CZ126296A3 - Amorphous and crystalline modifications of 1, 1°, 1°°-nitrilo{tri-2-propyl-tris£2,2°-ethylidenebis(4,6-ditert-butylphenyl)| phosphite, process of their preparation and their use for stabilizing organic materials - Google Patents

Abstract

A cpd. 1,1'-1"-nitrilo (tri-2-propyl-tris(2,2'-ethylidene-bis (4,6-di-tert.-butylphenyl)) phosphite of formula (I) is new. The cpd. has a glass transition temp. (Tg) of 137-142 deg C. (DSC) and an X-ray diffraction pattern which is featureless. The prepn. of the amorphous form of (I) involves heating a melt of (I) and rapidly cooling. A compsn. with stability against thermal, oxidn. and actinic-induced degradation comprises an organic material subjected to degradation and an effective stabilising amt. of (I).

Description

SUMMARY OF THE INVENTION

It has now been found that the compound of formula I can be obtained in an amorphous and different crystalline modification that exhibits acceptable handling, apparent density, flowability, measurability, storage stability, stability against hydrolysis and improved migration to polymeric substrates.

The new amorphous form is characterized by a glass transition temperature (I) in the range. 1.37-142 ° C, does not. no endo.t.ermní. the peak melts above a temperature of < 142. > C to 200 < 0 > C as determined by differential, scaling calorimetry. In addition, the amorphous form of the present invention exhibits a poor diffraction pattern obtained by X-ray diffractometry. .za, co-existence of Cu-Kci.

The new crystalline modification is characterized by a melting point in the range 254. -2-4 ° C as determined by the temperature peak of the endotherm obtained by differential scanning calorimetry (DSC) and by the diffraction pattern obtained by X-ray diffractometry using Cu-Κα, very high intensity diffraction angles (2Θ) at 7.9 and 15.6, high intensity lines at ', 3, 8.9, 14.7,' 16. ', 8, 13.3, 18.9, 19.8 and 20.6, medium intensity lines at 13.9, 22.6 and 24.0, and a low intensity line at 21.4.

The invention relates to a modification of the sulfone of said compound

Of interest is the compound of the formula

r in the formula: a process for the preparation of a novel amorphous 2 which comprises melting a rapid cooling of the melt.

the true new amorphous modification involves pouring molten material onto a cold surface maintained by a pcd temperature of 100 cC, particularly close to 25 C. C.

The invention also relates to a process for preparing a novel crystalline modification of a compound of formula I which comprises heating the melt of said compound of formula I to a temperature in the range of 170 to 200 ° C and crystallizing the new crystalline modification.

Of interest is a process for preparing a new crystalline modification of a compound of formula I which comprises seeding the melt with a new crystalline form in order to increase the rate and efficiency of melt crystallization.

Especially interesting is the way preparation new crystals lucké modification of the compound formula I, oři kte rhem melts 3 Π 2_ P. 3. heats at reduced pressure cd 53329? A to 13.33 ? a a blood melting; ny se pro v row in sx z ruder (dreams kovém

extrusion machines) or kneading machines. \

The new amorphous and new crystalline modification with the formula vhodná is suitable for stabilizing organic materials by oxidative, thermal or light-induced blowing.

illustrative examples of such materials include:

1. Polymers of mono-olefins and diolefins, for example polypropylene, polyisobutylene, co-1-butene, poly-4-ethyl-1-pentene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example cycloocene or no menu or polyethylene (optionally crosslinked) , for example high density polyethylene (NM0?,), high density high molecular weight polyethylene (H2P2-NMW. '), high density very high molecular weight (low density oolvethlene (M0? E), low;

µJpn-UHMW), medium-grade oolvethlene, D? S}, linear low-density polyethylene (ILDPEk, low density polyethylene (BLDPE)).

The polyolefins, i.e. the polymers of monoolefins, examples of which are given in the previous paragraph, in particular polyethylene and polypropylene, can be prepared in various ways, in particular using the following procedures:

(a) radical polymerization (usually at high pressure and elevated temperature),

(b) catalytic polymerization using a catalyst which typically contains one or more of Group IVb, Vb, VIb or VIII metals of the Periodic Table. These metals typically have one or more ligands, such as typically oxides, halides, and alkoxides. esters, ethers, amines, alkyls / alkenyls and / or aryls; which 'can be either' or 'coordinated'. These metal complexes may be in free form or fixed on substrates, typically on activated magnesium chloride, titanium chloride, alumina, or the like. The catalysts may be soluble or insoluble in the polymerization medium. polymerization used as.

such or other activators may be used, such as typically metal alkyls, metal hydrides, alkyl alkyl metal halides, metal alkyl oxides or metal alkyls,

La,

IIa and / or IIIa metals are elements of the periodic table groups. These activators may conveniently be modified. Other ester, ether, amine or silyl ether systems are typically Phillips, Standard CII (DuPont), detailed with xuomamer. labeled Indiana, I

These are catalytic catalysts (-Matta), Thi reorer catalysts or catalysts

SSC (single site catalysts!).

2. Mixtures of polymers of said mixtures of polypropylene with olyisobutylene; and polyethylene (for example ?? / Η2ΡΞ, PS / 12ΡΞ; and mixtures

Different types of polyethylene (eg LD? £ / KD? £)

3. Copolymers of polyolefins and diolefins between themselves or with other vinyl monomers, for example ethylene-propylene copolymers, linear low density polyethylene (LLD?) And mixtures thereof with low density polyethylene (LD? S), copolymers of propylene and 1-butene, copolymers of propylene and isobutylene, copolymers of ethylene and 1-butene, copolymers of ethylene and hexane, copolymers of ethylene and methylpentene, copolymers of ethylene and heptene, copolymers of ethylene and octene, copolymers of propylene and butadiene, copolymers of isobutylene and isoprene, copolymers of ethylene and ethylene ethylene and alkyl methacrylate, copolymers of ethylene and vinyl acetate and copolymers thereof with carbon monoxide, or copolymers of ethylene and acrylic acid and their salts; terpolymers of ethylene with propylene and mucus; polypropylene and ethylene with propylene, copolymers LC2 and ethylene with vinyl acetate (ZVA), copolymers of LD9Z and ethylene with acrylic acid (ΞΑΑ ;, LiD? £ / ZVA., ZLD9Z / ΞΑΑ), and alternating or random copolymers of polyalkylene and carbon monoxide and mixtures thereof with other polymers such as polyamides.

(ioncomers) as well as ye nexadiene,

4. hydrocarbon resins (for example from 5 to 9 carbon monomers), including hydrogenated modifications thereof (for example, adhesives for the preparation of adhesives) and mixtures of polyalkylenes and starch.

5, 10-oystyrene, poly (p-methystyrene), poles (α-methylstyrene).

6. Kopc-iyme: acetylene, acetylenes, dlen / alkyl acres of diene or cis-methyisyrene with dyes or styrene / butadiene, styrene / akyl methacrylate, styrene / butastyrene (butadiene) aikyi methacrylate,

- styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate, high impact strength mixtures of copolymers of styrene and another polymer, for example polyacrylate, palm polymer or ethylene / propylene / ethylene terpolymer, and styrene block copolymers 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 copolymer or on polybutadiene / acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene, styrene, acrylonitrile and methyl; and anhydride. maleic acid on polybutadiene, styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene, styrene and maleimide on polybutadiene, styrene and alkyl acrylates or methacrylate. ocivbutadiene, hardened and acrylonitrile. on terpolymers. ethylene / propylene / ethylene, styrene and acrylonitrile. styrene and acrylonitrile, as well as mixtures thereof on acrylate / butadiene copolymers, with the copolymers referred to in paragraph 6, for example mixtures of the polymers known as A3S, MBS, ASA or ΑΞ3 polymers,

8. Halogen-containing polymers such as polychloroprene, black rubber, chlorinated and bulk copolymer of isobutviene and isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene; Sulfuric acid, e.g., 1-adcclyvinyichicride, pvinylviridenchicride, polyvinyitiucride, polyvinylidene fluoride. as well as copolymers thereof, such as copolymers of vinyl chloride and vinylidene dichloride, vinyl chloride and vinyl acetate or vinyl chloride and vinyl acetate.

5. Polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates, polymethyl methacrylates, polyacrylamides and polyacrylonitriles, the impact strength of which is modified with butyl acrylate.

10. Copolymers of the monomers referred to in paragraph 9 with each other or with other unsaturated monomers, for example acrylonitrile and butadiene copolymers, acrylonitrile and alkyl acrylate copolymers, acrylonitrile and alkoxyvalkylacrylate copolymers, acrylonitrile and vinyl halide acrylate and methacrylate copolymers, terpolymer acrylate .

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

benzcases, polyvinylamine maleate, polyvinyl butyral, polyphthalic phthalate or polyphenylamine, and their copolymers with the olefins mentioned in paragraph 1 above.

12. Copolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polyprocylene oxide or copolymers thereof with diglycidyl ethers.

12. Polyacids such as polyoxymethylene, as well as those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetylenes modified with thermoplastic polyurethanes, acrylates or 13S.

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

? * 3 *

-i Sř15. Polyurethanes derived from hydroxyls; polyimethers, polyesters or polymers of polyisocyanates having their cursors.

- Γι ’* 3

15. Polyamides and copolyamides derived from diamine and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lazams, for example polyamide 4, by means of polyamides.

6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides formed from m-xylene, diamine and adipic acid, polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acids and optionally with an elastomer as modifying agent, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyl-

Fen-isophthalamide, and also shotgun cooolymervs mentioned above - '' '5. polyamides with polyol olefins, copolymers of olefins, ionomers or chemically bound or grafted eiastomers, or p

polyethers, for example with polyethylene glycol, polyprocylene glycol or polytetramethylene glycol, as well as polyamides or cooolyamides modified with EPDM or AS5, and polyamides condensed during processing (RIM polyamide systems).

17 .. Polymočcvi polyimides; polyamide-imides, polyether 'Imides, polyester-ir :ides, colyhydantoins and polybenzimidazoles. 13 . Polyester; r derived from dicarboxylic acids a diols and / or from hy: of hydroxycarboxylic acids or ..ajících. lactones ,. r * .Example *. pol.ys.thyien-terett-aiée, · pol-y ----- · - · - -...... butylene terephthalate po 1 y- i, 4 · - dime t n y io i c y kl o he x an-1 e re fz a i á t ' and polyhydroxybenzenes and block copolyezner esters derived from polyeth hydroxyl-terminated ers; and Polyester mod: "Polycarbonate or MBS".

19. Polycarbonates and polyester carbonates

20. Polysulfor .alpha.,. beta.-ether sulfones and colezether ketones. - - 21. Cross-linked polymers derived from aldehydes and / both from phenols, - ureas and - melami. formaldahydcvé prys) resins, urea-formaldehyde resins

and melamine-formaldehyde resins.

22. Absorbent and non-absorbent alvd squashes.

23. Unsaturated Polyester resins derived from copolyesters saturo and unsaturated dicarboxylates polyhydric acids; Alcohols and vinyl compounds such as

crosslinking agents, as well as their Cszk; containing modifications.

flammable halogen

24. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates.

