CA1149092A - Phosphite heat stabilized graft diene copolymers - Google Patents
Phosphite heat stabilized graft diene copolymersInfo
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- CA1149092A CA1149092A CA000342141A CA342141A CA1149092A CA 1149092 A CA1149092 A CA 1149092A CA 000342141 A CA000342141 A CA 000342141A CA 342141 A CA342141 A CA 342141A CA 1149092 A CA1149092 A CA 1149092A
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- phosphite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Abstract:
Hydrolytically stable triaryl phosphites.
The tris-(o-alkylphenyl)phosphites are more stable to hydrolgsis than the tris-(p-alkylphenyl)phosphites and this makes them more useful as heat-stabliizing additives in certain graft copolymer compositions, especially in ABS resin compositions. The alkyl groups are those having 3-12 carbon atoms.
Hydrolytically stable triaryl phosphites.
The tris-(o-alkylphenyl)phosphites are more stable to hydrolgsis than the tris-(p-alkylphenyl)phosphites and this makes them more useful as heat-stabliizing additives in certain graft copolymer compositions, especially in ABS resin compositions. The alkyl groups are those having 3-12 carbon atoms.
Description
TRIS-(0-~LKYLP~ENYL)PH~SPHITES
Description This invention relates to phosphite esters which are unusually stable to hydrolysis. `iIore particularly, it relates to the use of such stable phosphite esters as heat~stabilizin~ agents for certain graft copolymer compo-sitions.
The normal processing operations ~o which the graIt copoiymers herein are normally suojected invaliably in~,701ve high temperatures and these promote ~he deterioration OI
the polymers. The formulation of a pol~mer composition i.e., one ~hich contains the various stabilizing additiTies ordinarily required, usuall~- is accomplished on a heated two-roll mill, or in a heated Banbury*r.lixer, or both, and the temperatures at which such mixin~ sleps are carried out are quite high, well above the temperature at nhich the polymer becomes fluid. ~t these ~emperatures the poly,mer will develop color, become brittle, etc., and such evidence of deterioration cannot be tolerated in the finai product.
There are a number of heat-s~abilizing acI~itives available which are effective to protect thermoplastic polymers from wuch deterioration. .~mong these are the organic phosphites. IVhile these are very effecti~-e hezt-stabilizi~g additives, their usefulness is limited by their suceptibility IO hydrolytic decomposition in a humid environment. Such hydrolysis is accompanied by a corres-pondiIlg loss of heat-stabilizing effectiveness with respect to the polymer compositions in which they are used for that purpose. .~Ioreoever, where the phosphite is a solid, such hydrolysis also frequentl~ is accompanied by a tendency to blocking, i.e., a tendency for the ordinarily granular phosohite material to congeal into a singie solid block.
Trade mark '' ' ' ~
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.~,larly atternpts have been made to sol~e this proble~..
.~dditives such as triisopropanolamine have been found to impart a significant hgdroly-cic stability to organic phosphite esters. The solid phosphites can be stored in moisture-proof containers such as polyethylene bags until just before use. All of these have been very helpful, but they have not elimi~ated -the problem, nor the deslr-ability of a solution to the problem.
~-.K. 1,490,938 (Ciba-Geigy) shows symmetrical tri-arylphosphites having the formula:
Description This invention relates to phosphite esters which are unusually stable to hydrolysis. `iIore particularly, it relates to the use of such stable phosphite esters as heat~stabilizin~ agents for certain graft copolymer compo-sitions.
The normal processing operations ~o which the graIt copoiymers herein are normally suojected invaliably in~,701ve high temperatures and these promote ~he deterioration OI
the polymers. The formulation of a pol~mer composition i.e., one ~hich contains the various stabilizing additiTies ordinarily required, usuall~- is accomplished on a heated two-roll mill, or in a heated Banbury*r.lixer, or both, and the temperatures at which such mixin~ sleps are carried out are quite high, well above the temperature at nhich the polymer becomes fluid. ~t these ~emperatures the poly,mer will develop color, become brittle, etc., and such evidence of deterioration cannot be tolerated in the finai product.
There are a number of heat-s~abilizing acI~itives available which are effective to protect thermoplastic polymers from wuch deterioration. .~mong these are the organic phosphites. IVhile these are very effecti~-e hezt-stabilizi~g additives, their usefulness is limited by their suceptibility IO hydrolytic decomposition in a humid environment. Such hydrolysis is accompanied by a corres-pondiIlg loss of heat-stabilizing effectiveness with respect to the polymer compositions in which they are used for that purpose. .~Ioreoever, where the phosphite is a solid, such hydrolysis also frequentl~ is accompanied by a tendency to blocking, i.e., a tendency for the ordinarily granular phosohite material to congeal into a singie solid block.
Trade mark '' ' ' ~
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.~,larly atternpts have been made to sol~e this proble~..
.~dditives such as triisopropanolamine have been found to impart a significant hgdroly-cic stability to organic phosphite esters. The solid phosphites can be stored in moisture-proof containers such as polyethylene bags until just before use. All of these have been very helpful, but they have not elimi~ated -the problem, nor the deslr-ability of a solution to the problem.
~-.K. 1,490,938 (Ciba-Geigy) shows symmetrical tri-arylphosphites having the formula:
2 \ ~ ,~ 0 _ _ p _ R3 _ 3 wherein Rl represents tertiarybutyl, l,l-dimethylpropyl, cyclohexyl or phenyl, and one of R2 and R3 is hydrogen and the other is hydrogen, methyl, tertiarybutyl, l,l-dimethyl-propyl, cyclohexyl or phenyl. The use of these compounds in combination with phenolic antioxidants in polyolefins is also shown.
U.S. 2,733,226 (Hunter) shows aryl phosphites sub-stituted with alkyl groups containing eight or more carbon atoms and their use as stabilizers for synthetic rubber.
The alkyl groups may be ortho, para or meta to -the oxygen.
U.S. 3,578,620 (Prucnal) shows the stabilization of non-rubbery, unsaturated interpolymers of cyclic polyenes by means of a mixture of a tri-(alkylphenyl) phosphite in whic~ the alkyl group has from 8 to 30 carbon atoms and an epoxi~e. Tri-(o-octylphenyl)phosphite is shown.
U.S. 3,080,338 (Nudenberg et al) shows the use of "any conventional phosphite" in combination with a phenolic antioxidant to s-tabilize synthetic rubbery polymers.
