GB2087399A - Polyol esters of alkylidene-2,2'-bis-phenyl cyclic phosphites - Google Patents

Abstract

Abstract of the Disclosure Compounds of formula <IMAGE> where R is 1-18C alkyl, R<1> is H or 1-18C alkyl, R<2> is 1-12C alkylene or arylene, R<3> is a selected n-valent organic radical, X is O or S and n is 2 to 6, are prepared by reacting alkylated 2,2'-alkylidene-bis-phenols with phosphorus trichloride in an organic solvent and then reacting the intermediate phosphorochlordite with a polyol. Said phosphites are useful stabilizers of organic polymers and lubricating oils, especially as processing stabilizers for polyolefins, elastomers, polyesters and polycarbonates.

Description

SPECIFICATION Polyol esters of alkylidene-2,2'-bis-phenyl cyclic phosphites Organic polymeric materials such as plastics and resins, lubricating and mineral oils are subject to thermal, oxidative and photodegradation. A great variety of stabilizers are known in the art for stabilizing various substrates. Their effectiveness varies depending on the causes of degradation and the substrate stabilized. During the course of this work, it was discovered that stabilizers that are very effective long term antioxidants are relatively poor process stabilizers and do not protect the substrate against thermal degradation for a short time at relatively high process temperatures. Many stabilizers are relatively incompatible with organic substrates creating problems during the life of a product and lessening the stabilizer's effectiveness.Some stabilizers are either too volatile or thermally or hydrolytically unstable to be practical as commercial stabilizers.

The phosphites of this invention possess an unusual combination of desirable properties as compared to the prior art phosphites which makes these compounds particularly effective and useful as stabilizers.

Phosphites are disclosed in a number of publications. U.S. 4,196,117 discloses biphenylcyclic phosphites wherein the phosphorus atom is substituted by 0- or S-hydrocarbyl or a second hydrocarbyl biphenyl cyclic phosphite group. Soviet Union patents 378,389, 429,070 and 440, 390 disclose the stabilization of various polymers with organic phosphites or mixtures including said phosphites wherein the phosphites are methylene-bisphenyl cyclic phosphites.

Additional 2,2'-biphenyl phosphites are disclosed in Chemical Abstracts, 68, 12597s (1968), 73, 15657c (1970) and 75, 130242g (1971). These various compounds are indicated to be stabilizers of various polymers. However, the instant polyol esters are significantly more effective as process stabilizers, as color stabilizers and in resistance to hydrolysis.

Accordingly, it is the primary object of this invention to provide biphenyl cyclic phosphite compounds which exhibit improved process stabilization performance as contrasted with previously known phosphite compounds.

Various other objects and advantages of this invention will become evident from the following description thereof.

The compounds of this invention correspond to the formula:

wherein R is an alkyl group of 1 to 18 carbon atoms; R1 is hydrogen or an alkyl group of 1 to 18 carbon atoms; R2 is alkylene or arylene of 1 to 1 2 carbon atoms; R3 is an n-valent radical selected from the group consisting of a straight- or branched-chain alkylene of 2 to 12 atoms; a straight-or branched-chain alkane-triyl, -tetrayl, -pentayl or -hexayl of 3 to 6 carbon atoms; alkenylene of 4 to 6 carbon atoms; cycloalkylene of 6 to 12 carbon atoms; 1 ,4-cyclohexanedimethylene; arylene or arenetriyl of 6 to 10 carbon atoms; p-xylylene; phenylene-E-phenylene where E is a direct bond, -0-, -S-, -NR4-, where R4 is alkyl of 1 to 18 carbon atoms; a straight- or branched-chain alkylene or alkylidene or 1 to 12 carbon atoms or cycloalkylidene of 5 to 6 carbon atoms; said arylene or said phenylene-E-phenylene substituted by 1 to 4 alkyl groups each having 1 to 8 carbon atoms, (CH2)pX(CH2)p where p is 2 to 6, dipentaerythrityl, and

where Y is hydrogen, methyl or ethyl and z is 1 to 10; x is oxygen or sulfur: and n is an integer of 2 to 6.

A preferred subclass of compounds falling under formula I is that in which R is located in the ortho position to the phosphite oxygen in each phenyl ring.

