzo-triazole, 2- {5'-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (2'-hydrpxy-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'-methylphenyl) -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) benzotriazole, 2- (3 5'-bis- (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, mixtures of 2- (3'-tert-butyl-2 '-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) - 5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxy-phenyl) -5-chloro-benzotriazole, 2- (3' -tert-butyl-2'-hydroxy-5 '- (2-methoxy-carbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3' - tert-butyl-2'-hydroxy-5 '- (2- methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '"(2-oc tyloxycarbonylethyl) phenyl) benzotriazole, 2- (3 '' tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy- 5'-methylphenyl) -benzotriazole, and 2- (3'-tert-butyl -2 '-hydroxy-51 ~ (2-isooctyloxycarbonylethyl) phenylbenzotriazole, and 2' (3 '-tert-butyl-2' -hydroxy-5) - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3% 3 ”tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH 2 CH 2 -C00 (CH 2) 3] 2-, wherein R = 3 '"tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2.2 2-hydroxyl benzophenones. for example, the 4-hydroxy, 4-methoxy-4-oc-tyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2Λ Esters of substituted and unsubstituted benzoic acids such as, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-3-tert-butyl -di-tert-butyl-4-hydroxybenzoate, hexadecyl 3% 5 "di-tert-butyl-4-hydroxybenzoate, octadecyl 3" 5 "di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6 di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4 Acrvaten. for example ethyl α-cyano-β, β-diphenyl acrylate, iso-octyl α-cyano-β, β-di-phenyl acrylate, methyl ct-carbomethoxycinnamate, methyl α-cyano-B-methyl-p-methoxycinnamate, butyl α-cyano- Bp-methoxycinnamate, methyl α-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-tetraaethylbutyl) phenol], such as the Ijl or 1j2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N- cyclohexyldiethanolamine, nickel dibutyl dithiocarbamate, nickel salts of the monoalkyl esters, eg the methyl or ethyl ester of 4-hydroxy-3 »5" di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, eg of 2-hydroxy-4-methylphenyl imdecylketoxime, 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-piperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis- (1,2,2,6,6-pentamethylpiperidyl) sebacate, bis ( 1,2,6,6,6-pentamethylpiperidyln-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl -4-hydroxypiperidine and succinic acid, the condensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1. 3,5-triazine, tris- (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacate, 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-tetra-methylpiperidine, 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-triazaspi-ro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidy l) succinate, the condensate of N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexanomethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5 "triazine and 1,2-bis (3-aminopropylamino) ethane, the condensate of 2-chloro-4,6-di- (4-n-butylamino-1,2,6,6,6-pentamethylpiperidyl) -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-4-piperidyl) pyrrolidin-2,5-dione, 3 "dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione.

2.7 Oxamides. for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5 * -di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethoxanilide , N, N'-bis (3-dimethylamino-propyl) 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 paramethoxy disubstituted oxanilides and mixtures of o- and p-ethoxy disubstituted oxanilides.

2 ^ 8 2- (2-hydroxyphenyl) -1,3.5-triazines. for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4- dimethylphenyl) -1,3.5 "triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis- {2,4-dimethylphenyl) -1,3.5" triazine, 2,4-bis (2-hydroxy-4 -propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3.5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3.5-triazine, 2 - (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3.5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butoxy) 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 .. Metal deactivators. for example, Ν, Ν'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine , 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-di-acetyladipoyldihydrazide, N, N'-bis (salicyloyl) oxalyldihydraz N'-bis (salicyloyl) -thiopropionyl dihydrazide.

4. Other phosphites and phosphonites. for example, triphenylphosphite, diphenylalkylphosphite, phenyl dialkylphosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite (2,4-di-tert-butylphenylphenyl) phosphite butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite, diisodecyloxypentaerythri-diphosphite, 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 diphosphite, 6-iso-octyloxyl-2 4,8,10-tetra-tert-butyl-12H-dibenz [d, g] - 1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-butyl-12-methyl- di-benz [dg] -1,2,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite .

5, - Peroxide weighers. for example esters of B-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptoben-zimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetlethyl propetylis (capododetro) tetrakis.

è .. Polamide stabilizers. for example copper salts together with iodides and / or phosphorus compounds and salts of divalent manganese.

2 · Basic co-stabilizers. for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, calcium stearate, zinc stearate, magnesium stearate, potassium kali-amicric acid, or tin pyrocatecholate.