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

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic giycidyl compounds, for example the product of diglycidyl ethers of bisphenol ?. and bisphenol Έ, which are crosslinked by conventional _λ

.... ....... ...,,. account for boiling prisacam, yaxo are anr.ycricy something amines, in the presence or absence of accelerators.

27. Natural rubber and polymers such as cellulose, mud and their chemically modified homologous derivatives, for example, cellulose acetates, cellulose butyrates, or cellulose ethers, cellulose, as well as natural resins and their derivatives, natural

Al · z o ρ i n a t y cellulose and ^: r y, like is methyl- " .CD ejich der 2_ 5. c, y.

ipclybiends), specifying a radius for example ??? / EPCM, polyamide / EPCM or A33, PVC / EVA, PVC / A3S, PVC / MBS, PC / ABS, P3T? / ABS, PC / ASA, PC / PBC, PVC / CPE, PVC / acrylic, PGM / thermoplastic PC?, PC / thermoplastic PUP, PGM / acrylate, PGM t MBS, PPG i / HIPS, PPG / PA 6 , 5 and cocolymers, PA / HOPE, / PPG, PST / PC / ABS or P3C / PET / PC.

23. Mixtures

PP / PP, PA /? G * / ** τ <p., · * C With materials that are pure monome: mixtures of such compounds, animal and vegetable fat, c * w and wax at the ointment of the world. , or oleic, fat, and aarpate, including a non-esters with a molar; ratios (e.g. mixtures, as well as aqueous trimellitates) and also mixtures of synthetic oils in any weight that are used as a spinning emulsion of such materials.

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

31. Polysiloxa and polysiloxanes disclosed in U.S. Patent 4,259, for example, in a patent such as soft hydrophilic, for example, in U.S. Patent 467, and hard polyorganosiloxanes described in United States Patent 4,355,147.

32. Cetyl ketimines in combination with unsaturated acrylic γ-γ and γ-γ-γ-γ-γ-γ-γ. acrylic resins: include urethane-acrylic; acrylic copolymers, non-laminated, with resins. or unsaturated.

; emi. The unsaturated acrylic resins [alpha] - [gamma], polyether acrylates, vinyl or with unsaturated scoins and ketones for the clarity of the ketones are prepared from polyamines. and i. an acid catalyst.

33. A radiation curable composition comprising ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic cligomer.

34. Polyme melarin resins such as light stable epoxy resins crosslinked with epoxy functional b

an epoxy functional coetherified high solids melamine resin such as' LSI'-4I03 (Monsanto) '.'

Included in the ..

The invention also relates to compositions wherein the organic material subject to exidative, thermal or light-induced degradation and lb) an effective stabilizing amount of an amorphous or crystalline modification of a compound of formula I, wherein the amorphous modification is characterized by a glass transition temperature (Τ _τ ) 137-142 ^e C '(as determined by differential scanning calorimetry (DSC)) and am notable by the diffraction pattern obtained by X-ray diffractometry, and the crystalline modification is characterized by a melting point in the range of 254-274 ° C. and a diffraction pattern obtained by X-ray diffractometry using Cu-Xa, which exhibits very high intensity diffraction angles (2Θ) at 7.9 and 15.6, high intensity lines at 7.3,

8.9, 14.7, 16.8, 18.3, 18.9, 19.8 and 20.6, medium intensity lines at 13.9, 22.6 and 24.0, and a weak intensity line at 21.4.

Preferably, the organic materials to be protected are ^1, o is a natural, poiosyntetické or preferably synthetic polymers. Particularly preferred are thermoplastic polymers, especially polyolefins, most preferably polyethylene and polypropylene.

A preferred organic material is also a lubricant, lubricating oil, natural fat or wax, or a synthetic ester grease or wax.

In particular, the action of the novel compounds against thermal and oxidative degradation, in particular when exposed to heat, as in the case of thermoplastic processing, thus the compounds are very suitable for use as stabilizers in the processing of ouoenma an, v: 025 z no s t

Preferably, the amorphous and crystalline modification s1 of the formula 'is added to the material to be sufficient from 0.01 to 5%, typically 0.01 to 3%, preferably up to 3%, even more preferably 0.05 to 1%, based on organicxeno matena.v, xa.ma tyt staom;

In addition to the compounds of Formula 1, the novel compositions may contain other co-stabilizers, such as typically the following:

1. Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,5-dimethylphenol, 2,6-di-tert. butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylenenol,

2,6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,5-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6- tricyclic oxyphenol, 2,6-di-tert. butyl-4-methoxymethylphenol, nonyl solvates which are linear or branched in the side chains, for example

2,6-dinonyl-4-methylphenol, 2,4-dimethyl-S- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-δ- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-rethyltridec-1'-yl) phenol and mixtures thereof.

1.2., .Alpha.-alkylthiorsylphenols, e.g. 2 ', 4-dioctylthiomethyl-6-tert-butylphenol, 2,1'-dioctylthiomechyl-o-methylphenol / 2,4-dioctylthiomethyl-6-ethylphenyl, 2,6-didodecylthiomethyl- 4-nonylpheno1.

1.3. Hydroquinones and alkylated hydroquinones, for example

2,6-di-tert-butyl-1-methoxycarbonyl, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydrinquinone, 2,5-diphenyl-4-ocradecvloxyphenol, 2,6-di-tert-butylhydricquinone, 2,5-di-tert. butyl-4-hydroxyanisole, 3,5-di-tert-butyl-1-hydroxyarisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipo.

. 1.4. Tocopherols, for example α-tocopherol, β-cocofsrol, γ-tocopherol, δ-tocopherol and mixtures thereof (vicamin · E);

1.5. Hydroxylated chiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-rechylphenyl, 2,2,2'-thiofcis Uypktylyphenol), 4,4'-thiocis; 6-1 (tert-butyl-3-methylphenol), -4,4'-thiobis (6-tert-butyl-2-reonylphenyl, 4,4'-chicbis-3,6-disecamylphenol), 4,4'-bis-2,6-dimethyl-4- hydroxyphenylidisul13.

1.5. Alkylidsbisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylsulfonyl), 2,2'-methylenebis (6-tert-butyl-4-ethylene), 2,2'-methylenebis-4-methyl-5- (α-methylcyclohexyl} reapers], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol),

2,2 '-methyienbis! s-nonyl-4-methylphenol), 2,2'-methylenebis (4,4'-di-tert-butylene), 2,2'-ethyidenebis (4,4'-di-tert-butylphenol), 2,2'-ethylidene (5-tert-butyl-4-isobutylenenol),

2,2'-methylenebis [5- (α-methylbenzyl) -4-nitzeno], 2,2'-methylenebis [5- (α, α-dimethylbenzyl) -4-nonyzeno], 4,4'-methylenebist2 , o-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenylhutyl), 2,5- bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methyl-phenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) buzene, 1,1-bis5 tert -butyl-4-hydroxy-2-methylphenyl-3-n-dodecylaminoctactobutane, ethylenegycyl-b5,3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3 tert-butyl-4- (1-hydroxy-5-methylphenyl) dicyclocentadiene, bis (2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-d-methylphenyl) 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-dimethyl-2-hydroxyphenyl) butane, 1,4-bis (3,5-dimethyl-2-hydroxyphenyl) butane ·

1-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaputobutane, 1,1,3,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) centane.

1.7. 0-,

5-benzyl compounds, for example

3,5,3- ', 3'-tetratercylbutyl-4,4'-dihydropyloxydibenzyl.ther, octadecyl-1-ydroxy-5,3-dimethylethylbenzyl-4,4'-dihydropyloxydibenzyl.

-4-hydroxy-3,5-di-tert-butylbenzyl mercaptacetate,

dihydro-4-hydroxybenzyl amine diers,. bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithicetherate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hyeroxybenzemercetecacetate .

tridecyltris (3,5-chloro-1, decyl) hydroxybenzylated malonates, for example, dicta-tert-butyl-2-pyridylbenzylacetate, caoctate and tert-butyl-4-hydroxy-5- methylbenzyl) malonase, dido14.

decylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate; bis [4- (1,1,2,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4- hydroxybenzyl) -2,3,5,6-cetramethyibenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy1.10) Triazine compounds, for example 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyimercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5 -oriazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,4-tris- {3,5- di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-1-hydroxyxysyl) isocyanurate, 3,5-tris (4-tert-butyl-3-hydroxy-2,5-dimethyibenzyl) isocyanurate; 2,4,6-tris (3,5-di-4-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris, 3,5-ditro. B. ut.y.1 r.4. = hy.dro.x.yřelip.rop-ionyl.) - hexah-ydro-i -, - 3 ·, -5 -...

(3,5-Dicyclohexyl-4-hydroxybenzyl) iso -1,3,5-.

kvanurát.

'1.11. Sensylphosphonates, for example dimethyl-2,5,5-di-tert-butyl-4-hydroxylene-4-hydroxyphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl tert-butyl 4-hydroxy-3-methylbenzylphosphonate, the calcium salt of 3,5-di-monoethyl ester. butyl-4-hydroxybenzylphosphonic acid.

1.12. Phenols, for example 4-hydroxyiauraniid,

4-Hydroxyearania, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate. ...... .......... .......... .., ........... 1,1 'picn for example ok ~ adekar ·

Β- (3,5-di-butyl-4-hydroxyphenyl) prosines 5 with monohydric or polyhydric alcohols, methanol, ethanol, n-ocaneate, isoctanoic acid, m, 1,1'-hexanedioic acid, , 9-nonanediol, ethylene 15 glycol, 1,2-propanediol, neopentyl glycol, thiodihyleneglycol, diethylene glycol, triethylene glycol, pentaerythritium, tris (hydroxyethyl) isocyanurate, Ν, Ν'-cis (hydroxyethyl) oxamide, 3-thiaadium, 3-thiaadium trimethylhexanediol, trimethylolpropane, 1,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.14. Β - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid esters with monovalent or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, peotaerythritol, tris (hydroxyethyl) isocyanurate, Μ, Μ'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, trimethylol, trimethylol, 3-thiapentane

4-Hydroxymethyl-1-furo-2,6,7-trioxabicyclo [2.2.2] ckta:

m, ”« 3 ’|

1.15. Esters of β- (3,5-dicyclonexyl-4-hydroxyphenyl) propionic acid with monovalent or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol,

1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thicdiethylsilyl glycol, diethylene glycol, triethylene glycol, pentaerythritium, tris (hydroxyethyl) isocyanurate, Μ, Ν'-bis (hydroxyethyl} oxamide thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, J-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.16. Esters of 3,5-difluorobutyl-4-hydroxyphenylacetic acid with monovalent nonalcoholic alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol , thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritium, tris (hydroxyethyl 'isocyanurate, Ν, N'-bis (hydroxyethyl) oxamide, β-tetraunuexa);

r d

nolem, 3-thiapentadecarciem, trimethylhexanediol, methylolproppan, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17. Β- (3,5-di-tert-butyl-4-hydroxyphenyl) amides for pionic acids, for example Ν, Ν'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, Ν, N'-bis (3 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, Ν, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

