DE4312066A1 - New piperidine-triazine co-oligomers for use as stabilizers for organic materials - Google Patents

Description

The present invention relates to novel piperidine-triazine co-oligomers which Use of these as light stabilizers, heat stabilizers and oxidas tion stabilizers for organic materials, in particular for syntheti polymers and the thus stabilized organic materials.

The stabilization of synthetic polymers by triazine oligomers and copolymers Oligomers having 2,2,6,6-tetramethylpiperidine groups are disclosed in U.S. Pat numerous patents have been described, in particular in US Pat. No. 4,086,204, US Pat. A-4315859, US-A-4331586, US-A-4335242, US-A-4412020, US-A-4459395, US-A- 4477615, US-A-4547548, EP-A-1 17 229 and EP-A-2 17 149 and JP-A-Sho 63-196654.

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

having a number average molecular weight of 1,000 to 20,000 and a (Ia): (Ib) ratio of 4: 1 to 1: 4, wherein R _{1 is} a group

wherein R₅, R₆ and R₇, which may be the same or different, is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl which is unsubstituted or mono-, di or tri-substituted by C ₁ -C ₄ -alkyl; C ₃ -C ₁₈ alkenyl, phenyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy; C ₇ -C ₉ phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl is C ₁ -C ₄ -alkyl; Tetrahydrofurfuryl, 1,2,2,6,6-pentamethyl-4-piperidyl or C ₂ -C ₄ -alkyl substituted in the 2-, 3- or 4-position by C ₁ -C ₈ -alkoxy, by di (C C ₁ -C ₄ -alkyl) amino or by a group of the formula (II)

wherein A is a direct bond, -O -, - CH ₂ -, -CH ₂ CH ₂ - or <N-CH ₃ , or R ₁ is a group of the formula (II) or one of the groups of the formulas (IIIa) - (IIIc)

wherein R ₈ is C ₁ -C ₁₈ -alkyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ -alkyl; C ₇ -C ₉ phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by C ₁ -C ₄ -alkyl; or 1,2,2,6,6-pentamethyl-4-piperidyl, m is an integer from 2 to 6, n is zero or 1, X is -O- or <N-CH ₃ and R ₉ is as above defined for R ₈ or is hydrogen, R ₂ is defined as for R ₈ or is hydrogen, R ₃ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkylene interrupted by 1, 2 or 3 oxygen atoms or by a group <N-CH ₃ ; C ₅ -C ₇ -cycloalkylene, C ₅ -C ₇ -cycloalkylenedi (C ₁ -C ₄ -alkylene), C ₁ -C ₄ -alkylenedi (C ₅ -C ₇ -cycloalkylene), C ₂ -C ₄ -alkylidene di ( C ₅ -C ₇ -cycloalkylene) or phenylenedimethylene, and R ₄ is C ₂ -C ₁₂ -alkylene, C ₄ -C ₁₂ -alkylene interrupted by 1, 2 or 3 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C ₂ -C ₁₅ -diacyl, C ₄ -C ₁₅ -dicarbamoyl, a group - (CH ₂ ) _p CO- wherein p is an integer from 1 to 10, or a group -COO R ₁₀ -OOC- wherein R _{10 is} defined as for R ₃ .

The co-oligomers of the invention may have different end groups, depending on the type and molar ratios of the reagents used in the preparation. In particular, the end group attached to the triazine ring of the formula (Ia) - hereinafter referred to as X ₁ - is, for example, Cl, OH, ONa, OK or a group R ₁ or a group

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

wherein X _{1 is} as defined above, or a group -R ₄ OH. In the individual corresponding groups of the formulas (Ia) and (Ib), the groups R ₁ , R ₂ , R ₃ and R _{4 may} be the same or different in each case.

Examples of alkyl having not more than 18 carbon atoms are methyl, Ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2- Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, Dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Examples of C ₂ -C ₄ -alkyl substituted by C ₁ -C ₈ -alkoxy, preferably by C ₁ -C ₄ -alkoxy, in particular methoxy or ethoxy, are 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl , 3-butoxypropyl, 3-octoxy-propyl and 4-methoxy-butyl.

Examples of C ₂ -C ₄ -alkyl substituted by di (C ₁ -C ₄ -alkyl) amino, preferably by dimethylamino or diethylamino, are 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylamino-propyl, 3 Dibutylaminopropyl and 4-diethylaminobutyl.

A representative example of C ₂ -C ₄ alkyl substituted by a group of formula (II) is the group of the formula

is preferred.

Examples of unsubstituted or substituted C ₅ -C ₁₂ -cycloalkyl are cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, t-butylcyclohexyl, cyclooctyl, cyclodecyl and cyclododecyl. Unsubstituted or C ₁ -C ₄ alkyl substituted cyclohexyl is preferred.

Examples of C ₃ -C ₁₁ alkenyl are allyl, 2-methylallyl, butenyl, hexenyl decenyl, undecenyl and oleyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.

Examples of substituted phenyl are methylphenyl, dimethylphenyl, Trimethylphenyl, t-butylphenyl, di-t-butylphenyl, 3,5-di-t-butyl-4-methylp henyl, methoxyphenyl and ethoxyphenyl. Examples of phenylalkyl, the is unsubstituted or substituted on the phenyl ring, benzyl, Methylbenzyl, dimethylbenzyl, trimethylbenzyl, t-butylbenzyl and 2-phenyl lethyl. Benzyl is preferred.

Examples of C ₂ -C ₁₂ -alkylene are ethylene, propylene, Trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, Hexamethy len, trimethylhexamethylene, octamethylene, decamethylene and dodecamethylene.

Examples of C ₄ -C ₁₂ -alkylene, interrupted by 1, 2 or 3 oxygen atoms, are 3-oxapentane-1,5-diyl, 4-oxaheptan-1,7-diyl, 3,6-dioxaoctan-1,8 - diyl, 4,7-dioxadecane-1,10-diyl, 4,9-dioxadodecane-1,12-diyl and 3,6,9-trioxaundecane-1,11-diyl.