4~ Z
077206-~ - 3 -Tri-(ortho-octyl-phenyl) phosphite is shown.
U.S. 2,752,319 (Lipke et al) shows the stabilization of polyvinyl chloride compositions by means of a combination of a glycol ester of an organic acid, a triaryl phosphite (to stabilize the ester), and a metal compound. The aryl phosphite can be tri-(orthocyclohyexylphenyl)phosphite.
The invention here is a polymer composition comprising a graft copolymer such as an ~BS resin, for example, and a minor amount, sufficient to impart improved heat stability to said polymer, of a tris-(alkylphenyl)phosphite or tris-(cycloalkylphenyl)phosphite mixture wherein (1) the alkyl group contains 3-12 carbon atoms, (2) at least about 85~o of one of the ortho positions in each phenyl group are substituted by said alkyl or cycloalkyl groups, and (3) at least about 85ao of the para positions in each phenyl group are unsubstituted, or substituted by methyl groups. The phosphite can be represented, in most instances, by the structure:
U~P
wherein at least about 85~o of R is alkyl of 8-12 carbon atoms or ~ycloalkyl, the reaminder being hydrogen, and at least about 85% of R is methyl or hydrogen.
The preparation of these substituted phosphites requires, first, preparation of the alkylphenol or cyclo-alkylphenol and then, reaction of this phenolic compound with phosphorous trichloride. The first of these reactions can be accomplished by hydroge~ating an acylphenol. This may be done conveniently by means of zinc plus hydrochloric acid.
077206~ 4 _ ~n alternatlve method affords somewhat better yields;
it involves alkylation of phenol (or p-cresol) with an appropriate olefin in the presence of a ca~alyst. A
preferred catalyst is alumln-wn po~.ler, or, more parti-cularly, the aluminum phenate which results from thereaction of aluminum and the pheno]ic reactant. Such alkylation yields a high proportion of ortho isomer and relatively little or no para isomer.
The reaction of the o-alkylphenol and phosphorous trichloride proceeds with good yields, at rela-tively high temperatures. The product may be distilled to yield a clear, colorless liquid product; alternatively, it may be stripped in vacuo and the residual liquid taken as the product~
This product, i.e., a tris-(o-alkylphenyl)phosphite is as indicated characterized by unusual hydrolytic stability and, correspondingly, long-lived effectiveness as a stabilizer in polymer compositions, especially in ABS compositions. It is particularly effective in such compositions which also contain a phenolic antio~idant.
The graft copolymer herein is of the type represented by an ABS resin. It has a graftable rubber substrate con-taining a diene rubber-forming monomer component and a super-strate of an interpolymer consisting at least principally of a monovinylidene aromatic hydrocarbon and an ethylenically unsaturated nitrile or ester. The rubber substrate is a diene rubber having a second order transition temperature not higher than 0C and preferably not higher than -20C
as determined by AST~f Test D-746-52T. It is a polymer of one or more conjugated 1, 3 dienes, e.g., butadiene, isoprene, piperylene, chloroprene, etc. Such rubbers include homo-polymers and interpolymers of conjugated l, 3-dienes with up to an equal amount by weight of one or more copolymerizable monoethylenically unsaturated monomers, such as monovinylidene aromatic hydrocarbons (e~g., styrene; an aralkylstyrene, , . .
077206-i`/I - 5 ~
such as the o-, m-, and p-methylstyrenes, 2, 4-dimethyl-styrene, the ar-ethylstyrenes, p-tert-butylstyrene, etc.;
an alpha-alkylstyrene, such as alpha-methylstyrene, alpha-ethylstyrene, alpha-methyl-p-methylstyrene, etc.; vinyl naphthalene, etc.); arhalo monovinylidene aromatic hydro-carbons (e.g., the o-, m-, and p-chlorostyrenes, 2, 4-dibromostyrene, 2-methyl-4-chlorostyrene, etc.); acrylonitrlle;
methacrylonitrile; alkyl acrylates (e.g., methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), the corres-ponding alkyl methacrylates; acrylamides (e.g., acrylamide,methacrylamide, ~- butyl acrylamide, etc.); unsaturated ketones (e.g., vinyl methyl ketone, methyl isopropenyl ketone, etc.); alpha-olefins (e.g., ethylene~ propylene, etc.); pyridines; vinyl esters (e.g., vinyl acetate, vinyl stearate, etc.); vinyl and vinylidene halides (e.g., the vinyl and vinylidene chlorides and bromides, etc.);
and the like.
Although the rubber may contain up to about 2 percent of a cross-linking agent, based on the weight of the rubber-forming monomer or monomers, cross-linking may present problems in dissolving the rubber in the monomers for the graft polymerization reaction, particularly for a mass or suspension polymeri~ation reaction. In addition, excessive cross-linking can result in loss of the rubbery characteristics. The cross-linking agent can be any of the agents conventionally employed for cross-linking diene rubbers, e.g., divinylbenzene, diallyl maleate, diallyl fumarate diallyl adipate, allyl acrylate, allyl methacrylate, diacrylates and dimethacrylates of polyhydric alcohols, e.g., ethylene glycol dimethacrylate, etc.
A preferred group of rubbers are those consisting essentially of 75 to 100 percent by weight of butadiene and/or isoprene and up to 2~ percent by weight of a monon,er selected from the group consisting of monovinylidene Z
077206-~1 - 6 -aromatic hydrocarbons (e.g., styrene) and unsaturated nitriles (e.g., acrylonitrile), or mixtures thereof.
Particularly advantageous substrates are butadiene homo-polymer or an interpolymer of 90 to 95 percent by weight butadiene and 5 to 10 percent by weight of acrylonitrile or styrene.
The interpolymer of the superstrate consists at least principally of a monovinylidene aromatic hydrocarbon and an unsaturated nitrile and/or ester, i.e., such monomers comprise at least 75 percent by weight and preferably at least 90 percent by weight of the interpolymer.
