WO1987007286A1 - Ethers de polyphenylene a fonction epoxyde et procede de preparation - Google Patents

Ethers de polyphenylene a fonction epoxyde et procede de preparation Download PDF

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WO1987007286A1
WO1987007286A1 PCT/US1987/001125 US8701125W WO8707286A1 WO 1987007286 A1 WO1987007286 A1 WO 1987007286A1 US 8701125 W US8701125 W US 8701125W WO 8707286 A1 WO8707286 A1 WO 8707286A1
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composition according
polyphenylene ether
formula
ether
epoxide
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PCT/US1987/001125
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English (en)
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Paul Dean Sybert
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General Electric Company
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Priority claimed from US06/885,112 external-priority patent/US4732937A/en
Application filed by General Electric Company filed Critical General Electric Company
Publication of WO1987007286A1 publication Critical patent/WO1987007286A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • This invention relates to functionalized poly- phenylene ethers and their preparation and use.
  • the polyphenylene ethers are a widely used class of thermoplastic engineering resins characterized by excel ⁇ lent hydrolytic stability, dimensional stability and dielec ⁇ tric properties. They are also resistant to high tempera- ture conditions under many circumstances. Because of the brittleness of many compositions containing polyphenylene ethers, they are frequently blended with impact modifiers such as elastomers to form molding compositions.
  • a disadvantage of the polyphenylene ethers which militates against their use for molding such items as automotive parts is their low resistance to non-polar solvents such as gasoline.
  • resins which have a high degree of crystallinity and therefore are highly resistant to solvents.
  • Illustra ⁇ tive of such resins are polyamides and linear polyesters, including poly(al ylene dicarboxylates) .
  • such blends frequently undergo phase separation and delamination. They typically contain large, incompletely dispersed poly- phenylene ether particles and no phase interaction between the two resin phases. Molded parts made from such blends are typically characterized by extremely low impact strength.
  • a principal object of the present invention therefore, is to prepare novel polyphenylene ether composi ⁇ tions.
  • a further object is to prepare functionalized polyphenylene ethers which are capable of compatibilizing blends of polyphenylene ethers with such polymers as poly- amides and linear polyesters.
  • a still further object is to prepare novel poly ⁇ phenylene ether-polyamide compositions with desirable properties.
  • the present invention is directed to epoxide-functionalized polyphenylene ethers containing at least one moiety having the formula
  • R is a divalent bridging radical containing at least one compound selected from the group consisting of:
  • R is a polyvalent bridging radical containing at least one hydrocarbon group
  • m is from 1 to about 5 and n is from 1 to about 10.
  • the polyphenylene ethers (also known as polypheny- lene oxides) used in this invention are a well known class of polymers. They are widely used in industry, especially as engineering plastics in applications requiring toughness and heat resistance. Since their discovery, they have given rise to numerous variations and modifications all of which are applicable to the present invention, including but not limited to those described hereinafter.
  • the polyphenylene ethers comprise a plurality of structural units having the formula
  • each is independ ⁇ ently halogen, primary or secondary lower alkyl (i.e., alkyl containing up to 7 carbon atoms), phenyl, haloalkyl, a ino- alkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen
  • any alkyl radicals are straight chain rather than branched. Most often, each is alkyl or phenyl, haloalkyl, hydro ⁇ carbonoxy or halohydrocarbonoxy as defined for Q .
  • suitable primary lower alkyl groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl and the corresponding heptyl groups.
  • secondary lower alkyl groups are isopropyl, sec-butyl and 3-pentyl.
  • any alkyl radicals are straight chain rather than branched. Most often, each is alkyl or phenyl, especial-
  • Suitable polypheny ⁇ lene ethers are disclosed in a large number of patents. Both homopolymer and copolymer polyphenylene ethers are included. Suitable homopolymers are those containing, for example, 2,6-dimethyl-l,4-phenylene ether units. Suitable copolymers include random copolymers containing such units in combination with (for example) 2,3,6-trimethyl-l,4-phenylene ether units. Many suitable random copolymers, as well as homopolymers, are disclosed in the patent literature. Also included are polyphenylene ethers containing moieties which modify properties such as molecular weight, melt viscosity and/or impact strength.
  • Such polymers are described in the patent literature and may be prepared by grafting onto the polyphenylene ether in known manner such vinyl monomers as acrylonitrile and vinylaromatic compounds (e.g., styrene), or such polymers as polystyrenes and elastomers.