A representative example of the meaning C ₄ -C ₁₂ -alkylene at R ₃ and R ₁₀ , interrupted by a group <N-CH ₃ , is the group

Representative examples of groups having one or two C ₅ -C ₇ cycloalkyl groups are cyclohexylene, methylcyclohexylene, cyclohexylenedimethylene, methylenedicyclohexylene and isopropylidene-dicyclohexylene.

Representative examples of C ₂ -C ₁₅ -diacyl at R ₄ are oxalyl, malonil, ethylmalonil, butylmalonil, benzylmalonil, succinyl. Glutaryl, adipoyl, trimethyl adipoyl, sebacoyl, oxydiacetyl, cyclohexanedicarbonyl, phthaloyl, isophthaloyl and terephthaloyl, C ₂ -C ₁₅ alkanedioyl unsubstituted or substituted by benzyl; C ₄ -C ₁₅ alkanedioyl in which the alkane radical is interrupted by oxygen; (C ₅ -C ₇ cycloalkane) dicarbonyl, phthaloyl, isophthaloyl and terephthaloyl are preferred.

Representative examples of C ₄ -C ₁₅ dicarbamoyl R ₄ are hexamethylenedicarboxylic, trimethylhexamethylenedicarbamoyl, cyclohexylendicarbamoyl, phenylenedicarbamoyl, tolylenedicarbamoyl or a group

(C ₂ -C ₁₃ alkylene) dicarbamoyl, (C ₅ -C ₇ cycloalkylene) dicarbamoyl, phenylenedicarbamoyl, tolylenedicarbamoyl and the groups

are preferred.

There are preferred such co-oligomers, the recurring units of Formula (Ia) and (Ib) having a number average molecular weight of Have 1000 to 10000 and a (Ia): (Ib) ratio of 3: 1 to 1: 3, wherein  R₁ is a group -OR₅, -SR₅ or

in which R₅, R₆ and R₇, which can be identical or different, are hydrogen, C ₁ -C ₁₆ -alkyl, C ₅ -C ₈ -cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ - C ₄ alkyl: C ₃ -C ₁₂ alkenyl phenyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; Benzyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by C ₁ -C ₄ -alkyl; Tetrahydrofurfuryl, 1,2,2,6,6-pentamethyl-4-piperidyl or C ₂ -C ₃ -alkyl substituted in the 2- or 3-position by C ₁ -C ₄ -alkoxy, by di (C ₁ -C ₄ -alkyl) amino or by a group of the formula (II) in which A is a direct bond. -O-, -CH ₂ - or -CH ₂ CH ₂ -, or R ₁ is a group of the formula (II ) or one of the groups of the formulas (IIIa) - (IIIc) in which R _{8 is} C ₁ -C ₁₂ -alkyl), C ₅ -C ₈ -cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ - C ₄ alkyl; Benzyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by C ₁ -C ₄ -alkyl; or 1,2,2,6,6-pentamethyl-4-piperidyl, m is 2, 3 or 4, n is zero or 1. X is -O- or <N-CH ₃ and R ₉ is as above for R ₈ or is hydrogen, R ₂ is as defined above for R ₈ or is hydrogen, R ₃ is C ₂ -C ₁₀ alkylene, C ₄ -C ₁₀ alkylene interrupted by 1, 2 or 3 oxygen atoms or by an <N -CH ₃ group; Cyclohylene, cyclohexylenedimethylene. Methylenedicyclohexylene, isopropylidene-dicyclohexylene or phenylenedimethylene, and R ₄ is C ₂ -C ₁₀ -alkylene, C ₄ -C ₁₀ -alkylene interrupted by 1, 2 or 3 oxygen atoms; 2-Hydroxytrimethyl, phenylenedimethylene, carbonyl, C ₂ -C ₁₀ -diacyl, C ₄ -C ₁₂ -dicarbamoyl, a group - (CH ₂ ) _p CO- wherein p is an integer from 1 to 5, or a group - COO-R ₁₀ -OOC- wherein R _{10 is} as defined for R ₃ .

Particularly preferred co-oligomers which have recurring units of the formulas (Ia) and (Ib) having a number-average molecular weight of from 1000 to 8000 and a (Ia): (Ib) ratio of from 2: 1 to 1: 3 in which a group -OR ₅ , SR ₅ or

wherein R₅ is C₁-C₁₂ alkyl, cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ alkyl; Allyl, undecyl, phenyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6-pentamethyl-4-piperidyl, R ₆ and R ₇ , which may be the same or different, are as defined above for R ₅ or Is hydrogen or C ₂ -C ₃ alkyl substituted in the 2- or 3-position by C ₁ -C ₄ alkoxy, by dimethylamino, by diethylamino or by a 4-morpholinyl group, or R ₁ is 4-morpholinyl or one of the groups of formulas (IIIa) - (IIIc) wherein R _{8 is} C ₁ -C ₈ alkyl, cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ alkyl; Benzyl or 1,2,2,6,6-pentamethyl-4-piperidyl, m is 2 or 3, n is zero or 1, X is -O- or <N-CH ₃ and R ₉ is as above for R ₈ or is hydrogen, R ₂ is as defined above for R ₈ or is hydrogen, R ₃ is C ₂ -C ₈ -alkylene, C ₆ -C ₁₀ -alkylene interrupted by 2 or 3 oxygen atoms: cyclohexylenedimethylene, methylenedicyclohexylene or phenylenedimethylene, and R ₄ is C ₂ -C ₈ alkylene, C ₄ -C ₈ alkylene interrupted by 1 or 2 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C ₂ -C ₈ -diacyl, C ₄ -C ₁₀ -dicarbamoyl, a group - (CH ₂ ) _p CO- wherein p is 1, 2 or 3 or a group -COO-R ₁₀ -OOC- wherein R _{10 is} as defined for R ₃ .