1.13. Ascorbic acid (vitamin C).

1.19. Amine-based antioxidants such as N, N'-di. isopropyl-p-phenylenediamine, Ν, Ν'-dis-butyl-p-phenylenediamine Ν, Ν'-bis (1,4-dimethyipentyl) -p-phenylenediamine, Ν, Ν'-bis (1-ethyl-3-methylpentyl) 1'-p-phenylenediamine, 'Ν, N'-bis' (1-methyl-1'-hephyl) -p-phenylenediamine; Ν, N'-dicyclchexyl-p-phenylenediamine Ν, N'-diphenyl-p-phenylenediamine, Ν, N'-bis-2-naphthyl) -o-phenylene diamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-Dimethylbutyl) -4'-phenyl-p-phenylenediamine, N- (1-methylsulfonyl) -1'-phenyl-p-phenylenediamine, N-cyclionexyl-N * -phenyl-c- phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine,. Ν, N'-dimeryl-N, N'-disks. butyl-p-phenylenediamine; ‘Di.phenyl amine,. N-α-yldienyl amine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. ρ, p ' di-tert-octyidiphenylamine 4-n-butylaminophenol, 4-butyrylaminophen, 4-pentaminoamino phenol ,. 4-dcdecanoylaminophenol, 4-octadecanoylaminophenol, cis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl phenol. 2,4'-diaminodiphenylmethane, 4 ', 4'-diaminodiphenylmethane Ν, Ν, N', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) aminojeman, 1,2- bis (phenylamino) propane, (o-tolyl) biguanide, bis (4-: 1 ', 3'-dimethylbutyl: phenyl) amine, tertiocylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated: tert-butyl / tert-octylciphenylamines, a mixture of mono- and dlalkylated nonyldiphenylamines, a mixture of mono- and dialkylated dcdecyl diphenylamines, a mixture of mono- and di-alkylated isocropyl-osohexyl diphenylamines, a mixture of mono- and di-alkylated 2-tert-butylated. 3-dihydro-3,3-dimethyl-4 H -1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and diaylated tert-octylphenothiazines, N-allylphenethiazine, N, N, N ', N'-tetrafsnyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylciperid-4-yl) hexamethylenediamine, bis (2,2, 6-tetramethylciperid-4-yl) 5,6-tetramethylpiperid-4-yl) sebacate,

2,2,6,6-t = framethylpiperidin-4-one, 2,2,6,0-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilizers

2.1. 2- (2'-hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2- (3 ', 5'-di-butyl-2'-hydroxyphenyl) benzotriazole ,, 2- (5 2'-tert-butyl-2'-hydroxyphenyl} benzofriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl; benzotriazole, 2- (3', 5 ' 2- (3'-tert-butyl-2'-hydroxy-5'-methyl-phenyl) -3-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-phenyl) -5-chicrbenzotriazole; sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (35'-di-tert-amyl-2'-hydroxyphenyl) - z benzotriazole, 2-) 3 ', 5'-bis (α, α-dimethylienzyl) -2'-hydroxy-phenyl) benzotriazole, a mixture of 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-octyloxycarbonylezyl) phenyl) -5-chlorobenzotriazole;

tert -Butyl-5 [2- (2-methylhexyioxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylephenyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 (2-methoxycarbonylethyl) phenyl) benzothiazole, 2- (3'-tert-butyl-2'-hydroxy-5 2- (3'-tert-butyl-5 '- (2- (2-ethylhexyloxy) carbonylethyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-dceryl) - (2-octyloxycarbonylethyl; phenyl) benzotriazole; 2'-hydroxy-3'-methiphenyl-4'-benzofriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isoocthoxycarbonylvethyl) phenyl) benzotriazole, hibutyl-1' -;

2,2'-methylene-bis (4- (1,1,3,3-tetamethylethyl) -ethoxy-α, β-mephenoxy

crocuxf transestenr (carbonyl) -2 '-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol. 300, a compound of formula [R-CH.CH.-COO (CH3), wherein R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2.2. 2-hydroxybenzophenones, for example 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy -4,4'-dimethoxy derivatives of 2-hydroxybenzophenone.

2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl-resorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoyl-resorcinol, 2,4-di-tert-butylphenyl -3,5-di-tert-butyl-4-hydroxybenzoate, hexade3

S-r 7 - Z - '' mih v _ _ / 1 -½ τ.νϊ mv: 7 ·· · - - l J i L ·, f terc'.buryl-4-hyroxxybenzcét ', ·. 2-methyl-1, β-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate

2.4.

rso * carbonyl;

Acrylates, for example ethyl-α-cyan-β, β-diphenyl Dktyl-α-cyan-β, β-diphenylacrylase. . methyl .alpha.-mesnamate; methyl-1-cyano-4-methyl-p-methoxycinnamic acid, 7-methyl-β-methyl-β-methylamino-β-methoxycinnamate, methyl. α-methoxycarbonyl-p-methoxycinnamate and N- (β-mechycarbonyl-β-cyanvinyl) -2-mechylindoline.

2.5. Nickel compounds, for example, nickel complexes with 2,2'-tin-bis [4- (1,1,3,3-tetramethynylbutyl) phenol] such as a 1: 1 or 1: 2 complex, optionally with other ligands such as n-butylamine, triethanolamine or amine, nickel dibucyldithiocarbamate, 4-hydroxy-3,5-di-tert-butylbutyl esters: for example with its methyl ester, or

N-cyclohexyidiethanation of nickel with monoalzyiphosphonic acid,

Ξ1Ω '/ LSS t Θ Γ ΓΓί _of 3'<C 2_ ICC ^Λ XV nickel-s .. kecoximy, apříkiad -.- S- hydroxy-2-.4--methylfenul undecylkstoximem, nickel complexes of 1-phenyl-4- lauroyl-5-hyd pyrazole, optionally with other ligands.

orange amines, for example, brs (2,2,6,6-tetramechyl-4-piperidyl) sebacic acid, bis ', 2, 2, 6, 6 -1 e' frames o h v i xv15

4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetranethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-Pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piceridyl) hexamethylenedianine and 4-tert-octylanino-2, c-dichior-1, 3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- butane tetracarboxylate, 1,1'- 1,2 1,2-ethanedi-bis (3,3,5,5-tetraraethylpiperazinone), 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-1,3,3-triazaspiro-4,5,5-decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy -2,2,6,6-tetramethylpiper idylsuccinate, condensation product produkt, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholin-2,6-diohloro-1,3,5-triazine, condensation product 2-chicr -4,6-di (4-n-butylamino-2,2,6,6-tramethyl). hylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aninopropylaminoaminethane), the condensation product of 2-ohior-4,6-di (4-n-butylamino-1,2,2,6, c-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-amincpropylamino) ethane, 3-acezyl-3-dcecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4, 5] deca-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1, 2, 3, 4, 3, 4, 3, 4, 5, 6, 7); 2,2,6,6-pentamezhyl-4-piperidyl) pyrrolidin-2,5-dione, 4-hexadeoyloxy- and 4-stearyioxy-2,2, c, 6-tetramethylpiperidine, condensation product W, '- bis { 2,2,5,5-zetramethyl-4-piperidyl) hexamethylenedianine and 4-cyclohexylamino-2, 6-dichloro-1 / 3,5-triazine, the condensation product 1,2-bis (3-aminopropylamino) ethane and 2, 4,6-trichior-1,3,5-triazine as well as 4-butylamino-2,2,5,6-tetramethyioiperidine (CA3 Registration Number [136224-96-6]), (2, 2, 6 6-tetramethyl-4-ciceridyl) -n-dodeoylsuccinimide, 1 ', 1', 2 ', 2', 6 ', 6'-pentylmethyl-n-dodecylsuccinimide, 2-undecyl-7,7,9, 9-tetramethyl-1-oxa-3,3-diaza-4-oxosulfur [4,5] dia kan, reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,3-diaza-4-oxospiro [4,5] decane and ecichlorohydrin.

2.7. Oxamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butxanilide 2-ethoxy-2'-ethyloxanilide, Μ, N'-bis (3-dinethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanide and its mixture with 2-ethoxy-2'-ethyl -5,4'-di-tert-butoxanilide, and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of crtho- and para-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-dimethylthiphenyl) -1,3,5-triazine, 2,4-bis. -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-dodecyloxyisnyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,5-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyioxypropylpyioxy) phenyl] -4,6-bis (2,4-dimethyl) - 1,3,5-triazine, 2- [4- (dcdecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,5-bis [2,4-dimethylphenyl] -1,3,5-triazine, 2 - [2-hydroxy-4- (2-hydroxy-3-dodecyloxyprocoxy) phenyl] -4,10-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, yl) -4,6-diphenyl-1,3,5-triazine,

butoxy-2-hydroxypropoxy; phenyl] -1,3,5-triazine, phenyl) -4-'-4-methoxyphenyl-6-phenyl-1,3,5-triazine

2- (2-hydroxy-4-methoxyphenyl) -4,6,6-tris [2-hydroxy-4- {32- [2-hydroxy3] metal reactivators, for example N, N'-diphenyioxamide, 54-acetyl-N - saazzvio-nzrazm, 1, H-isois (sulfonyl) - hydrazine, Ν ', Ν'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyioylamino-1,2,4- triazole, bis (benzylidene) oxaiyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl- bisphenylhydrazide, Ν, Ν'-diacetyladipoyl dihydrazide, N, N'-bis (salicylcyl) oxaiyl dihydrazide (N, N'-bis) salicylovl) thiopropionyl dinidraz id.

4. Phosphates and phosphonites; for example triphenyl phosphite, diphenyl-alkyl-phosphites, phenyl-dialkyl-phosphites, tris (nonylphenyl) -phosphite, trilauryl-phosphite, trioctadecyl-phosphite, distearyl-pentaerythritol-a-phosphite, tris (2,4-di-tert-butylphenyl) -phosphite , diisodecyl-pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl)} -pentaerythritol diphosphite, his (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite, diisodeoyioxypentaerythritol diphosphite, bis (2 , 4-di-tert-butyl-6-methylphenyl) pencaryeryrityl-dizesite, _and bis (2,4, c-frityl-butylphenyl) -pentaerythrityl-diphosphite, triszearyl-sorbitol-trisecrif, tetrakis (2,4-ditercibutyl-phenyl) -4 4'-biphenyien-diphosphonitrile, c-isooctyl-oxy-2,3,3,10-tetrater-butyl-12K-dibenzoide, g] -1,3,2-dioxaphosphincin, 5-fluoro-2,4,3,10 -tetrafer-butyl-12-methyl-dibenzyl) d] g -1,3,2-dioxaphosphcoin, bis (2,4-di-tert-butyl-c-methylphenyl) methylphosphite, cis (2,4-di-tert-butyl) (c-methylphenyl) ethylphosphite.