8. Precipitating agents, for example, 4-tert-butyl benzoic acid, adipic acid, diphenylacetic acid.

9 .. Fillers and reinforcing agents. for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon, graphite.

10. Other suffixes. for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, anti-static agents and blowing agents.

11. Benzofuranones and Indolinones. for example, those described in US-A-4,325,863 or US-A-4,338,244.

The compounds of the invention can also be used as stabilizers, especially as light stabilizers, for almost all materials known in photographic reproduction and other reproduction techniques, such as described, for example, in Research Disclosure 1990, 31429 (pp. 474 to 480).

Several examples of the preparation and use of the co-oligomers comprising recurring units of formulas (Ia) and (Ib) are described for a more detailed illustration of the present invention; these examples are given as illustrations later on and do not limit them in any way.

The compounds described in Examples 1, 3, 4, 7 and 8 relate to a preferred embodiment of the present invention.

Example 1: 20.8 g (0.1 mol) of 2,4-dichloro-6-isopropoxy-1,3,5 "triazine, 9.3 g (0.1 mol) of epichlorohydrin, 82.9 (0.21 mol) of N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine and 100 ml of 4-methyl-2-pentanol are stirred at 80 for 1 hour ° C and then under reflux for another 8 hours, 12 g (0.3 mol) of NaOH is slowly added during the last 6 hours of the reaction.

After the addition of the NaOH was complete, the reaction mixture is heated under reflux for an additional 2 hours. The water of the reaction and most of the 4-methyl-2-pentanol are then distilled off; 400 ml of xylene are added and 100 ml of solvent are slowly distilled off to completely remove the 4-methyl-2-pentanol.

A mixture containing 21.2 g (0.46 mol) formic acid and 14.4 g (0.48 mol) methanol-free 30% formaldehyde is added over 3 hours to the xylene solution thus obtained, heated to 110 ° C, with simultaneous azeo-tropical removal of the added water and the water from the reaction.

The mixture is cooled to 70 ° C, a solution of 3 g of NaOH in 60 ml of water is added, and the mixture is stirred for an additional 30 minutes. The aqueous layer is separated, and the organic phase is washed with water, dried over Na2SO4 and evaporated under reduced pressure.

This gives a product with a melting point of 77 ~ 85 ° C and an average molecular weight of Mn = 2800.

Example 2; By using the method described in Example 1, a product is obtained with a melting point of 8-88 ° C and an average molecular weight of Mn = 3800 by conversion of 22.2 g (0.1 mol) 2-butoxy-4, 6-dichloro-1,3,5-triazine, 9.3 g (0.1 mol) epichlorohydrin and 78.9 g (0.2 mol) N, N'-bis (2,2,6,6-tetramethyl -4-piperidyl) -1,6-hexanediamine in 100 ml 4-methyl-2-pentanol and subsequent methylation in xylene with formic acid / formaldehyde mixture as indicated in Example 1.

Example 3: Using the method described in Example 1, a compound is obtained with a melting point of 103-112 ° C and an average molecular weight of Mn = 3500 by conversion of 22.1 g (0.1 mol) 2.4 -dichloro-6-diethylamino-1,3,5-triazine, 9.3 g (0.1 mol) epi-chlorohydrin and 78.9 g (0.2 mol) N, N'-bis (2,2,6,6- tetramethyl-4-piperidyl) -1,6-hexanediamine in 100 ml of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid / formaldehyde mixture as indicated in Example 1.

Example 4: Using the method described in Example 1, a compound is obtained with a melting point of 110-117 ° C and an average molecular weight of Mn = 4000 by conversion of 27.7 g (0.1 mol) of 2,4-dichloro- 6-octylamino-1,3,5 * triazine, 9.3 g (0.1 mol) epichlorohydrin and 78.9 g (0.2 mol) N, N'-bis (2,2,6,6 -tetramethyl-4-piperidyl) - 1,6-hexanediamine in 100 ml of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid / formaldehyde mixture as indicated in Example 1.

Example 5; By using the method described in example 1, a compound is obtained with a melting point of 94-102 ° C and an average molecular weight of Mn = 4100 by conversion of 24.7 g (0.1 mol) 2,4-dichloro-6 -cyclohexylamino-1,3,5-triazine, 18.5 g (0.2 mol) epichlorohydrin and 118.4 g (0.3 mol) N, N'-bis (2,2,6,6-tetramethyl- 4-piperidyl) -!, 6-hexanediamine in 150 ml of 4-methyl-2-pentanol and subsequent methylation in xylene with a mixture containing 31.8 g (0.69 mol) formic acid and 72.1 g (0.72 mol) ) contains methanol-free 30 # / formaldehyde.