  • the product typically contains both grafted and ungrafted moieties.
  • Other suitable polymers are the coupled polyphenylene ethers in which the coupling agent is reacted in known manner with the hydroxy groups of two polyphenylene ether chains to produce a higher molecular weight polymer containing the reaction product of the hydroxy groups and the coupling agent.
  • Illustrative coupling agents are low molecular weight polycarbonates, quinones, heterocycles and formals.
  • the polyphenylene ether generally has a number average molecular weight within the range of about 3,000- 40,000 and a weight average molecular weight within the range of about 20,000-60,000, as determined by gel permea ⁇ tion chro atography. Its intrinsic viscosity is most often in the range of about 0.35-0.6 dl./g., as measured in chloroform at 25°C.
  • the polyphenylene ethers are typically prepared by the oxidative coupling of at least one corresponding monohy- droxyaromatic compound.
  • Particularly useful and readily available monohydroxyaromatic compounds are 2,6-xylenol
  • each Q 1 is methyl and each Q2 is hydrogen
  • each Q 1 is methyl and each Q2 is hydrogen
  • each Q 1 is methyl and each Q2 is hydrogen
  • the polymer may be characterized as a poly(2,6-di- methyl-1,4-phenylene ether), and 2,3,6-trime hylphenol
  • each 1 and one Q2 is methyl and the other 2 is hydrogen
  • catalyst systems are known for the preparation of polyphenylene ethers by oxidative coupling. There is no particular limitation as to catalyst choice and any of the known catalysts can be used. For the most part,. they contain at least one heavy metal compound such as a copper, manganese or cobalt compound, usually in combination with various other materials.
  • a first class of preferred catalyst systems consists of those containing a copper compound. Such catalysts are disclosed, for example, in U.S. Patents
  • They are usually combinations of cuprous or cupric ions, halide (i.e., chloride, bromide or iodi'de) ions and at least one amine.
  • Catalyst systems containing manganese compounds constitute a second preferred class. They are generally alkaline systems in which divalent manganese is combined with such anions as halide, alkoxide or phenoxide.
  • the manganese is present as a complex with one or more complexing and/or chelating agents such as dialkyl- amines, alkanola ines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds and w-hydroxyoximes.
  • complexing and/or chelating agents such as dialkyl- amines, alkanola ines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds and w-hydroxyoximes.
  • polyphenylene ethers which are useful for the purposes of this invention are those which comprise molecules having at least one of the end groups of the formulas
  • each R3 is independently hydrogen or alkyl, with the proviso that the
  • each R is independently hydrogen or a C 1.— c o
  • each R is hydrogen and
  • each R is alkyl, especially methyl or n-butyl.
  • Polymers containing the aminoalkyl-substituted end groups of formula III may be obtained by incorporating an appropriate primary or secondary monoamine as one of the constituents of the oxidative coupling reaction mixture, especially when a copper- or manganese-containing catalyst is used.
  • Such amines, especially the dialkylamines and preferably di-n-butyl ine and dimethylamine frequently become chemically bound to the polyphenylene ether, most often by replacing one of the o-hydrogen atoms on one or more Q radicals.
  • the principal site of reaction is the Q radical adjacent to the hydroxy group on the terminal unit of the polymer chain.
  • the a inoalkyl-substituted end groups may undergo various reactions, probably involving a quinone methide-type intermediate of the formula
  • Polymers with 4-hydroxybiphenyl end groups of formula IV are typically obtained from reaction mixtures in which a by-product diphenoguinone of the formula
  • polyphenylene ethers contemplat ⁇ ed for use in the present invention include all those presently known, irrespective of variations in structural units or ancillary chemical features.
  • the polyphenylene ether is linked to the structure shown in formula I.
  • the R values in that formula may be polyvalent (i.e., divalent or greater) aliphatic, alicyclic or aromatic hydrocarbon radicals, substituted hydrocarbon radicals or radicals containing at least one non-carbon linking atom, provided they contain at least one hydrocarbon group.
  • Illustrative linking atoms are oxygen and sulfur, with oxygen being preferred.
  • Illustrative substituents are hydroxy, halo, nitro, alkoxy, carboxy, carbalkoxy and carbaryloxy. They may be relatively low molecular weight radicals or polymeric radicals, the formula weight of the latter typically being up to about 500.
  • R values may be generically defined in a manner similar to R . They may also be low molecular weight or polymeric radicals, the latter generally having a formula weight up to about 1000.