Exemplary of the monovinylidene aromatic hydrocar~ons which may be used in the interpolymers are styrene; alpha-alkyl monovinylidene monoaromatic compounds, e.g., alpha-methylstyrene, alpha-ethylstyrene, alpha-methylvinyltoluene, alpha-methyl dialkylstyrenes, etc.; ring~substituted alkyl styrenes, e.g., vinyl toluene, o-ethylstyrene, p-ethyl-styrene, 2,4-dimethylstyrene, etc.; ring-substituted halo-styrenes, e.g., o-chlorostyrene, p-chlorostyrene, o-bromo-styrene, 2,4-dichlorostyrene, etc.; ring-alkyl, ring-halo-substituted styrenes, e.g., 2-chloro-4-methylstyrene, 2,6-dichloro-4-methylstyrene, etc.; vinyl naphthalene; vinyl anthracene, etc. The alkyl substitutents generally have 1 to 4 carbon atoms and may include isopropyl and isobutyl groups. If so desired, mixtures of such monovinylidene aromatic monomers may be employed.
Exemplary of the unsaturated nitriles which may be used in the interpolymers are acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof.
Exemplary of the unsaturated esters which may be used in the interpolymers are methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl methacrylate and mixtures thereof.
, . . .
' . , Z
Exemplary oE the monomers which may be inter-polymerized with the monovinylidene aromatic hydrocarbons, unsaturated nitriles and/or esters are conjugated 1,3 dienes, e.g., butadiene, isoprene, etc.; alpha- or heta-unsaturated mono-basic acids and derivatives thereof, e.g., acrylic acid, methacrylic acid, acrylamide, methacrylamide;
vinyl halides such as vinyl chloride, vinyl bromide, etc.;
vinylidene chloride, vinylidene bromide, etc.; vinyl esters such as vinyl acetate, vinyl propionate, etc.; dialkyl maleates or fumarates such as dimethyl^maleate, diethyl maleate, dibutyl maleate, the corresponding fumarates, etc.
As is known in the art, the amount of these comonomers which may be included in the interpolymer will vary as the result of various factors.
Various techniques are customarily employed in the preparation of the graft copolymers of this invention, and these are well known in the art and do not form a part of the invention.
ABS (acrylonitrile-butadiene-styrene) resins are especially preferred for the purposes of the invention.
MBS (methacrylate-butadiene-styrene) resins and MABS
(methacrylate-acrylonitrile-butadiene-styrene) resins are also preferred.
The alkyl groups in the tris-(alkylphenyl)phosphite contain, as indicated earlier, 3-12 carbons atoms. Thus, octyl, nonyl, decyl, undecyl and dodecyl groups are specifically contemplated. These groups may be attached to the phenolic ring through a primary, secondary or tertiary carbon atom.
The cycloalkyl groups contemplated are cyclopentyl and cyclohexyl.
The tris-(alkylphenyl)phosphite herein is derived from an alkylphenol of the structure:
dm:
where Rl is methyl or hydro~en and R2 is alkyl of 3-12 carbon atoms.
The amount of the tris-(o-alkylphenyl)phosphite or tris-(o-cycloalkylphenyl)phosphite which is to be used ranges from about 0.05 phr (parts per 100 parts of resin) to about 5.0 phr.
The phenolic antioxidants are well known. Specifi-cally contemplated are the following: 2,6-di-tert.-butyl-4-methylphenol, 2)6-di-tert.-butyl-4-methoxymethylphenol or 2,6-di-tert.-butyl-4-methoxyphenol; 2,~'-methylene-bis-(6-tert.-butyl-4-methylphenol). 2,2'-methylene-bis-(6-tert.-butyl-4-ethylphenol), 2,2'-methylene-bis-~4-methyl-6( ~methylcyclohexyl)-phenol], 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.butyl-4-hydroxyphenyl)-propane, 1,1,3-~ris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butane, 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-pentane, ethylene glycol-bis[3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)-butyrate], 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-butane, or 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol); 1,3,5-tri-(3,5-di-tért.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonic acid-dioctadecyl ester, 1,3,5-tris-(3,5-di-tert,-butyl-4-hydroxybenzyl)-iso-cyanurate, or 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid-diethyl ester; amides of 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, such as 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; esters of 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with methanol, octadecanol, 1,6-hexanediol, ethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, tris-hydroxy-ethyl-isocyanurate; diphenolic spiro-diacetals or spiro-diketals, such as 2,4,~,10-tetrao~aspiro-~5,5]-undecane substituted in the 3- and 9-position with phenolic radicals, such as 3,9-bis-(3,5-di-tert.butyl-4-hydroxyphenyl)-2,4, ~,10-tetraoxaspiro-[5,5]-undecane, 3,9-bis-[1,1-dimethyl-2-(3,5-ditert.-butyl-4-hydroxyphenyl)-ethyl]-2,4,8,10-tetraoxaspiro-[5,5]-undecane.
Particularly preferred are: 1,3,5-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-tri-methylbenzene, penta-erythritol-tetra~3~3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate], ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid-n-octadecyl ester, thiodiethylene glycol-e - [4-hydroxy-3,5-di-tert.-butyl-phenyl]-propionate, 2,6-di-tert.-butyl-4-methyl-phenol, and 3,9-bis [l,l-dimethyl-2-(3,5-ditert.-butyl-4-hydroxyphenyl)-ethyl]-2,4,8,10-tetraoxaspiro[5,5]-undecane, and 2,2'-methylene-bis-(6-tertiarybutyl-4-ethyl-phenol).
The amount of phenolic antioxidant which is to be used ranges from about 0.05 phr to about 1.0 phr.
Preparation of the phosphite esters herein is illustrated by the following specific examples.
Example 1 To 200 g. of aMalgamated zinc there is added a solution of 200 ml. of concentrated hydrochloric acid in 300 ml. of water, then a 25% ethanolic solution of 72 g.
(0.29 mol) of ~-methyl-2-nonanoyl-phenol. The mixture i5 heated at reflux for nine hours with stirrin~, treated with 200 ml. of toluene and then permitted to cool. The organic layer is isolated, washed with water, filtered and freed of solvents by stripping. The residue is distilled to yield 57C,o (of the theor~) of 4-methyl-2-n-nonylphenol.
077206~ 10 -~x~nple 2 The procedure of Example 1 is repeated using S0 g.
(0.29 mol) OI 4-methyl-2-dodecanoylphenol as a reactant instead of ~-methyl-2-nonanoylphenol. The yield of 4-~ethyl-2-dodecylphenol is 56% of the theory.
Example 3 An S3-g. sample of phenol is dried by axeotropic distillation until no more water distills, t~len heated at 155C and treated portionwise, under argon, with 0. 83 g, of aluminum granules. After the evolution of hydrogen has ceased, the temperature is allowed to drop to 145C
and 50 g. of l-nonene is added slowly. The temperature is maintained with stirring, at 145-150C for six hours.