The R and R1 groups are preferably straight-chain or branched alkyl with 4-8 carbon atoms, such as n-butyl, sec.-butyl, tert.-butyl, tert.-pentyl, 2-ethylhexyl, n-octyl and tert-octyl.* The groups tert-butyl, tert-pentyl and tert-octyl are especially preferred. Also especially preferred is for the R1 group to be in the para position to oxygen, particularly if R1 is tert.-alkyl.

1 1 , 1 , 3, 3-tetramethylbutyl Although R1 can be hydrogen or alkyl of 1 to 18 carbons, preferably it is an alkyl group of 1 to 8 carbon atoms either straight-chain or branched-chain. Especially preferred is tert.-alkyl of 4 to 8 carbon atoms.

R2is preferably alkylene or arylene of the formula

wherein R5 and R6 are independently hydrogen, alkyl of 1 to 11 carbon atoms or aryl, provided that the total number of carbon atoms does not exceed 11. Typical aryl groups for purposes of these various substituents include phenyl, tolyl, mesityl, xylyt and 1- and 2-naphthyl. Especially preferred as R2 is methylene or ethylidene.

R3 is preferably ethylene, hexamethylene, 3-thia-pentamethylene or a group of formulae

The alkylated alkylidene -2,2'-bis-phenyl cyclic phosphites of this invention can be prepared by reacting an alkylated 2,2'-alkylidene-bisphenyl with phosphorus trichloride in a solvent to give the corresponding phosphorochlorodite which, in turn, is reacted with a polyol in the presence of a proton acceptor, such as a tertiary amine, to yield the desired product.

The solvent is preferably aromatic, such as benzene, toluene, xylene and the like. The reaction temperature is from about room temperature to the reflux temperature of the reaction medium.

The tertiary amine may be a trialkyl amine such as triethyl amine or other hydrocarbyl tertiary amines such as pyridine or substituted pyridines. The synthesis of the compounds of this invention is represented by the following sequences of equations (depicted in terms of the preferred compounds).

where B is a cyclic or acyclic tertiary amine useful as a proton acceptor and the other symbols are as previously defined.

An analogous synthetic method involves substituting alkali metal hydroxides or alkali metal carbonates for tertiary amines in the synthetic scheme shown above. The above reaction sequences can be conducted to yield the compounds of this invention without isolation of the intermediate chlordite 11.

The compounds of this invention are effective light stabilizers and/or antioxidants in a wide range of organic polymers. Polymers which can be stabilized include: 1. Polymers of monoolefins, for example polyethylene (which optionally can be crosslinked), polypropylene, polyisobutylene, polybutene1, polymethylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyethylene or with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as, for example, ethylene/propylene, propylene/butene- 1, propylene/isobutylene, ethylen e/ butene- 1, propylene/ butadiene, isobutylene/isoprene, ethylene/ethyl acrylate, ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene.

4. Polystyrene 5. Random copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylates, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer of an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/ butylene/styrene or styrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known as ABS-, MBS-, or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, polymers from halogen-containing vinyl compounds, as for exzample, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinylidene chloride vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

8. Polymers which are derived from a,-saturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other or with other unsaturated monomers, such as, for instance, acrylonitrile/butadiene, acrylonitrile/alkyl acrylate or acrylonitrile/vinyl chloride copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolym- ers.

10. Polymers which am derived from unsaturated alcohols and amines, or acyl derivatives thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer.

13. Polyphenylene oxides and sulfides.

14. Polyurethanes which are derived from polyethers, polyesters or polybutadienes with terminal hydroxyl groups on the one side and aliphatic or aromatic polyisocyanates on the other side, as well as precursors thereof.

15. Polyamides and copolyamides which are derived from di-amines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-2,4,4trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide, as well as copolymers thereof with polyethers, such as, for instance, with polyethylene glycol, polypropylene glycol or polytetra-methylene glycols.

16. Polyureas, polyimides and polyamide-imides.

16. Polyesters which are derived from dicarboxylic acids and glycols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-l ,4-dimethyiol-cyclohexane terephthalate and polyhydroxybenzoates as well as block-copolyether esters derived from polyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones and polyethersulfones.

20. Crosslinked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/ formaldehyde resins and melamine/formaldehyde resins 21. Drying and non-drying alkyd resins.

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

23. Thermosetting acrylic resins, derived from substituted acrylic esters, such as epoxyacrylates, urethane-acrylates or polyester-acrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture with melamine resins, urea resins, polyisocyanates or epoxide resins as cross-linking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, for example from bis glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivatives thereof which are chemically modified in a polymer-homologous manner, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methylcellulose.

27. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, which materials may be used as plasticizer for polymers or as textile spinning oils, as well as aqueous emulsions of such materials.

28. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolmers.

Compounds of this invention are also particularly effective in stabilizing mineral and synthetic fluids such as lubricating oils, circulating oils, etc.

The compounds of this invention are particularly useful as stabilizers, expecially for the protection of polyolefins, for instance, polyethylene, polypropylene, polyisobutylene, poly(butene-1), poly(pentene- 1), poly(3-methylbutene- 1), poly(4-methylpentene-1), various ethylenepropylene copolymers and the like.

Other substrates in which the compounds of this invention are particularly useful are polystyrene, including impact polystyrene, ABS resin, SBR, isoprene, as well as natural rubber, polyesters including polyethylene terephthalate and polybutylene terephthalate including copolymers. Also stabilized are polyurethanes, polycarbonates, polyamides such as nylon 6, 6/6 and the like as well as the copolyamides and polysulfones.

The compounds of this invention may be used alone as the sole stabilizer having either mainly an antioxidant function or a light stabilizing function or the stabilizer may combine utility as an antioxidant and light stabilizer. The stabilizers may be used with phenolic antioxidants, lubricants such as calcium stearate, pigments, colorants or dyes, UV absorbers, light stabilizers such as hindered amines, metal deactivators, talc and other fillers, etc.

In general, the stabilizers of this invention are employed from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 2%, and especially 0.1 to about 1%.

Compounds of this invention stabilize polymers especially during high temperature processing with relatively little change in color, even though the polymer may undergo a number of extrusions. Among the polymers in which this property is especially apparent are polypropylene, polyethylene, styrenics such as ABS, polyethylene- and polybutylene-terephthalates, polycarbonates, natural rubber, synthetic rubber such as SBR. While many compounds which have been used as process stabilizers are sufficiently effective as process stabilizers for polyolefins only in the presence of costabilizers such as phenolic antioxidants, compounds of this invention are effective also in the absence of phenolic antioxidants. Many of the compounds of this invention combine process stabilizing properties with the ability to confer light stability on the polymer.

This is particularly important for polymer fibers where processing temperatures are among the highest and where stability to actinic light is a prime requirement.

A particularly important property for stabilizers which are trivalent phosphorus esters is their non-hygroscopicity and resistance to hydrolysis in the presence of moisture in the atmosphere during ambient storage, especially at temperatures during summer sub-tropical as well as tropical conditions. Hygroscopicity frequently results in difficulty in incorporating the process stabilizer uniformly into the polymer causing stickiness and blockage during compounding, while hydrolysis of the phosphorus ester stabilizers during storage frequently results in compounds which are less effective.

The stabilizers of this invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The stabilized polymer compositions of the invention may optionally also contain various conventional additives, such as the following: 1. Antioxidants 1.1 Simple 2,6-dialkylphenols, such as, for example, 2,6-di-tert.-butyl-4-methylphenol, 2 tert.-butyl-4, 6-dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-di-octadecyl-4methylphenol.

1.2 Derivatives of alkylated hydroquinones, such as, for example, 2,5-di-tert.-butyl-hydroqui- none, 2, 5-di-tert.-amylhydroquinone, 2, 6-di-tert.-butyl-hydroquinone, 2, 5-di-tert.-butyl-4-hy- droxy-anisole, 3, 5-di-tert.-butyl-4-hydroxy-anisole, tris-(3, 5-di-tert.-butyl-4-hydroxyphenyl) phosphite, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) adipate.

1.3 Hydroxylated thiodiphenyl ethers, such as, for example, 2,2'-thio-bis-(6-tert.-butyl-4methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'thio-bis-(3,6-di-sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulphide.

1.4 Alkylidene-bisphenols, such as, for example, 2,2'-methylene-bis-(6-tert.-butyl-4-methyl- phenol), 2,2'-methylene-bis-(6-tert.-butyl-4-ethylphenol), 4,4'-methylene-bis-(6-tert.-butyl-2-methylphenol), 4,4'-methylene-bis-(2, 6-di-tert.-butyl-phenol), 2, 6-di-(3-tert.-butyl-5-methyl-2-hydrox- ybenzyl)-4-methylphenol, 2,2'-methylene-bis-[4-methyl-6-)&alpha;;-methylcyclohexyl)-phenol], 1,1-bis- (3, 5-d imethyl-2-hydroxyphenyl)-buta ne, 1,1 1 , 1 -bis-(5-tert.-butyl-4-hyd roxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hyd roxy-2-methylphenyl)-4-n-dodecylmercapto-butane, 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-pentane and ethylene glycol bis- [ 3,3-bis (3 '-tert.-butyl-4'-hydroxyphenyl)-butyrate ] .