  • n may be from 1 to about 5. It is usually 1, but values higher than 1 are possible by reason, for example, of the possibility of grafting involving more than one maleic anhydride moiety at a single site on the polyphenylene ether molecule.
  • n may be greater than 1 when the epoxide reactant is a polyepoxy compound such as an epoxy novolak resin. Most often, n is from 1 to 5.
  • the moieties of formula I may be linked to the polyphenylene ether in various ways, depending on reactants and conditions as described hereinafter. For example, reactions involving the use of such compounds as terephth- aloyl chloride or trimellitic anhydride acid chloride will result in a bond with one or both terminal oxygen atoms of the polyphenylene ether.
  • the compositions thus obtained which are often preferred for the purposes of the invention, may be represented by the formula
  • A is a polyphenylene ether moiety
  • R is as pre ⁇ viously defined
  • R is a divalent aliphatic, alicyclic or aromatic hydrocarbon or substituted hydrocarbon radical
  • p is 1 or 2.
  • R is C, . alkylene and most desirably methylene and R is an aromatic hydrocarbon radical and most desirably p-phenylene.
  • Maleic anhydride and fumaric acid are believed to react with polyphenylene ethers via grafting on the Q groups or the aromatic rings, forming one or more' aliphatic groups attached to the polyphenylene ether by carbon-carbon bonds. In general, an average of about 1-5 moieties of formula I are then present per polyphenylene ether molecule.
  • the epoxide-functionalized polyphenylene ethers of this invention may be prepared by the reaction of an acid- functionalized polyphenylene ether with a functionalized epoxide. Suitable functionalized epoxides include, for example, hydroxy-substituted compounds of the formula
  • Glycidol is a particularly preferred functionalized epoxide.
  • functionalized epoxides are polyepoxy compounds such as bisphenol A diglycidyl ether, glycidyl methacrylate polymers and epoxy novolaks. Their use may result in the formation of a composition containing moieties of formula I wherein n is greater than 1, and wherein R 2 is a polymeric moiety.
  • "D.E.N. 485" is the designation of an epoxy novolak commercially available from Dow Chemical Company, which may be represented by the formula
  • acid-functionalized polyphenylene ether as used herein, generically denotes the reaction product of a polyphenylene ether with any of various car- boxylic acids or functional derivatives thereof, including salts, esters, anhydrides, amides and imides.
  • One method of preparing acid-functionalized polyphenylene ethers is by reaction of the polymer with at least one compound contain ⁇ ing (a) a carbon-carbon double or triple bond, hydroxy group, alkoxy group, aryloxy group or acyl halide group, and also (b) a carboxylic acid, acid salt, acid anhydride, acid amide, acid ester or imido group.
  • a wide variety of such compounds are suitable for this purpose.
  • R is an aromatic or saturated aliphatic radical
  • X is halogen (especially chlorine)
  • ⁇ is one or two carboxylic acid, acid salt, acid amide or acid ester groups or a dicarboxylic acid anhydride or imide group.
  • Illustrative compounds of this type are carboxymethylsuc- cinic anhydride acid chloride and trimellitic anhydride acid chloride (TAAC).
  • Particularly preferred functionalizing agents are maleic acid and its derivatives (especially maleic anhy ⁇ dride), fumaric acid, trimellitic anhydride acid chloride and terephthaloyl chloride.
  • These functionalizing agents may be reacted with the polyphenylene ether by heating a mixture thereof, typically at a temperature within the range of about
  • reaction of the acid-functionalized poly ⁇ phenylene ether with the functionalized epoxide takes place under conditions known in the art for the type of reaction involved.
  • acid-functionalized polyphenylene ethers containing acyl chloride groups react with glycidol at temperatures as low as -50°C under certain conditions; in any event, temperatures in the range of about 20-50°C are satisfactory.
  • reaction of an epoxy novolak with a carboxylic acid or anhydride may require temperatures in the range of about 100-250°C.
  • the proportion of functionalized epoxide is generally about 1-10 and preferably about 3-6 parts by weight per 100 parts of acid-functionalized polyphenylene ether.
  • the reaction is generally conveniently conducted in a solvent, suitable solvents being aromatic hydrocarbons such as toluene and xylene, chlorinated aromatic - 1 3 -
  • hydrocarbons such as chlorobenzene, and compounds having solvent properties similar thereto.
  • the preparation of the epoxide-functionalized polyphenylene ethers of this invention is illustrated by the following example.