The e~cess phenol and unreacted nonene are removed by distillation at reduced pressure and the residue washed with 5% aqueous hydrochloric acid solùtion, then with water until the washings are neutral to litmus. Distillation of the residue yields 30 g. (34~O of the theory, 93~O
conversion) of a clear, colorless liquid boiling at 94C/
10 mm. Over 98,~o of it is the o-(l-methyloctyl)phenol.
Example 4 The procedure of Example 3 is repeated using l-octene instead of l-nonene. The product, a clear, ~ater-white liquid boiling at 100-107C/10-0.1~ mm., contains 93~o of the desired o-(l-methylheptyl)phenol; it was obtained in a 76% (of the theory) yleld.
Example 5 The procedure of Example 3 is repeated using propylene trimer instead of l-nonene. The product is a clear, water-white liquid boiling at 105-110C/0.25 m~. It is obtained in a 39C~ yield and contains ~% of the desired o-nonylphenol.
- Example ~
The procedure of Example 3 is repeated using diisobutylene instead of l-nonene. A 45',~ yield O:e clear, water-white liquid is obtained containing 89/o of the desired o-octylphenol.
The hydrolytically stable phosphites o~ the invention may be prepared as follows:
To l.0 mol of the o-alkylp~enol, at 55C, there is added, slowly, 0.30 mol of phosphorous trichloride.
- 10 The reaction initially is exothermic, but later, external heating is required to maintain the temperature at 55C.
When all of the phosphorous trichloride has been added, the temperature is raised, in an argon atmosphere, to 180-250C and kept there for 23-33 hours. The residue is distilled yielding a clear, colorless liquid.
The followin~ tris-(o-alkylphenyl~phosphites, having the structural lormula ~ R ~ 0 ~ P
are prepared by this method:
R' R Yiel~
__ _ _ Example 7 methyln-nonyl - 99%
Example 8 methyln-dodecyl 99%
Example 9 II l-~ethylheptyl 59%
E~ample 10 H l-methyloctyl ~1%
Example 11 ~I cyclohexyl 99%
Example 12 ~I n-butyl 99~
The purity of the products obtained as above is high, ranging ~rom 93G' to 99%.
077206~ 12 -The hydrolytic stability of these tris-(o-alkyl-phenyl)phosphites may be shown by the results of a test carried out in aqueous tetrahydrofuran. A 2G,o solution of the phosphite sample in a mixture of 80 parts of tetrahydrofuran and 20 parts of ~vater is maintained at 44C and a pH of 4.5 for 48 hours. The disappearance of phosphite is monitored by means of liquid chromatographic analyses.
A commercial sample of tris-(nonylphenyl)phosphite containing 92qo of the para isomer, 6~o of the ortho isomer and 2% of the dinonyl compound, is found to be completely hydrolyzed after 140 hours. A corresponding sample of tris-(nonylphenyl)phosphite containing 88$
of the ortho isomer and 12~o Of the para isomer is 10%
hydrolyzed a~ter 140 hours and only 50% hydrolyzed after 760 hours.
Similarly, a sample of trls-(l-methylheptylphenyl) phosphite (wherein 92% of the alkylphenyl groups are 2-alkylphenyl and 7% are 2,4-dialkylphenyl) was only 50% hydrolyzed after 700 hours.
The hydrolytic stability of these tris-(o-alkyl-phenyl)phosphites in acidic aqueous emulsions is shown by the results of a test where 10 parts of a phosphite sample is mixed with a solution of 2.1 parts of an anionic organic phosphate in 34 parts of water. 'he resulting emulsion is added to 400 parts of water, warmed to 55C and the p~ adjusted to 2.5 by the addition o~ concentrated hydrochloric acid. This diluted emulsion is allowed to cool and stand for 10 hou-rs. The pH is ad,justed to 7 with dilute aqueous potassium hydroxide solution and the emulsion poured into 600 parts of 5% aqueous calcium chloride solution at 85C. The mixture is cooled, extracted with benzene and the benzene extract dried and evaporated to an oily residue. The extent of hydrolysis is determined by 077206--.?'~' -- 13 liquid chromatographic analysis.
Samples of the above commercially available tris-(nonyl-phenyl) phosphite and tris-(ortho-l-methyl-heptylphenyl)phosphite are subjected to the above ; 5 test: the former is cornpletely hydrolyzed; the latter is hydrolyzed to the extent of 30%.
The e~fec-tiveness of the tris-(o-alkylphenyl)phosphiles herein as polymer stabilizers in a hydrolyzing en-vironment is shown as follows: A stabilizing emulsion is prepared by adding a solution of 6.25 parts ol the phosphite and 1.15 parts of oleic acid to a hot solution of 0.55 part of triethanol amine in 17 parts of de-mineralized water and mixing with a high speed stirrer for one minute. The resulting emulsion is added to 325 parts of polybutadiene latex and the mixture : stirred for 12 hours. The mixture then is coagulated ~ at 85C by addition of 1.5~o aqueous sulfuric acid and - the polybutadiene crumb collected, washed and dried.
The dried crumb is aged in an oven at 100C anA the time required for the development of an overall brown color taken as a measure of the stability of the polybutadiene.
Samples of the above commercially available tris-(nonyl-phenyl)phosphite (A) and the tris-(ortho-l-methylheptylphenyl)phosphite (B) of Example 9 are subjected to this test, vrith the following results: -Phosphite ours to Coloration ~ 130 none 30 The superiorlty of the o-alkylphenyl-substituted phosphite is apparent.
077206~ 14 -The effectiveness of the phosphites herein as a stabilizer for ABS resins is shown by a comparison o~
stability clata collected as ~ollows: A m.ixture of 5.0 parts of phosphite and 2~0 parts of bis-(3-ethyl-5-tertiarybutyl-6-hydroxypilenyl)methane is added to 20 parts of an ABS (prepared by copolymerizing styrene and acrylonitrile in a polybutadiene late~) latex, so as to provide l.O phr of stabilizer (phosphite plus phenol).
~e latex is coagulated ~vith 2' aqueous sulfuric acid and oven dried at 50C. The solid is stampecl into 1.5-inch (diameter) discs of 12-15 mil thickness, and these are placed in an oven with circulating air at 150C. The time required for the development of brittleness, discoloration or cracking is noted.