5. Hydroxyamines such as N, N-dibenzylhydroxyamine,

N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-di-laurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecadecylamine heptadecyl-N-octadecylhydrolamine, Ν, Ν-dialkylhydroxyamines, based on hydrogenated tallow amines,

6. Nifrons, for example, N-benzyl-alpha-phenylnitrone, N-ef-hyaline, α-meth-hyinitrone, N-octyl-alpha-hepphylinone, N-auryi-aif and undecyinitrone, N-tetradecyl-aifa- tridecyirone, N-hexadecyl-aifa-centadecyinitrone, Nc-kt adecyl-ait α-heptadeoyinitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-22-alpha-pentadecylnitrone, N-heptadecylnitrone N-octadecyl-.alpha.-hexadecylnitrone, nitrons derived from N-dialkylhydroxylamines produced from hydrogenated tallow amines.

7. Synergistic thio-containing additives, for example dilauryl thiodiproionate or distearyl thiodipropionate.

Peroxide-destroying compounds, for example, β-thiodipropionic acid estrogen, for example its lauryl stearyl ester, myristyl ester or tridecyl ester, mercap benzimidazole or zinc 2-mercaptobenzimidazole dibutyldithiocarbamate zinc di-tetadecyl disulfide diphosphate disulfide, dioctadecyl disulfide diphosphate disulfide.

5. Polyamide stabilizers, for example, sword salts in combination with iodides or phosphorus compounds and with divalent manganese. .

10. Sazic co-stabilizers, for example, melamine, lyyinyipyrrolidone, ureas, zinc alkaline earth metal salts of higher alkaline earth salts, sodium behenate and palmitate dicyandiamide. tr ia 1 lyl ·. ^- cyanurac ,. derivatives of hydrazine, amines, polyamides, alkali metal polyururetic acids and, for example, calcium stearate, magnesium stearate, magnesium stearate, potassium ricinol, antimony pyrocatecholate, or tin pyrocatechacetate.

Nucleating agents, for example inorganic substances such as talc, metal oxides such as, - titanium dioxide or magnesium oxide, - phosphates, carbonates or sulphates are preferred for alkaline earth, organic compounds as the mono-polycarboxylic acid axis and their salts, for example

4-Butylbenzoic acid, adipic acid, 11ΈΓ acetic acid, rium succinate or sodium benzoate, peiyne compounds such as copolymers containing c:

(ionomers).

12. Fillers and reinforcing agents, for example carbonate calcium, silicas those glass fibers, glass marbles, asbestos, talc, kaolin, mica, sulfate barbed, oxides and hydroxides metals, soot, graphite, sawdust and fibers of others

natural products, synthetic fibers.

13. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, organic additives, catalysts, flow control agents, fluorescent whitening agents, flame retardants, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, such as those described in US-A-5 175 312, DE-A-4 31β 611,

US-A-4,333,244, US-A-5,252,543, DE-A-4,316,371,

EP-A-G in US-A-4,325,363,

US-A-5,216,052,

DE-A-4 316 622

339 or EP-AG 591 102 or 3- (4- (2-acetoxyethoxy) phenyl) -5,7-di-tert-butylbenzoturan-2-one, 5,7-difluorobutyl-3-; 4- (2-stearcyicxyethoxy) phenyl] cenzofuran-2-one, 3,3'-bis (5,7-di-tert-butyl-3- (4- [2-hydroxysthoxy] phenyl) benzofuran-2-one], 5,7-citerno-butyl -3- (4-ethoxyphenyl) butyran-2-cu,

3- (4-azethoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivoyoyloxyphenyl) -5,7-di-tert-butylbenzofuran-2- he.

The auxiliary stabilizers, with the exception of the benzofurancans mentioned in point 14 of the PCD, are typically added at a concentration of 0.01 to 10%, based on the total weight of the material to be stabilized.

Other preferred compositions comprise, in addition to components (a) and an amorphous or crystalline modification of the compound of formula (I), further additives, preferably phenolizing antioxidants, light-protective agents and / or processing stabilizers.

In particular, the advantages of the additive are a conventional antioxidant; substances (list item 1), sterically hindered amines (list item), phosphites and phosphonites (list item 4; and serve:

Peripheral peroxides (point S of the list).

Particularly interesting phenolic antioxidants are selected from the group consisting of n-octaecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, necpentantetrayl-tetrakis (3,5-tert-butyl-4-hydroxyhydrocinnamate, di-n-octadecyl-3,5- di-tert-butyl-4-hydroxybenzylphosphate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isckyanurate, thiodiethylenebis (3,5-di-tert-butyl-4-hydroxyhydro-tinnamate), 1,3, S-trimethyl-2,4,6-tris [3,5-di-tert-butyl-4-hydroxybenzyl) benzene, -3,6-dioxaoctamethylenebis (3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2, 6-di-tert-butyl-p-cresol, 2,2-ethylidenebis (4,6-di-tert-butylphenol),

1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,

1,3,5-tris (2- (3,5-diyl) isocyanurate, 3, sitol, hexamethylenate), 1- [3,5-di-triazole-5-triazine, N, N'-oxycyclinamine; amide ; Droxyphenyl: butyrate], mercaptoacetate,. N-N (N-cyclobutyl-4-hydroxyhydrofinnamoyioxy) et: -di (3,5-di-tert-butyl-4-hydroxybenzyl) methyl (3,5-di-tert-butyl-4) -Hydroxyhydro-tin-butyl-4-hydroxy-anilino) -3,5-di (octylthilexamethynylbis (3,5-di-tert-butyl-4-hydroxy-4-hydroxy-ethyl) -1,5-di-srcibutyl-4-hydroxy) thiene-bis [3,3-di (3-tert-butyl-4-hyoctyl-3,5-di-tert-butyl-4-hydroxybenzyl) (3,5-tert-butyl-4-hydroxyhydrocinnamos [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] oxam

The most preferred phenolic antioxidants are neopentantetray-retrakis; 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimerhyl-2,4, -tris ^: (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, nurate,

-diterc

1,1,5-tris (2,5-tert-butyl-4-hydroxybenzyl) isocylamino-2,6-di-tert-butyl-p-cresol or 2,2-ethylidenebis4,6,6-butylcyclol; .

In particular, a hare comprising bis bis (1,2,2,5, δ-penta (1,2,2,6,6-centamet cranene amines) are you;

sxuomv, 6,6-tetramethylpiperidin hylpiperidin-4-vi) cipendin-4-yl sebacate - (3,5-child)

4-yl) sebacate, dimethylbutyl-4-yl (hydroxybenzyl) butyl malonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl -7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione; tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,6, o-tetramethyl-3-oxo-piperazin-4-yl) ethane, 2,2, 4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro [5,1,11,2] heneicosane, a polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4, 4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine, polycondensation product of 1- (2-hydroxyethyl) -2,2,6, c-tetramethyl-4-hydroxypiperidine and succinic acid, polycondensation product 4,4 ' -hexamethylenebis (amino-2,2,6,6-tetramethylenepiperidine) and 1,2-dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-Pentaethylethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, polycondensation product of 2,4-dichloro-o-morpholino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), Ν, Ν ', Ν' ', N' '- tetrakisf (4,6-bis (butyl 2,2,2,6, o-tetramethylpiperidin-4-yl)) amino-s-triazin-2-yl] -1,10-dzaminc-4,7-diazadecane, mixed (2,2,6,6-tetramethylpiperidin-4-β / β, β, β ', β'-tetr methyl 3,9- (2,4,3, 1H-tetraoxaspiro [5,5] ur.dear) diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6, 6-pentametrylpiperidin-4-yl / 3, β, β ', β'-tetramethyl-3,9- (2,4,3,10-tetraoxaspiro [5,5] undecane) diethyl] -1,2,3, 4-butanetetracarboxylate, octamethylene bis (2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4'-ethylenebis (2,2,6,6-tetraethylpiperazin-3-one) and bis (1- octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

methyl droxyetyl (preferably Lperidin-4-yl) -2,2,6-tetramethylamine-s-triazine and -tetramethylpiperidine), the hindered amines being bis (2,2-yl) sebacate, a polycondensate product, 6- tetramethyl-4-hydroxypiperidine polycondensation product 2,4-dichloro, 6,6-tetra-1- (2-acyl-5-tert).

Γ ·

4,4'-hexamethylenebis (amino-2,2,6,6N, Ν ', Ν' ', N' '' -tetrakis [1,4-bis (butyl 2,2,6, c-tetramethylpiperidine- 4-yl) amino-s-triazin-2-l, 10-diamino-4,7-diazadecane, or bis (1-octyloxy-2-yl) 26

-tetrainethylpiperidin-4-yl sebacate.

Also particularly preferred other additives (stabilizers) are benzofuran-2-ones, for example as described, inter alia, in US-A-4,325,863, US-A-4,333,244, US-A-5,175,312, US-A- 5,216,052, US-A-5,252,643,

5Ϊ-Α-4 316 511

DE-A-4,316,622, EP-A-0 591 102.

DE-A-4 316 876

EP-A-3 53 9 331

Examples of such benzofuran-2-ones include compounds of formula

: About and which

R _u '. represents an unsubstituted or substituted carbocyclic or heterocyclic arthmatic ring system,

Ri; ' represents a hydrogen atom, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group or a chlorine atom;

R ₁₃ 'has význam'symbolu R. T or _R', or is a radical of formula a?

(CH

O

->) - é-OR

16 ’

O 11 mCH 1 - C-O-A-O

-O.

0 II —ÍTFO .Γ-VR ·. 0 0 0 II II .4- ₍ β-Γ-ΙΥΉΏ -F · —ICHnk-C-NRk ^ -AO-C-fCH ^ LE -

'3'- ^Λ ι-u ₁₃ <k VV, * ⁰ zV ⁰ n ¹¹ / \ - <CH,) - -C - NN — C — fCHe — E. <H, -SR- ₁₉ , -CH (C ₆ H <) - C-01 ^S \ _ / something -DE, where

_1S R 'represents a hydrogen atom, an alkyl group

include: C1-C18alkyl group containing 2 to 13 carbon atoms interrupted; : for oxygen or sulfur, dialkylamino- alkyl sheep or a group comprising a total of 3 to 15 atoms carbon, cyclopentyl, cyclohexyl With X7U. C i. Γ- u. T phenyl or zenyl substicuc one to three alkyl radicals contain from: rum cc together, at most id atoms ur.uzku, s has hodc.c: : u 0, 1 sky 2, substituent * /? are independently of each other atom in c cu alkyl, containing from 1 to 13 atom already cyclopentyl, cyclopentyl, hexylcvc ·. A group, a phenyl group, a phenyl group a group; substituted with one or two alkyl-

Remaining residues not exceeding 15 combined

uhi atoms iku, the radical of formula -CH, OH, -C _; H ₄ -OC · H _; or -2 ! 1 , -1-2, something scc_ecně s atomom nitrogen, on which they are crowned, they form

dincvv or an immolar residue,

t nccnztu of ac Ld, R '' b ^ta '2U ---- ¹ i.menu vocrx atom, ausus competition

(C 1 -C 22) or C (C 5 -C 12) alkyl group;

A represents a C 2 -C 22 alkylene group optionally interrupted by nitrogen, oxygen or sulfur,

R ₁₃ 'represents a hydrogen atom, an alkyl group containing and R 6'; : D h rhmi □ NB * 1 I / m / z ^ LRL Rion BT / 1 nu i elnmí - - - - - j, _i.e., cyclohexyl, phenyl, n phenyl substituted with one or two alkyl radicals together having not more than 15 carbon atoms or benzyl,