There are those co-oligomers of particular interest, the recurring units of the formulas (Ia) and (Ib) having a number average Molekularge weight of 1500 to 6000 and a (Ia): (Ib) ratio of 2: 1 to 1: 2 in which R _{1 is} a group -OR ₅ or

R ₇ is wherein R _{5 is} C ₁ -C ₈ alkyl, cyclohexyl, allyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6-pentamethyl-4-piperidyl, R ₆ and R _{1 are} the same or are different as defined above for R ₅ or are hydrogen, or R ₁ is 4-morpholinyl or one of the groups of formulas (IIIa) - (IIIc), wherein R _{8 is} 1,2,2,6,6-pentamethyl 4 is piperidyl, m is 2, n is zero or 1, X is -O- or <N-CH ₃ and R ₉ is hydrogen or 1,2,2,6,6-pentamethyl-4-piperidyl, R ₂ is hydrogen, methyl or 1,2,2,6,6-pentamethyl-4-piperidyl, R ₃ is C ₂ -C ₆ -alkylene, C ₆ -C ₁₀ -alkylene interrupted by 2 or 3 oxygen atoms; Cyclohexylendimethy len, methylenedicyclohexylene or phenylenedimethylene and R ₄ is C ₂ -C ₆ alkylene, 2-hydroxytrimethylene, phenylenedimethylene, C ₂ -C ₆ -diacyl-CH ₂ CO- or a group -COO-R ₁₀ -OOC- wherein R _{10 has} the meaning C ₄ -C ₆ -alkylene.

There are those co-oligomers of particular interest, the recurring units of the formulas (Ia) and (Ib) with a number average Molekularge weight of 2000 to 5000 and a (Ia): (Ib) ratio of 1: 1 to 1: 2 in which R _{1 is} a group -OR ₅ or

in which R _{5 has} the meaning C₁-C₄-alkyl or tetrahydrofurfuryl, R ₆ and R ₇ which may be identical or different are C ₁ -C ₈ -alkyl, cyclohexyl or 1,2,2,6,6-pentamethyl 4-piperidyl, or R ₆ may also be hydrogen, or R ₁ is 4-morpholinyl or a group of formula (IIIa) 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 ) _2-4 -O- (CH ₂ ) ₃ - and R ₄ is 2-hydroxytrimethylene.

The compounds of the present invention can be prepared by methods are made, which are known per se, z. B. by N-methylation of corresponding co-oligomeric compounds containing the 2,2,6,6-tetramethylpipe containing ridin groups, using one of the known N-methyl tion process, for example by reaction of 2,2,6,6-Tetramethylpi peridin compounds with formaldehyde and formic acid when working in Water or in an aromatic hydrocarbon solvent, or by reacting this with formaldehyde and hydrogen in the presence of a Hydrogenation catalyst such as Pt, Pd or Ni, as in US-A-4459395, the EP-A-3 19 480 and in EP-A-3 65 469.

The co-oligomers that are not in the 1-position of the 2,2,6,6-tetramethylpipe Ridin groups are methylated, can be prepared by known methods for example as described in US-A-4547548.

The co-oligomers of the present invention are highly effective at Improvement of light stability, heat stability and oxidation stability of organic materials, in particular of synthetic polymers ren for example of polyolefins.

In particular, the remarkable light-stabilizing effect in poly propylene, especially in fiber form, surprising.

Examples of organic materials that can be stabilized are:

