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United States Patent m Spivack [ii] 4,233,208 [45] Nov. 11, 1980 [54] POLYMER COMPOSITIONS STABILIZED WITH HINDERED PHENYL SECONDARY PHOSPHITES [75] Inventor: John D. Spivack, Spring Valley, N.Y. [73] Assignee: Ciba-Geigy Corporation, Ardsley, N.Y. [21] Appl. No.: 923,836 [22] Filed: Jul. 12, 1978 Related U.S. Application Data [63] Continuation of Ser. No. 661,585, Feb. 26, 1976, aban doned. [51] Int. CU..........................C08K 5/51; C08K 5/52 [52] U.S. Cl..................... 260/45.8 NT; 260/45.7 PH; 260/45.85 B; 260/45.85 S; 260/45.9 NC; 260/45.95 D; 260/45.95 H [58] Field of Search ................ 260/45.7 PH, 45.85 S, 260/45.8 NT [56] References Cited U.S. PATENT DOCUMENTS 2,437,046 3.115,465 3,188,298 3,206,431 3,281,506 3,301,816 3,425,987 3,487,044 3,636,031 3/1948 12/1963 6/1965 9/1965 10/1966 1/1967 2/1969 12/1969 1/1972 Rothrock, Jr. et al...... 260/45.7 PH Orloffetal................. 260/45.7 PH Williamson et al............ 260/45.95F Doyle et al........................ 106/182 Shepard et al..................... 260/960 Burgess ...................... 260/45.95 F Oswald et al............... 260/45.7 PH Tholstrup ................... 260/45.85 S Drake et al................. 260/45.8 NT 3,637,555 1/1972 Marinacci et al............ 260/45.85 S 3,781,242 12/1973 Mathis et al................ 260/45.8 NT FOREIGN PATENT DOCUMENTS 763491 7/1967 Canada . Primary Examiner--Howard E. Schain Assistant Examiner--R. A. White Attorney, Agent, or Firm--Harry Falber [57] ABSTRACT Organic polymeric materials normally subject to oxida tive and ultraviolet light deterioration are stabilized by incorporating therein a compound of the formula wherein R is hydroxyl or chlorine, Y and Y' are inde pendently alkyl, aralkyl or halogen, and Z is indepen dently hydrogen, halogen, alkyl or aralkyl. 26 Claims, No Drawings 4,233,208 12 Y and Y' are independently alkyl having from 1 to 12, POLYMER COMPOSITIONS STABILIZED WITH especially 3 to 12 carbon atoms, aralkyl having HINDERED PHENYL SECONDARY PHOSPHITES from 7 to 12 carbon atoms or halogen, preferably chlorine and bromine, and This is a continuation of application Ser. No. 661,585 5 Z is independently hydrogen, halogen, alkyl having filed on Feb. 26, 1976, now abandoned. from 1 to 12 carbon atoms or aralkyl having from BACKGROUND OF THE INVENTION 7 to 12 carbon atoms. Y and Y' can be straight- or branched-chain alkyl Most organic polymers, especially polyolefins such as having from 1 to 12, especially 3 to 12, carbon atoms. polyethylene or polypropylene, which are used for 10 Examples of Y and Y' are 1,1-dimethylpropyl, 1,1,3,3- manufacturing articles tend to develop color with pas tetramethylbutyl, 1,1,2-trimethylpropyl, isopropyl, tert- sage of time. The discoloration may be due to various butyl, 1,1-dimethylbutyl, nonyl, and dodecyl. Prefera factors such as the decomposition of the polymer, the bly, Y and Y' are isopropyl and tert-butyl groups, most antioxidant or to the presence of residual metal catalyst preferably tert-butyl groups. or residual peroxides used to control polymerization. It 15 Y and Y' can be aralkyl having from 7 to 12 carbon may also be due to the basic nature of polymeric mate atoms. One or two alkyl substituents may be present on rial, the additives used in the polymeric material or the the aromatic ring of the aralkyl group. Examples of effect of heat on the polymeric material. The develop such aralkyl groups are benzyl, phenylethyl, phenyl- ment of color is undesirable because it indicates poly propyl, p-methylbenzyl, phenylhexyl, 3,5-dimethylben- mer degradation and results in further reduction of the 20 zyl, a,a-dimethylbenzyl, and a,p-dimethylbenzyi. quality of the polymer. Thus, one of the objects of this Z can be hydrogen, halogen, preferably hydrogen invention is to provide a stabilized composition which and chlorine, alkyl having from 1 to 12 carbon atoms, would improve the quality of polymers by preventing preferably methyl, isopropyl, tert-butyl and nonyl, or the discoloration of the polymer. aralkyl having from 7 to 12 carbon atoms, preferably The prior art discloses many materials which inhibit 25 benzyl, phenylethyl and phenylpropyl. the discoloration of polymers on exposure to heat and Z can be straight- or branched-chain alkyl having light. It is well known to stabilize polyolefins and sty- from 1 to 12 carbon atoms. Examples are methyl, iso renic polymers by the use of phosphites. Thus, for ex propyl, tert-butyl, nonyl and dodecyl. Preferably, Z is ample, phosphites can be used in conjunction with UV methyl or tert-butyl. absorbers such as benzophenones and benzotriazoles to 30 Z can be aralkyl having from 7 to 12 carbon atoms. achieve improved stabilization of polypropylene on One or two alkyl substituents may be present on the outdoor exposure to sunlight. However, a phosphite is aromatic ring of the aralkyl group. Examples are ben generally not used as the sole light stabilizer in polypro zyl, phenylethyl, phenylpropyl, p-methylbenzyl, a-p- pylene because of its limited effectiveness. Unexpect dimethylbenzyl, phenylhexyl, 3,5-dimethylbenzyl, and edly, it has been found that the phosphites of this inven 35 a,a-dimethylbenzyl. tion can be used effectively in polymers, such as poly It is understood that although R has been defined as propylene, as the sole light stabilizer. Furthermore, it OH, compounds of formula I consist of 2 tautomers in has also been surprisingly found that these phosphites equilibrium with one another: act as effective antioxidants for polymers, both when used alone and in combination with thiosynergists. 40 It is also well known in the art to use phosphites in conjunction with hindered phenols as stabilizers for unsaturated elastomers. A notable example of a phos phite widely used in such a combination is trinonylphenyl phosphite (TNPP). It has now been found that the 45 R'O OR" R'O phosphites of this invention are surprisingly much more where R' and R" represent % OR" effective color stabilizers and antioxidants than trino- nylphenyl phosphite. DETAILED DISCLOSURE 50 This invention accordingly relates to compositions comprising organic materials stabilized with com pounds having the formula Z P cr wherein R is hydroxyl or chlorine, preferably hydroxyl, 55 The compositions of matter of this invention which are stabilized against deterioration comprise a polymer normally subject to deterioration containing from about 0.005% to 5% by weight of the polymer of the com pounds of formula I. Organic materials such as, for 60 example, the following polymers, can be stabilized using the compounds of the formula I. 1. Polymers which are derived from hydrocarbons with single or double unsaturation, such as polyole fins, for example, polyethylene which can option 65 ally be crosslinked, polypropylene, polyisobutyl ene, polymethylbutene-1, polymethylpentene-1, polybutene-1, polyisoprene, polybutadiene, poly styrene, polyisobutylene, copolymers of the mono- 4,233,208 34 mers on which the homopolymers mentioned are cellulose propionates and cellulose butyrates, or based, such as ethylene-propylene copolymers, the cellulose ethers, such as methylcellulose. propylene-butene-1 copolymers, propyleneisobu- 17. High molecular monomeric substances, for exam tylene copolymers, styrene-butadiene copolymers ple, mineral oils, animal and vegetable fats, oils and and terpolymers of ethylene and propylene with a 5 waxes, or oils, waxes and fats based on synthetic diene, such as, for example, hexadiene, dicyclopen- esters. tadiene or ethylidene-norbornene; mixtures of The compounds of this invention are paticularly use above mentioned homopolymers, such as for exam ful as UV light stabilizers, especially for the protection ple, mixtures of polypropylene and polyethylene, of polyolefins, for instance, polyethylene, polypropyl polypropylene and polybutene-1, or polypropylene to ene, poly(butene-l), poly(pentene-l), poly(3-methylbu- and polyisobutylene. tene-1), poly (4-methylpentene-l), various ethylene- 2. Vinyl polymers containing halogen, such as polyvi propylene copolymers and the like. nyl chloride, polyvinylidene chloride, polyvinyl Other substrates in which the compounds of this fluoride, but also polychloroprene and chlorinated invention are particularly useful are polystyrene, in rubbers. 