Table lI
Phosphite Eours to Failure 1. Product of E~ample 9 6 2. A tris-(nonylphenyl)phosphite where S8% of the nonyl groups are ortho and 11~ are para 4
U.S. 2,733,226 (Hunter) shows aryl phosphites sub-stituted with alkyl groups containing eight or more carbon atoms and their use as stabilizers for synthetic rubber.
The alkyl groups may be ortho, para or meta to -the oxygen.
U.S. 3,578,620 (Prucnal) shows the stabilization of non-rubbery, unsaturated interpolymers of cyclic polyenes by means of a mixture of a tri-(alkylphenyl) phosphite in whic~ the alkyl group has from 8 to 30 carbon atoms and an epoxi~e. Tri-(o-octylphenyl)phosphite is shown.
U.S. 3,080,338 (Nudenberg et al) shows the use of "any conventional phosphite" in combination with a phenolic antioxidant to s-tabilize synthetic rubbery polymers.
4~ Z
077206-~ - 3 -Tri-(ortho-octyl-phenyl) phosphite is shown.
U.S. 2,752,319 (Lipke et al) shows the stabilization of polyvinyl chloride compositions by means of a combination of a glycol ester of an organic acid, a triaryl phosphite (to stabilize the ester), and a metal compound. The aryl phosphite can be tri-(orthocyclohyexylphenyl)phosphite.
The invention here is a polymer composition comprising a graft copolymer such as an ~BS resin, for example, and a minor amount, sufficient to impart improved heat stability to said polymer, of a tris-(alkylphenyl)phosphite or tris-(cycloalkylphenyl)phosphite mixture wherein (1) the alkyl group contains 3-12 carbon atoms, (2) at least about 85~o of one of the ortho positions in each phenyl group are substituted by said alkyl or cycloalkyl groups, and (3) at least about 85ao of the para positions in each phenyl group are unsubstituted, or substituted by methyl groups. The phosphite can be represented, in most instances, by the structure:
U~P
wherein at least about 85~o of R is alkyl of 8-12 carbon atoms or ~ycloalkyl, the reaminder being hydrogen, and at least about 85% of R is methyl or hydrogen.
The preparation of these substituted phosphites requires, first, preparation of the alkylphenol or cyclo-alkylphenol and then, reaction of this phenolic compound with phosphorous trichloride. The first of these reactions can be accomplished by hydroge~ating an acylphenol. This may be done conveniently by means of zinc plus hydrochloric acid.
077206~ 4 _ ~n alternatlve method affords somewhat better yields;
it involves alkylation of phenol (or p-cresol) with an appropriate olefin in the presence of a ca~alyst. A
preferred catalyst is alumln-wn po~.ler, or, more parti-cularly, the aluminum phenate which results from thereaction of aluminum and the pheno]ic reactant. Such alkylation yields a high proportion of ortho isomer and relatively little or no para isomer.
The reaction of the o-alkylphenol and phosphorous trichloride proceeds with good yields, at rela-tively high temperatures. The product may be distilled to yield a clear, colorless liquid product; alternatively, it may be stripped in vacuo and the residual liquid taken as the product~
This product, i.e., a tris-(o-alkylphenyl)phosphite is as indicated characterized by unusual hydrolytic stability and, correspondingly, long-lived effectiveness as a stabilizer in polymer compositions, especially in ABS compositions. It is particularly effective in such compositions which also contain a phenolic antio~idant.
The graft copolymer herein is of the type represented by an ABS resin. It has a graftable rubber substrate con-taining a diene rubber-forming monomer component and a super-strate of an interpolymer consisting at least principally of a monovinylidene aromatic hydrocarbon and an ethylenically unsaturated nitrile or ester. The rubber substrate is a diene rubber having a second order transition temperature not higher than 0C and preferably not higher than -20C
as determined by AST~f Test D-746-52T. It is a polymer of one or more conjugated 1, 3 dienes, e.g., butadiene, isoprene, piperylene, chloroprene, etc. Such rubbers include homo-polymers and interpolymers of conjugated l, 3-dienes with up to an equal amount by weight of one or more copolymerizable monoethylenically unsaturated monomers, such as monovinylidene aromatic hydrocarbons (e~g., styrene; an aralkylstyrene, , . .
077206-i`/I - 5 ~
such as the o-, m-, and p-methylstyrenes, 2, 4-dimethyl-styrene, the ar-ethylstyrenes, p-tert-butylstyrene, etc.;
an alpha-alkylstyrene, such as alpha-methylstyrene, alpha-ethylstyrene, alpha-methyl-p-methylstyrene, etc.; vinyl naphthalene, etc.); arhalo monovinylidene aromatic hydro-carbons (e.g., the o-, m-, and p-chlorostyrenes, 2, 4-dibromostyrene, 2-methyl-4-chlorostyrene, etc.); acrylonitrlle;
methacrylonitrile; alkyl acrylates (e.g., methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), the corres-ponding alkyl methacrylates; acrylamides (e.g., acrylamide,methacrylamide, ~- butyl acrylamide, etc.); unsaturated ketones (e.g., vinyl methyl ketone, methyl isopropenyl ketone, etc.); alpha-olefins (e.g., ethylene~ propylene, etc.); pyridines; vinyl esters (e.g., vinyl acetate, vinyl stearate, etc.); vinyl and vinylidene halides (e.g., the vinyl and vinylidene chlorides and bromides, etc.);
and the like.
Although the rubber may contain up to about 2 percent of a cross-linking agent, based on the weight of the rubber-forming monomer or monomers, cross-linking may present problems in dissolving the rubber in the monomers for the graft polymerization reaction, particularly for a mass or suspension polymeri~ation reaction. In addition, excessive cross-linking can result in loss of the rubbery characteristics. The cross-linking agent can be any of the agents conventionally employed for cross-linking diene rubbers, e.g., divinylbenzene, diallyl maleate, diallyl fumarate diallyl adipate, allyl acrylate, allyl methacrylate, diacrylates and dimethacrylates of polyhydric alcohols, e.g., ethylene glycol dimethacrylate, etc.
A preferred group of rubbers are those consisting essentially of 75 to 100 percent by weight of butadiene and/or isoprene and up to 2~ percent by weight of a monon,er selected from the group consisting of monovinylidene Z
077206-~1 - 6 -aromatic hydrocarbons (e.g., styrene) and unsaturated nitriles (e.g., acrylonitrile), or mixtures thereof.