• 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and polymers of cycloolefins such. From cyclopentene or norbornene; also polyethylene (which can be optionally cross-linked), z. High density polyethylene (HDPE), zero density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (VLDPE).
  Polyolefins, ie polymers of monoolefins, as exemplified in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by various methods, in particular by the following methods:
  • a) radical (usually at high pressure and high temperature).
  • b) by means of a catalyst, wherein the catalyst usually contains one or more metals of group IVb, Vb, VIb or VIII. These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be either π- or σ-coordinated. These metal complexes may be free or supported, such as on activated magnesium chloride, titanium (III) chloride, alumina or silica. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts may be active as such in the polymerization, or other activators may be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkoxides or metal alkyloxanes, where the metals are elements of groups Ia, IIa, and / or IIIa. The activators can be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
• 2. mixtures of the polymers mentioned under 1), for. B. mixtures of polypropylene with Polyisobutylene, polypropylene with polyethylene (eg PP / HDPE, PP / LDPE) and Mischun various types of polyethylene (eg LDPE / HDPE).
• 3. Copolymers of monoolefins and diolefins with each other or with other vinyl mono  mers, such as For example, ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene Butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, Ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene-co polymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-iso pren copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copoly mers, 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 ethyli dennorbornen; furthermore, mixtures of such copolymers with one another and with 1) ge called polymers, eg. As polypropylene / ethylene-propylene copolymers, LDPE / ethylene Vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers and alternating or statis table constructed polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such. B. polyamides.
• 4. Hydrocarbon resins (eg C ₅ -C ₉ ) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.
• 5. polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).
• 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as. B. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkylacry lat and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength from styrene copolymers and another poly mer, such as As a polyacrylate, a diene polymer or an ethylene-propylene Diene terpolymer; and block copolymers of styrene, such as. Styrene-butadiene Styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propyne len-styrene.
• 7. graft copolymers of styrene or α-methylstyrene, such as. Styrene on polybutadiene, Styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and Acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methylmeth acrylate 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 alkyl methacrylates  Polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and Acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile Acrylate-butadiene copolymers, and mixtures thereof with the mentioned under 6) Co polymers, such as. B. known as so-called ABS, MBS, ASA or AES polymers are.
• 8. Halogen-containing polymers, such as. As polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, Epi chlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl connections, such. As polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, poly vinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride Ride vinyl acetate or vinylidene chloride vinyl acetate.
• 9. Polymers derived from α, β-unsaturated acids and their derivatives, such as Polyacrylates and polymethacrylates, polymethyl impact-modified with butyl acrylate methacrylates, polyacrylamides and polyacrylonitriles.
• 10. Copolymers of the monomers mentioned under 9) with each other or with other unge saturated monomers such. For example, acrylonitrile-butadiene copolymers, acrylonitrile alkylacry lat copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide Copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
• 11. Polymers derived from unsaturated alcohols and amines or their acylderiva derived or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins mentioned in point 1.
• 12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropyleneoxydide or their copolymers with bisglycidyl ethers.
• 13. Polyacetals, such as polyoxymethylene, as well as those polyoxymethylenes, the Comono mere, such. For example, ethylene oxide; Polyacetals made with thermoplastic polyurethane NEN, acrylates or MBS are modified.
• 14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or Polyamides.  
• 15. Polyurethanes which are derived from polyethers, polyesters and polybutadienes Hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates dererseits, as well as their precursors.
• 16. polyamides and copolyamides derived from diamines and dicarboxylic acids and / or derive from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, Polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromati typical polyamides starting from m-xylene, diamine and adipic acid; Polyamides, manufactured from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally one Elastomer as modifier, z. B. poly-2,4,4-trimethylhexamethylene terephthalamide or Poly-m-phenylene isophthalamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or ge grafted elastomers; or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Further modified with EPDM or ABS poly amides or copolyamides; as well as condensed polyamides during processing ( "RIM polyamide systems")
• 17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
• 18. Polyesters derived from dicarboxylic acids and dialcohols and / or hydroxy derived carboxylic acids or the corresponding lactones, such as polyethylene terephthalate, Polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzo ate, as well as block polyether esters derived from hydroxyl-terminated polyethers th; also with polycarbonates or MBS modified polyester.
• 19. polycarbonates and polyestercarbonates.
• 20. polysulfones, polyethersulfones and polyetherketones.
• 21. Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or Derive melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and Melamine-formaldehyde resins.
• 22. Drying and non-drying alkyd resins.  
• 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated di carboxylic acids with polyhydric alcohols, as well as vinyl compounds as Vernetzungsmit derive tel, as well as their halogen-containing, flame-retardant modifications.
• 24. Crosslinkable acrylic resins derived from substituted acrylic acid esters, such as. B. of epoxy acrylates, urethane acrylates or polyester acrylates.
• 25. Alkyd resins, polyester resins and acrylate resins containing melamine resins, urea resins zen, polyisocyanates or epoxy resins are crosslinked.
• 26. Crosslinked epoxy resins derived from polyepoxides, e.g. B. of bis-glycidyl ethers or cycloaliphatic diepoxides.
• 27. Natural polymers, such as cellulose, natural rubber, gelatin, and their polymer homologous chemically modified derivatives, such as cellulose acetates, propionates and butyric rate, or the cellulose ethers, such as methylcellulose; as well as rosin resins and Deri vate.
• 28. mixtures (polyblends) of the aforementioned polymers, such as. PP / EPDM, poly amid / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM / Thermoplastic PUR, PC / Thermo plastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.
• 29. Natural and synthetic organic substances, the pure monomeric compounds or mixtures of such, for example mineral oils, animal or vegetable Fats, oils and waxes, or oils, waxes and fats based on synthetic esters (eg phthalates, adipates, phosphates or trimellitates), as well as mixtures of synthetic Ester with mineral oils in any weight ratios, as z. B. as a spin finish apply, and their aqueous emulsions.
• 30. Aqueous emulsions of natural or synthetic rubbers, such as. B. Natural chew latex or latices of carboxylated styrene-butadiene copolymers.

The compounds of the present invention may be used in mixtures with organi materials in different proportions depending on the type the material to be stabilized, the end use and the Presence of other additives are used.

In general, for use, for example, 0.01 to 5% by weight the compounds of the invention in relation to the weight of the stabi lisierenden material suitable, preferably between 0.05 and 1%. in the In general, the compounds of the present invention, the polyme ren materials before, during or after the polymerization or Ver wetting of the said materials are added.

The compounds of the present invention may be incorporated into the polymeric material For example, in pure form or encapsulated in waxes, oils or Are introduced polymers.

The compounds of the present invention may be incorporated into the polymeric material Rialien be introduced by various methods, such as Trockenver mixture in the form of powder, or wet mixing in the form of solutions or Suspensions or in the form of a standard batch; in such proceedings The polymer can be used in the form of powders, granules, solutions, Suspensions or in the form of latices can be used.

The materials stabilized with the products of the present invention can be used for the production of fittings, foils, tapes, monofilaments, Fibers, surface coatings and the like can be used.

If desired, other additives customary for synthetic polymers, such as antioxidants, UV absorbers, nickel stabilizers, pigments, Fillers, plasticizers, antistatic agents, flame retardants, lubricants tel, corrosion inhibitors and metal deactivators the mixtures of Ver Compounds of the present invention with the organic materials be added.

Specific examples of additives, in admixture with the compounds of Formula (I) can be used are:  

1. Antioxidants

1.1. Alkylated monophenols, e.g. For example, 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-di methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di- tert -butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclo hexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl 6- (1'-methyl-undec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2,4- Dimethyl 6- (1'-methyl-tridec-1'-yl) -phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, eg. B. 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di- octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecyl thiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyl oxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl-stearate, bis (3,5-di-tert-butyl) 4-hydroxyphenyl) adipate.

1.4. Hydroxylated thiodiphenyl ethers, e.g. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis (6-tert-butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec.amylphenol), 4,4'-bis (2,6-di methyl-4-hydroxyphenyl) disulfide.

1.5. Alkylidene Bisphenols, e.g. 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-methyl cyclohexyl) phenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylene bis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethyl lidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis (6- (α-methylbenzyl) -4-nonylphenol), 2,2'-methylene-bis (6- (α, α-di methylbenzyl) -4-nonylphenol), 4,4'-methylene-bis- (2,6-di-tert-butylphe nol-), 4.4, -methyl len-bis- (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol 1,1,3-tris- (5- tert -butyl-4-hydroxy-2-methylphenyl) -butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl  phenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis (3,3-bis- (3'-tert-butyl-4'-hydroxy phenyl) -butyrate), bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) -dicyclopentadiene, bis (2-tert-butyl) (3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl) -6-tert-butyl-4-methyl-ph-enyl) terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxy phenyl) -propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercapto Butane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.6. O, N and S benzyl compounds, e.g. B. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxy dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris- (3,5-di tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -di thioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert butyl-4-hydroxybenzyl-mercaptoacetate.