Example 6; By using the method described in example 1, a compound is obtained with a melting point of 75-84 eC and an average molecular weight of Mn = 2200 by conversion of 25 g (0.1 mol) 2,4-dichloro-6-tetrahydrofurfuryloxy- 1,3,5-triazine, 9.3 g (0.1 mol) epichlorohydrin and 88.8 g (0.225 mol) N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) - 6-hexanediamine in 110 ml of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid / formaldehyde mixture as indicated in Example 1.

Example 7: Using the method described in Example 1, a compound with a melting point of 100-103 ° C and an average molecular weight of Mn = 2000 is obtained by conversion of 18.7 g (0.05 mol) 2.4- dichloro-6- [N- (2,2,6,6-tetramethyl-4-piperidyl) -piperazine] -1,3,5 ”triazine, 4.6 g (0.05 mol) epichlorohydrin and 41.4 g (0.105 mol) N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine in 75 ml of 4-methyl-2-pentanol and subsequent methylation in xylene with the mere acid / formaldehyde mixture as indicated in example 1.

Example 8; Using the method described in Example 1, a compound with a melting point of 105-109eC and an average molecular weight of Mn = 3150 is obtained by conversion of 11.7 g (0.05 mol) of 2,4-dichloro-6-morpholine -1,3f5-triazine, 4.6 g (0.05 mole) epichlorohydrin and 4l, 4 g (0.105 mole) N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) 1,6-hexanediamine in 75 ml of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid / formaldehyde mixture as indicated in Example 1.

In the examples, the average molecular weight was determined using a vapor pressure osmometer (®Gonotec) as described in EP-A-255,990.

Example 9: (Light stabilizing effect in polypropylene fibers) 2.5 g of each of the products shown in Table 1, 1 g of tris (2,4-di-tert-butylphenyl) phosphite, 0.5 g of calcium monoethyl-3,5 ~ di-tert-butyl-4-hydroxybenzylphosphonate, 1 g calcium stearate and 2.5 g titanium dioxide were mixed in a slow mixer with 1000 g polypropylene powder with a melt index = 12 g / 10 minutes (calculated at 230 ° C and 2.16 kg ).

The blends were extruded at 200-230 ° C to yield polymeric granulates which were then converted to fiber using a pilot type device (®Leonard-Sumirago (VA) Italy) under the following conditions:

extruder temperature: 200-230 ° C

cup temperature j 255 "260eC

stretch ratio: 1: 3 * 5 count: 11 dtex per filament

The fibers thus prepared were exposed stacked on a white card, in a model 65 WR Weather-O-Meter (ASTM D2565-85) with a black panel temperature of 63 ° C.

The residual toughness is calculated on samples taken after different times of exposure of the light by means of a constant velocity tensometer and the exposure time in hours (T50) required to halve the initial toughness is then calculated.

Fibers prepared under the same conditions as indicated above, but without adding the stabilizers of the invention, are tested for comparison.

The results obtained are given in Table 1.

TABLE 1

Stabilizer T50_iuur}.

Not 190

Compound of Example 1 20O0

Compound of Example 2 1980

Compound of Example 3 20 ^ 0

Connection of Example 4 2000

Compound of Example 5 1970

Connection of example 6 2010

Claims (11)

1. Co-oligomer containing recurring units of formulas (Ia) and (Ib)

(Yes) (Ib), with an average molecular weight of 1000 to 20,000 and a (Ia) :( Ib) ratio of 4: 1 to 1: 4, where ^ is a group -0R-, -SRg or

where R5, Rg and R? are the same or different and represent a hydrogen, C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl which is unsubstituted or 1, 2 or 3 times substituted by a C 1 -C 18 alkyl; C 3 -C 18 alkenyl, phenyl which is unsubstituted or 1, 2 or 3 sews substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy; C7 -C8 phenylalkyl which is unsubstituted 1, 2 or 3 times substituted on the phenyl group by alkyl; tetrahydrofurfuryl, 1,2,6,6,6-pentamethyl-4-piperidyl or C 2 -C 7 alkyl substituted at the 2, 3 or 4-p position by C 1 -C 6 alkoxy, by di-C; , alkyl) amino or by a group of formula (II)