15 cluding impact polystyrene, ABS resin, SBR, isoprene, 3. Polymers which are derived from a,/3-unsaturated as well as natural rubber, polyesters including polyeth acids and their derivatives, such as polyacrylates ylene terephthalate and polybutylene terephthalate, and polymethacrylates, polyacrylamides and poly including copolymers. acrylonitrile, as well as their copolymers with In general, the stabilizers of this invention are em other vinyl compounds, such as acrylonitrile/- 20 ployed from about 0.01 to about 5% by weight of the butadiene/styrene, acrylonitrile/styrene and stabilized composition, although this will vary with the acrylonitrile/styrene/acrylic ester copolymers. particular substrate and application. An advantageous 4. Polymers which are derived from unsaturated al range is from about 0.05 to about 2%, and especially 0.1 cohols and amines or their acyl derivatives or ace to about 1%. tals, such as polyvinyl alcohol, polyvinyl acetate, 25 For addition to polymeric substrates, the stabilizers polyvinyl stearate, polyvinyl benzoate, polyvinyl can be blended before polymerization or after polymeri maleate, polyvinyl butyral, polyallyl phthalate, zation, during the usual processing operations, for ex polyallyl melamine and their copolymers with ample, by hot-milling, the composition then being ex other vinyl compounds, such as ethylene/vinyl truded, pressed, blow-molded or the like into films, acetate copolymers. 30 fibers, filaments, hollow spheres and the like. The heat 5. Homopolymers and copolymers which are derived stabilizing properties of these compounds may advanta from epoxides, such as polyethylene oxide or the geously stabilize the polymer against degradation dur polymers which are derived from bis-glycidyl ing such processing at the high temperature generally ethers. encountered. The stabilizers can also be dissolved in 6. Polyacetals, such as polyoxymethylene and poly 35 suitable solvents and sprayed on the surface or films, oxyethylene, as well as those polyoxymethylenes fabrics, filaments or the like to provide effective stabili which contain ethylene oxide as the comonomer. zation. Where the polymer is prepared from a liquid 7. Polyphenylene oxides. monomer as in the case of styrene, the stabilizer may be 8. Polyurethanes and polyureas. dispersed or dissolved in the monomer prior to poly 9. Polycarbonates. 40 merization or curing. 10. Polysulphones. In the case of crosslinked polyethylene, the com 11. Polyamides and copolyamides which are derived pounds are added before the crosslinking. from diamines and dicarboxylic acids and/or from The following may be mentioned as examples of fur aminocarboxylic acids or the corresponding lac ther additives with which the compounds of the for tams, such as polyamide 6, polyamide 6/6, polyam 45 mula I can be co-employed: ide 6/10, polyamide 11 and polyamide 12. 12. Polyesters which are derived from dicarboxylic 1. Antioxidants 1.1 Simple 2,6-dialkylphenols, such as, for example, acids and dialcohols and/or from hydroxycarboxy- 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6- lic acids or the corresponding lactones, such as dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethyl- polyethylene glycol terephthalate or poly-14-dime- 50 phenol, 2,6-dioctadecyl-4-methylphenol, thylol-cyclohexane terephthalate. 1.2 Derivative of alkylated hydroquinones, such as, for 13. Crosslinked polymers which are derived from example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.- aldehydes on the one hand and phenols, ureas and amylhydroquinone, 2,6-di-tert.-butylhydroquinone, melamines on the other, such as phenol-formalde 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.- hyde, urea-formaldehyde and melamine-formalde 55 butyl-4-hydroxyanisole, tris-(3,5-di-tert.-butyl-4- hyde resins. hydroxyphenyl)-phosphite, 3,5-di-tert.-butyl-4- 14. Alkyd resins, such as glycerine-phthalic acid res hydroxyphenyl stearate and bis-(3,5-di-tert.-butyl-4- ins and their mixtures with melamine-formalde hydroxyphenyl) adipate. hyde resins. 1.3 Hydroxylated thiodiphenyl ethers, such as, for 15. Unsaturated polyester resins which are derived 60 example, 2,2'-thio-bis-(6-tert.-butyl-4-methyl- from copolyesters of saturated and unsaturated phenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis- dicarboxylic acids with polyhydric alcohols, with (6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di vinyl compounds as cross-linking agents, and also sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2- their halogen-containing modifications of low in methylphenol) and 4,4'-bis-(2,6-dimethyl-4- flammability. 65 hydroxyphenyl)-disulphide. 16. Natural polymers such as cellulose, rubber, prote 1.4 Alkylidene-bisphenols, such as, for example, 2,2'- ins and their polymer-homologously chemically methylene-bis-(6-tert.-butyl-4-methylphenol), 2,2'- modified derivatives, such as cellulose acetates, methylene-bis-(6-tert.-butyl-4-ethylphenol), 4,4'- 4,233,2U8 56 methylene-bis-(6-tert.-butyl-2-methylphenol), 4,4'- 1.12 Esters of 3,5-di-tert.-butyl-4-hydroxyphenylacetic methylene-bis-(2,6'-di-tert.-butyl-phenol), 2,6-di-(3- acid with monohydric or polyhydric alcohols, such tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methyI- as, for example, with methanol, ethanol, octadecanol, phenol, 2,2'-methylene-bis-[4-methyl-6-(a-methylcy- 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- clohexyl)-phenol], 1,1 -bis-(3,5-dimethyl-2-hydroxy- 5 propanediol, diethylene glycol, thiodiethylene gly phenyl)butane, 1,1 -bis-(5-tert.-butyl-4-hydroxy-2- col, neopentylglycol, pentaerythritol, 3-thia- methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4- undecanol, 3-thia-pentadecanol, trimethyl hexane- hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di- diol, trimethylolethane, treimethylolpropane, tris- tert.-butyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5- hydroxyethyl isocyanurate and 4-hydroxymethyl-l- tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2- 10 phospha-2,6,7-trioxabicyclo[2,2,2]octane. bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n- 1.13 Acylaminophenols, such as, for example, N-(3,5-di- dodecylmercapto-butane, l,l,5,5-tetra-(5-tert.-butyl- tert.-butyl-4-hydroxyphenyl)stearic acid amide, 4-hydroxy-2-methylphenyl)-pentane and ethylene N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenyl)-thiobis- glycol bis-[3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)- acetamide and thiophosphoric acid O.O-diethyl ester butyrate]. 15 3,5-di-tert.-butyl-4-hydroxy anilide. 1.5 O-, N- and S-benzyl compounds, such as, for exam 1.14 Benzylphosphonates, such as, for example, 3,5-di- ple, 3,5,3',5'-tetra-tert.-butyI-4,4'-dihydroxydibenzyl tert.-butyl-4-hydroxybenzyl-phosphonic acid di ether, 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic methyl ester, 3,5-di-tert.-butyl-4-hydroxybenzyl- acid octadecyl ester, tris(3,5-di-tert.-butyl-4-hydrox- phosphonic acid diethyl ester, 3,5-di-tert.-butyl-4- ybenzyl)-amine and bis-(4-tert.-butyl-3-hydroxy-2,6- 20 hydroxybenzyl-phosphonic acid dioctadecyl ester dimethylbenzyl)-dithioterephthalate. and 5-tert.-butyl-4-hydroxy-3-methylbenzyl-phos- 1.6 Hydroxybenzylated malonic esters, such as, for phonic acid diotadecyl ester. example, 2,2-bis-(3,5-di-tert.-butyI-2-hydroxybenzyl)- 1.15 Aminoary1 derivatives, such as, for example, phe malonic acid dioctadecyl ester, 2-(3-tert.-butyl-4- nyl- 1-naphthylamine, phenyl-2-naphthylamine, N,N'- hydroxy-5-methylbenzyl)-malonic acid dioctadecyl 25 diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p- ester, 2,2-bis-(3,5-di-tert.