1.7. Hydroxybenzylated malonates, e.g. For example, dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxy benzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, di- dodecylmercaptoethyl 2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di (4- (1,1,3,3-tetramethylbutyl) phenyl) -2,2-bis- (3,5-di-tert-butyl-4-hydr-oxybenzyl) malonate.

1.8. Hydroxybenzyl aromatics, e.g. B. 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-tetramethylbenzo-1, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.9. Triazine compounds, e.g. For example, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxy anilino) -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-tri-azine, 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-dimethyl benzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyleth-yl) -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.

1.10. Benzylphosphonates, e.g. Dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphos phonate, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.  

11.1. Acylaminophenols, e.g. 4-hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbaminsäureoctylester.

1.12. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with one or more valent alcohols, such as. With methanol, ethanol, 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) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- (2.2.2) - octane.

1.13. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with or without polyhydric alcohols, such as. With methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, tri methylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- (2.2.2) octane.

1.14. Esters of β- (3,5-dicydohexyl-4-hydroxyphenyl) propionic acid with one or more valent alcohols, such as. With methanol, ethanol, octadecanol, 1,6-hexanediol, 1.9- Nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'- Bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo - (2.2.2) - octane.

1.15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyvalent ones Alcohols, such as. With methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, Triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxy ethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylolpropane, 4-hydroxymethyl-1-phospha, 2,6,7-trioxabicyclo- (2.2.2) -octane.

16.1. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, such as. N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di  tert -butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hydrazine.

2. UV absorber and sunscreen

2.1.2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (5'-tert-butyl) Butyl 2'-hydroxy-phenyl) -benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethyl-butyl) -phenyl) -benzotriazole, 2- (3', 5'-di-tert -butyl-2'-hydroxyphenyl) -5-chlorobenztriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benztriazole, 2- (3'-sec- Butyl-5'-tert-butyl-2'-hydroxy-phenyl) -benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-amyl-2 '-Hydroxyphenyl) benzotriazole, 2- (3', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, mixture of 2- (3'-tert-butyl-2'-hydroxy -5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benztriazole, 2- (3'-tert-butyl-5' - (2- (2-ethylhexyloxy) -carbonylethyl) -2'-hydroxyphenyl) -5 -chlorobenztriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonyl-ethyl) -phenyl) -5-chloro-benztriazole, 2, (3'-tert-butyl-2' -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -benztr iazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - (2- (2-ethylhexyloxy ) carbonylethyl) -2'-hydroxy-phenyl) -benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methyl-phenyl) -benztriazole, and 2- (3-tert-butyl-2'-hydroxy-5 ' (2-isooctyloxycarbonylethyl) phenylbenztriazole, 2,2'-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6-benztriazol-2-yl-phenol), transesterification product of 2- (3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxy-phenyl) -benz-triazole with poly ethylene glycol 300; [R-CH ₂ CH ₂ -COO (CH ₂ ) ₃ ] ₂ with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benztriazol-2-ylphenyl.

2.2. 2-hydroxybenzophenones, such as. As the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyl oxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy 4,4'-dimethoxy Derivative.

2.3. Esters of optionally substituted benzoic acids, such as. B. 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylfresorcinol, bis (4-tert-butyl benzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butyl butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3, 5-di-tert-butyl butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2 methyl-4,6-di-tert-butylphenyl ester.  

2.4. Acrylates, such as. B. α-cyano-β, β-diphenylacrylic acid ethyl ester or isooctyl ester, α-Carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxycinnamic acid methyl ester or butyl ester, α-carbomethoxy-p-methoxycinnamic acid methyl ester, N- (β-Carbo methoxy-β-cyanovinyl) -2-methyl-indoline.

2.5. Nickel compounds, such as. B. nickel complexes of 2,2'-thio bis (4- (1,1,3,3-tetra methylbutyl) -phenol), such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, Nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl phosphonic monoalkyl esters, such as methyl or ethyl esters, nickel complexes of Ketoximes, such as 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.

2.6. Sterically hindered amines, such as. Bis (2,2,6,6-tetramethylpiperidyl) sebacate, Bis (2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis (1,2,2,6,6-pentamethylpipe ridyl) ester, condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxy piperidine and succinic acid, condensation product of N, N'-bis- (2,2,6,6-tetramethyl- 4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperi dyl) -1,2,3,4-butantetraoat, 1,1 '- (1,2-ethanediyl) -bis- (3,3,5,5-tetramethyl-thyl-piperazinone), 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) -decane-2,4-dione, bis (1-octyloxy) 2,2,6,6-tetramethylpiperidyl (-sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) - succinate, condensation product of N, N-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa methylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-t-riazine and 1,2-bis- (3-aminopropylamino) ethane, condensation product of 2-chloro-4,6-di- (4-n-butylamino) 1,2,2,6,6-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) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-penta methyl-4-piperidyl) -pyrrolidine-2,5-dione.

2.7. Oxidesäurediamide, such as. 4,4'-dioctyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert butyl oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide,  N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy as well as of o- and p-ethoxy-di-substituted oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazines, such as. B. 2,4,6-tris (2-hydroxy-4-octyloxy phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) - 1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis- (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxy phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- (2-hydroxy-3-butyl oxy-propyloxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine.

3. Metal deactivators, such as. N, N'-diphenyloxalic acid diamide, N-salicylal-N'- salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxy phenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) -oxalic acid hydrazide, oxanilide, isophthalic dihydrazide, sebacic acid bis-phenylhydrazide, N, N'- Diacetyl-adipic acid dihydrazide, N, N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis- salicyloyl thiopropionic dihydrazide.