1.5 0-, N- and S-benzyl compounds, such as, for example, 3,3',5,5'-tetra-tert.-butyl-4,4'dihydroxydibenzyl ether, octadecyl 4-hydroxy-3, 5-di methyl benzyl-mercaptoacetate, tris-(3, 5-di- tert.-butyl-4-hydroxybenzyl)-am i ne and bis-(4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithioterephthalate.

1.6 Hydroxybenzylated malonates, such as, for example, dioctadecyl 2,2-bis-(3,6-di-tert.butyl-2-hydroxybenzyl)-malonate, dioctadecyl 2-(3-tert.butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercapto-ethyl 2, 2-bis-(3, 5-di-tert.-butyl-4-hydroxybenzyl)-malonate and di [ 4-(1 , 1 '3,3tetramethylbutyl)-phenyl ] 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyis-malonate.

1.7 Hydroxybenzyl-aromatic compounds, such as, for example, 1 ,3,5-tris(3,5-di-tert.-butyl-4- hydroxybenzyl)-2,4,6-trimethyl-benzene, 1 , 4-d i-(3, 5-d i-tert.-butyl-4-hydroxybenzyl)-2, 3,5, 6-tet- ramethylbenzene and 2,4,, 6--tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-phenol .

1.8 s-Triazine compounds, such as, for example, 2,4-bis-octylmernapto-6-(3,5-diAert.-butyl-4- hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyanilino)-s-triazine, 2-octyl mercapto-4, 6-bis(3, 5-d i-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4, 6-tris-(3, 5-di-tert.-bu- tyl-4-hyd roxyphenoxy)-s-triazine, 2,4,6-tris(3,5-di-tert.-butyl-4-hydroxyphenylethyl)-s-triazine and 1 3, 5-tris-(3, 5-d i-tert.--butyl-4-hyd roxybenzyl) isocyanurate.

1.9 Amides of (ss-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, such as, for example, 1,3,5-tris(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine, N,N'-di(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine and N, N'-bis-ss-( (3, 5-di4--butyl-4-hy- droxyphenyl)-propionylhydrazine.

1.10 Esters of ss-(3, 5-di-tert.-butyl-4-hydroxypheny!)-propionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 ,2-propanediol, diethylene glycol, thiodiethyleneglycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl- 1 -phospha- 2,6, 7-trioxabicyclo- [ 2,2,2 ] )octane.

1.11 Esters of fi-(5-tert. -butyl-4-hydroxy-3-methyl-phenyl)-propionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1 ,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethyleneglycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethyl-hexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1 -phospha- 2,6,7 trioxabicyclo[2,2,2]octane.

1.12 Esters of 3,5-di-tert.-butyl-4-hydroxyphenyl-acetic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, ocatdecanol, 1,6-hexanediol, 1,9nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiglycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylol propane, tris-hydroxyethyl isocyan urate and 4-hydroxymethyl- 1 -phospha-2, 6, 7-trioxa- bicyclo [ 2,2,2 ] -octane, especially the tetra-bis ester of pentaerythritol.

1.13 Benzylphosphonates, such as, for example, dimethyl 3,5-di-tert.-butyl-4-hydroxybenzyl- phosphonates, diethyl 3, 5-di-tert.-butyl-4-hydroxybenzyl-phosphonate, dioctadecyl 3, 5-di-tert.- butyl-4-hydroxybenzyl-phosphonate and dioctadecyl 5-d i-tert.-butyl-4-hydroxy-3-methyl benzylphosphonate.

The following may be mentioned as examples of further additives that can be used together with the stabilizer of this invention and the antioxidant: 1. Aminoaryl derivatives, e.g. phenyl-1-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylene-diamine, N, N '-di-2-naphthyl-p-phe- nylenediamine, N,N'-di-sec.-butylo-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2, 2,4-trimethyl-1 , 2-dihydro-quinoline, mono- and dioctyliminodibenzyl, polymerized 2, 2,4-trimethyl- 1 , 2-dihydroquinoline. Octylated diphenylamine, nonylated diphenylamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-pehnyl-N '-isopropyl-p-phenylenediamine, N, N '-di sec. octyl-p-phenylenediamine, N, N'-di-( 1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-dimethyl N,N'-di-(sec.-octyl)-p-phenylenediamine, 2, 6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec.-butylaniline, diphenylamine-acetone condensation product, aldol-1-naphthylamine and phenothiazine.