_I3 R 'represents an alkyl group containing from .1 to 13 carbon atoms _r,

D is O, S, -30-,

-S0-- or -C _(R, ' ) ₂ , R, ' independently always an atom hydrogen or an alkyl group containing 1 to 15 carbon atoms, wherein approx R @ 1 together contain 1 to 15

or R ' ₁ ' is furthermore a phenyl group or a radical of formula

OO. ... - (CH,> ^ - COR _{'16 or -O} - (CH 2 -NR 4''), wherein the symbols s, R, / and R ₁₇ ' have the meanings defined above,

E represents a product of the general formula

wherein the symbols R _U 'of R _u and R _u' are as defined above, Ar ₁₅ represents a hydrogen atom, alkylevou group having up to 20 carbon atoms, cyclopentyl, cyklohexyiovou skuoinu, chloro or a radical of the formula

O O

11,

-CH ₂ -C-OR _'l6 or _-CH2 -CN (R _{[7) 2} R _t are _u' ^and R ^₁₇ 'MOUNT defined, or R _XI and R _u' together form a tetramethylene radical.

ahead of group atoms

Preferred benzofuran-2-ones in which R /: avuje hydrogen atom, an alkyl group having 1 to 12 atoms, cyclopentyl, cyclohexyl .u, chloro or a radical of the formula _R R ·. , i? ...

fCH ₂ n-C-OR _1a . - (CHiJyC-NXR [7) 2, n ^ or -D-Ξ, where the s, R, R, _T ', D and S are as defined above, and is preferably a hydrogen atom, an alkyl group containing i up to 13 carbon atoms, a cyclopentyl group or a cyclohexyl group.

Also represented are such benzofuran-2-cry, phenyl or phenyl groups substituted with m or two alkyls containing a common atom. C1-C4, R1-containing hydrogen;

y not more than 12 carbon atoms, R is hydrogen íedstavuje to 12 carbon atoms, R _u 'oin.u containing 1-12 residues at ew Rh is

Or alkyl means an atom of the group -CH _; > ^ - C-OR '. ₅ , -CN (R ' _[7 ) _2, or -1-1, R' is hydrogen, C 1 -C 20 alkyl;

, '· H ff alkyl group with CH ₂ -C-OR' _Io ^nsbo -CH ₂ -CN (R _'17 j _2> NECC.? .. _s and

R ₁₄ 'together form a tetramethylene radical, in which the symbols R _Ie' of R _t? \ D and E are as defined at the outset.

Of particular interest are also those benzofuran-2-ones in which R, h represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group -D-Ξ, the symbols independently of each other being a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. carbon atoms, and R _S 'represents alkyl group having 1 to 20 carbon atoms,' wherein D and E are as defined at the outset.

In particular, the "interesting" are finally. also those benzofuran-2-ones, _L3 .in which R ^J is an alkyl group. containing 1 to 4 carbon atoms or -O-Ξ, R _L. and R ₁₄ 'are each hydrogen, and R ₁₅ ' is alkyl of 12 groups containing a group of non-externally-occurring structures.

cy: <denoted by D

J represents a -C (λ--) group and an alkyl group. in (-, 1 ---—

wherein the carbon and the substituents' are the same or different and the alkyl group containing from 1 to 4 atoms: R 1 ', R 1', R 2 ', and R k' have the meanings defined above.

The enzofuran-2-one cosulfurate may be modified by the novel mixtures, typically in amounts of 0.0005 to 10% by weight, preferably

0.001 to 5 wt.%, Most preferably 0.01 to 2 wt.

The amorphous and crystalline modification of the compound of formula I and any other additives are incorporated into the polymeric organic material by known methods, typically before or during molding, or alternatively by applying dissolved or dispersed compounds to the polymeric organic material, followed by evaporation of the solvent if used. The amorphous and crystalline modification of the compound of the formula I can also be added to the materials to be stabilized in the form of a masterbatch which contains these compounds typically in a concentration of from 2.5 to 25% by weight.

Amorphous and crystalline modifications of a compound of formula I may also be added before or during polymerization or prior to crosslinking.

The amorphous and crystalline modification of the compound of formula (I) may be incorporated into the material to be stabilized in pure form or encapsulated in waxes, oils or substances.

• ’.l ·. · *

The ammonium and crystalline dampening of the compound of formula I can also be sprayed onto the polymer to be stabilized.

They are capable of diluting other additives (for example, the aforementioned conventional additives) or their melt, so that they can also be sprayed together with these additives on the polymer to be stabilized. Especially preferred is the spray application during deactivation of the polymerization catalysts, and the steam used for deactivation may be used for spraying.

· »

The amorphous and crystalline modification of the compounds of formula (I) may be suitably applied by spraying, if desired together with other additives, in the case of spherically polymerized olefins.

The materials stabilized by this agent can be used in a variety of forms, for example, as films, fibers, strips, molded materials, profiles, or as binders for lacquers, adhesives or sealants.

As already mentioned, the organic materials to be protected are preferably organic polymers, in particular synthetic polymers. In particular, the excellent action of the amorphous and crystalline modification of the compound of formula I as processing stabilizers (heat stabilizers) is preferred. For this purpose, these substances are preferably added to the polymer before or during processing. Stabilize against degradation. like... it _is; light induced by thermal or thermal radiation. oxidative. but ... the same. next.

* polymers (for example ... elastic.). or: lubricants or hybrids. Examples of elastomers are listed above in the list of possible organic materials. .

other suitable lubricants and hydraulic fluids may be other chemical or synthetic oils. their mixtures, known to those skilled in the art and described in the relevant literature, such as in Dieter Klamann, Schmierstoffe und Verwandte Produkte (Veriag Chemie, Weinheim / 1982), Schewe-Kobek, 'Das Schmiermittei-Taschénbuch (Dr. Alfred Hiithig-Veriag). , Heidelberg, 1974);

JHlimanns Enzyklooadie_ber technischen * Chemistry /, page 85-94 · (Veriag Chemie, Weinheim, 1977).

svazex

The lubricating oil may be a mineral oil, a synthetic oil, or any mixture of such oils. Preferred are mineral oils and, for example, paraffinic hydrocarbon oils, for example mineral oils having a viscosity of 4 mm ^; / s' at 40 ° C, 150 Solvent Neutral, solvent-refined neutral mineral oil having a viscosity of 32 mm mm / s at 40 ^and C, and solvent bright-stocks, high boiling residue from a mineral oil refining process, showing a viscosity 46 mitf / s at 40 ° C.

ΐ

Synthetic lubricating oils that may be present may be synthetic hydrocarbons such as spring pclybutsny. alkyibenzenes and poly-alpha-olefins, as well as simple di-, tri- and tetraesters, complex esters and polyesters derived from carboxylic acid esters of the general formula G.-CCC-alkylis.n-COOG ₂ , wherein the term alkylene denotes an alkylene radical containing from The C 2 to C 14 atoms and the G _L and G- symbols are the same or different and each represent an alkyl group containing from 6 to 18 carbon atoms. Triesters which are suitable as starting materials for lubricating oils are those derived from. trimethylolpropane and C 6 -C 18 monocarboxylic acids or mixtures thereof, while suitable tetraesters include those derived from pentaerythritol C 6 -C 18 monocarboxylic acids or mixtures thereof. Complex esters suitable for use as components of the present invention include, but are not limited to, acids, dibasic acids, and polyhydric alcohols, for example, a complex ester derived from frimethyiolprooane. caprylic acid and sebacic acid.

Suitable polyesters are those derived from any aliphatic dicarboxylic acid containing from 4 to 14 carbon atoms and at least one aliphatic dihydric alcohol containing from 3 to 12 carbon atoms, for example cd derived from azelaic acid or sebacic acid and

2,2,4-trimethylhexane-1, c-diol.

The amorphous and crystalline compounds of the formula (1) according to the invention are effective as additives in lubricants, even when used in very small amounts, they are added to the amounts.

^! 0o and from nmct. and in particular in an amount of 0.1 to 1% by weight, in each case based on the lubricant in the water. J 4- C - '-

0.01

> vi.CC ..;

The application environment may include other additives which have essential lubricant properties, viscosity index improvers, dispersants, corrosion, extreme wear additives, and antioxidants.

Lubricating oils may also be added to improve, for example, metal passivators, ity, temperature lowering agents, detergents, other pressure inhibitors, anti-additive additives. A number of such compounds can be found, for example, in the above list i. Antioxidants, in particular in items 1.1 to 1.19. Examples include the following additives:

Examples of other antioxidants:

Asteric acids of thvl-tetramet or aromatic phosphates, thiodipropionic esters: orthic acid, or dithiocarboxylic acid or dicarboxylic acid, 2,2,12,12-te9-dihydricxy-3,7,11-trithiatridecane and 2,2,15,15-5,12-dihydroxy-3,7,10,14-fetrathiahexadecane.

Among the examples are the actives;

For example, for copper, oatrr:

Benzetriazoles and derivatives thereof, for example 4- or

5-alkyibenzotriazoles (for example toiutriazole) and derivatives thereof, 4,5, c, 7-tetrahydrobenzotriazole and 5,5'-methylenebisobenzotriazole, Mannich bases of benzotriazole or tolut riazole ', for example 1- [bis (2-ethylhexyl) amincmethyiltoiutriazole and 1 - [bis (2-ethylhexyl) aminomethyl] beuzotriazole, and alkoxyalkylbenzetriazole such as 1- (nitroxylmethyl) benzotriazole, 1'-butoxyethyl) benzoziazole. and i -. (1-cyclohexvio.xvcutvlj.uc.iutria.zo.i ..___________ ___

1,2,4-triazclxy and their derivatives such as 3-aikvi '~ -CO RVI and' - ', 7, j - ¹ r ^ and oiya? ^r a - ~ - ow base i _z o _y j -

-triazoles such as 1-bis (2-ethylhexyl) aminomethyl] 35

- 1,2,4-triazole, alkoxyalkyl-1,2,4-triazoles such as

1- (1-butoxyethyl) -1,2,4-triazole, and acylated 3-amino-1,2,4-triazoles.

c) Imidazole derivatives such as 4,4'-methylenebis (2-undecyl-5-methylimidazole) and bis ((N-methyl) imidazol-2-yl) methanol octyl ether.

d) Sulfur-containing heterocyclic compounds, for example

2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and derivatives thereof, and 3,5-bis [di (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one.

e) Amino compounds such as salicylidene propylenediamine, salicylaminguanidine and salts thereof.

Examples of corrosion inhibitors include:

Organic acids, their esters, metal salts, ammonium salts and anhydrides, for example alkyl and alkenylsuccinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy and alkoxyethoxycarboxylic acids acids such as dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid and their ammonium salts, as well as N-olecyisarcocine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydrides, for example, di-deceny succinic anhydrides, 2-carboxymethyl-1-dodecyl-3-methylglycerol its ammonium salts.