4. Other phosphites and phosphonites, such as. B. triphenyl phosphite, Diphenylalkylphos phite, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, Tniocta decyl phosphite, 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, bis-isodecyloxy-penta erythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis- (2,4,6-tri-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-dibenz (d, g) -1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl 12-methyldibenz (d, g) -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl 6-methylphenyl) - methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

5. peroxide-destroying compounds, such as. B. esters of β-thio-dipropionic acid, for example example, the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the Zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, Pentaerythritol tetrakis (p-dodecylmercapto) propionate.  

6. polyamide stabilizers, such as. As copper salts in combination with iodides and / or Phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilizers, such as. Melamine, polyvinylpyrrolidone, dicyandiamide, tri allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, Alkali and alkaline earth salts of higher fatty acids, for example Ca-stearate, Zn-stearate, Mg-behenate, Mg-stearate, Na-ricinoleate, K-palmitate, antimony catechinate or tin catecholate.

8. nucleating agents, such as. For example, 4-tert-butylbenzoic acid, adipic acid, Diphenylessig acid.

9. Fillers and reinforcing agents, such as. Calcium carbonate, silicates, glass fibers, Asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Other additives, such as. As plasticizers, lubricants, emulsifiers, pigments, Optical brighteners, flame retardants, antistatic agents, propellants.

11. Benzofuranones or indolinones, such as. In US-A-4,325,863 or US-A-4,338,244 described.  

The compounds according to the invention can also be used as stabilizers especially as light stabilizers for almost all materials, those of the prior art for photographic reproduction or other reproduction techniques are known, such. B. described in Research Disclosure 1990, 31429 (pages 474-480).

There will be various examples of the preparation and use of Oligomers containing the repeating units of formulas (Ia) and (Ib) for a more detailed explanation of the present invention described; these examples are for illustrative purposes only and not for restriction.

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

example 1

20.8 g (0.1 mol) of 2,4-dichloro-6-isopropoxy-1,3,5-triazine, 9.3 g (0.1 mol) Epichlorohydrin, 82.9 g (0.21 mol) of N, N'-bis (2,2,6,6-tetramethyl-4-piperi dyl) -1,6-hexanediamine and 100 ml of 4-methyl-2-pentanol were added for 1 hour Heated to 80 ° C and refluxed for 8 hours, with 12 g (0.3 mol) of NaOH were slowly added during the last 6 hours of the reaction.

After completion of the addition of NaOH, the reaction mixture was added Reflux heated for a further 2 hours. The water of reaction and the main part of 4-methyl-2-pentanol was then distilled off; there were 400 ml of xylene are added and 100 ml of solvent are distilled off slowly, to complete the removal of 4-methyl-2-pentanol.

A mixture containing 21.2 g (0.46 mol) of formic acid and 14.4 g (0.48 mol) methanol-free 30% formaldehyde, was in 3 hours to the so added xylene solution, heated to 110 ° C with simultaneous aceotropic removal of the added water and the water of reaction.

The mixture was cooled to 70 ° C, a solution of 3 g NaOH in 60 ml Water was added and continued for 30 minutes. The watery  Layer was separated and the organic phase washed with water, dried over sodium sulfate and evaporated under reduced pressure.

This resulted in a product that melted at 77 to 85 ° C and paid a price average molecular weight of n = 2800 had.

Example 2

After the procedure described in Example 1 was a compound obtained, which melted at 78 to 88 ° C and a number average Molekularge weight of n = 3800, by reaction of 22.2 g (0.1 mol) of 2-butoxy 4,6-dichloro-1,3,5-triazine, 9.3 g (0.1 mol) of epichlorohydrin and 78.9 g (0.2 Mole) of 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 the amei sensäure / formaldehyde mixture, which was pointed out in Example 1.

Example 3

Following the procedure described in Example 1 was a compound obtained, which melted at 103 to 112 ° C and a number average molecular weight of n = 3500, by reaction of 22.1 g (0.1 mol) of 2,4- Dichloro-6-diethylamino-1,3,5-triazine, 9.3 g (0.1 mol) of epichlorohydrin and 78.9 g (0.2 mol) of 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 referred to in Example 1 has been.

Example 4

After the procedure described in Example 1 was a compound which melted at 110 to 117 ° C and a number average molecular weight of n = 4000 had by reaction of 27.7 g (0.1 mol) of 2,4-di Chloro-6-t-octylamino-1,3,5-triazine, 9.3 g (0.1 mol) of epichlorohydrin and 78.9 g (0.2 mol) of 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 was referred to in Example 1.

Example 5

After the procedure described in Example 1 was a compound  obtained, which melted at 94 to 102 ° C and a number average molecular had a weight of n = 4100, by reaction of 24.7 g (0.1 mol) of 2,4- Dichloro-6-cyclohexylamino-1,3,5-triazine, 18.5 g (0.2 mol) of epichlorohydrin and 118.4 g (0.3 mol) of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexane diamine in 150 ml of 4-methyl-2-pentanol and subsequent methylation in Xylene with a mixture consisting of 31.8 g (0.69 mol) of formic acid and 72.1 g (0.72 mol) of methanol-free 30% formaldehyde.

Example 6

After the procedure described in Example 1 was a compound obtained, which melted at 75 to 84 ° C and a number average Molekularge weight of n = 2200, by reaction of 25 g (0.1 mol) 2,4-dichloro-6- tetrahydrofurfuryloxy-1,3,5-triazine, 9.3 g (0.1 mol) of epichlorohydrin and 88.8 g (0.225 mol) of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanedi amine in 110 ml of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid / formaldehyde mixture referred to in Example 1 has been.

Example 7

Following the procedure described in Example 1 was a compound obtained, which melted at 100 to 103 ° C and a number average molecular had a weight of n = 2000, by reaction of 18.7 g (0.05 mol) of 2,4-di chloro-6- (N- (2,2,6,6-tetramethyl-4-piperidyl) piperazino) -1,3,5-triazi n-, 4.6 g (0.05 mol) of epichlorohydrin and 41.4 g (0.105 mol) of N, N'-bis (2,2,6,6-tetra methyl-4-piperidyl) -1,6-hexanediamine in 75 ml of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid / formaldehyde Mixture referred to in Example 1.