Discoloration effects have to be taken into account when using the above antioxidants.

2. UV-Absorbers and light-stabilising agents 2.1 2-(2'-Hydroxyphenyl)-benzotriazoles, e.g. the 5'-methyl-, 3',5'-di-tert.-butyl-, 5'-tert. butyl-, 5'-(1 1 ,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.-butyl-, 5-chloro-3'-tert.-butyl-5'-me- thyl-, 3'-sec.-butyl-5'-tert .-butyl, 3'-a-methylbenzyl-5 '-methyl-, 3 '-a-methylbenzyl-5'-methyl-5chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.-amyl-, 3 'methyl-5'-carbomethoxyethyl- and 5-chloro-3',5'-di-tert.-amyl-derivative.

2.2 2, 4-bis-(2'-Hydrnxyphenyll-6-alkyl-s-tnazines, e.g. the 6-ethyl-, 6-heptadecyl- or 6-undecyl-derivative.

2.3 2-Hydroxybenzophenones, e.g. the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy- or 2'-hydroxy-4,4'- dimethoxy-derivative.

2.4 1,3-bis-(2'-Hydroxybenzoyl)-benzenes, e.g. 1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1 , 3 ,-bis(2'-hydroxy-4'-octyloxy-benzoyl)-benzene or 1 , 3-bis--(2'-hydroxy-4'-dodecyloxy-ben- zoyl)-benzene.

2.5 Esters of optionally substituted benzoic acids, e.g. phenylsalicylate, octylphenylsalicylate, dibenzoylresorcin, bis-(4-tert.-butylbenzoyl)-resorcin, benzoylresorcin, 3, 5-di-tert.-butyl-4- hydroxybenzoic acid-2,4-di-tert.-butylphenyl ester or -octadecyl ester or -2-methyl-4,6-di-tert.butyl ester.

2.6 Acrylates, e.g. -cyano-,ll, fi-diphenylacrylic acid-ethyl ester or -isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-P--methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester or N-(fi-carbomethoxyvinyl)-2-methyl-indoline.

2.7 Sterically hindered amines, e.g. 4-benzoyl-2-,2,6,6-tetrnmethylpiperidine, 4-stearyl-oxy2,2,6, 6-tetramethylpiperidine, bis-(2,2,6, 6-tetramethylpiperidyl)-sebacate or 3-n-octyl-7,7,9,9tetramethyl-1,3,8-triaza-spiro[4,5]decane-2,4-dione.

2.8 Oxalic acid diamides, e.g. 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.-butyloxanilide, 2, 2'-di-dodecyloxy-5, 5'-di-tert.-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N '-bis-(3 dimethyl-aminopropyl)-oxalamide, 2-ethoxy-5-tert.-butyl-2'-ethyl-oxanilide and the mixture thereof with 2-ethoxy-2'-ethyl-4,5'-di-tert.-buWl-oxanilide, or mixtures of ortho- and para-methoxy- as well as o- and p-ethoxy-disubstituted oxanilides.

3. Metal deactivators, e.g. oxanilide, isophthalic acid dihydrazide, sebacic acid-bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetal-adipic acid dihydrazide, N,N'diacetal-adipic acid dihydrazide, N,N'-bis-salicyloyl-oxalic acid dihydrazide, N,N'-bis-salicylol- hydrazine, N,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)-hydrazine, N-salicyloyl-N'-salicylalhydrazine, 3-salicyloyl-amino-1,2,4-triazole or N,N'-bis-salicyloyl-thiopropionic acid dihydrazide.

4. Basic co-stabilizers, e.g. alkali metal salts and alkaline-earth metal salts of higher fatty acids, for example Ca-stearate, Zn-stearate, Mg-behenate, Na-ricinoleate or K-palmitate.

5. Nucleation agents, e.g. 4-tert.-butylbenzoic acid, adipic acid or diphenylacetic acid.

6. Phosphites, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldi- alkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9 isodecyloxy-2,4, 8,1 0-tetraoxa-3, 9-diphospha [ 5, 5 ] -undecane and tri-(4-hydroxy-3, 5-di-tert.-butyl- phenyl) phosphite.