  • the polyphenylene ether used in the examples herein was an unfunctionalized poly-(2,6-dimethyl- 1,4-phenylene ether) having a number average molecular weight of about 20,000, an intrinsic viscosity (IV) in chloroform at 25°C of 0.48 dl./g. and 0.084% (by weight) hydroxy groups.
  • a mixture of 99 parts of polyphenylene ether and 1 part of maleic anhydride is extruded on a single-screw extruder at temperatures in the range of 120-330°C.
  • the extrudate comprising the desired maleic anhydride-functionalized polyphenylene ether, is quenched in water, pelletized, dissolved in chloroform, precipitated with methanol, filtered and vacuum dried at 60°C.
  • the epoxide-functional ⁇ ized polyphenylene ethers of this invention are useful in the preparation of compatibilized blends of polyphenylene ethers with such polymers as polyamides and linear polyes- ters.
  • said functionalized polyphenylene ethers form copolymers with polyesters and polyamides, which may be used for compatibilization of such blends.
  • Composi ⁇ tions comprising polyphenylene ether-polyester copolymers are disclosed and claimed in the aforementioned application Serial No. 866,661, filed May 27, 1986.
  • compositions comprising at least one polyphenylene ether and at least one polyamide, at least a portion of said polyphen- ylene ether being an epoxide-functionalized polyphenylene ether of this invention. It is within the scope of the invention to include both functionalized and unfunctional- ized polyphenylene ether in said composition, the latter being present in an amount up to about 90% by weight of total polyphenylene ether.
  • Polyamides suitable for use in said compositions may be made by any known method, including the polymeriza ⁇ tion of a monoamino-monocarboxylic acid or a lactam thereof having at least 2 carbon atoms between the amino and carbox ⁇ ylic acid group, of substantially equimolar proportions of a diamine which contains at least 2 carbon atoms between the amino groups and a dicarboxylic acid, or of a monoaminocar- boxylic acid or a lacta thereof as defined above together with substantially equimolar proportions of a diamine and a dicarboxylic acid.
  • the dicarboxylic acid may be used in the form of a functional derivative thereof, for example, an ester or acid chloride.
  • Examples of the aforementioned monoa ino-monocar- boxylic acids or lactams thereof which are useful in prepar ⁇ ing the polyamides include those compounds containing from 2 to 16 carbon atoms between the amino and carboxylic acid groups, said carbon atoms forming a ring with the -CO-NH- group in the case of a lactam.
  • aminocarboxylic acids and lactams there may be mentioned ⁇ -aminocaproic acid, butyrolactam, pivalolactam, ⁇ -caprolac- ta , capryllactam, enantholactam, undecanolactam, dodecan- olactam and 3- and 4-aminobenzoic acids.
  • Diamines suitable for use in the preparation of the polyamides include the straight chain and branched chain alkyl, aryl and alkaryl diamines. Such diamines include, for example, those represented by the general formula
  • n is an integer of from 2 to 16.
  • Illustrative diamines are trimethylenediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, hexamethylenediamine (which is often preferred), trimethylhexamethylenediamine, m-phenylenediamine and m-xylylenediamine.
  • the dicarboxylic acids may be represented by the formula
  • Y is a divalent aliphatic or aromatic group contain ⁇ ing at least 2 carbon atoms.
  • aliphatic acids are sebacic acid, octadecanedioic acid, suberic acid, glu- taric acid, pimelic acid and adipic acid.
  • Aromatic acids such as isophthalic and terephthalic acids, are preferred.
  • polyamides or nylons as these are often called, include, for example, polyamide-6,
  • polyamides from terephthalic acid and/or isophthalic acid and trimethylhexa ⁇ methylenediamine; from adipic acid and m-xylylenediamines; from adipic acid, azelaic acid and 2,2-bis-(p-aminocyclo- hexyl)propane and from terephthalic acid and 4,4'-dia ino- dicyclohexylmethane.
  • Mixtures and/or copolymers of two or more of the foregoing polyamides or prepolymers thereof, respectively, are also within the scope of the present invention.
  • Preferred polyamides are polyamide-6, 66, 11 and 12, most preferably polyamide-66.
  • R is a divalent aliphatic or alicyclic radical
  • Q containing about 2-10 carbon atoms and R is a divalent aliphatic, alicyclic or aromatic radical containing about
  • polyesters are typically prepared by the known reaction of dihydroxy compounds with dicarboxylic acids or functional derivatives thereof such as anhydrides, acid chlorides or lower alkyl (especially methyl) esters, preferably the esters.