Example 8

After the procedure described in Example 1 was a compound which melted at 105 to 109 ° C and a number average molecular had a weight of n = 3150, by reaction of 11.7 g (0.05 mol) of 2,4-di Chloro-6-morpholino-1,3,5-triazine, 4.6 g (0.05 mol) of epichlorohydrin and 41.4 g (0.005 mol) of 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 referred to in Example 1.  

In the examples, the number average molecular weight was determined by means of a vapor pressure osmometer (®Gonotec), as in EP-A-2 55 990 be wrote.

Example 9

Light stabilizing effect in polypropylene fibers.

2.5 g of each of the products listed in Table 1 and 1 g of tris (- 2,4-di-t-butylphenyl) phosphite, 0.5 g of calcium monoethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 1 g of calcium stearate and 2.5 g of titanium dioxide were mixed in a Langsammischer with 1000 g of polypropylene powder having a melt index of 12 g / 10 minutes (measured at 230 ° C and 2.16 kg). The blends were extruded at 200 to 230 ° C to yield polymer granules which were subsequently converted to fibers using a pilot plant (® Leonard-Sumirago (VA) Italy) operating under the following conditions:
Extruder temperature: 200 to 230 ° C,
Head temperature: 255 to 260 ° C,
Stretch ratio: 1: 3.5,
Fineness: 11 dtex per filament.

The fibers produced in this way were applied to a white one Card, in a weathering gauge (ASTM D2565-85) exposed with a Blackboard temperature of 63 ° C.

The residual tensile strength in the samples, after being exposed to light for different times, was measured using a constant speed strain gauge, and the exposure time in hours (T ₅₀ ) was then calculated, which required half the initial tensile strength has been.

Fibers made under the same conditions as shown above were added, but without the addition of the stabilizer according to the invention, were Comparison exposed.

The results obtained are shown in Table 1.

stabilizer T₅₀ (hours) without 190 Compound of Example 1 2080 Compound of Example 2 1980 Compound of Example 3 2050 Compound of Example 4 2000 Compound of Example 5 1970 Compound of Example 6 2010

Claims (11)