Other additives that can be incorporated in the stabilized compositions are thiosynergists such as dilaurylthiodiproprionate or distearylthiodipropionate, lubricants such as stearyl alcohol, fillers, carbon black, asbestos, kaolin, talc, glass fibers, pigments, optical brighteners, flameproofing agents and antistatic agents.

While the instant phosphites can be beneficially used as stabilizers for a variety of substrates, particularly the polyolefins, both alone and in conjunction with other coadditives, the combination of the instant phosphites with selected hindered phenolic antioxidants exhibits enhanced and particularly salubrious protection to such substrates.The phenolic antioxidants found to be particularly useful are selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, 4,4'-thio-bis(6-tert-butyl-3-methylphenol), 2,2 '-methylene-bis(6-tert-butyl-4-methylphenol), 4,4' methylene-bis-(2,6-d i-tert-butyl phenol), 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1 , 3, 5-tris(3, 5-di-tert-butyl-4-hydroxybenzyl)-2, 4, methylbenzene, 2- octylthio-4,6-bis(3, 5-di- tert-butyl-4-hydroxyanilino)-s-triazine, n-octadecyl 3, 5-d i-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3, 5-d i-tert-butyl-4-hyd roxy-hydrocinnamate), 1 , 3, 5-tris(3, 5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate thiodiethylene bis(3,5-d 5-di-tert-butyl-4-hydrnxy-hydrncinnamate) and tris (2-hydroxyethyl) isocyanate ester of ss-3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid.

The compositions comprise (1) a substrate, preferably a polyolefin such as polypropylene, (b) about 0.01 to about 5% by weight of the composition, preferably about 0.025 to about 2% and most preferably 0.025 to 1 % of an instant phosphite compound mixture thereof, and optionally, (c) a phenolic antioxidant or mixture of said antioxidants selected from the group cited directly above and also in a range of 0.01 to 5%, preferably 0.05 to 1%, by weight of the composition.

Likewise, the following light stabilizers are preferred for use, either alone or in conjunction with the listed phenolic antioxidants, as additives for incorporation with the instant stabilizers into the listed substrates: 2-(2'-hydroxy-5 '-methylphenyl)benzotriazole; 2-(3'5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2-(2 '-hydroxy-3 '5 '-d i-tert-amyl phenyl) benzotriazole; nickel bis [ 0- ethyl-(3,5-di-tert-butyl-4-hydroxybenzyl) ]phosphonate; bis (1,2,2,6,6-phentamethyl-4-piperidyl)- 2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate ; bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate; dimethylsuccinate polymer with 4-hydroxy-2, 2,6, 6-tetramethyl-1 -piperidinethanol; and polymer of 2,4-dichloro-6-octylamino-s-triazine with N '-(2,2,6, 6-tetramethyl-4-piperidyl) hexamethylene diamine.

The following examples illustrate the preferred embodiment of the invention. In these examples, all parts are given by weight unless otherwise specified.

EXAMPLE A O1,O-[2,2'-methylene-bis)4,6-di-tert-butylphenyl)]phosphorochlorodite A 500 ml flame-dried flask under nitrogen was charged with 6.87 grams phosphorus trichloride and 100 mis of toluene. Maintaining the temperature at 10-15, a solution of 21.27 grams 2,2'-methylenebis(4,6,-di-tert-butylphenol) and 1 grams triethylamine was added over 15 minutes. The reaction was stirred at ambient temperature until disappearance of starting bisphenol as shown by IR and TLC. The reaction was filtered, rotary evaporated, and recrystallized from heptane yielding 11.0 grams white crystals M.P. 207-217.

Analysiscalculated: C, 71.22; H, 8.66. Found: C, 71.44; H, 8.62.