Particularly advantageous substrates are butadiene homo-polymer or an interpolymer of 90 to 95 percent by weight butadiene and 5 to 10 percent by weight of acrylonitrile or styrene.
The interpolymer of the superstrate consists at least principally of a monovinylidene aromatic hydrocarbon and an unsaturated nitrile and/or ester, i.e., such monomers comprise at least 75 percent by weight and preferably at least 90 percent by weight of the interpolymer.
Exemplary of the monovinylidene aromatic hydrocar~ons which may be used in the interpolymers are styrene; alpha-alkyl monovinylidene monoaromatic compounds, e.g., alpha-methylstyrene, alpha-ethylstyrene, alpha-methylvinyltoluene, alpha-methyl dialkylstyrenes, etc.; ring~substituted alkyl styrenes, e.g., vinyl toluene, o-ethylstyrene, p-ethyl-styrene, 2,4-dimethylstyrene, etc.; ring-substituted halo-styrenes, e.g., o-chlorostyrene, p-chlorostyrene, o-bromo-styrene, 2,4-dichlorostyrene, etc.; ring-alkyl, ring-halo-substituted styrenes, e.g., 2-chloro-4-methylstyrene, 2,6-dichloro-4-methylstyrene, etc.; vinyl naphthalene; vinyl anthracene, etc. The alkyl substitutents generally have 1 to 4 carbon atoms and may include isopropyl and isobutyl groups. If so desired, mixtures of such monovinylidene aromatic monomers may be employed.
Exemplary of the unsaturated nitriles which may be used in the interpolymers are acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof.
Exemplary of the unsaturated esters which may be used in the interpolymers are methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl methacrylate and mixtures thereof.
, . . .
' . , Z
Exemplary oE the monomers which may be inter-polymerized with the monovinylidene aromatic hydrocarbons, unsaturated nitriles and/or esters are conjugated 1,3 dienes, e.g., butadiene, isoprene, etc.; alpha- or heta-unsaturated mono-basic acids and derivatives thereof, e.g., acrylic acid, methacrylic acid, acrylamide, methacrylamide;
vinyl halides such as vinyl chloride, vinyl bromide, etc.;
vinylidene chloride, vinylidene bromide, etc.; vinyl esters such as vinyl acetate, vinyl propionate, etc.; dialkyl maleates or fumarates such as dimethyl^maleate, diethyl maleate, dibutyl maleate, the corresponding fumarates, etc.
As is known in the art, the amount of these comonomers which may be included in the interpolymer will vary as the result of various factors.
Various techniques are customarily employed in the preparation of the graft copolymers of this invention, and these are well known in the art and do not form a part of the invention.
ABS (acrylonitrile-butadiene-styrene) resins are especially preferred for the purposes of the invention.
MBS (methacrylate-butadiene-styrene) resins and MABS
(methacrylate-acrylonitrile-butadiene-styrene) resins are also preferred.
The alkyl groups in the tris-(alkylphenyl)phosphite contain, as indicated earlier, 3-12 carbons atoms. Thus, octyl, nonyl, decyl, undecyl and dodecyl groups are specifically contemplated. These groups may be attached to the phenolic ring through a primary, secondary or tertiary carbon atom.
The cycloalkyl groups contemplated are cyclopentyl and cyclohexyl.
The tris-(alkylphenyl)phosphite herein is derived from an alkylphenol of the structure:
dm:
where Rl is methyl or hydro~en and R2 is alkyl of 3-12 carbon atoms.
The amount of the tris-(o-alkylphenyl)phosphite or tris-(o-cycloalkylphenyl)phosphite which is to be used ranges from about 0.05 phr (parts per 100 parts of resin) to about 5.0 phr.
The phenolic antioxidants are well known. Specifi-cally contemplated are the following: 2,6-di-tert.-butyl-4-methylphenol, 2)6-di-tert.-butyl-4-methoxymethylphenol or 2,6-di-tert.-butyl-4-methoxyphenol; 2,~'-methylene-bis-(6-tert.-butyl-4-methylphenol). 2,2'-methylene-bis-(6-tert.-butyl-4-ethylphenol), 2,2'-methylene-bis-~4-methyl-6( ~methylcyclohexyl)-phenol], 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.butyl-4-hydroxyphenyl)-propane, 1,1,3-~ris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butane, 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-pentane, ethylene glycol-bis[3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)-butyrate], 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-butane, or 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol); 1,3,5-tri-(3,5-di-tért.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonic acid-dioctadecyl ester, 1,3,5-tris-(3,5-di-tert,-butyl-4-hydroxybenzyl)-iso-cyanurate, or 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid-diethyl ester; amides of 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, such as 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; esters of 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with methanol, octadecanol, 1,6-hexanediol, ethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, tris-hydroxy-ethyl-isocyanurate; diphenolic spiro-diacetals or spiro-diketals, such as 2,4,~,10-tetrao~aspiro-~5,5]-undecane substituted in the 3- and 9-position with phenolic radicals, such as 3,9-bis-(3,5-di-tert.butyl-4-hydroxyphenyl)-2,4, ~,10-tetraoxaspiro-[5,5]-undecane, 3,9-bis-[1,1-dimethyl-2-(3,5-ditert.-butyl-4-hydroxyphenyl)-ethyl]-2,4,8,10-tetraoxaspiro-[5,5]-undecane.
Particularly preferred are: 1,3,5-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-tri-methylbenzene, penta-erythritol-tetra~3~3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate], ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid-n-octadecyl ester, thiodiethylene glycol-e - [4-hydroxy-3,5-di-tert.-butyl-phenyl]-propionate, 2,6-di-tert.-butyl-4-methyl-phenol, and 3,9-bis [l,l-dimethyl-2-(3,5-ditert.-butyl-4-hydroxyphenyl)-ethyl]-2,4,8,10-tetraoxaspiro[5,5]-undecane, and 2,2'-methylene-bis-(6-tertiarybutyl-4-ethyl-phenol).
The amount of phenolic antioxidant which is to be used ranges from about 0.05 phr to about 1.0 phr.
Preparation of the phosphite esters herein is illustrated by the following specific examples.
Example 1 To 200 g. of aMalgamated zinc there is added a solution of 200 ml. of concentrated hydrochloric acid in 300 ml. of water, then a 25% ethanolic solution of 72 g.