  • R radicals may be one or more aliphatic or alicyclic hydrocarbon radicals, alicyclic radicals being known to those skilled in the art to be equivalent to aliphatic radicals for the purposes of the invention. They may be derived from such dihydroxy compounds as ethylene glycol, 1,4-butanediol (both of which are preferred), propylene glycol, 1,3-propanediol, 1,6-hexanediol, 1,10- decanediol, 1,4-cyclohexanedimethanol and 2-butene-l,4-diol. They may also be radicals containing substituents which do not substantially alter the reactivity of the dihydroxy compound (e.g., alkoxy, halo, nitrile) or hetero atoms
  • R radicals are usually saturated
  • R radicals may be derived from such acids as succinic, adipic, maleic, isophthalic and terephthalic acids or similar substituted and hetero atom-containing acids.
  • R 7 and R8 are hydrocarbon radicals, typically containing about 2-10 carbon atoms.
  • R 7 is aliphatic and R8 is aromatic.
  • the polyester is most desirable a poly(alkylene terephthalate), particularly poly(ethylene terephthalate) or poly(l,4-butylene tere- phthalate) (hereinafter sometimes simply “polyethylene terephthalate” and “polybutylene terephthalate”, respec ⁇ tively) and especially the latter.
  • poly(alkylene terephthalate) particularly poly(ethylene terephthalate) or poly(l,4-butylene tere- phthalate) (hereinafter sometimes simply "polyethylene terephthalate” and “polybutylene terephthalate”, respec ⁇ tively) and especially the latter.
  • Such polyesters are known in the art as illustrated by the following patents:
  • polyesters most often have number average molecular weights in the range of about 10,000-70,000, as determined by intrinsic viscosity (IV) at 30°C in a mixture of 60% (by weight) phenol and 40% 1,1,2,2-tetrachloroethane.
  • polyesters are known in the art; they are exemplified by compositions in which a portion of the R 7 values are soft segment radicals such as polyoxyalkylene (typically polyoxyethylene or polyoxytetramethylene) and units derived from lactones such as ⁇ -caprolactone.
  • Numer- ous elastomeric polyesters of this type are commercially available; they include those sold by DuPont under the trademark HYTREL and by General Electric under the trademark LOMOD.
  • the epox- ide-functionalized polyphenylene ether and polyester or polyamide are heated together in solution or in the melt.
  • the reaction temperature is typically within the range of about 100-350°C, preferably about 150-290°C for polyesters.
  • the proportions of epoxide-functionalized polyphenylene ether and polyester or polyamide are not critical and may be adjusted over a wide range to yield copolymer compositions having the desired properties.
  • the polyphenylene ether- polya ide compositions generally contain about 5-75% by weight polyphenylene ether and about 25-95% poly ⁇ amide.
  • the copolymer compositions comprise only partially copolymer, with the balance being a poly- phenylene ether-polyester or polyamide blend.
  • the approxi ⁇ mate proportion of copolymer in the composition may often be conveniently expressed as the percentage of copolymerized polyphenylene ether based on total polyester or polyamide. It may be determined by extracting unreacted polyphenylene ether with a suitable solvent, typically toluene or chloro ⁇ form, and analyzing the insoluble residue (copolymer and residual polyester or polyamide) by proton nuclear magnetic resonance.
  • a solution of 250 grams of a poly(butylene tereph ⁇ thalate) having a number average molecular weight of about 40,000 and a carboxy end group concentration of 24.7 micro- equivalents per gram in 3.8 liters of 1,2,4-trichlorobenzene was heated to 200°C and 250 grams of the epoxide-functional ⁇ ized polyphenylene ether of Example 1 was added under nitrogen, with stirring. Stirring at 200°C was continued for 60 hours, after which the copolymer composition was precipitated by pouring into acetone, extracted with meth- anol and dried under vacuum. Analysis showed the presence of 28% copolymerized polyphenylene ether.
  • Example 3 The procedure of Example 3 was repeated, using a polyester which had been preextruded on a twin-screw extrud ⁇ er at about 260°C, and which had a carboxylate end group concentration of 34.3 microequivalents per gram. Analysis showed the presence of 39% copolymerized polyphenylene ether.
  • the above-described copolymer compositions, and polyphenylene ether-poly(alky- lene dicarboxylate) blends in which they are incorporated have high impact strength, good solvent resistance and other advantageous properties. These properties make them useful for the preparation of molded and extruded articles.