In a similar manner the following phosphorchlorodites were made: * O1,O-[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)]phosphorochlorodite * O1,O-[2,2'-methylene-bis(4,6-di-tert-amylphenyl)]phosphorochlorodite Ol ,02 [ 2, 2'-methylene-bis(4-methyl-6Aert-butylphenyl)3 phosphorchlorodite * 0',02-C2,2'-b utyl ide ne-bis(4, 6-d i-tert-butyl phosphorochlorodite O1,O-[2,2'-(2-hexylidene)-bis(4,6-di-tert-butylphenyl)] phosphorochlorodite 0 02-C2, 2 '-dodecyl iden e-b is(4. 6-di-tert-butylphenyl) ] ) phosphorochlorodite Ol ,02- [ 2,2'-methylene-bis(4, 6-diAert-octyIphenyI) phosphorochlorodite O1,O-[2,2'-methylene-bis(4-tert-butyl-6-n-octadecylphenyl)] phosphorochlorodite O1,O-[2,2'-ethylidecne-bis(4,6[di-tert-amylphenyl)]phosphorochlorodite * characterized by IR spectra EXAMPLE I 0,0 '-Hexameth ylene-bisfO , 02-2, 2 '-meth ylene-bis (4, 6-di-tert-butylphenyl)phosphite ] A one-liter flame-dried flask under nitrogen was charged with 18.75 grams phosphorus trichloride and 200 ml toluene. Maintaining the temperature between 10 to 15 C,a solution of 58 grams 2,2'-methylene-bis(4,6-di-tert-butylphenol) and 27.64 grams triethylamine in 250 mis toluene was added. The reaction was stirred at ambient temperature until disappearance of starting bisphenol by IR and TLC. A solution of 8.7 grams 1,6-hexanediol in 13.82 grams triethylamine was added at 10 C. The reaction was stirred at ambient termperature until complete by IR and TLC. The reaction was filtered, rotary evaporated, and recrystallized from toluene: acetone yielding 46.1 grams white powder M.P. 259-267*C. Analysis Calculated: C, 75.11; H, 9.46. Found: C, 75.23; H, 9.06.

Employing the procedure of EXAMPLE I, other compounds of the invention were prepared as shown in TABLE I.

TABLE I EXAMPLES 2 to 17

EX R1 R R2 n X R3 M.P. C. Form Recryst. Solvent CH3 -CH2 8 4,4'-t-Butyl t-Butyl -CH- 3 0 -CH2-C-CH2-CH3 285-295 White Crystals Acetonitrile -CH2 9 4,4'-t-Butyl t-Butyl -CH2- 2 0 -CH2CH2-S-CH2CH2- 239-247 White Crystals Trituration CH3 with Acetone 10 4,4'-t-Butyl t-Butyl -CH3- 2 0 -CH2CH2-S-CH2CH2- 257-75 White Crystals Toluene CH3 n-Heptane 11 4,4'-t-Amyl t-Amyl -CH- 2 0 -CH2CH2-S-CH2CH2- 157-165 White Crystals 2-Butanone CH3 12 4,4'-t-Amyl t-Amyl -CH 2 0 -(CH2)6- 189-209 White Crystals 2-Butanone 13 4,4'-t-Amyl t-Amyl -CH2- 2 0 -(CH2)6- 175-178 White Crystals Toluene14 4,4'-t-Octyl t-Octyl -CH2- 2 0 -CH2CH2- Acrylonitrile 15 4,4'-n-Octa- t-Butyl -CH2- 2 0 -CH2-(CH)-4-CH2 decyl 16 4,4'-t-Butyl t-Butyl -CH2- 2 5 -CH2CH217 3,3'-CH3 t-Butyl -CH2- 2 0 -CH2(CH2)10CH2

EX R1 R R2 n X R3 M.P. C. Form Recryst. Solvent CH3 -CH2 8 4,4'-t-Butyl t-Butyl -CH- 3 0 -CH2-C-CH2-CH3 285-295 White Crystals Acetonitrile -CH2 9 4,4'-t-Butyl t-Butyl -CH2- 2 0 -CH2CH2-S-CH2CH2- 239-247 White Crystals Trituration CH3 with Acetone 10 4,4'-t-Butyl t-Butyl -CH- 2 0 -CH2CH2-S-CH2CH2- 257-75 White Crystals Toluene CH3 n-Heptane 11 4,4'-t-Amyl t-Amyl -CH- 2 0 -CH2CH2-S-CH2CH2- 157-165 White Crystals 2-Butanone CH3 12 4,4'-t-Amyl t-Amyl -CH 2 0 -(CH2)6- 189-209 White Crystals 2-Butanone 13 4,4'-t-Amyl t-Amyl -CH2- 2 0 -(CH2)6- 175-178 White Crystals Toluene14 4,4'-t-Octyl t-Octyl -CH2- 2 0 -CH2CH2- Acrylonitrile 15 4,4'-n-Octa- t-Butyl -CH2- 2 0 -CH2-(CH)-4-CH2 decyl 16 4,4'-t-Butyl t-Butyl -CH2- 2 5 -CH2CH217 3,3'-CH3 t-Butyl -CH2- 2 0 -CH2(CH2)10CH2 EXAMPLE 18 Processing Stability of Polypropylene Base Formulation:: Polypropylene* 100 parts Calcium stearate 0.10 parts Pentaerythrityl tetrakis - [ 3-(3, 5-di-tert.-butyl-4- hydroxyphenyl)-propionate 0.10 parts * Profax 6801 from Hercules Chemical Stabilizers were solvent blended into polypropylene as solutions in methylene chloride and, after removal of the solvent by evaporation at reduced pressure, the resin was extruded using the following extruder conditions: Temperature ( C) Cylinder 1 - 232 Cylinder 2 - 246 Cylinder 3 - 260 Die &num;1 - 260 Die &num;2 - 260 Die &num;3 - 260 RPM - 100 During extrusion (after each of the first, third and fifth extrusions) the internal extruder pressure was determined using a pressue transducer.