(0.29 mol) of ~-methyl-2-nonanoyl-phenol. The mixture i5 heated at reflux for nine hours with stirrin~, treated with 200 ml. of toluene and then permitted to cool. The organic layer is isolated, washed with water, filtered and freed of solvents by stripping. The residue is distilled to yield 57C,o (of the theor~) of 4-methyl-2-n-nonylphenol.
077206~ 10 -~x~nple 2 The procedure of Example 1 is repeated using S0 g.
(0.29 mol) OI 4-methyl-2-dodecanoylphenol as a reactant instead of ~-methyl-2-nonanoylphenol. The yield of 4-~ethyl-2-dodecylphenol is 56% of the theory.
Example 3 An S3-g. sample of phenol is dried by axeotropic distillation until no more water distills, t~len heated at 155C and treated portionwise, under argon, with 0. 83 g, of aluminum granules. After the evolution of hydrogen has ceased, the temperature is allowed to drop to 145C
and 50 g. of l-nonene is added slowly. The temperature is maintained with stirring, at 145-150C for six hours.
The e~cess phenol and unreacted nonene are removed by distillation at reduced pressure and the residue washed with 5% aqueous hydrochloric acid solùtion, then with water until the washings are neutral to litmus. Distillation of the residue yields 30 g. (34~O of the theory, 93~O
conversion) of a clear, colorless liquid boiling at 94C/
10 mm. Over 98,~o of it is the o-(l-methyloctyl)phenol.
Example 4 The procedure of Example 3 is repeated using l-octene instead of l-nonene. The product, a clear, ~ater-white liquid boiling at 100-107C/10-0.1~ mm., contains 93~o of the desired o-(l-methylheptyl)phenol; it was obtained in a 76% (of the theory) yleld.
Example 5 The procedure of Example 3 is repeated using propylene trimer instead of l-nonene. The product is a clear, water-white liquid boiling at 105-110C/0.25 m~. It is obtained in a 39C~ yield and contains ~% of the desired o-nonylphenol.
- Example ~
The procedure of Example 3 is repeated using diisobutylene instead of l-nonene. A 45',~ yield O:e clear, water-white liquid is obtained containing 89/o of the desired o-octylphenol.
The hydrolytically stable phosphites o~ the invention may be prepared as follows:
To l.0 mol of the o-alkylp~enol, at 55C, there is added, slowly, 0.30 mol of phosphorous trichloride.
- 10 The reaction initially is exothermic, but later, external heating is required to maintain the temperature at 55C.
When all of the phosphorous trichloride has been added, the temperature is raised, in an argon atmosphere, to 180-250C and kept there for 23-33 hours. The residue is distilled yielding a clear, colorless liquid.
The followin~ tris-(o-alkylphenyl~phosphites, having the structural lormula ~ R ~ 0 ~ P
are prepared by this method:
R' R Yiel~
__ _ _ Example 7 methyln-nonyl - 99%
Example 8 methyln-dodecyl 99%
Example 9 II l-~ethylheptyl 59%
E~ample 10 H l-methyloctyl ~1%
Example 11 ~I cyclohexyl 99%
Example 12 ~I n-butyl 99~
The purity of the products obtained as above is high, ranging ~rom 93G' to 99%.
077206~ 12 -The hydrolytic stability of these tris-(o-alkyl-phenyl)phosphites may be shown by the results of a test carried out in aqueous tetrahydrofuran. A 2G,o solution of the phosphite sample in a mixture of 80 parts of tetrahydrofuran and 20 parts of ~vater is maintained at 44C and a pH of 4.5 for 48 hours. The disappearance of phosphite is monitored by means of liquid chromatographic analyses.
A commercial sample of tris-(nonylphenyl)phosphite containing 92qo of the para isomer, 6~o of the ortho isomer and 2% of the dinonyl compound, is found to be completely hydrolyzed after 140 hours. A corresponding sample of tris-(nonylphenyl)phosphite containing 88$
of the ortho isomer and 12~o Of the para isomer is 10%
hydrolyzed a~ter 140 hours and only 50% hydrolyzed after 760 hours.
Similarly, a sample of trls-(l-methylheptylphenyl) phosphite (wherein 92% of the alkylphenyl groups are 2-alkylphenyl and 7% are 2,4-dialkylphenyl) was only 50% hydrolyzed after 700 hours.
The hydrolytic stability of these tris-(o-alkyl-phenyl)phosphites in acidic aqueous emulsions is shown by the results of a test where 10 parts of a phosphite sample is mixed with a solution of 2.1 parts of an anionic organic phosphate in 34 parts of water. 'he resulting emulsion is added to 400 parts of water, warmed to 55C and the p~ adjusted to 2.5 by the addition o~ concentrated hydrochloric acid. This diluted emulsion is allowed to cool and stand for 10 hou-rs. The pH is ad,justed to 7 with dilute aqueous potassium hydroxide solution and the emulsion poured into 600 parts of 5% aqueous calcium chloride solution at 85C. The mixture is cooled, extracted with benzene and the benzene extract dried and evaporated to an oily residue. The extent of hydrolysis is determined by 077206--.?'~' -- 13 liquid chromatographic analysis.
Samples of the above commercially available tris-(nonyl-phenyl) phosphite and tris-(ortho-l-methyl-heptylphenyl)phosphite are subjected to the above ; 5 test: the former is cornpletely hydrolyzed; the latter is hydrolyzed to the extent of 30%.
The e~fec-tiveness of the tris-(o-alkylphenyl)phosphiles herein as polymer stabilizers in a hydrolyzing en-vironment is shown as follows: A stabilizing emulsion is prepared by adding a solution of 6.25 parts ol the phosphite and 1.15 parts of oleic acid to a hot solution of 0.55 part of triethanol amine in 17 parts of de-mineralized water and mixing with a high speed stirrer for one minute. The resulting emulsion is added to 325 parts of polybutadiene latex and the mixture : stirred for 12 hours. The mixture then is coagulated ~ at 85C by addition of 1.5~o aqueous sulfuric acid and - the polybutadiene crumb collected, washed and dried.
The dried crumb is aged in an oven at 100C anA the time required for the development of an overall brown color taken as a measure of the stability of the polybutadiene.