-butyI-4-hydroxybenzyI)- phenylenediamine, N,N'-di-sec.-buty!-p- malonic acid didodecylmercaptoethyl-ester and 2,2- phenylenediamine, 6-ethoxy-2-2,4-trimethyl-l,2- bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonic acid dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-l,2- di-[4-( 1,1,3,3-tetramethylbutyl)-phenyl]-ester. dihydroquinoline, monoocylyiminodibenzyl and di- 1.7 Hydroxybenzyl-aromatics, such as, for example, 30 octyliminodibenzyl and polymerised 2,2,4-trimethyl- l,3,5-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6- 1,2-dihydroquinoline. Octylated diphenylamine, trimethylbenzene, 1,4-di-(3,5-di-tert.-butyl-4-hydrox- nonylated diphenylamine, N-phenyl-N'-cyclohexyl- ybenzyI)-2,3,5,6-tetramethylbenzene and 2,4,6-tri- p-phenylenediamine, N-phenyl-N'-isopropyl-p- (3,5-di-tert.-butyl-4-hydroxybenzyl)-phenol. phenylenediamine, N,N'-di-sec.-octyl-p- 1.8 s-Triazine compounds, such as, for example, 2,4-bis- 35 phenylenediamine, N-phenyl-N'sec.-octyl-p- octylmercapto-6-(3,5,di-tert.-butyl-4-hydroxy- phenylenediamine, N,N'-di-(l ,4-dimethyIpentyI)-p- ani!ino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di- phenylenediamine, N,N'-dimethyl-N,N`di-(sec.- tert-butyl-4-hydroxy-anilino)-s-triazine, 2-octylmer- octyl)-p-phenylenediamine, 2,6-dimethyl-4-methox- capto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyphenoxy)- yaniline, 4-ethoxy-N-sec.-butylaniline, the condensa s-triazine, 2,4,6-tris-{3,5-di-tert.-butyl-4-hydroxy- 40 tion product of diphenylamine and acetone, aldol-1- phenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4- naphthylamine and phenothiazine. hydroxyphenylethyl)-s-triazine and l,3,5-tris-(3,5-di- 2. UV absorbers and light stabilizers tert.-butyl-4-hydroxybenzyl)-isocyanurate. 2.1 2-(2'-Hydroxyphenyl)-benztriazoles, such as, for 1.9 Amides of /3-(3,5-di-tert.-butyl-4-hydroxyphenyl)- example, the 5'-methyl-, 3'5'-di-tert.-butyl-, 5'-tert.- propionic acid, such as, for example, l,3,5-tris-(3,5-di- 45 butyl-, 5'-(l,l,3,3-tetramethylbutyl)-, 5-chloro-3',5'- tert.butyl-4-hydroxyphenyl-propionyl-hexahydro-s- di-tert.-butyl-, 5-chloro-3'-tert.-butyl-5'-methyl-, 3'- triazine and N,N'-di-(3,5-di-tert.-butyl-4-hydroxyphe- sec.-butyl-5'-tert.-butyl', 3'-a-methylbenzyl-5'-meth- nyl-propionyl)-hexamethyIenediamine. y]-, 3'-a-methylbenzyl-5'-methyl-5-chloro-, 4'- 1.10 Esters of /?-{3,5-di-tert.-butyl-4-hydroxyphenyl- hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.-amyl- propionic acid with monohydric or polyhydric alco 50 , 3'-methyl-5'-carbomethoxyethyl- and 5-chloro-3',5'- hols, such as, for example, methanol, ethanol, octa- di-tert.-amyl- derivative. decanol, 1,6-hexanediol, 1,9-nonanediol, ethylene 2.2 2,4-Bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, such glycol, 1,2-propanediol, diethylene glycol, thiodieth- as, for example, the 6-ethyl-, 6-heptadecyl, or 6- ylene glycol, neopentylglycol, pentaerythritol, 3- undecylderivative. thia-undecanol, 3-thia-pentadecanol, trimethylhex- 55 2.3 2-Hydroxy-benzophenones, such as, for example, anediol, trimethylolethane, trimethylolpropane, tris- the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, hydroxyethyl isocyanurate and 4-hydroxymethyl-1- 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy- and phospha-2,6,7-trioxabicyclo[2,2,2]-octane. 2'-hydroxy-4,4'-dimethoxy-derivative. 1.11 Esters of /3-(5-tert.-buty1-4-hydroxy-3-methyl phe 2.4 l,3-Bis-(2'-hydroxy-benzoyl)-benzenes, such as for nyl propionic acid with monohydric or polyhydric 60 example, 1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)- alcohols, such as, for example, methanol, ethanol, benzene, 1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)- octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene benzene and l,3-bis-(2'-hydroxy-4'-dodecyloxy-ben- glycol, 1,2-propanediol, diethylene glycol, thiodieth- zoyl)-benzene. ylene glycol, neopentylglycol, pentaerythritol, 3,thia- 2.5 Esters of optionally substituted benzoic acids, such undecanol, 3-thia-pentadecanol, trimethylhexanediol, 65 as, for example, phenyl salicylate, octylphenyl sali trimethylolethane, trimethylolpropane, tris-hydrox- cylate, dibenzoylresorcinol, bis-(4-tert.-butylben- yethyl isocyanurate and 4-hydroxymethyl-1-phos- zoyl)-resorcinol, benzoyl-resorcinol and 3,5-di-tert.- pha-2,6,7-trioxabicycIo-[2,2,2]octane. butyl-4-hydroxybenzoic acid 2,4-di-tert.-butyl-phe- 4,233,208 78 nyl ester, octadecyl ester or 2-methyl-4,6-di-tert.- 10. Other additives, such as, for example, plasticizers, butyl-phenyl ester. lubricants, emulsifiers, fillers, carbon black, asbestos, 2.6 Acrylates, such as, for example, a-cyano-/2,/3- kaolin, talc, glass fibres, pigments, optical brighten- diphenylacrylic acid ethyl ester or isooctyl ester, ers, flameproofing agents, antistatic agents, pourpoint a-carbomethoxycinnamic acid methyl ester, a- 5 depressants, corrosion and rust inhibitors, dispersing cyano-/3-methyl-p-methoxycinnamic acid methyl agents, demulsifiers, antifoaming agents, accelerators ester or butyl ester and N-(/3-carbomethoxy-vinyl)- and the other chemicals used in rubber compounding, 2methyl-indoline. dyes, pigments, metal chelating agents, dyesites and 2.7 Nickel compounds, such as, for example, nickel the like. complexes of 2,2'-thio-bis-[4-(l,l,3,3-tetramethyI- 10 The hindered phosphites are particularly useful in butyl)-phenol], such as the 1:1 or 1:2 complex, option stabilizing polymer systems containing reinforcing ally with additional ligands such as n-butylamine, agents and flame retardants, e.g., the compounds of this triethanolamine or N-cyclohexyl-di-ethanolamine, invention help to stabilize polyesters, e.g., polybutylene nickel complexes of bis-[2-hydroxy-4-(l,l,3,3-tet- terephthalate containing fiber glass and also polyesters ramethylbutyl)-phenyl]-sulphone, such as the 2:1 15 containing flame-retardants, e.g., polyethylene or poly- complex, optionally with additional ligands such as butylene terephthalate containing halogenated (e.g., 2-ethyl-caproic acid, nickel dibutyldithiocarbamate, brominated) aryl flame-retardants. nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyI- The hindered phosphites of this invention are particu phosphonic acid monoalkyl esters, such as of the larly useful in preventing discoloration due to process methyl, ethyl or butyl ester, nickel complex of ketox- 20 ing as well as thermal aging and light exposure of poly imes such as of 2-hydroxy-4-methyl-phenyl undecyl mer compositions containing polyarcylonitrile and ketonoxime, nickel 3,5-di-tert.-butyl-4-hydroxybenx- polymethacrylonitrile resins. For example, a rubber oate and nickel isopropylxanthate. modified polyacrylonitrile used for beverage bottles is 2.8 Oxalic acid diamides, such as, for example, 4,4'dioctyl-oxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.- 25 inhibited from discoloration when a hindered phosphite of this invention is included in the formulation. butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.- Often combinations such as these, particularly the butyl-oxanilide 2-ethoxy-2'-ethyI-oxanilide, N,N'-bis- sulfur-containing esters (Section 4, page 18), and/or the (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5tert.-butyl-2'-ethyl-oxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert.-butyl-oxanilide and mixtures of ortho- and para-methoxy- as well as of oand p-ethoxy-disubstituted oxanilides, 3. Metal deactivators, such as, for example, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenyl- 30 35 ultraviolet light stabilizers (Section 2, pages 15-17), will produce superior results in certain applications to those expected from the properties of the individual compo nents. The following formula represents co-stabilizers which are in certain instances very useful in combina tion with the stabilizers of this invention: hydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis- o salicyloyloxalic oxalic acid dihydrazide, N,N'-bis- salicyloyl-hydrazine, N,N'-bis-(3,5-di-tert.