: anm · nitrogen,

Primary, secondary or cycloaliphatic organic or tertiary aliphatic amines and ammonium salts of inorganic acids, for example oil-soluble alkyl ammonium carboxylates, as well as 1- [N, N-bis (2-hydroxyethyl) amino] -3- (4-n.o36) -.

nylphenoxy) propan-2-ol.

II. Heterocyclic compounds, for example substituted imidazolines and oxazolines, and 2-heptaacenyl-1- (2-hydroxyethyl) imidazoline.

c) Phosphorus-containing compounds, for example, ammonium salts of partial phosphoric acid esters or phosphonic acid partial esters, and zinc dialkyldithiophosphates.

d) Sulfur containing compounds, for example, barium dinonylnaphthalenesulfonates, calcium petroleum sulfonates, alkylthiosubstituted aliphatic carboxylic acids, aliphatic 2-sulfocarboxylic acid esters and salts thereof.

e) Glycerol derivatives, for example glycerol 1-monooleate. 1- (alkylphenoxy) -3- (2-hydroxyethyl) glycerols, 1- (alkylphenoxy) -3- (2,3-dihydroxypropyl) glycerols and 2-carboxylate yc e roles ·.

Among others, viscosity index enhancing agents will not be used

Polyacrylates, polymethacrylates, copolymers of vinylpyrrolidone and methacrylates, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene-acrylate copolymers and polyethers.

Examples of freezing point depressants include: *

Polymethacrylates and alkylated naphthalene derivatives.

Examples of reagents include:

.Amides or imides in cbybutenyl polybutenylphosphonic acid s oo v rc.no in tartaric acids, zinc sulfonates,

magnesium, calcium and barium salicylates.

Examples of anti-wear agents include:

Sulfur and / or phosphorus and / or halogen containing compounds such as sulfurized olefins and vegetable oils, zinc dialkyldithiophosphates, alkylated triphenylphosphates, tritolylphosphates, tricresylphosphates, chlorinated paraffins, alkyl- and aryl-di- and trisulfides, ammonium salts of mono- and di-diphosphates, ammonium salts of methylzosphonic acid, diethanolaminomethyltlyitriase T / bis (2-ethylhexyl) aminomethylthiolyl thiazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, ethyl 3 - [(diisopropoxyphosphinothioyl) thio] propionate, triphenylphosphate, triphenylphosphate, triphenylphosphate, triphenylphosphate ), tris (alkylphenyl) phosphorothioases and mixtures thereof (e.g. tris (isonoylphenyl) trans-thiothioate), diphenylmonononylphenyl phosphorothioate, isetylphenyl-diphenylphosphorothioate, dodecviammonium 3-hydroxy-1,5-thiaphosphetan-3-oxide, dodecviammonium salt, 5,5-tris [isooctyl-2-acetate] trithiophosphoric acids, 2-mercaptobenzothiazole derivatives such as 1-N, N-bis (2-ethylhexyl / aminomethyl) -2-mercapto-1H-1,3-benzothiazole, and ethoxycarbone vi-5-o kt in 1 dihicarbonate amat.

Accordingly, the preferred embodiment of the invention is

OOUZlti amorphous or crystalline modifications of a compound of formula i for stabilizing organic materials against oxidative, thermal and / or light-induced degradation.

The ammonium and blood-borne exemplifications of the present invention are preferably used as processing agents (stabilizers against the effects of thermostabi- lizer or thermoplastic co-merv).

heat dissipation, the invention equals tyx and causes sterilization of the organic material against the thermal, thermal or light-induced degradation, which involves incorporating an amorphous or crystalline metabolism of the compound of formula. or applying an amorphous or crystalline modification of the compound of formula r to the material.

The following examples illustrate the invention in more detail. The parts and percentages given are parts and percentages by weight.

Differential Scanning Calorimetry (DSC) measurements are performed on a TA Instrument Inc, 910 differential scanning calorimeter, with a nitrogen purge of 100 ml / min, with an aluminum pan attached, at a temperature shift of 5 ° C / min to a 230 ° C theolof.

Diffraction patterns are obtained by X-ray diffractometry on a Philips Norelco X-ray Diffractometer unit, using Cu-Κα radiation, with a nickel filter.

EXAMPLES Preparation of the crystalline modification of the compound of formula I

Compound of formula. 1,1,1 ', 1' '-nitrile-tri-2-propyltris [2,2'-ethylidenebis (4,6-di-tert-butylphenyl)] phosphite}, prepared according to the procedure of US Pat. 4,313 Pa (13.33 Pa) per melt is heated to form a crystalline crystalline mass with Example 9 from the U.S. Pat.

345. The product obtained is heated under vacuum at 200 ° C to obtain a melt. This was at a temperature of 200 ° C until the mass was approximately -16 hours. This is then used to spread a white powder using a mortar and pestle. A 90% yield of a new modification of the compound of formula I is obtained with a melting point. The melting point is determined by the differential scanning calorific value.

The X, X-ray diffraction pattern using Cu-Kct exhibits very high intensity diffraction angles (2Θ) at 7.9 and 15.6, high intensity lines at 7.3, 8.9, 14, 7, 16.8, 13.3, 13.9, 19.8 and 20.6, guard intensity lines at 13.9, 22.6 and 24.0, and a weak intensity line at

21.4.

Example 2 Comparative Example. . . .

The diffraction pattern obtained by X-ray diffractometry of the compound of Formula I, prepared according to Example 9 of U.S. Patent No. 4,313,345, shows diffraction angles (2 °) that are similar to the angles shown for the compound of Example 1 of the invention but additional rungs in 4,5, 12,0, 15,5 and 24,5 that miss the diffraction pattern obtained by X-ray diffractometry of the new crystalline modification of the compound of formula mru

Example 3

Fluidity

This example illustrates the exceptional flow properties of the novel crystalline modification of the compound of formula vzorce prepared in Example 1, as compared to the flowability of the compound of formula I prepared according to the procedure of Example 9 of U.S. Patent 4,318,345.

The angle of repose is measured according to the procedure described by G. Goid et al. J. Pharm. Sci. 55, 1291 (1956). Lower pitch angle means better flowing solid product.

Table i.

vs rad's 1S-.

Lir, i. IN

Table 1

compound saturated angle « (in apartments) from Example 1 (new crystalline modification) 42 from Example 9 of the patent U.S. Pat. 4,318,845 (prior art) 43

These results suggest that the crystalline modification of the present invention exhibits less flowability than the prior art compound.

Example 4

Bulk weight

This example of the bleaching aspect of the novel Formula I prepared in the form of the compound of the illustration illustrates the extraordinary property of the crystalline modification of the compound of Example 1 as compared to the Powder Example 9 of the United States Patent

US 4,313,345.

The bulk density of the solids was measured by pcd D-1895 (79). Higher bulk density - represents per unit of volume, which means product benefits such as lowering the cost of halic! :

In the ASTM method, the weight of the solid mass is lower, the lower the mass in the orifice table in Table 2;

Table 2 sl is the bulk density (in g / ml) of Example I 0.55 (new crystalline modification) of Example 9 of the patent

U.S. Pat. 4,313,845 0.31 '(prior art) .....

These data suggest that the novel crystalline modification exhibits much better packaging properties compared to the prior art compound.

Example 5

Stabilization of coivoroovelocation at 274 ° C; avu ‘

Pre-base (PRO FAR 5501, H imc nt) calcium. Unstabilized polypropylene tested containing 0.075 wt. stearate additives are incorporated into the polypropylene by dry mixing or, if the additive is liquid, using a minimum amount of methylene chloride as solvent. The solvent was then removed by evaporation under reduced pressure. The stabilized formulation is extruded in a 2.54 cm diameter extruder at 90 rpm at 274 ° C with a holding time of 90 seconds. The melt flow index (in grams per 10 minutes!) Is determined on pellets obtained from the extruder after the first, third and fifth extrusions using the ASTM F1233 method.

cocttxace coo_e vyna ± e;

(from the example

1) j <

it is believed that the minimal change in melt index in the presence of a representative phenolic antioxidant is substantially as effective as the prior art compound of U.S. Pat. 4,313,345.

The pellets obtained after the first, third and fifth extrusions are molded at a temperature of 232 ° C at a thickness of 3.2 mm and the values of the yellowness index (Yl) are determined by the ASTM D1925 method. A lower Yl value means less color change.

Crystalline modification to stabilize polypropylene against minimal change in yellowing index to thive. phenolic antioxidant and active as a compound of the prior art. U.S. Pat. 4,315 345.

according to the invention there is a color change, as the presence of rep is essentially prior art, effective as evidenced by the patent

Example 5

Solubility in linear low density polyethylene (LLDP5) film at different temperatures

They are carried out experiments to determine the solubility of the crystalline polymorph of the compound of Formula I (of Example 1) in the films of linear low density polyethylene (LLDPS) at 20 ° C, 40 ° C and 60 ° C prcdifundováním test sample with a relatively homogenous particle size (less than 70 _of µm) suspended in silicone oil.

Each sample is carefully rubbed using a mortar and pestle and particles smaller than 70 µm are sieved through a 0.074 sieve. This powder is then suspended in silicone oil (polydimethylsiloxane, L-45, Union Carbide Chemicals) at a concentration about 33% (w / w). A few kaoeks of this susoenzy are placed on a 0.254 mm thick sheet of 5.08 cm x 5.08 cm, and a second sheet of the same size is placed on top. The films are gently pressed together so that the slurry forms a thin layer of liquid between the polymer films. The excess suspension was removed and the process repeated until a layer of eight films (six films for evaluation) was prepared. The layer is then placed between two 6.35 cm x 6.35 cm ceramic tiles, wrapped in aluminum foil and

G-clamp. Each layer is stored at 20 and 60 ° C in a nitrogen atmosphere. At specified intervals, one film is removed from the layer each time and the excess suspension is washed from the film with hexane. The total phosphorus content of the film is then analyzed by X-ray fluorescence.

y for this X-ray method attach to 'C, 40' C

As standard kont r fluorescence se use e containing 0.1000 ppm a: Crystalline modifi 1) according to the invention is ro: polyethylene than sioučs of Example J.S. 4 315 3 4:

Example 7

Stabilization of unsaturated elastomers

The crystalline modification of the compound of formula (I) of Example 1 according to the invention was evaluated in an SSBP emulsion (cold polymerized, 23.5% styrene with a viscosity (Mconey) 52). 60 g of unstabilized S = K are added to the mixing chamber of the Brabender Plastiorderorder set at 150 ^J and 60 cpm per minute. After 30 seconds, 0.5 wt. of the compound of Example L of the invention. Stability 53P. is determined by the time until the start of the rubber crosslinking, which is determined by increasing the torsion curve. The sample stabilized by the compound of the invention has a longer induction time until crosslinking begins than unstabilized SBR.