Samples of the above commercially available tris-(nonyl-phenyl)phosphite (A) and the tris-(ortho-l-methylheptylphenyl)phosphite (B) of Example 9 are subjected to this test, vrith the following results: -Phosphite ours to Coloration ~ 130 none 30 The superiorlty of the o-alkylphenyl-substituted phosphite is apparent.
077206~ 14 -The effectiveness of the phosphites herein as a stabilizer for ABS resins is shown by a comparison o~
stability clata collected as ~ollows: A m.ixture of 5.0 parts of phosphite and 2~0 parts of bis-(3-ethyl-5-tertiarybutyl-6-hydroxypilenyl)methane is added to 20 parts of an ABS (prepared by copolymerizing styrene and acrylonitrile in a polybutadiene late~) latex, so as to provide l.O phr of stabilizer (phosphite plus phenol).
~e latex is coagulated ~vith 2' aqueous sulfuric acid and oven dried at 50C. The solid is stampecl into 1.5-inch (diameter) discs of 12-15 mil thickness, and these are placed in an oven with circulating air at 150C. The time required for the development of brittleness, discoloration or cracking is noted.
Table lI
Phosphite Eours to Failure 1. Product of E~ample 9 6 2. A tris-(nonylphenyl)phosphite where S8% of the nonyl groups are ortho and 11~ are para 4
3. Tris-(o-tert-butylphenyl)phosphite 2 ~. ~one Other additives can also be added to the thermoplastic polymer compositions of this invention, including ultra-violet stabilizers, anti-static agents, fillers, pigments, lubricants and the like.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polymer composition comprising a graft copolymer having a graftable rubber substrate containing a diene rubber-forming monomer component and a superstrate of an interpolymer consisting at least principally of a monovinylidene aromatic hydrocarbon and an ethylenically unsaturated nitrile or ester, and a minor amount, sufficient to impart improved heat stability to said polymer, of a tris-(alkylphenyl)phosphite or tris-(cycloalkylphenyl)phosphite wherein (1) the alkyl group contains 1-12 carbon atoms, (2) at least about 85% of one of the ortho positions in each phenyl group are substituted by alkyl groups of 3-12 carbon atoms, and (3) at least about 85% of the para-positions in each phenyl group are unsubstituted, or substituted by methyl groups.
2. A polymer composition comprising a graft copolymer having a graftable rubber substrate containing a diene rubber-forming monomer component and a superstrate of an interpolymer consisting at least principally of a monovinylidene aromatic hydrocarbon and an ethylenically unsaturated nitrile or ester, and a minor amount, sufficient to impart improved heat stability to said polymer, of an organic phosphite material having the structure:
wherein at least about 85% of R2 is alkyl of 3-12 carbon atoms or cycloalkyl, the remainder being hydrogen, and at least about 85% of R1 is methyl or hydrogen.
wherein at least about 85% of R2 is alkyl of 3-12 carbon atoms or cycloalkyl, the remainder being hydrogen, and at least about 85% of R1 is methyl or hydrogen.
3. A polymer composition comprising the graft copolymer of Claim 1 and a minor amount, sufficient to impart improved heat stability to said polymer, of a tris-(alkylphenyl)phosphite having the structure:
wherein R is alkyl of 8-12 carbon atoms.
wherein R is alkyl of 8-12 carbon atoms.
4. The polymer composition of Claim 1 wherein the graft copolymer is an ABS resin.
5. The polymer composition of Claim 1 wherein the graft copolymer is an MBS resin.
6. The polymer composition of Claim 4 wherein the ABS resin is prepared by copolymerizing styrene and acrylonitrile in a polybutadiene latex.
7. The polymer composition of Claim 1 wherein the composition contains also a phenolic antioxidant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US252579A | 1979-01-11 | 1979-01-11 | |
| US2,525 | 1979-01-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1149092A true CA1149092A (en) | 1983-06-28 |
Family
ID=21701174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000342141A Expired CA1149092A (en) | 1979-01-11 | 1979-12-18 | Phosphite heat stabilized graft diene copolymers |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5594950A (en) |
| CA (1) | CA1149092A (en) |
| DE (1) | DE3000744B2 (en) |
| FR (1) | FR2446304A1 (en) |
| GB (1) | GB2039282B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03162443A (en) * | 1989-11-20 | 1991-07-12 | Adeka Argus Chem Co Ltd | Abs-based resin composition |
| US5561181A (en) * | 1994-11-16 | 1996-10-01 | General Electric Company | Ultra high ortho nonyl phenyl phosphite and resin compositions stabilized therewith |
| US8183311B2 (en) * | 2006-06-20 | 2012-05-22 | Chemtura Corporation | Liquid phosphite composition derived from cresols |
| US8178005B2 (en) * | 2006-06-20 | 2012-05-15 | Chemtura Corporation | Liquid phosphite compositions having different alkyl groups |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2733226A (en) * | 1951-10-12 | 1956-01-31 | Triaryl phosphite stabilizers for | |
| DE1283523B (en) * | 1961-11-15 | 1970-02-05 | Monsanto Co | Stabilization of molding compounds containing styrene polymers |
| GB1165488A (en) * | 1967-06-02 | 1969-10-01 | Polymer Corp | Modified Resins |
| US3661825A (en) * | 1970-04-21 | 1972-05-09 | Goodyear Tire & Rubber | Stabilization systems for polymers |
| GB1358537A (en) * | 1970-08-17 | 1974-07-03 | Macguire Cooper | Mechanical break-up spray nozzles |
| FR2204697B1 (en) * | 1972-10-30 | 1975-01-03 | Metaux Speciaux Sa |
-
1979
- 1979-12-18 CA CA000342141A patent/CA1149092A/en not_active Expired
-
1980
- 1980-01-04 GB GB8000296A patent/GB2039282B/en not_active Expired
- 1980-01-10 FR FR8000486A patent/FR2446304A1/en active Granted
- 1980-01-10 DE DE19803000744 patent/DE3000744B2/en not_active Ceased
- 1980-01-11 JP JP201380A patent/JPS5594950A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3000744A1 (en) | 1980-07-17 |
| JPS6326137B2 (en) | 1988-05-28 |
| GB2039282B (en) | 1983-01-12 |
| FR2446304B1 (en) | 1983-03-04 |
| JPS5594950A (en) | 1980-07-18 |
| DE3000744B2 (en) | 1981-02-19 |
| FR2446304A1 (en) | 1980-08-08 |
| GB2039282A (en) | 1980-08-06 |
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