-butyi-4- hydroxyphenyl-propionyl)-hydrazine, N-salicyloyl- 40 N'-salicylal-hydrazine, 3-salicyloylamino-1,2,4- triazole and N,N'-bis-salicyloyl-thiopropionic acid dihydrazide. s R1--O--C--C,,H2,, II o 4. Compounds which destroy peroxide, such as, for wherein R1 is an alkyl group having from 6 to 24 carbon example, esters of j3-thiodipropionic acid, for exam 45 atoms, and n is an integer from 1 to 6. Especially useful ple the lauryl, stearyl, myristyl or tridecyl esters, compounds of this type are dilauryl-/3-thiodipropionate mercapto-benzimidazole or the zinc salt of 2-mercap- (DLTDP), distearyl-/3-thiodipropionate (DSTDP), and to-benzimidazole. dimyristyl-/3-thiodipropionate. The above co-stabilizers 5. Polyamide stabilizers, such as, for example, copper are used in the amount of from 0.005 to 5% by weight salts in combination with iodides and/or phosphorus 50 of the organic material, and preferably from 0.1 to 1%. compounds and salts of divalent manganese. Another co-stabilizer found to be very effective in 6. Basic co-stabilizers, such as, for example, melamine, combination with the stabilizers of this invention has the benzoquanamine, polyvinylpyrrolidone, dicyandia- formula mide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali 55 metal salts and alkaline earth metal salts of higher R3 fatty acids, for example, Ca stearate, Zn stearate, Mg stearate Na ricinoleate and K palmitate, antimony pyrocatechloate or zinc pyrocatecholate. 7. PVC stabilizers, such as, for example, organic tin 60 compounds, organic lead compounds and barium- cadmium salts of fatty acids. 8. Nucleating agents, such as, for example, 4-tert. butyl- wherein benzoic acid, adipic acid and diphenylacetic acid. R2 is hydrogen, chlorine or lower alkyl containing 9. Urea derivatives, such as, for example, N-cyclohexyl- 65 from 1 to 6 carbon atoms, N'-l-naphthylurea, N-phenyl-N,N'-dicyclohexylura, wherein N-phenyl-N'-2-naphthylurea, N-phenylthiourea and R2 is hydrogen, chlorine or lower alkyl containing N,N'-dibutylthiourea. from 1 to 6 carbon atoms, 4,233,208 9 10 R3 is hydrogen, alkyl containing 1 to 12 carbon ence, are disclosed in greater detail in the following atoms, phenyl or benzyl, and patents: R4 is hydrogen, chlorine or (lower) alkyl containing Netherlands Patent Specification No. 67/1119, issued from 1 to 6 carbon atoms. Feb. 19, 1968; Netherlands Patent Specification No. In a preferred embodiment, R4 is hydrogen, chlorine 5 68/03498, issued Sept. 18, 1968; U.S. Pat. Nos. or a methyl group; R2 is hydrogen, chlorine, t-butyl, 3,255,191; 3,330,859; 3,644,482, 3,281,505; 3,531,483; t-amyl; and R3 is alkyl of from I to 12 carbon atoms such 3,285,855; 3,364,250; 3,368,997; 3,357,944 and as methyl, ethyl, hexyl, octyl, dodecyl, t-butyl, t-amyl, 3,758,549. isopropyl and the like. The compounds of this invention are generally pre The above benzotriazoles are added to the polymer 10 pared according to procedures described in U.S. Pat. substrate in an amount of from about 0.005% to about No. 3,281,506. This patent, however, does not disclose 5% by weight based on the weight of the polymer and the preparation or properties of bis-(2,4,6-tri-t-butyIphe- more preferably from 0.05% to 2%. nyl) phosphite. In the present work, this compound Although the compounds of this invention are to could not be made by the alkaline hydrolysis process some degree also effective as thermal stabilizers, if the 15 disclosed in the above patent. Instead, bis-(2,4,6-tri-t- processing of the polymer is carried out at high temper butylphenyl)phosphite was successfully prepared from atures it is advantageous to incorporate additional anti the chloridite by treatment with alcohols such as, meth oxidants. In most applications, it is desirable to incorporate into anol, ethanol and butanol. In particularly advantageous embodiment of the in the resins composition, sufficient thermal antioxidants 20 vention, the hindered phosphites are employed in com to protect the plastic against thermal and oxidative degradation. The amount of antioxidant required will be comparable to that of the actinic stabilizer. Namely, bination with p-hydroxybenzoates having the general formula from about 0.005% to 5% and preferably from 0.01% to 2% by weight. 25 r5 h The best results have been obtained with the pre ferred class of thermal antioxidants, the hindered phe nols. These compounds have been found to provide the best thermal stabilization with the lease discoloration in the compositions of the invention. Among the preferred 30 class of thermal antioxidants may be mentioned the following: di-n-octadecyl(3,5-di-butyl-4-hydroxybenzyl)malonate 2.6- di-t-butylp'nenol 2,2'-methylene-bis(6-butyl-4-methylphenol) 2.6- di-t-butylhydrcquinone octadecyl-(3,5-di-t-buty!-4-hydroxybenzylthio) acetate 1,1,3-tris(3-t-butyl-6-methyl-4-hydroxyphenyl) butane 1.4- bis(3,5-di-t-butyl-4-hydroxybenzyl)-2,3-5,6-tet- ramethyl'oenzene 2.4- bis-(3,5-di-t-butyl-4-hydroxyphenoxy)-6-(n-octyl- wherein R5 is (lower) alkyl containing from 1 to 6 carbon 35 atoms, R6 is hydrogen or (lower) alkyl containing from 1 to 6 carbon atoms, and R7 is alkyl or alkenyl of from 1 to 24 carbon atoms, preferably alkyl of from 1 to 24 carbon atoms, 40 phenyl, lower alkyl substituted phenyl, benzyl or lower alkyl substituted benzyl groups, such that no thio)-l,3,5-triazine 2.4- bis-(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octyl- more than two lower alkyl substituents are present in said phenyl or benzyl groups. Preferred among thioethylthio)-l,3,5-triazine the above phenyl and benzyl groups defining R7 2.4- bis-(n-octylthio)-6-(3,5-di-t-butyl-4-hydroxy- 45 are phenyl and phenyl substituted by one or two anilino)-l,3,5-triazine alkyl groups of 1 to 12 carbon atoms. 2.4.6- tris-(4-hydroxy-3,5-di-t-butylphenoxy)-l,3,5-tria- In a preferred embodiment, R5 and R6 are t-butyi or zine t-amyl groups and R7 is a di(lower alkyl) phenol. Illus n-octadecyl-/8-(3,5-di-t-butyi-4-hydroxyphenyl) propio trative examples of hydroxybenzoates are given below: nate 50 (2',4'-di-t-butylphenyl)-3,5-di-t-butyl-4-hydroxybenzo- 2.4.6- tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanu- ate rate methyl-3-methyl-5-isopropyl-4-hydroxybenzoate di-n-dodecyl-6-tert-butyl-2,3-dimethyl-4-hydroxybenzyl phosphonate ethyl-3,5-diisopropyl-4-hydroxybenzoate propyl-3,5-di-sec-butyl-4-hydroxybenzoate steararmdo N,N-bis-[ethylene 3-(3,5-di-t-butyl-4- 55 isobutyl-3,5-di-tert-amyl-4-hydroxybenzoate hydroxyphenyl)propionate] decyi-3,5-di-tert-octyl-4-hydroxybenzoate 1,2-propylene glycol bis[3-(3,5-di-t-butyI-4-hydroxy- cyclohexyl-3,5-di-tert-amyl-4-hydroxybenzoate phenyl)propionate] dodecyl-3-methyl-5-isoamyl-4-hydroxybenzoate pentaerythritol tetrakis-[3-(3,5-di-t-butyl-4-hydroxy- octadecyl-3,5-diisopropyl-4-hydroxybenzoate phenyl)propionate] 60 hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphon- 3-fluoropropyl-3,5-di-tert-amyl-4-hydroxybenzoate ate allyl-3,5-di-tert-butyl-4-hydroxybenzoate di-n-octadecyI-l-(3,5-di-t-buty!-4-hydroxyphenyl)- 2-butenyl-3,5-diisopropyl-4-hydroxybenzoate ethanephosphonate oleyl-5-methyI-5-tert-amyl-4-hydroxybenzoate The above phenolic hydrocarbon stabilizers are 65 phenyl-3,5-diisopropyl-4-hydroxybenzoate known and many are commercially available. p-t-octylphenyl-3,5-di-tert-amy]-4-hydroxybenzoate The above exemplified antioxidants and other related (2',4'-dimethylphenyl)-3,5-di-tert-octyl-4-hydroxyben- antioxidants which are incorporated herein by refer zoate 4,233,208 11 12 p-isopropylphenyl-3-methyl-5-tert-amyl-4-hydroxybenzoate naphthyl-3,5-di-tert-butyl-4-hydroxybenzoate 6-methylnaphthyl-3,5-di-tert-hexyl-4-hydroxybenzoate 5 p-chlorophenyl-3,5-di-tert-butyl-4-hydroxybenzoate 2,4-dibromophenyl-3,5-diisopropyl-4-hydroxybenzoate The p-hydroxybenzoate light stabilizers of Formula II are added to the polymer substrate in an amount of from about 0.005% to 5% by weight based on the 10 weight of polymer, and more preferably from 0.05% to 2%. The following examples, presented for illustration and not limitation, will further serve to typify the nature 15 of the present invention. ___________ TABLE I___________ Puerto Rico Exposure Eilolangieys of Puerto Rico Exposure to SO Percent Retention of Tensile Strength 5 Mil Monofilaments Formulation Kilolangleys 1. 