(II) wherein A is a direct bond, -0-, -CH2-, -CH2CH2- or> N-CH3, or is a group of formula (II) or one of the groups of formulas (IlIa) - (IIIc )

wherein R 8 is C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl which is unsubstituted or 1, 2 or 3 times substituted by a C 1 -C 18 alkyl; C7-C9 phenylalky! which is unsubstituted or substituted 1, 2 or 3 times on the phenyl by door ^ - (¾alkyl; or 1,2,6,6,6-pentamethyl-4-piperidyl, m is an integer from 2 to 6, n is zero or 1, X is -0- or> N-CH3 and R9 has the same meaning as Rg or is hydrogen, R2 has the same meaning as Rg or is hydrogen atom, R3 is C2-C12 alkylene, 0 * -012 alkylene interrupted by 1, 2 or 3 oxygen atoms or by a group> N-CH 3; C - C 1 cycloalkylene, C 5 -C 7 cycloakylene di (C: 1-C 4 alkylene), alkylene di (C 5-C 7 cycloalkylene), C2 -C4 alkylenedi (C5-C7 cyeloalkylene) or phenylenedimethylene, and R /, C2-C12 alkylene, C / j-C12 alkylene is interrupted by 1, 2 or 3 oxygen atoms; 2-hydroxytrimethylene, phenylene dimethylene, carbonyl, C2-C15 diacyl, C 1 -C 15 dicarbamoyl, a group - (CH 2) p-C0- where p is an integer from 1 to 10, or a group -COO-R10-OOC-where R10 has the same meaning as R3. The recurring unit oligomer of formulas (Ia) and (Ib) of claim 1, having an average molecular weight of 1000 to 10,000 and a (Ia); (Ib) ratio of 3 ^ 1 to 1.3; wherein R: is a group -0RS, -SR5 or

wherein R5, R6 and R7 may be the same or different and represent hydrogen, alkyl, C5-C8 cycloalkyl which is unsubstituted or substituted 1, 2 or 3 times by a C 1 -C 1 alkyl; C 3 -C 12 alkenyl, phenyl which is unsubstituted or 1, 2 or 3 times substituted by a C 1 -C 18 alkyl or C 1 -C 18 alkoxy; benzyl which is unsubstituted or substituted 1, 2 or 3 times on the phenyl by a C 1 -C 4 alkyl; tetrahydrofururyl, 1-S-pentamethyl-piperidyl or C 2 -C 3 alkyl substituted at the 2- or 3 "position by C 1 -C 6 alkoxy, by di-C 1 alkyl) amino or by a group of formula (II) in which A is a direct bond, -0-, -CH2- or -CH2CH2-, or R1 is a group of formula (II) or one of the groups of formulas (lilac) - (IIIc) wherein R 9 is C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl which is unsubstituted or 1, 2 or 3 times substituted by C * - (¾ alkyl; benzyl which is unsubstituted or 1, 2 or 3 times substituted in the phenyl by Ct - C 1, alkyl; or 1, 2,2,6,6-pentamethyl-4-piperidyl. 11 is 2, 3 or 4, n is zero or 1, X is -0- or> N-CH 3 and R 9 has the same meaning if Rg or is hydrogen atom, R2 has the same meaning as R8 or is hydrogen, R3 is C2-C10 alkylene, C2, -C10 alkylene interrupted by 1, 2, or 3 oxygen atoms or by a> N-CH3 ~ group; cyclohexylene, cyclo -hexylene dimethylene, methylene dicyclohexylene, isopropylidene dicyclohexylene or phenylene dimethylene, and R4 is C 2-C10 alkylene, C 1 -C 12 alkylene interrupted by 1, 2 or 3 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C2-C10 diacyl, 0ή-012 dicarbamoyl, a group - (CH2) pC0- where p is an integer from 1 to 5. or a group -C00-Rlo-00C- where R10 has the same meaning as R3. Recurrent unit co-oligomer of formula (Ia) and (Ib) according to claim 1, having an average molecular weight of 1000 to 8000 and a (Ia) :( Ib) ratio of 2: 1 to 1: 3. wherein R2 is a group -0R5, -SR5 or