  • the weight ratio of polyester to total polypheny- lene ether in the copolymer-containing blend is generally in the range of about 0.5-3.0:1, most often about 0.9-2.5:1.
  • the proportion of copolymerized polyphenylene ether therein is capable of wide variation, essentially any quantity thereof affording some improvement in properties. For the most part, said proportion is in the range of about 10-80% by weight of total resinous components.
  • the blends may also contain ingredients other than the copolymer, polyphenylene ether and polyester.
  • a par ⁇ ticularly useful other ingredient in many instances is at least one elastomeric impact modifier which is compatible
  • polyphenylene ether is generally present in the amount of about 5-25% by weight of resinous components.
  • Impact modifiers for polyphenylene ether-polyester or polyamide compositions are well known in the art. They are typically derived from one or more monomers * selected from the group consisting of olefins, vinyl aromatic mono ⁇ mers, acrylic and alkylacrylic acids and their ester deriv ⁇ atives as well as conjugated dienes. Especially preferred impact modifiers are the rubbery high-molecular weight materials including natural and synthetic polymeric materi ⁇ als showing elasticity at room temperature. They include both homopolymers and copolymers, including random, block, radial block, graft and core-shell copolymers as well as combinations thereof.
  • Polyolefins or olefin-based copolymers employable in the invention include low density polyethylene, high density polyethylene, linear low density polyethylene, isotactic polypropylene, poly(l-butene), poly(4-methyl- 1-pentene), propylene-ethylene copolymers and the like.
  • Additional olefin copolymers include copolymers of one or more o-olefins, particularly ethylene, with copolymerizable monomers including, for example, vinyl acetate, acrylic acids and alkylacrylic acids as well as the ester deriva ⁇ tives thereof including, for example, ethylene-acrylic acid, ethyl acrylate, methacrylic acid, methyl methacrylate and the like.
  • the ionomer resins which may be wholly or partially neutralized with metal ions.
  • a particularly useful class of impact modifiers are those derived from the vinyl aromatic monomers. These include, for example, modified and unmodified polystyrenes, ABS type graft copolymers, AB and ABA type block and radial block copolymers and vinyl aromatic conjugated diene core- shell graft copolymers.
  • Modified and unmodified polystyrenes include homopolystyrenes and rubber modified polystyrenes, such as butadiene rubber-modified polystyrene (otherwise referred to as high impact polystyrene or HIPS).
  • Additional useful polystyrenes include copolymers of styrene and various monomers, including, for example, poly(styrene- acrylonitrile) (SAN), styrene-butadiene copolymers as well as the modified alpha- and para-substituted styrenes and any of the styrene resins disclosed in U.S. Patent 3,383,435, herein incorporated by reference.
  • SAN poly(styrene- acrylonitrile)
  • styrene-butadiene copolymers as well as the modified alpha- and para-substituted styrenes and any of the styrene resins disclosed in U.S. Patent 3,383,435, herein incorporated by reference.
  • ABS types of graft copolymers are typified as comprising a rubbery polymeric backbone derived from a conjugated diene alone or in com ⁇ bination with a monomer copolymerizable therewith having grafted thereon at least one monomer, and preferably two, selected from the group consisting of monoalkenylarene monomers and substituted derivatives thereof as well as acrylic monomers such as acrylonitriles and acrylic and alkylacrylic acids and their esters.
  • An especially preferred subclass of vinyl aromatic monomer-derived resins is the block copolymers comprising monoalkenyl arene (usually styrene) blocks and conjugated diene (e.g., butadiene or isoprene) or olefin (e.g., ethy- lene-propylene, ethylene-butylene) blocks and represented as AB and ABA block copolymers.
  • the conjugated diene blocks may be partially or entirely hydrogenated, whereupon the properties are similar to the olefin block copolymers.
  • Suitable AB type block copolymers are disclosed in, for example, U.S. Patents 3,078,254; 3,402,159; 3,297,793; 3,265,765 and 3,594,452 and UK Patent 1,264,741, all incorporated herein by reference.
  • SBR polystyrene-polybutadiene
  • Such AB block copolymers are available commercially from a number of sources, including Phillips Petroleum under the trademark SOLPRENE.
  • SBS polystyrene-polyisoprene-polystyrene
  • SIS poly( ⁇ -methylstyrene)-polybutadiene-poly-S-S-styrene
  • triblock copolymers are available commercially as CARIFLEX®, KRATON D® and KRATON G® from Shell.