Example 5

Polyol stabilization

To 200 g of a 3000 MW polyvether polyol containing a set of stabilizers (control is 2000 ppm of 2,6-di-tert-butyl-4-methylenenol (ΒΗΤ) and 2000 ppm of NAUGARD 445 (diphenylamine antioxidant, Uniroyal), the set of stabilizers according to the invention contains above of this compound plus 1000 ppm of the compound of Example 1) is added a premix containing 10 g of water, 0.25 g of triethylenetetramine, 2 g of L-5740 (silicone surfactant, ⁱⁿ Union. Carbide) and 2O'-g -ANTIBLAZE A3- 100 (chlorinated aromatic quencher. Albright &amp; Wilson). The mixture is stirred for 5 minutes on a high speed lightning mixer. 0.4 g of sintered octoate is then added and the mixture is stirred for 5 seconds. Eventually

idá. 125 g- t o lu e n - d i i s o an á-tu (S 0 % 2,6-isomer, -20% 4-iscmer at;. omes to disappear po dcbi ; 7 seconds high 'Chlostí and then poured into leoenkc Size boxes 4 cm x 25.4 cm x 12.7 cm. Foam up let it rise completely.

After maturing for 5 minutes, the box is removed and the sample is cured in a microwave oven for 5 minutes at 50¾ power. The foam is immediately cured in a drier at 125 ° C for 3 minutes. The foams are then cut in half for visual evaluation of color change or vulcanization.

Visual assessment of the two foams indicates that the foam containing the stabisomer set of the invention in which the compound of Example 1 is present exhibits less color change than the foam stabilized by the stabilizer control set. Crystalline modification to protect orcci scorch.

I shows better

Example 9

Stabilization of polycarbonate

Bisphenol A-based polycarbonate without additives (LEXAN 141-1 µM, General Electric) is dried and mixed with 0.3 wt. % benzotriazole UV absorbing agent (TINUVin 329, Ciba-Geigy) and 0.08 wt. of the compound of Example 1 of the invention. The mixture is extruded and pelletized at 288 ° C on a single screw extruder (2.54 cm). In a BOY 30M injection molding machine, plates 5.03 cm x 5.08 cm x 3.173 mm are prepared at a temperature of 293 ° C and a mold temperature of 150 ° C. The resulting platelets are measured with a yeliowness index (Y1) using ASTM D ± 925-70. The plates containing the compound of Example 1 according to the invention exhibit lower yellowness index values than the plates containing only the UV absorbing agent alone, indicating better stabilization in the presence of phosphite according to the invention.

Example 10

Stabilization of poles (ethnyient terephthalate) • • fti

FA • f in * <'· $

Polymers (ethylene terephthalate), PET (KODAPAK. 7352, Eastman Chemical) are mixed with 0.5 wt. of the compound of Example 1 of the invention. The polymer is then extruded and pelletized at 260 ° C on a single screw MPM (2.54 cm) extruder. The pellets are collected five times, dried and extruded again. The pellets are removed from each extrusion and the intrinsic viscosity of the polymer is measured. PET containing the compound of Example 1 according to the invention shows a higher retention of the original intrinsic viscosity during five extrusions than a PET without a stabilizer:

Example 11

Stabilization of poles (butylene terephthalate)

Polymers (butylene terephthalate), PBT (RYNITB 9160, DuPont) are mixed with 0.3 wt. of the compound of Example 1 of the invention. The polymer is then extruded and pelletized at 260 ° C. A portion of the collected pellets is again extruded a second time under the same conditions. Plates of 5.03 cm x 5.03 cm x 3.175 mm are prepared from the first extrusion residue in a BOY 30M injection molding machine at 232 ° C and 100 ° C mold temperature. The intrinsic viscosities of the extruded extrudate and injection molded plates are determined. P5T containing the compound of Example 1 of. of the invention exhibits better intrinsic viscosity retention than 53T without a stabilizer.

iček platelets are measured ¹ yellow index · (color) using ASTM D 1925-70. Plates containing the compound of Example 1 according to the invention show lower yellowness index values. lower: color change) than platelets prepared from: control:. r.stabilized PBT.

Example 12

Stabilization of 6,6-nylcene

....... 6 jo-nylon '(ZY3ZL' 101, 'DuPont)' is' thoroughly 'dried in a vacuum oven and mixed in a drum with' 0.5% hmct: compounds from

cc containing a compound of the example below the yellowness index:

unstabilized control plates.

Example 13

Stabilization of ASS

A solution of 0.25 g of the compound of Example 1 in 40 ml of hexane / methanol was added to a rapidly stirred suspension of 100 g of ABS (acrylonitrile / butadiene / styrene terpolymer) in 600 g of water. The suspension was filtered and dried in vacuo at 40 ^e C for 40 hours. 2% (w / w) was added to the dried powder in a two-roll mill at 130 ° C over 4 minutes. % titanium dioxide; N, N'-ethylenebisstearamide. Three temperature 175 ° C with;

Plates of 0.3 mm thickness and placed in an oven at 150 ° C; as yellow index values using ASTM D 1925-70. The plates containing the compound of Example 1 according to the invention show a lower yellowness index value (lower color change) than the control plates of unstabilized ABS.

umet. N, M '-ethy- adjusts 1iscvane cbu 45 minu 'to _y icek se

Preparation of the ammonium mcizixation with the xenoxide formula

The compound of formula I, 1,1 ', 1''- nitriio (tri-2-propyltris [2,2'-ethylidenebis (4,6-di-tert-butylphenyl)] phosphite}, was prepared according to the procedure of Example 9 from No. 4,315,545, and the product obtained is heated under vacuum (13.33 psi) to a temperature of 210 ° C to obtain a clear melt, which is rapidly cooled to room temperature to give a glassy solid. a glass transition zeolite (T _i, as determined by differential scanning calorimetry (ISO) 137-142 ^and C. This white solid is smeared into a white powder using a mortar and pestle. The diffraction pattern obtained by X-ray diffractometry is faint.

using Cu-Κα is

Example 15

Bulk weight

This example illustrates the extraordinary properties, in terms of packaging, of the novel amorphous modification of the compound of Formula I, as prepared in Example 14, as compared to the powder form of the compound of Example 9 of United States Patent 4,313,845.

The bulk density of solids is measured according to the ASTM method

D-1895 (79). Higher bulk 'per unit volume', giving p products such as lower.

Required storage space etc. Table 3

motncst. represents a &quot; greater &quot;, weight adds to the advantages of packaging: fixed, cost, packaging material. lower

The results are summarized in

Table. 3 sic per bulk density (in g / ml) of Example 14 0.43 (new amorphous modification) of Example 9 of the patent

U.S. Pat. No. 3,313,345 0.31 (prior art) The amorphous vv solid modification prepared in Example 14 according to the prior art compound of U.S. Pat. No. 4,318, related to the improved Example 9,845, has a much more loose properties in the United States Patent. weight, in terms of bleaching.

Example 16

Stabilization of polypropylene during processing at ^S 274 C

The matrix is unstabilised polypropylene (PROFAX 6501, Himont) containing 0.075 wt. calcium stearate. The test additives are incorporated into the polypropylene by dry mixing or, if the additive is liquid, using a minimum amount of methylene chloride as solvent. The solvent was then removed by evaporation under reduced pressure. The stabilized formulation is extruded in a 2.54 cm diameter extruder at 90 rpm obtained from the extruder after the first, third extrusion is determined by A3TM D1233: melt (in grams per 10 minutes).

Amorphous modifications of compound vz;

zi r. _ /

nut u pro pel . etácn 3, fifth iex L 0 idu 14 is else a

effective in stabilizing polypropylene against oxidative degradation, as evidenced by minimal change in melt index in the presence of representative phenolic antioxidants, and is substantially as effective as the prior art compound of U.S. Pat. 4,313,345.

The pellets obtained after the first, third and fifth extrusions are pressed at a temperature of 232 ° C at a thickness of 3.2 mm and the yellowness index, ΥΣ, is determined by the ASTM D1925 method. Lower value ΥΣ means lower color change.

The amorphous modification of the compound of Formula 14 of Example 14 is effective in stabilizing polypropylene for worm change, as evidenced by minimal variation in yellowing in the presence of a representative phenolic antioxidant, and is substantially as effective as the prior art compound of U.S. Pat. 4,318 -845.

Example 17

Solubility in lubricating oil

The following experiments were carried out to determine the solubility of the amorphous modification of the compound of Formula I (Compound A, Example 14) and the prior art compound (Compound 3, Example 2) in Mobil 33 oil. 70, um). ’_ ... ..

Tested; compounds:

Compound A: amorphous modification 1,1,1 ', 1' '- nitrile-tri-2-propyl-tetris [2,2'] - ethylidenbis. ' 4, 6-di-tert-butylphenyl)] phosilicate, crispy steel. 14..oodle invention ..

ii

Compound 3: Powder: Orma

1,1 ', 1''-nitrile-tri-2-yl-t-ris (2,2'-ethylidenebis 4,6-di-tert-butylphenyl)] fossil prepared according to the United States patent

No. 4,313,345 (Example 2 of this application).

Experiment 17a: To a vial containing 980 mg of Mobil 53 oil was added 20 mg of Compound 3 at room temperature. The vial is shaken every 15 minutes for the first 60 minutes. After an initial 60 minutes, the vial is allowed to stand. All compound A. was dissolved in the oil after 4 hours to give a -pure-gray ---- - -----------------——— ------ Experiment 17b: Dc ampoules were added with 20 mg of a compound using 951 mg of Mobil 33 oil at room temperature. During i

for the first 60 minutes, the vial is shaken every 15 minutes. After an initial 60 minutes, the vial is allowed to stand. After 4 hours, compound S provides a cloudy suspension. A clear solution is obtained after 16 hours.

Experiment 17c: To a vial containing 930 mg of Mobil 33 oil was added 20 mg of Compound A at room temperature. The vial was then placed in a 60 ° C oil bath. After 45 minutes, all of Compound A is dissolved to give a clear solution.

Experiment 17d: To a vial containing 930 mg of Mobil 33 oil was added 20 mg of compound 3 at room temperature. The vial was then placed in an oil bath at 60 ° C. After 45 minutes, compound 3 gives a cloudy suspension. The clear solution was obtained after about 7 hours.

Experiment 17e: To a vial containing 990 mg of Mobil 33 oil was added 10 mg of Compound A at room temperature. The vial is shaken every 15 minutes for the first 50 minutes. After an initial 60 minutes, the vial is allowed to stand. All Compound A was dissolved in the oil every 3 hours to give a clear solution.

Experiment 17f: To a vial containing 990 mg of Mobil 33 oil was added 10 mg of compound 3 at room temperature. During

1 / first 60 min ut se * initial 60 minutes the mixture is cloudy suspe Vvsiedkv j sou

Table 4

try concentration test compounds (% w / w) temperature observation time' 17a 2% .TM clear solution 4 o'clock 17b. 2 ΐ Ξ  i n * i slurry 4 hours ^x 17c 2% 60 ° C clear solution 45 minutes I7d 2% B 60 'C * cloudy suspension 45 minutes ***. 17e 1% TM clear solution 3 hours 17f 1% B TM cloudy suspension . 3 hediny ** Table legend. 4: TM room temperature ti Ř temperature .is temperatures ou. oil bath t * t 4i clear '.' solutions '' s e gain after 16 hours at temperature

rooms.