0.25% bis(2,4,6-tri-tert. buty!phenyl)phosphite 2. 0.25% bis(2,4,6-tri-tert. butylphenyl)phosphite + 0.25% n-octadecyl 3,5-di-tert.butyl-4-hydroxybenzoate 3. 0.50% 2-(2'-hydroxy-3',5'di-tertamylphenyl)benzotriazole 4. 0.50% n-octadecyl 3,5-di-tertbutyl-4-hydroxybenzoate 5. Blank 105 180 94 106 62 EXAMPLE 1 Each of the samples tested and the blank contain 0.10 octadccyl-3-0\5'-di-lert.butyl-4-hydroxyphenyl) propionate + 0.3% dilaurylthiodipropionate + 0.1% Bis(2,4,6-tri-tert.-butylphenyl)phosphite calcium stearate. 20 To 58.9 grams of bis(2,4,6-tri-tert-butylphenyl) phos- The above results show that the hindered phosphite phorochloridite, (0.10 moles), dissolved in 120 ml. of of this invention is particularly effective as a light stabi toluene at 55, was added 60 ml. of methanol, the reac lizer in 5 mil polypropylene monofilament on outdoor tion mixture being heated at 64 C. for 19 hours. The aging both as the sole light stabilizer present as well as reaction product was isolated by evaporation of the 25 in combination with another light stabilizer, n-octadesolvent and retreated product showed a negative test cyl-3,5-di-tert-butyl-4-hydroxybenzoate. for halogen. The crude product was isolated by evapo EXAMPLE 3 ration of the solvent at reduced pressure. The residual Unstabilized polypropylene powder (Hercules Pro product was purified by trituration with 100 ml. of ethyl 30 fax 6501) was thoroughly blended with the indicated acetate followed by crystallization from the same sol amounts of additives (Tables II, III and IV). The vent, yielding white crystals melting at 239-244 C. blended materials were then milled on a two-roll mill at 182 C. for 5 minutes, after which time the stabilized polypropylene was sheeted from the mill and allowed Analysis: % c % H 35 to cool. Calculated Found 75.75 10.42 Part of the milled polypropylene sheets were then cut 75.89 10.44 into pieces and compression molded on a hydraulic press at 220 C., 175 psi into 25 mil thick plaques and part into 5 mil thick films. EXAMPLE 2 40 Testing Methods Outdoor Exposure Tests (a) Rotary Oven-Aging Test The indicated amounts of additives (Table I) were The resulting plaques of 25 mil thickness were tested solvent blended onto polypropylene powder (Hercules for resistance to accelerated aging in a rotary oven at Profax 6501), the powder was agitated for 5 minutes in 45 150 C. Specimen colors were determined during the oven aging. When the plaques showed the first signs of a Kitchen Aid planetary mixer and the powder mixture decomposition (e.g., cracking or brown edges) they was dried in a vacuum oven at a vacuum of 30 inches of were considered to have failed. The results are shown water overnight. below in Tables II and III. The amounts of the additives The polypropylene powder containing the additives 50 are expressed in weight percent based on the weight of was extruder compounded at 232 C. into pellets, and the polymer. the pellets were melt spun at 260 C. into 5 mil monofil (b) Artificial Light Exposure Test aments. The filaments were air cooled and oriented at a This test is conducted in an FS/BL unit, basically of 4:1 ratio between hot (125 C.) and cold godets and wound onto a fiber spool. The filament was mounted on 55 the American Cyanamid design, which consists of 40 tubes of alternating fluorescent sunlamps and black lights (20 of each). The 5 mil sample films are mounted wooden exposure frames and exposed at 45 south di on 3" X 2" IR card holders with 174 " X 1" windows and rect weathering inland in Puerto Rico. Samples were are placed on a rotating drum 2 inches from the bulbs in removed from exposure periodically and tensile tested the FS/BL unit. The time in hours is noted for the on the Instron Table Model tensile tester using fiber 60 development of 0.5 carbonyl absorbance units as deter grips. mined on an Infra-red Spectrophotometer. The devel The results indicated below show the Kilolangleys of opment of carbonyl functional groups in the polymer is Puerto Rico Exposure to 50 percent retention of tensile strength. A Langley is a measure of energy in the ultra 65 proportional to the amount of degradation caused by the ultraviolet light exposure. The test results reported below in Tables III and IV violet region to which the samples have been exposed. are obtained according to the procedures described The amounts of the additives are expressed in weight above. The amounts of the additives are expressed in percent based on the weight of the polymer. weight percent based on the weight of the polymer. 4,233,208 13 TABLE II Additives Time in Hours to Failure in Rotary Gardner Oven Aging 0 Hours Color 100 Hours !. 0.30 bis(2,4t6-tri-tert.-butylphenyl) phosphite + 0.1% tetrakis-[methylene- 3-(3,,5'-di-tert'butyl-4'-hydroxy- phenyl)propionate]methane 1105 0 1 2. 0.2% tetrakis-[methylene-3-(3\5*- di'tert-butyl-4-hydroxyphenyl) propionatejmethane 1190 0 2 On Failure 3 Tan 5 14 Additives 1. 0.3% bis-(2,6-di-t-butylphenyl) phosphite + 0.1% tetrakis[methylene-3-(3`.5'-di*tertbutyl-4'-hydroxypheny!) propionate]methane 2. 0.2% tetrakis-[methylene-3(3',5'-di'tert*butyl-4'hydroxyphenyl)propionate] methane 3. 0.1% tetrakis-[methylene-3(3'.5'-di-tert-butyl-4'hydroxyphenyl)propionate] methane + 0.3% distearylthiodipropionate TABLE III Time in Hours to Failure in Gardner Rotary Oven Aging 0 Hours Color On 100 Hours Failure Time in Hours to .5 Carbonyl Absorbance Units 1330 1185 . 0 0 2160 0 Tan I4 Tan 24 Tan 25 420 170 250 TABLE IV Time in Hours to 0.5 Carbonyl butyl-4-hydroxyaniline)-l,3,5-triazine, octadecyl 3- (3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, di- Additives Absorbance Units octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, 1. 0.5% bis (2,4.6-tri-tert'butylpheny() tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,6- phosphite + 0.5% 2-(3',5'*di-tertbutyl-2'-hydroxyphenyl)-5-chlorobenzotriazole + 0.2% di-noctadecyl-3,5di-tert-buiyl-4-hydroxy benzyl phosphonate 35 di-tert-butyl-4-methylphenol, N,N,N-tris-(3,5-di-tertbutyl-4-hydroxybenzyI)isocyanurate, and 2,4,6-tris(3,5di-tert-butyI-4-hydroxybenzyl)-1,3,5-trimethylbenzene. 1965 The hindered phosphite composition of Table II is 2. 0.5% bis (2,4,6-tri-tert-butylphenyl) phosphite + 0.5% 2,4-di-tert-butyJphenyl 3,5-di-tert*butyl-4-hydroxybenzoate + 0.2% di-n-octadecyl-3,5-di-iert-butyI4-hydroxy benzyl phosphonate also stabilized when 2(2'-hydroxy-3',5'-di-t-butyl- 40 phenyl)-5-chlorobenzotriazole is replaced with the fol lowing UV absorbers: 1895 (a) 2-hydroxy-4-methoxy-5-sulfobenzophenone trihy drate The above results show that the phosphites of this (b) 2-hydroxy-4-n-octoxybenzophenone invention are good synergists for phenolic antioxidants 45 (c) 2,2'-thiobis(4-t-octylphenolate)-1 -n-butylamine such as tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'hy- nickel II droxyphenyl)propionate]methane yielding polypropyl ene plaques of low color even on failure. While the data (d) p-octylphenyl salicylate (e) 2,2'-dihydroxy-4,4'-dimethoxybenzophenone shows that formulations containing a phenolic antioxi (f) 2(2'-hydroxy-5'-methylphenyl)-benzotriazole. dant and DSTDP experience longer oxidation times to 50 The compositions of Tables II, III and IV are also failure than formulations containing phenolic antioxi dant and phosphite, the data also shows that the phos stabilized when bis(2,4,6-tri-tert-butylphenyl)phosphite and bis(2,6-di-t-butylphenyl)phosphite are replaced phite of the present invention contributes much more to with the following phosphites: light stability in the presence of a phenolic antioxidant (a) bis(2,6-di-t-butyl-4-methylphenyl)phosphite than does DSTDP (Table III). 