  • conjugated dienes Another class of impact modifiers is derived from conjugated dienes. While many copolymers containing conju ⁇ gated dienes have been discussed above, additional conjugat ⁇ ed diene modifier resins include, for example, homopolymers and copolymers of one or more conjugated dienes including, for example, polybutadiene, butadiene-styrene copolymers, butadiene-glycidyl methacrylate copolymers, isoprene-iso- butylene copolymers, chlorobutadiene polymers, butadiene- acrylonitrile copolymers, polyisoprene, and the like. Ethylene-propylene-diene monomer rubbers may also be used.
  • EPDM's are typified as comprising predominantly ethylene units, a moderate amount of propylene units and up to about 20 mole percent of non-conjugated diene monomer units.
  • Many such EPDM's and processes for the production thereof are disclosed in U.S. Patents 2,933,480; 3,000,866; 3,407,158; 3,093,621 and 3,379,701, incorporated herein by reference.
  • Suitable impact modifiers are the core-shell type graft copolymers.
  • these have a predomi- nantly conjugated diene rubbery core or a predominantly cross-linked acrylate rubbery core and one or more shells polymerized thereon and derived from monoalkenylarene and/or acrylic monomers alone or, preferably, in combination with other vinyl monomers.
  • core-shell copolymers are widely available commercially, for example, from Rohm and Haas
  • the core-shell copolymers wherein an interpenetrating network of the resins employed charac ⁇ terizes the interface between the core and shell.
  • Espec ⁇ ially preferred in this regard are the ASA type copolymers available from General Electric Company and sold as GELOYTM resin and described in U.S. Patent 3,944,631.
  • the core-shell elastomers containing, for example, a poly(alkyl acrylate) core attached to a polystyrene shell via an interpenetrating network are frequently useful; they are more fully disclosed in co ⁇ pending, commonly owned application Serial No. 811,800, filed December 20, 1985.
  • Suitable impact modifiers include Thiokol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (e.g., polypropylene oxide), epichlorohydrin rubber, ethylene-propylene rubber, thermoplastic polyester elastomers and thermoplastic ether- ester elastomers.
  • the preferred impact modifiers are block (typical ⁇ ly diblock, triblock or radial teleblock) copolymers of alkenylaromatic compounds and olefins or dienes.
  • At least one block is derived from styrene and at least one other block from at least one of butadiene, isoprene, ethylene and butylene.
  • the triblock copolymers with polystyrene end blocks and olefin- or diene-derived midblocks.
  • the weight average molecular weights of the impact modifiers are typically in the range of about 50,000-300,000.
  • Block copolymers of this type are commercially available from Shell Chemical Company under the trademark KRATON, and include KRATON D1101, G1650, G1651, G1652, G1657 and G1702.
  • copolymer-containing blends include fillers, flame retardants, colorants, stabilizers, antistatic agents, mold release agents and the like, used in conventional amounts.
  • resinous components include impact modifiers compatible with the polyester, such as various graft and core-shell copolymers of such monomers as butadiene, styrene, butyl acrylate and methyl methacrylate.
  • impact modifiers compatible with the polyester such as various graft and core-shell copolymers of such monomers as butadiene, styrene, butyl acrylate and methyl methacrylate.
  • the presence of such copolymers frequently improves the low-temperature ductility of the blends.
  • the preparation of copolymer-containing blends is normally achieved under conditions adapted for the formation of an intimate resin blend.
  • Such conditions often include extrusion, typically at temperatures in the range of about 100-300°C and otherwise under the conditions previously described. Extrusion may be conveniently effected in a screw-type or similar extruder which applies a substantial shearing force to the composition, thereby decreasing the particle size thereof. It is sometimes found that the impact strength of the composition is increased if it is extruded more than once, thereby insuring effective blend ⁇ ing.
  • polyphenylene ether-polyester and polyamide blend compositions are illus ⁇ trated by the following examples.
  • a resin blend was prepared by extrusion, under conventional conditions in a twin-screw extruder, of a mixture of 75.4 parts of the composition of Example 3, 0.5 part of unfunctionalized polyphenylene ether, 14.1 parts of the poly(butylene terephthalate) used as a reactant in Example 3, and 10 parts of a commercially available triblock copolymer in which the polystyrene end blocks have weight average molecular weights of 29,000 and the ethylene/buty- lene midblock has a weight average molecular weight of 116,000. It had the following physical properties.
  • Izod impact strength (notched) - 753 joules/ .