*** clear clear s.e is obtained after 7 hours at 60 ° C

In summary, the amorphous modification of the compound of Formula I of Example 14 of the present invention exhibits a greater dissolution rate and better solubility in lubricants as compared to the prior art powder form. This means better compatibility and more uniform dispersion of the compound of the present invention. organic material during the formulation as compared to the prior art compound.

Example '13 '~'

Solubility in Flax (LLDPE) c:

foil. a variety of linear thiotecies;

.us i otníhc

· Experiments are conducted to determine the solubility of the amorphous modification of the compound of Formula I (from Example 14) in linear low density polyethylene (LLDPC) films at 20 ° C, 40 ° C and 60 ° C by diffusing the test sample with a relatively homogeneous particle size (less than 70 _of µm suspended in silicone oil.

Each sample se.opatrně triturated using a mortar and pestle and a particle size _of less than 70 microns is separated through a sieve with apertures of 0, 074 mm. This powder was then suspended in silicone oil (polydimethylsiloxane, L-45, Union Carbide Chemicals) at a concentration of approximately 33% (w / w). A few drops of this suspension are placed on a compressed film 0.254 mm thick and 5.03 cm by 5.03 cm in size and a second film of the same size is placed on top. The films are gently pressed together so that the slurry forms a thin layer of liquid between the coil films. The excess suspension was removed and the process repeated until a layer of eight films (six films for evaluation) was prepared. The layer was then placed between two 6.35 cm x 6.35 cm ceramic tiles, wrapped in aluminum foil and.

G-clamp. Each layer is stored between 20 and 60 ° C in a nitrogen atmosphere. At specified intervals, one film is removed from the layer each time and the excess suspension is washed from the film with hexane. The total phosphorus content of the film is then analyzed by X-ray fluorescence. Linear low density polyethylene containing 0.1000 ppm and 2000 ppm test compound was used as standard controls for this X-ray fluorescence method.

Ammonium mcamkace ΙΐηβΞΓΤ compound of formula V 'in Sava .At days and no Oodle dissolve the ^Invention: Example 14) The osmolality than nizkohustctním polyethylene: Example 9 US 4,315,345

She knows

- 54 Example 19

Stabilization of cross-linked elastomer

The amorphous modification of the compound of Formula I of Example 14 is evaluated in an SBR emulsion (cold polymerized, 23.5% styrene with viscosity (Mooney) 52), 60 g of unstabilized SBR are added to the Brabender Plasticorder Set i salt mixing chamber. ® / - ~ 4- 4, x 1 ^ .4 "—I -., V., -1—. - '------ i- ilu kx a u v u ^ ά ^ Λαυι.ι cc. ui._lííulli. 0.5% by weight to the chamber was added to the chamber. of the compound of Example 14 of the invention. The stability of the SBR is determined by the time until the start of the crosslinking of the rubber, which is determined by increasing the torsion curve. The sample stabilized by the compound of the invention has a longer induction time to cross-linking than unstable SBR.

moment, the coffee starts

Example 20

Coivol stabilization ..

Ke 2 3000 content of 2,6-di-444 (clarification of water, -0.2; surface A3-100 (c?

The molecular weight of the stabilizer set (control is 2000 ppm of butyl-4-methylphenol (SHT) and 2000 ppm of NAUGARD, an amine anticoxidant, Unircyal), the stabilizer set contains the above substances plus 1000 ppm of Example 14. A premix containing 10 g of Lg-triezethylenetetramine, -2 g of L-5740 [silicone active agent, -Union Carbide] and 20 g of ANTIBLAZE (chlorinated aromatic quencher, Albright & Wilson) are added. The mixture is stirred for 5 minutes on a high speed mixer. 0.4 g of stannous is then added and the mixture is stirred for 5 seconds. Eventually

2,4-isomer at the rate of fo-n-diisocyanate (30 The mixture is stirred for a period of% 2,5-isomer, 20% high and poured into a cardboard box of dimensions

25.4 cm χ 25.4 cm χ 12.7 cm. The foam is allowed to rise completely. After standing for 5 minutes, the box is removed and the sample is cured in a microwave oven for 5 minutes at 50% power. The foam is then immediately air over cured at 125 ^e C for 3 minutes. The foams are then cut in half for visual evaluation of color change or vulcanization.

Visual assessment of the two foams indicates that the foam containing the stabilizer set of the invention in which the compound of Example 14 is present exhibits less color change than the foam stabilized by the stabilizer control set. The amorphous modification of the compound of formula (I) according to the invention shows better protection against vulcanization.

Example 21

Stabilization of oolcarbonate

Bis-phenol A-based polycarbonate without additives (LEKAN 141-iN, General ilectric) is dried and mixed with 0.3% by weight absorbing agent (TINUVZN 329,

Ciba-Geigy; and 0.03 wt.

The UV radiation based on benzotriazium (MI) of Example 14 according to the invention. The mixture was extruded and pelletized at 233 ° C in a single screw extruder (2.54 cm). Ve. Plates of 5.03 cm x 5.03 cm x 3.175 mm are prepared at a temperature of 253 ° C and a temperature of Form 150 ^and C using a 30Y 30M injection molding machine. Yello / ness index, YTJ using ASTM D 1925-70 is measured for the resultant / platelets. Plates containing the compound of Example 14 of the invention exhibit lower yellow index values than platelets containing only the UV scavenger alone, indicating to achieve better stabilization in the presence of an amorphous modification of the compounds of the invention.

Example 22

Stabilization of poles (ethylene terephthalate)

Poly (ethylene terephthalate), PET (KODAPAR 7352, Eastman Chemical) .. is mixed with 0.5 wt. of the compound of Example 14 of the invention. The polymer is then extruded and pelletized at 260 ° C in a single screw MPM (2.5-4 cm) extruder. The pellets are collected five times, dried and extruded again. The pellets are removed from each extrusion and the intrinsic viscosity of the polymer is measured. PET containing the compound of Example 14 according to the invention shows a higher retention of the original intrinsic viscosity during five extrusions than PET without the stabilizer.

Example 23 stabilization of poles (butylene terephthalate)

Polys (butylene terephthalate), P3T (PYNTTE 9160, TuPont) is mixed in a drum with 0.3% pots, a compound of Example 14 according to the invention. The polymer is extruded and pelletized at a temperature of 260 ° C. A portion of the collected pellets is extruded a second time under the same conditions. Plates of 5.03 cm x 5.03 cm x 3.175 mm were prepared from the remainder of the first extrusion in a 30Y 30M injection molding machine at 232 ° C and a mold temperature of 100 ° C. second

I extrusion and injection molded plates. Containing the compound of Example 14 according to the invention shows better retention of intrinsic viscosity than P3T not containing a stabilizer.

(Yellow plate index is measured (color: ASTM D 1325-70. Plates containing the compound of the present invention exhibit lower color change index values) than the control pathways.

not plated PST.

Example 24_

Stabilization of 6,6-nylon

6, δ-nylon (ZYT3L 101, DuPont) was thoroughly dried in a vacuum oven and mixed in a drum with 0.5 wt. of the compound of Example 14 of the invention. The polyamide is extruded on an MPM extruder (2.54 cm) at. ^e at 302 C. The collected pellets are molded in a BOY 30M injection molder at 302 ° C and a mold temperature of 150 'C. Yellowing index values (Y1) are measured with the plates obtained using ASTM D 1925-70. Plates containing the compound of Example 14 of the invention exhibit lower yellowness index values (lower color change) than unstabilized control plates.

Example 25 '

Srabi-Lize AsS

A solution of 0.25 g of the compound of Example 14 according to the invention in 40 ml of hexane-methanol was added to a rapidly stirred suspension of 100 g of Α3Ξ (acrylonitrile / butadiene 7 / styrene terpolymer) in 600 g of water. The suspension is filtered and dried under vacuum at 40 ° C for 40 hours. To the dried powder in a two roll mill at 130 C ^and in the course of 4 minutes, add 2% by weight. % titanium dioxide and 1 wt. N, N'-ethylenebisstearamide. In the case of tecote 175 ^and C, the pressed aeszicx '

thickness of 0.3 mm and placed in an oven at 150 T for 45 minutes. The color of these plates is determined as yellowing index values using ASTM D 1925-70. Plates containing the compound of Example 14 of the invention exhibit lower yellowness index values (lower color change) than from xontrocal pathways <7 unstable in A35.

Claims (15)

Amorphous and crystalline modification of 1,1 ', 1' 'nitro (tri-2-propyltris [2,2'-ethylidenebis (4,6-di-tert-butylphenyl)] phosphite) of formula I CH, N (II s. e zim, it shows the glass transition temperature, differential scanning calorimetry, in the range 137 - 142 ^e C and its diffraction. the X-ray diffractometry pattern is bland, and the crystalline modification exhibits a melting point in the range of 234-274 ° C and its X-ray diffractometry pattern using Cu-Ka exhibits diffraction angles, 2 velmi, of very high intensity at 7.9 and 15.6, high intensity lines at 7.3, 8.9, 14.7, 16.8, 18.3, 13.9, 19.3 and 20.6, medium intensity lines at 13, 9, 22.6 and 24.0 and a weak intensity line at. 21.4. ujici τ, 7 'amorphous modification by determined potency 2. The method of claim 1, wherein said compounds are cooled. Amorphous modification of a compound of the formula characterized in that: it melts and the melt rapidly 3. A method as claimed in claim 2, wherein the cooked material is poured onto a cold surface. The method of claim 3, wherein the cold surface temperature is near 25 ° C. A process for preparing a crystalline modification of a compound of formula I according to claim 1, characterized in that the melt of said compound of formula I is heated to a temperature of 170 to 200 ° C and a new crystalline modification is crystallized. • 6. The method of claim 5, comprising inoculating the melt with a new crystalline modification to increase the melt crystallization rate and efficiency. The process according to claim 5, wherein the melt is heated under reduced pressure of from 1 to 50 psig. Process according to claim 5, characterized in that the melt crystallization is carried out in an extruder or kneading machine. 9. A composition comprising Se (a) organic material subject to oxidative, thermal and / or light-induced degradation, and / or crystalline b) an effective stabilizing amount of an amorphous modification of a compound of formula I according to claim 1. 10. The composition of claim 9, wherein the organic material is a lubricant, natural fat or wax or fat or wax on a betic acid ester. vnte A composition according to claim 9, characterized by - SO in that the organic material is a natural, semi-synthetic or synthetic polymer. 12. The composition of claim 9 wherein the organic material is a thermoplastic polymer. 13. The composition of claim 9 wherein the organic material is a polyolefin. 14. The composition of claim 9 wherein the organic polymer is polyethylene or polypropylene. 15. The composition of claim 9, wherein the organic material is polypropylene. 15. The composition of claim 9, further comprising a phenolic anti-oxidant base, an anti-light stabilizer, or a processing stabilizer. 17. The composition of claim 9, further comprising at least one benzofuran-2-one compound as an auxiliary additive. 13. A method of stabilizing an organic material against oxidative, thermal or light-induced degradation, wherein the material is incorporated into the material or an amorphous or crystalline modification of the compound of formula I is applied to the material of claim 1. . aouzoto amortn or ηοαΐΞΐ. <Ξ3 ~ merge pattern; Therefore, the material induced by the edition of claim 1 is added to thermal fusion.