55 The results of Table IV show that bis(2,4,6-tri-tert- butylphenyl)phosphite, when used in formulations con (b) bis(2,6-di-t-butyI-4-chlorophenyl)phosphite (c) bis(2,4,6-tri-t-butylphenyl)phosphorochlorodite (d) bis(2,6-di-t-butyl-4-chlorophenyl)phosphorochlori- taining commercial antioxidants, provides good light dite stabilization. (e) bis(2,6-di-t-butyl-4-methylphenyl)phosphorochlori- Comparatively good stabilization is obtained when the concentration of hindered phosphite varies from 60 dite (0 bis(2,4,6-tri-a-phenylethyl phenyl)phosphite 0.05% to 1%. Other hindered phenolic antioxidants may be used in (g) bis(2,6-di-t-butyl-4-nonylphenyl)phosphite (h) bis(2,4,6-tris-isopropylphenyl)phosphite place of tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'hydroxyphenyl)propionate]methane in the above men- 65 tioned compositions with hindered phosphites as, for EXAMPLE 4 Process Stability Test example, di-n-octadecyl a-(3-t-butyl-4-hydroxy-4-meth- 35 g of unstabilized polypropylene (Hercules Profax ylbenzyl) malonate, 2,4-bis(n-octyIthio)-6-(3,4-di-t- 6801) was solvent blended with the indicated amounts 4,233,208 15 16 of process stabilizers (Table V), using methylene chlo The amounts of the additives are expressed in weigh! ride as solvent. After blending, the solvent was re percent based on the weight polymer. moved under vacuum at room temperature. A Brabender Plasticorder was set up with a jacket temperature setting of 260" C.; shear rate 120 rpm; roller type 6; range XI; booster and control heater setting 240; preload position 0; lever arm setting 1:5; and damper setting 6 seconds. After the Brabender Plasticorder reached the desired TABLE VI Stabilizers 1. 0.1% bis(2.4,6-tri-terl- butylphenyl)phosphite 2. 0.05% tetrakis (methylene- 3(3',5'-di-tert-butyl-4'- Time in minutes to increase of torque 2 temperature (260 C.) and was maintained there in equi librium for 10 minutes, the rotor motor was turned on and the rotor speed brought to 120 rpm. The torque recording chart paper was set to the 9.5 minute mark hydroxyphenyl)propionate] methane 3. 0.1% bis(2,4,6-tri-tertbutylphenyl)phosphite + 0.05% tetrakis [methylene- 4 and the chart was turned on. When the recorder pen tip intersected the zero min ute line, the polypropylene formulation was added rap idly to the bowl of the Plasticorder. The Plasticorder 3(3',5'-di-tert-butyl-4'hydroxyphenyl)propionate] methane 4. Blank 9 n was run for 5 minutes under the above conditions with the torque being charted in meter-grams (m-g). The above data shows that bis(2,4,6-tri-tert-butyl- The torque in meter-grams which was recorded after 20 phenyl)phosphite acts synergistically in the process- 5 minutes of mixing time is shown below in Table V. stabilization of high molecular weight polyethylene Colors of the polypropylene formulations were also together with a hindered phenol such as tetrakis[methy- determined at the 5 minute point using the Hunter ALba lene-3(3',5'-di-tert-butyl-4'-hydroxyphenyl)pro- system and are shown below in Table V. The higher the pionatejmethane. torque and the lower the color number the more effec 25 EXAMPLE 6 tive is the stabilizer in preventing the degradation of the polypropylene during the processing operation. Acrylonitrile-butadiene-styrene terpolymer (Marbon The amounts of the additives are expressed in weight ABS resin) was thoroughly blended with the indicated percent based on the weight of the polymer. amounts of additives (Tables VII and VIII, by milling a 30 resin powder/stabilizer solvent blend at 325 F. for 5 TABLE V mins. 0.5% calcium stearate was added to the basic TORQUE COLOR formulation to aid milling. The milled sheet was com Additives* (meter-gams) (ALBA) pression molded into 125 mil thick plaques, and the 1. 0.05% bis(2,4,6- plaques were exposed to a Carbon Arc Fadeometer for tri-tert-butyl- 25 100 hours. After exposure, color and notched Izod im phenyl)phosphite 2. Blank 215 no 22 29 pact strengths were determined. Individual plaques were also oven aged for 190 hours at 190 F. Colors The formulation tested and the blank each contain 0.3% distearyllhiodipropionatc + 0 1% calcium stearate. were determined using the Hunter ALba system. The results are shown in Table VII and VIII. EXAMPLE 5 The amounts of the additives were expressed in weight percent based on the weight of the polyemer. 100 parts of unstabilized high density polyethylene with a molecular weight of ~ 500,000 (Lupolen 5260 Z, BASF) was mixed thoroughly with the stabilizers men tioned in the table below at the indicated concentra- 45 TABLE VII ABS Resin (Marbon) Oven-Aging 12S mil. Plaques ______Discoloration Tendencies tions. The mixtures were kneaded in a Brabender Plas ALBA After ticorder at 200 C. and 50 rpm during 20 minutes. Dur Oven-Aging at 190" F for ing this time the torque was recorded continuously. The Additives* 0 hrs. 190 hrs. torque remained constant during a period of time which 1. 0.330% bis(2,4,6-tri-tert.- is characteristic of the incorporated stabilizers. After 50 butylphenyl)phosphite the constant period the torque increased rapidly due to crosslinking of the polymer. The time in minutes of the 2. 1.657% trinonylphenylphosphite (TNPP) 3. Base resin constant period is shown in the table below. Each formulation contains 0.5% calcium stearate 1 2 0 4 4 9 TABLE VIII Additives^* ABS Resin (Marbon) Carbon Arc Fadeometer Exposure of __________ 125 Mil. Plaques__________ Color and Notched IZOD Original Color (ALBA) After 100 Hrs. CAF<'> Exposure % Ret. of Impact Strength 1 0.330% bis(2,4.6-trilert.-butylphenyl) phosphite 2 1.857% innonylphenylphosphite (TNPP) -2 -2 --3 -3 n 63 % Improve ment 43 24 4,233,208 17 Additives*2* TABLE VIH-continued ABS Resin (Marbon) Carbon Arc Fadeometer Exposure of __________ 125 Mil. Plaques__________ Color and Notched IZOD Original Color (ALBA) After 100 Hrs. CAFO Exposure % Ret. of Impact Strength % Improve ment 3. 0.085% bis(2,4,-6-tritert.-butylphenyl) phosphite + 0.15% 2,2'methylene-bis(6-t-butyl4-ethylphenoi) 4. 0.50% trinonylphenyl phosphite + 0.15% 2,2'methy!ene-bts(6,`t` butyl-4-ethylphenol) 5. Base resin 4 4 0 0 0 -1 Notes: ^'CAF Carbon Arc Fadeometer t2,Each formulation contains 0.5% calcium stearate 83 65 70 37 51 18 The results in Tables VII and VIII show that the hindered phosphite bis(2,4,6-tri-tert.-butylphenyl)- TABLE IX-continued phosphite provides equal stabilization of ABS resin against degradation by heat and light as demonstrated 25 by resistance to discoloration and retention of impact strength at a concentration about one fifth that of TNPP. It can, therefore, be concluded that the phos phite of this invention is about 5.5 times as efficient as the prior art compound TNPP as a light stabilizer for 30 ABS resin. Table VIII also shows that bis(2,4,6-tri-tert.-butyl- phenyl)phosphite is similarly superior to the prior art compound TNPP when used in ABS resin with a phe nolic antioxidant such as 2,2'-methylene-bis(6-t-butyl-4- 35 ethylphenol). Additives' Stabilization of Impact Polystyrene 20 mil, plaques Gardner Color After Oven-Aging at 80* C. for Hours 0 675 1400 2300 2. 0.2% trinonylphenylphosphite + 0.3% BHT 3. 0.1% bis(2,4,6-tri-tert.butylphenyl)phosphite + 0.1% octadecy!-3-(3\ 5'-di-tert.-butyI- 4'-hydroxyphcnyl)propionate 4. 0.2% trinonylphenylphosphite + 0.1% octadecyl-3-(3't5'-dttert.-butyl-4'-hydroxyphenyl) 2 i 3 1 55 35 The compositions of Tables VII and VIII are also stabilized with bis(2,4,6-tri-tert.-butylphenyl)phosphite is replaced with the following phosphites: propionate 5. Base resin 2 1 Each formulation contains 0.02% zinc stearate. 3 6 55 9 II (a) bis(2,6-di-t-butyl-4-chlorophenyl)phosphite (b) bis(2,4,6-tri-t-butylphenyl)phosphorochloridite (c) bis(2,4,6-tri-a-phenylethyl phenyi)phosphite (d) bis(2,6-di-t-butyl-4-nonylphenyl)phosphite 40 The results in Table IX show that impact polystyrene formulations containing bis(2,4,6-tri-tert.