Table II Extrusion Temp-260'C Transducer Pressure Phosphite After Extrusion (psi) 1 2 5 None 1450 1350 1150 0.05% EX.1 1600 1500 1500 0.05% EX.6 1600 1600 1450 0.05% EX.9 1800 1800 1700

Claims (15)

CLAI MS

1. A compound of the formula:

wherein R is alkyl or 1 to 18 carbon atoms, R' is hydrogen or alkyl or 1 to 18 carbon atoms, R2 is alkylene or arylene of 1 to 1 2 carbon atoms, R3 is an n-valent radical selected from the group consisting of a straight- or branched-chain alkylene of 2 to 12 atoms; a straight- or branched chain alkane-triyl, -tetrayl, -pentayl or -hexayl of 3 to 6 carbon atoms; alkenylene of 4 to 6 carbon atoms; cycloalkylene of 6 to 12 carbon atoms; 1 ,4-cyclohexanedimethylene; arylene or arenetriyl of 6 to 10 carbon atoms; p-xylylene; phenylene-E-phenylene where E is a direct bond -0-, -S-, -NR4-, where R4 is alkyl of 1 to 1 8 carbon atoms; a straight- or branched chain alkylene or alkylidene of 1 to 12 carbon atoms or cycloalkylidene of 5 to 6 carbon atoms; said arylene or said phenylene-E-phenylene substituted by 1 to 4 alkyl groups each having 1 to 8 carbon atoms, -(CH2)pX(CH2)p where p is 2 to 6, dipentaerythrityl, and -(CH2C HO)z(CH2CH) Y Y where Y is hydrogen, methyl or ethyl and z is 1 to 10; X is oxygen or sulfur; and n is an iteger of 2 to 6.

2. A compound as claimed in claim 1, wherein R is in the ortho position relative to the phosphite group in each phenyl ring.

3. A compound as claimed in claim 1 or 2, wherein R is alkyl of 4 to 8 carbon atoms

4. A compound as claimed in any preceding claim, wherein R is tert.-butyl, tert.-pentyl, or 1, 1 , 3, 3-tetramethylbutyl.

5. A compound as claimed in any preceding claim, where R' is alkyl of 1 to 8 carbon atoms

6. A compound as claimed in any preceding claim, wherein R2 is alkylene or arylene of the formula

wherein R5 and R6 are independently hydrogen, alkyl of 1 to 11 carbon atoms or aryl, provided that the total number of carbon atoms does not exceed 11.

7. A compound as claimed in any preceding claim, wherein R2 is methylene or ethylidine.

8. A compound as claimed in any preceding claim, wherein R3 is ethylene, hexamethylene, 3-thia-pentamethylene or a group of formulae

9. A composition of matter comprising an organic material subject to oxidative, thermal and actinic degradation stabilized with an effective stabilizing amount of a compound as claimed in any one of the preceding claims.

10. A composition as claimed in claim 9, wherein the organic material is a synthetic polymer.

11. A composition as claimed in claim 10, wherein said polymer is a polyolefin homopo lymer or copolymer.

12. A composition as claimed in any of claims 9 to 11, which also contains a phenolic antioxidant.

13. A composition as claimed in any of claims 9 to 12, which also contains a light stabilizer.

14. A compound as claimed in claim 1 substantially as hereinbefore described with reference to any one of Examples 1 to 17.

15. A composition as claimed in claim 9 substantially as hereinbefore described with reference to Example 18.