wherein R 5 is C 1 -C 12 alkyl, cyclohexyl which is unsubstituted or 1, 2 or 3 times substituted by C 1 -C 18 alkyl; allyl, undecenyl, phenyl, benzyl, tetrahydrofurfuryl or 1,2,6,6,6-pentamethyl-4-piperidyl, Rg and R18 which may be the same or different have the same meaning as R 5 or are hydrogen or C 2 -C 3 alkyl substituted at the 2- or 3 "position by C 1 -C 6 alkoxy, by dimethylamino, by diethylamino or by a 4-morpholinyl group, or Rx is 4-morpholinyl or one of the groups of formulas (IlIa) - (IIIc) wherein Rg is C 1 -C 6 alkyl, cyclohexyl which is unsubstituted or 1, 2 or 3 times substituted by (^ - (¾alkyl; benzyl) or 1.2.2.6.6-pentamethyl-4-piperidyl, m is 2 or 3. n is zero or 1, X is -0-or> N-CH3 and Rg is defined as Rö or is hydrogen, R2 is defined as R8 or is hydrogen, R 3 is C 2 -C 8 alkylene, C 8 -C 10 alkylene interrupted by 2 or 3 oxygen atoms; cyclohexylene dimethylene, methylene dicyclohexylene or phenylene dimethylene, and R 3 is C 2 -C 8 alkylene, C 1 -C 8 alkylene interrupted by 1 or 2 oxygen atoms; 2-hydroxytrimethylene, phenylene dimethylene, carbonyl, C 2 -C 8 diacyl, C 1 -C 10 dicarbamoyl, a group - (CH_ 2) pC0- where p is 1, 2 or 3. or a group -C0 0-R10 -00C- wherein R10 is defined as R3. The recurring unit oligomer of the formulas (Ia) and (Ib) of claim 1, having an average molecular weight of 1500 to 6000 and a (Ia) :( Ib) ratio of 2: 1 to 1: 2, wherein Rx is a group -0R5 or

wherein R5 is C1-C8 alkyl, cyclohexyl, allyl, benzyl, tetrahydrofurfuryl or 1.2.2.6.6-pentamethyl-4-piperidyl, Rg and R7 which may be the same or different are defined as R5 or hydrogen, or Rx is 4- morpholinyl or one of the groups of formulas (IlIa) - (IIIc) where Rg is 1.2.2.6.6-pentamethyl-4-piperidyl, m is 2, n is zero or 1, X is -0- or> N- CH3 and Rg is hydrogen or 1,2,2,6,6-pentamethyl-4-piperidyl. R2 is hydrogen, methyl or 1,2,2,6,6-pentamethyl-4-piperidyl, R3 is C2-C8 alkylene, C6-C10 alkylene interrupted by 2 or 3 oxygen atoms; cyclohexylene dimethylene, methylene dicyclohexylene or phenylene dimethylene, and R *, is C 2 -C 6 alkylene, 2-hydroxy trimethylene, phenylene dimethylene, C 2 -C 6 diacyl, -CH 2 CO 2 - or a group -COO-R 10 -OOC- where R 10 is C 1 -C 6 alkylene. Recurrent unit co-oligomer of formulas (Ia) and (Ib) according to claim 1, having an average molecular weight of 2000 to 5000 and a (Ia) :( Ib) ratio of 1: 1 to 1: 2, wherein Rx is a group -0R5 or

wherein Rg is C1 -C1 (alkyl or tetrahydrofurfuryl, Rg and R? which may be the same or different, are C1 -C8 alkyl, cyclohexyl or 1,2,2,6,6-penta-methyl-4-piperidyl or R6 may also be hydrogen, or R 1 is 4-morpholinyl or a group of formula (lila) wherein n is zero, R 2 is 1,2,2,6,6-pentamethyl-4-piperidyl. R 3 is a group - ( CH 2) 2-6- or - (CH 2) 3 -O- (CH 2) 2 -α (O) (CH 2) 3 - and R 1 is 2-hydroxy trimethylene. A mixture comprising an organic material sensitive to degradation by light, heat and oxidation and at least one recurring unit oligomer of formulas (Ia) and (Ib) according to claim 1. The mixture of claim 6, wherein the organic material is a synthetic polymer. A mixture according to claim 7 containing other conventional synthetic polymer additives together with the recurring unit oligomers of formulas (Ia) and (1b). Mixture according to claim 6, wherein the organic material is a polyolefin. The blend of claim 6, wherein the organic material is polyethylene or polypropylene. The use of a co-oligomer with recurring units of formulas (Ia) and (Ib) according to claim 1 for stabilizing an organic material against degradation caused by light, heat and oxidation.