-butylphenyl)phosphite are more resistant to discoloration then those containing, trinonylphenylphosphite, in the presence of EXAMPLE 7 45 phenolic antioxidants. Impact polystyrene (TMDH 5161--Union Carbide) The compositions of Table IX are also stabilized was thoroughly blended with the indicated amounts of when bis(2,4,6-tri-tert.-butylphenyI)phosphite is re additives (Table IX) by milling a resin/stabilizer blend placed with the following phosphites: at 127" C. for five minutes. 0.02% zinc stearate #44 (a) bis(2,6-di-t-butyl-4-methylphenyl)phosphite (Witco) was added to the basic formulation to aid mill- 50 (b) bis(2,6-di-t-butyl-4-chlorophenyl)phosphite ing. The milled sheet was compression molded into 20 (c) bis(2,4,6-tri-t-butylphenyl)phosphorochloridite mil thick plaques at 400' F. for 5 minutes. Specimens (d) bis(2,6-di-t-butyl-4-nonylphenyl)phosphite were die cut from the plaques and oven aged in a forced EXAMPLE 8 draft oven at 80' C. Specimen colors were determined during the oven aging. The results are shown below in 33 A. A quantity of SBR emulsion containing 100 g. of Table IX. The amount of the additives are expressed in rubber (500 ml of 20% SBR obtained from Texas U.S. weight percent based on the weight of the polymer. Synpol 1500), previously stored under nitrogen, is placed in a beaker and a resin acid salt emulsion of the TABLE IX indicated amount of additive in Table X is added and Stabilization of Impact Polystyrene 20 mil, plaques 60 the composition is stirred vigorously. The pH of the emulsion is adjusted to 10.5 with an 0.5 N NaOH solu Gardner Color After Oven-Aging at 80* C. for Hours ------A-d--d-i-ti-v-e--s-*-----------------------------0-------6-7-5--------1-4-0-0------2-3-0-0-- 65 1. 0.1% bis(2,4,6-tn-tert.- butylphenyl)phosphite + 0.3% 2,6-di*t-butyl-4- methyl-phenol (BHT) II 24 tion. To the emulsion is added 50 ml of 25% NaCl solution. A 6% NaCl solution adjusted with hydrochloric acid to a pH 1.5 is added in a thin stream with vigorous stirring. When pH 6.5 is reached, the rubber begins to coagulate and the addition is slowed down in order to maintain uniform agitation. The addition of the acidic 6% NaCl 4,233,208 19 20 solution is terminated when a pH 3.S is reached. The coagulated crumb-rubber slurry at pH 3.5 is stirred for hour. The coagulated rubber composition is isolated by filtration through cheese cloth, and rinsed with distilled 5 water. After three subsequent washings with fresh dis tilled water, the coagulated rubber is dried, first at 25 mm Hg and finally to constant weight under high vac Additive tert.-butylphenyl) Phosphite TABLE Xl-continued Hunter (L-b) Color After Hours Exposure Hours to Hunter (L-b) Color After Hours Exposure Embrittlement 0 10 20 30 10 77.0 41.1 33.0 29.4 uum (> 1 mm) at 40-45 C. The resultant formulation Base resin577,9 is compression molded at 125 C. into 25 mil plaques. 10 38.8 30.1 26.1 B. Gel Content and Color Development Method The results of Examples 8 and 9 show that the hin The 25 mil thick compression molded plaques from dered phosphites of the invention are effective stabiliz the above coagulated rubber are oven aged at 100 C. in ers of emulsion SBR and SBR latex foam. a forced draft oven. Toluene insoluble gel measure ments and Gardner colors are taken periodically. The 15 EXAMPLE 10 % gel content in the sample is calculated using the following expression: Unstabilized linear polyethylene is solvent blended in methylene chloride with 0.5% by weight of the sub strate of bis(2,6-di-t-butyl-4-methylphenyl)phosphite 20 and then vacuum dried. The resin is then extrusion compounded on a 1 inch 24/l = L/D extruder, melt temperature 450 F. (232 C.) and pressed for 7 minutes where W| is the weight of sample in 100 ml. toluene at at a temperature of 163' C. and a pressure of 2000 psi room temperature and W/is the weight of residue in 10 into a sheet of uniform thickness of 100 mil. The sheets ml. filtered solution after evaporation of solvent at 80 25 are then cut into plaques of 2"x2". The plaques are C. The amount of the additive is expressed in weight then exposed in an FS/BL exposure device and color percent based on the weight of the polymer. measurements made periodically using a Hunter Color Additive TABLE X Hours to Onset of Gel Gardner Color After Hours 0 20 70 120 Difference Meter Model D25. Polyethylene stabilized with the above compound is found to be much more 30 stable than the unstabilized polyethylene or the polyeth ylene stabilized only with an antioxidant. 0.5% bis^A^tri-tert.- EXAMPLE 11 butylphenyl)phosphite Base resin 42 10 04 5 9 05 9 -- To 50 g. of polyacetal resin containing 0.1% of an 35 acid scavenger, dicyandiamide, is added 0.2% by weight of bis(2,6-di-t-butyl-4-chlorophenyl)phosphite EXAMPLE 9 and the composition is milled for 7 minutes at 200 C. in a Brabender Plasti-recorder. The milled formulation is A rosin acid salt emulsion of the indicated amount of stabilizer in Table XI was added to SBR latex (Part A, 300 gm.) with stirring. To this mixture 27.03 gm Part B 40 and 6170 gm. Part C were added very slowly and the mixture was stirred vigorously for two minutes fol lowed by slow stirring for one minute. The resulting foam was poured onto jute between two 3/16" metal bars 10" apart and was leveled by means of a doctor 45 blade. The resulting foam on the jute was cured at 260" F. for 45 minutes. The 2"x2" samples of cured foamed subsequently pressed into a 40 mil sheet at 215 C. at 350 psi for 90 seconds then cooled quickly in the cold press at 350 psi. The stabilized sheets are then remolded for 2 minutes at contact pressure and for 3 minutes at 300 psi at 215 C. to give plaques li"X2i"X 125 mil. Thereaf ter, the testing procedure of Example 10, 3b is followed to determine the light stability of the samples. The stabi lized samples are found to be much more stable than the unstabilized samples. latex (5/16" thick on jute) were exposed to oven (270 EXAMPLE 12 F.) and to the Carbon Arc Fadeometer. After exposure, specimen colors were determined using the Hunter ALba system and hours to embrittlement were deter mined. Embrittlement was determined by bending the specimen back upon itself until the jute side was touched. The oven aged samples were allowed to cool at least one-half hour before flexing. Part A: Latex Part B: Filler supplied by TR+C Part C: NH4OH+Vulcanizing agent The amount of the additive is expressed in weight percent based on the weight of the polymer. 50 55 60 Unstabilized thoroughly dried polyethylene terephthalate chips are dry blended with 1.0% of bis(2,6-dit-butyl-4-methylphenyl)phosphorochloridite. 60/10 de nier multifilament is melt spun at a melt temperature of 209 C. The oriented fiber is wound on white cards and exposed in an Xenon Arc Fadeometer. Color measure ments are made periodically with a Hunter Color Dif ference Meter Model D25. The stabilized samples are found to be much more light stable than the unstabilized samples. EXAMPLE 13 Additive 0.125% bi$(2,4,6-tri- TABLE XI Hunter (L-b) Color After Hours Exposure Hours to Embrittlement Hunter (L-b) Color After Hours Exposure 0 10 20 30 (a) A composition comprising acrylonitrilebutadienestyrene terpolymer and 1% by weight of bis(2,6-di-t- butyl-4-nonylphenyI)phosphite resists embrittlement 65 due to exposure to ultraviolet light longer than one which does not contain the stabilizer. (b) A composition comprising polyurethane prepared from toluene diisocyanate and alkylene polyols and 4,233,208 21 22 1.0% by weight of bis(2,6-di-t-butyl-4-methylphenyl)- phosphorochloridite is more stable to sunlight, fluores cent sunlamps, black lights and fluorescent lights than the unformulated polyurethane. (c) A composition comprising a polycarbonate pre 5 Additives pared from bisphenol-A and phosgene and 1% by weight of bis(2,4,6-tri-a-phenylethyl phenyI)phosphite resists discoloration due to exposure to ultraviolet light phosphite Blank TABLE Xll-continued Oven Aging at 185' C. % Retention of Initial Tensile 4 8 II 12 weeks weeks weeks weeks 97 62 45 43 70 36 25 24 longer than one which does not contain the stabilizer. (d) A composition comprising polymethylmethacryl ate and 0.25% by weight of bis(2,4,6-tri-tert.