1. Co-oligomer, the recurring units of the formulas (Ia) and (Ib) having a number average molecular weight of 1,000 to 20,000 and a (Ia): (Ib) ratio of 4: 1 to 1: 4, wherein R _{1 is} a group OR ₅ , SR ₅ or wherein R ₅ , R ₆ and R _{7 may be} the same or different, is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C C ₁ -C ₄ -alkyl; C ₃ -C ₁₈ alkenyl, phenyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy; C ₇ -C ₉ phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by C ₁ -C ₄ -alkyl; Tetrahydrofurfuryl, 1,2,2,6,6-pentamethyl-4-piperidyl or C ₂ -C ₄ -alkyl substituted in the 2-, 3- or 4-position by C ₁ -C ₈ -alkoxy, by di (C C ₁ -C ₄ -alkyl) amino or by a group of the formula (II) wherein A is a direct bond, -O-, -CH ₂ -, -CH ₂ CH ₂ - or <N-CH ₃ , or R ₁ is a group of the formula (II) or one of the groups of the formulas (IIIa) - (IIIc) wherein R ₈ is C ₁ -C ₁₈ -alkyl, C ₅ -C ₁₂ -cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ -alkyl; C ₇ -C ₉ phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by C ₁ -C ₄ -alkyl; or 1,2,2,6,6-pentamethyl-4-piperidyl, m is an integer from 2 to 6, n is zero or 1, X is -O- or <N-CH ₃ and R ₉ is as above defined for R ₈ or is hydrogen, R ₂ is defined as for R ₈ or is hydrogen, R ₃ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkylene interrupted by 1, 2 or 3 oxygen atoms or by a group <N-CH ₃ ; C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylene di (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedio (C ₅ -C ₇ cycloalkylene) C ₂ -C ₄ alkylidene di (C ₅ -C ₇ cycloalkylene) or phenylenedimethylene, and R ₄ is C ₂ - C ₁₂ alkylene, C ₄ -C ₁₂ alkylene interrupted by 1, 2 or 3 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C ₂ -C ₁₅ -diacyl, C ₄ -C ₁₅ -dicarbamoyl, a group - (CH ₂ ) _p CO- wherein p is an integer from 1 to 10, or a group -COO R ₁₀ -OOC- wherein R _{10 is} defined as for R ₃ . 2. A co-oligomer comprising repeating units of the formula (Ia) and (Ib) according to claim 1, which has a number-average molecular weight of 1000 to 10,000 and a (Ia): (Ib) ratio of 3: 1 to 1: 3, wherein R _{1 is} a group -OR ₅ , -SR ₅ or wherein R ₅ , R ₆ and R ₇ , which may be the same or different, is hydrogen, C ₁ -C ₁₆ alkyl, C ₅ -C ₈ cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ alkyl; C ₃ -C ₁₂ alkenyl, phenyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; Benzyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by C ₁ -C ₄ -alkyl; Tetrahydrofurfuryl, 1,2,2,6,6-pentamethyl-4-piperidyl or C ₂ -C ₃ -alkyl substituted in the 2 or 3 position by C ₁ -C ₄ -alkoxy, by di (C ₁ -C _4- alkyl) amino or by a group of formula (II) in which A is a direct bond, -O-, -CH ₂ - or - CH ₂ CH ₂ -, or R ₁ is a group of formula (II ) or one of the groups of formulas (IIIa) - (IIIc) wherein R _{8 is} C ₁ -C ₁₂ alkyl, C ₅ -C ₈ cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ - C ₄ alkyl; Benzyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by C ₁ -C ₄ -alkyl; or 1,2,2,6 ', 6-pentamethyl-4-piperidyl, m is 2, 3 or 4, n is zero or 1, X is -O- or <N-CH ₃ and R ₉ is as above R ₈ defines or is hydrogen, R ₂ is as defined above for R ₈ or is hydrogen, R ₃ is C ₂ -C ₁₀ -alkylene, C ₄ -C ₁₀ -alkylene interrupted by 1, 2 or 3 oxygen atoms or by a < N-CH ₃ group; Cyclohylene, cyclohexylenedimethylene, methylenedicyclohexylene, isopropylidene-dicyclohexylene or phenylenedimethylene, and R ₄ is C ₂ -C ₁₀ -alkylene, C ₄ -C ₁₀ -alkylene interrupted by 1, 2 or 3 oxygen atoms; 2-Hydroxytrimethyl, phenylenedimethylene, carbonyl, C ₂ -C ₁₀ -diacyl C ₂ -C ₁₂ -dicarbamoyl, a group - (CH ₂ ) _p CO- wherein p is an integer from 1 to 5, or a group -COO R ₁₀ -OOC- wherein R _{10 is} as defined for R ₃ . 3. Co-oligomer comprising repeating units of the formulas (Ia) and (Ib) according to claim 1 having a number average molecular weight of 1000 to 8000 and a (Ia: (Ib) ratio of 2: 1 to 1: 3, wherein R _{1 is} a group -OR ₅ , SR ₅ or wherein R₅ is C₁-C₁₂ alkyl, cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ alkyl; Allyl, undecenyl, phenyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6-pentamethyl-4-piperidyl, R ₆ and R ₇ , which may be the same or different, are as defined above for R ₅ or Is hydrogen or C ₂ -C ₃ alkyl substituted in the 2- or 3-position by C ₁ -C ₄ alkoxy, by dimethylamino, by diethylamino or by a 4-morpholinyl group, or R ₁ is 4-morpholinyl or one of the groups of formulas (IIIa) - (IIIc) wherein R _{8 is} C ₁ -C ₈ alkyl, cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by C ₁ -C ₄ alkyl; Benzyl or 1,2,2,6,6-pentamethyl-4-piperidyl, m is 2 or 3, n is zero or 1, X is -O- or <N-CH ₃ and R ₉ is as above for R ₈ or is hydrogen, R ₂ is as defined above for R ₈ or is hydrogen, R ₃ is C ₂ -C ₈ -alkylene, C ₆ -C ₁₀ -alkylene interrupted by 2 or 3 oxygen atoms; Cyclohexylenedimethylene, methylenedicyclohexylene or phenylenedimethylene, and R ₄ is C ₂ -C ₈ -alkylene, C ₄ -C ₈ -alkylene interrupted by 1 or 2 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C ₂ -C ₈ -diacyl, C ₄ -C ₁₀ -dicarbamoyl, a group - (CH ₂ ) _p CO- wherein p is 1, 2 or 3 or a group -COO-R ₁₀ -OOC- wherein R _{10 is} as defined for R ₃ . 4. co-oligomer comprising repeating units of formulas (Ia) and (Ib) according to claim 1 having a number average molecular weight of 1500 to 6000 and a (Ia): (Ib) ratio of 2: 1 to 1: 2, wherein R _{1 is} a group -OR ₅ or wherein R _{5 is} C ₁ -C ₈ alkyl, cyclohexyl, allyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6-pentamethyl-4-piperidyl, R ₆ and R _{7 are} the same or different are as defined above for R ₅ or are hydrogen, or R ₁ is 4-morpholinyl or one of the groups of the formulas (IIIa) - (IIIc), wherein R _{8 is} 1,2,2,6,6-pentamethyl-4 -piperidyl, m is 2, n is zero or 1, X is -O- or <N-CH ₃ and R ₉ is hydrogen or 1,2,2,6,6-pentamethyl-4-piperidyl, R ₂ is Hydrogen, methyl or 1,2,2,6,6-pentamethyl-4-piperidyl, R ₃ is C ₂ -C ₆ -alkylene, C ₆ -C ₁₀ -alkylene interrupted by 2 or 3 oxygen atoms; Cyclohexylendimethylene, methylene-dicyclohexylene or phenylenedimethylene and R ₄ is C ₂ -C ₆ -alkylene, 2-hydroxytrimethylene, phenylenedimethylene, C ₂ -C ₆ -diacyl, -CH ₂ CO- or a group -COO-R ₁₀ -OOC- wherein R _{10 has} the meaning C ₄ -C ₆ -alkylene. 5. co-oligomer comprising repeating units of the formulas (Ia) and (Ib) according to claim 1 having a number average molecular weight of 2,000 to 5,000 and a (Ia): (Ib) ratio of 1: 1 to 1: 2, wherein R _{1 is} a group -OR ₅ or in which R _{5 has} the meaning C ₁ -C ₄ -alkyl or tetrahydrofurfuryl, R ₆ and R ₇ which may be identical or different are C ₁ -C ₈ -alkyl, cyclohexyl or 1,2,2,6,6- Pentamethyl-4-piperidyl, or R ₆ may also be hydrogen, or R ₁ is 4-morpholinyl or a group of formula (IIIa) 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 ) _2-4 -O- (CH ₂ ) ₃ - and R ₄ is 2- hydroxytrimethylene. 6. Composition containing an organic material that is resistant to a is susceptible to degradation caused by light, heat and oxidation, and at least one co-oligomer, the recurring units of the formula (Ia) and (Ib) according to claim 1. 7, A composition according to claim 6, wherein the organic material is a synthetic polymer is. 8. The composition of claim 7, the other conventional additives for syn Thetic polymers contain, in addition to the co-oligomers, again containing repeating units of the formulas (Ia) and (Ib). A composition according to claim 6, wherein the organic material is a Polyolefin is. 10. The composition of claim 6, wherein the organic material is poly ethylene or polypropylene. 11. Use of a co-oligomer, the recurring units of Formulas (Ia) and (Ib) according to claim 1 for stabilizing a organic material caused by light, heat and oxidation mining.