  • a mixture of 49 parts of the epoxide-functional ⁇ ized polyphenylene ether of Example 1, 41 parts of a commer ⁇ cially available poIyamide-66 and 10 parts of an impact modifier was tumble mixed in a jar mill and extruded at 120-330°C and 400 rpm. , using a twin-screw extruder.
  • the impact modifier was a commercially available styrene-ethy- lene/butylene styrene triblock copolymer in which the weight average molecular weights of the end blocks and midblock are 29,000 and 116,000, respectively.
  • the extrudate was quenched in water, pelletized and dried in a vacuum oven at 100°C. It was then injection molded into notched Izod test specimens at 300°C and 1100 psi.
  • the Izod impact strength of the specimens was 144 joules/m.

Abstract

Les éthers de polyphénylène à fonction époxyde, qui peuvent être préparés par la réaction de divers éthers de polyphénylène à fonction époxyde avec des époxydes fonctionnalisés, sont utiles dans la préparation de copolymères d'éthers de polyphénylène. Ces copolymères sont à leur tour utiles pour la compatibilisation de mélanges d'éthers de polyphénylène avec d'autres polymères tels que des polyesters et des polyamides.
PCT/US1987/001125 1986-05-27 1987-05-20 Ethers de polyphenylene a fonction epoxyde et procede de preparation WO1987007286A1 (fr)

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US86666186A 1986-05-27 1986-05-27
US06/885,112 US4732937A (en) 1986-05-27 1986-07-14 Epoxide-functionalized polyphenylene ethers and method of preparation
US885,112 1986-07-14
US866,661 1986-08-29

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US5017650A (en) * 1986-08-04 1991-05-21 Toray Industries, Inc. Composition of polyester, polyphenylene ether, diglycidyl dicarboxylate and impact modifier
EP0454004A2 (fr) * 1990-04-23 1991-10-30 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Polyarylate et procédé pour sa préparation
EP0672722A2 (fr) 1988-11-08 1995-09-20 Ge Plastics Japan Ltd. Composition de résine de polysulfure de phénylène
JP2014205774A (ja) * 2013-04-12 2014-10-30 Dic株式会社 変性ポリアリーレンエーテル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム
EP3336125A1 (fr) 2016-12-14 2018-06-20 Rohm and Haas Electronic Materials LLC Compositions de résine de polyarylène
EP3336124A1 (fr) 2016-12-14 2018-06-20 Rohm and Haas Electronic Materials LLC Compositions et procédés de polyarylène
US10790146B2 (en) 2016-12-05 2020-09-29 Rohm And Haas Electronic Materials Llc Aromatic resins for underlayers

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JPS63125526A (ja) * 1986-11-14 1988-05-28 Mitsubishi Petrochem Co Ltd ポリフエニレンエ−テル・ポリエステル共重合体樹脂
JPH0772228B2 (ja) * 1986-11-14 1995-08-02 三菱化学株式会社 ポリフェニレンエーテル・ポリアミド共重合体樹脂の製造方法
US8686079B2 (en) * 2012-04-13 2014-04-01 Sabic Innovative Plastics Ip B.V. Compatibilized composition, method for the formation thereof, and article comprising same

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Publication number Priority date Publication date Assignee Title
US5017650A (en) * 1986-08-04 1991-05-21 Toray Industries, Inc. Composition of polyester, polyphenylene ether, diglycidyl dicarboxylate and impact modifier
EP0672722A2 (fr) 1988-11-08 1995-09-20 Ge Plastics Japan Ltd. Composition de résine de polysulfure de phénylène
EP0454004A2 (fr) * 1990-04-23 1991-10-30 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Polyarylate et procédé pour sa préparation
EP0454004A3 (en) * 1990-04-23 1992-09-02 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Polyarylate and process for preparing the same
JP2014205774A (ja) * 2013-04-12 2014-10-30 Dic株式会社 変性ポリアリーレンエーテル樹脂、エポキシ樹脂組成物、その硬化物、プリプレグ、回路基板、及びビルドアップフィルム
US10790146B2 (en) 2016-12-05 2020-09-29 Rohm And Haas Electronic Materials Llc Aromatic resins for underlayers
EP3336125A1 (fr) 2016-12-14 2018-06-20 Rohm and Haas Electronic Materials LLC Compositions de résine de polyarylène
EP3336124A1 (fr) 2016-12-14 2018-06-20 Rohm and Haas Electronic Materials LLC Compositions et procédés de polyarylène

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