-butylphenyl)phosphite resists discoloration due to exposure to ultraviolet light longer than one which does not 10 What is claimed is: 1. Compositions comprising a polymer normally sub ject to deterioration stabilized with (a) 0.005 to 5% of a stabilizer having the formula contain the stabilizer. 15 EXAMPLE 14 (a) A stabilized polyamide (nylon 6,6) is prepared by incorporating therein 0.1% of bis(2,6-di-t-butylphenyl)- p or phosphite. The light stability of the stabilized composi tion is superior to that of an unstabilized polyamide. 20 (b) A stabilized polyphenylene oxide polymer (pre pared by polymerizing 2,6-dimethylphenol is prepared by incorporating therein 0.5% by weight ofbis(2,6-di-t- butyl-4-chlorophenyl)phosphorochloridite. The stabi lized compositions resist embrittlement due to exposure 25 to ultraviolet light longer than one which does not wherein contain the stabilizer. (c) A stabilized crystalline polystyrene is prepared by incorporating therein 0.1 % by weight of the bis(2,6-di-tbutyI-4-methylphenyl)phosphorochloridite. The stabi 30 lized composition resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer. R is hydroxy or chlorine, Y and Y' are independently alkyl having from 1 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms, and Z is independently hydrogen, halogen, alkyl hav ing from 1 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms. EXAMPLE 15 35 2. A composition according to claim 1 wherein R is hydroxy. The indicated amounts of additives (Table XII) were 3. A composition according to claim 1 wherein R is blended with dried Celanex 3300 (30% glass reinforced chlorine. polybutylene terephthalate), and then extruder com 4. A composition according to claim 1 wherein Y and pounded at a melt temperature of 465" F. Tensile test specimen, were prepared by injection molding. 40 Y' are each t-butyl. 5. A composition according to claim 1 wherein R is Aging of the tensile test specimens was conducted in hydroxy, a forced draft air oven at 185 C. The specimens were Y and Y' are each t-butyl, and tested for percent retention of initial tensile in the In- Z is hydrogen or t-butyl. stron Tensile Testing Apparatus (Instron Engineering Corporation, Quincy, Massachusetts). The test results 45 6. A composition according to claim 1 wherein the polymer is polyolefin. are reported in the following table. The amounts of the 7. A composition according to claim 1 wherein the additives are expressed in weight percent based on polymer is polypropylene. weight of the polymer. 8. A composition according to claim 1 wherein the Additives TABLE XII Oven Aging at 185* C. % Retention of Initial Tensile 4 8 n 12 weeks weeks weeks weeks 50 polymer is acrylonitrile-butadiene-styrene terpolymer. 9. A composition according to claim 1 wherein the polymer is polystyrene. 10. A composition according to claim 1 wherein the polymer is styrene-butadiene copolymer. 0.5% di-n-octadecyl-3,5di-tert'butyl-4-hydroxy- benzyl-pbosphonate 0.5% bis-<2.4,6-trwbutyl-phenyl>phosphite 0.25% di-n-ocladecyl-3,5di-tert-butyl-4-hydroxy* 55 11. A composition according to claim 1 wherein the 9! 56 35 39 polymer is a polyester composition containing polyalkylene terephthalate. 112 62 55 48 12. A composition according to claim 1 wherein the polymer is selected from polypropylene, polyeth 60 ylene, acrylonitrile-butadiene-styrene terpolymer, benzyl-phosphonate + 0.25% bis(2,4.6-tri-t*butylphenyl)phosphite 0.5% N,N'-hexamethyiene bis (3.5-di-tert-bulyl*4- 112 63 38 45 styrene-butadiene copolymer, polyalkylene terrphthalate and impact polystyrene. 13. The composition according to claim 1 which contains 0.005 to 5% of a thioco-stabilizer. hydroxy-hydro-cinnamamide 0.25% N.N'-he.xamethylene bis {3.5-di`tert-butyl-4-hydroxyhydro-cinnamamide) 4- 0 25% bis-(2,4.6-tri-l-butylphenyl) 88 49 38 34 65 14. A composition according to claim 13 comprising (i) from 0.005 to 5% of the hindered phosphite of formula (I) and from 0.005 to 5% of the thio-costabilizer and 4,233,208 23 24 (ii) a polymer selected from acrylonitrile-butadiene- butyl-4-methylphenoI, and tris 2,4,6-(3,5-di-t- styrene terpolymer, styrene-butadiene copolymer, butyl-4-hydroxybenzyl)isocyanurate. and polyalkylene terephthalate. 20. A composition according to claim 18 consisting 15. The composition according to claim 1 which essentially of contains 0.005 to 5% of a phenolic antioxidant. 5 16. A composition according to claim 15 consisting essentially of (i) polypropylene, (ii) a hindered phosphite of formula (I), (iii) 0.005 to 5% of a benzotriazole having the formula (i) a polymer selected from polypropylene, polyethyl ene, impact polystyrene, polyalkylene terephthal ate and acrylonitrile-butadiene-styrene terpolymer, 10 (ii) a hindered phosphite of formula (I), and RJ (iii) 0.005 to 5% of a phenolic antioxidant selected from tetrakis [methylene 3-(3',5'-di-tert-butyl-4'- hydroxyphenyl)propionate]methane, octadecyl 3-(3'-5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 15 di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, N,N'-hexamethylene bis(3,5-di-tert- butyl-4-hydroxy-hydrocinnamamide, 2,2'-methy- lene-bis(6-t-butyl-4-ethylphenol) and 2,6-di-t-butyl- 4-methylphenol. 17. A composition according to claim 15 consisting 20 essentially of wherein R2 is hydrogen, chlorine or lower alkyl containing from 1 to 6 carbon atoms, R3 is hydrogen, alkyl containing 1 to 12 carbon atoms, phenyl or benzyl, and R4 is hydrogen, chlorine or (lower) alkyl contain (i) polyolefin, ing from 1 to 6 carbon atoms, and (ii) a hindered phosphite of formula (I), and (iv) 0.005 to 5% of a phenolic antioxidant se (iii) 0.005 to formula 5% of a thio-co-stabilizer having the 25 O II r>-o-c-c,,h2,, I s 30 lected from tetrakis[methylene-3-(3',5'-di-tertbutyl-4'-hydroxyphenyl)propionate]methane, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, di-n-octadecyl-3,5-di-tertbutyl-4-hydroxybenzyl phosphonate, 2,6-di-tbutyl-4-methylphenol, and tris-2,4,6-(3,5-di-tbutyl-4-hydroxybenzyl)isocyanurate. 21. The composition according to claim 1 which R1 --O--C--C,,H2,, oII contains 0.005 to 5% of a UV absorber or light stabi lizer. 22. The composition according to claim 15 which wherein R1 is an alkyl group having from 6 to 24 35 contains 0.005 to 5% of a thio co-stabilizer. 23. The composition according to claim 13 which carbon atoms and n is an integer of from 1 to 6. contains 0.005 to 5% of a UV absorber or light stabi 18. The composition according to claim 15 which lizer. contains 0.005 to 5% of a UV absorber or light stabi 24. The composition according to claim 22 which lizer. contains 0.005 to 5% of a UV absorber or light stabi 19. A composition according to claim 18 consisting 40 lizer. essentially of (i) polyolefin, (ii) a hindered phosphite of formula (I) 25. The composition according to claim 19 which contains 0.005 to 5% of a thio-co-stabilizer having the formula (iii) 0.005 to 5% of a p-hydroxybenzoate having the formula 45 O R5 HO--^(3^-- coor7 11 50 S R1--O--C--C,,H},, II O wherein R1 is an alkyl group having from 6 to 24 carbon R6 atoms and n is an integer of from 1 to 6. wherein 55 26. The composition according to claim 20 which contains 0.005 to 5% of a thio-co-stabilizer having the R5 is (lower) alkyl containing from 1 to 6 carbon formula atoms, R6 is hydrogen or (lower) alkyl containing from 1 to 6 carbon atoms, and o R7 is alkyl of from 1 to 24 carbon atoms, phenyl or 60 phenyl substituted by one or two alkyl groups of 1 to 12 carbon atoms, and (iv) 0.005 to 5% of a phenolic antioxidant se lected from tetrakis[methylene 3-(3',5'-di-tertbutyl-4'-hydroxyphenyl)propionate]methane, 65 s r1-- o-c-c,,h2,, II o octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxy- wherein R1 is an alkyl group having from 6 to 24 carbon phenyl)propionate, di-n-octadecyl-3,5-di-tertbutyl-4-hydroxybenzyl phosphonate, 2,6-di-t- atoms and n is an int*ege*r fr*om* 1 t*o 6.