Trialkyalmine salt-functionalized polyphenylene ethers, methods for their preparation, and compositions containing them

Abstract: Functionalized polyphenylene ethers are prepared by mixing with various trialkylammonium maleates or fumar­ ates in the melt, in the absence of free radical initiators. They are useful in the preparation of resinous compositions com­ prising polyphenylene ethers and polyamides or polyesters. Such resinous compositions preferably also contain impact modifiers.

Description: This invention relates to the functionalization of polyphenylene ethers, and to uses for the polyphenylene ethers so functionalized. Various compositions comprising polyphenylene ethers (also known as polyphenylene oxides) and polyamides or linear polyesters, illustrated by Nylon-6, Nylon-66, poly(ethylene terephthalate) and poly(butylene terephthalate), are of interest because of their high solvent resistance and potentially high impact strength. However, such compositions typically undergo phase separation and delamination because of the presence therein of large, incompletely dispersed polyphenylene ether particles and the lack of phase interaction between the two resin phases. According to U.S - A -4,315,086 and European patent application 24,120, compositions comprising polyphenylene ethers and polyamides, having high impact strength and solvent resistance, may be prepared by melt blending the two polymers with various olefinic or acetylenic carboxylic acids, functional derivatives thereof or other functionalized compounds, and optionally with impact modifiers such as high impact polystyrenes and partially hydrogenated styrene-butadiene block copolymers. Japanese Kokai 84/66452 describes similar compositions prepared by using a polyphenylene ether which has been pretreated with a similar olefinic compound in the mandatory presence of a free radical initiator. There is, however, continuing interest in preparing compositions of this type having still higher impact strengths and other improvements in properties. A principal object of the present invention, therefore, is to provide novel polyphenylene ether compositions. A further object is to provide functionalized polyphenylene ethers which form compatible compositions when blended with such polymers as polyamides and linear polyesters. A still further object is to provide polyphenylene ether-polyamide compositions having high impact strength and solvent resistance. Other objects will in part be obvious and will in part appear hereinafter. It has been discovered that polyphenylene ethers may be functionalized with trialkylamine or tribenzylamine salts of certain olefinic polycarboxylic acids, and that the functionalized polyphenylene ethers thus prepared form compatible blends having high impact strength with such resins as polyamides and polyesters. Such compatibilization may be achieved prior to or simultaneously with blending with said resins. In one of its aspects, therefore, the present invention includes functionalized polyphenylene ethers and a method for their preparation, said method comprising mixing said polyphenylene ether in the melt with at least one functionalizing compound comprising a trialkylamine or tribenzylamine salt of maleic or fumaric acid. The polyphenylene ethers used in the present 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 In each of said units independently, each Q¹ is independently halogen, primary or secondary lower alkyl (i.e., alkyl containing up to 7 carbon atoms), phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Q² is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹. Examples of 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. Examples of secondary lower alkyl groups are isopropyl, sec-butyl and 3-pentyl. Preferably, any alkyl radicals are straight chain rather than branched. Most often, each Q¹ is alkyl or phenyl, especially C₁₋₄ alkyl, and each Q² is hydrogen. Suitable polyphenylene 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-1,4-phenylene ether units. Suitable copolymers include random copolymers containing such units in combination with (for example) 2,3,6-trimethyl-1,4-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 3,000-40,000 and a weight average molecular weight within the range of 20,000-80,000, as determined by gel permeation chromatography. Its intrinsic viscosity is most often in the range of, 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 monohydroxyaromatic compound. Particularly useful and readily available monohydroxyaromatic compounds are 2,6-xylenol (wherein each Q¹ is methyl and each Q² is hydrogen), whereupon the polymer may be characterized as a poly(2,6-dimethyl-1,4-phenylene ether), and 2,3,6-trimethylphenol (wherein each Q¹ and one Q² is methyl and the other Q² is hydrogen). A variety of 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.- A - 3,306,874, 3,306,875, 3,914,266 and 4,028,341. They are usually combinations of cuprous or cupric ions, halide (i.e., chloride, bromide or iodide) 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. Most often, the manganese is present as a complex with one or more complexing and/or chelating agents such as dialkylamines, alkanolamines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds, ω-hydroxyoximes (monomeric and polymeric), o-hydroxyaryl oximes and β-diketones. Also useful are known cobalt-containing catalyst systems. Suitable manganese and cobalt-containing catalyst systems for polyphenylene ether preparation are known in the art by reason of disclosure in numerous patents and publications. Particularly useful polyphenylene ethers for the purposes of this invention are those which comprise molecules having at least one of the end groups of the formulas wherein Q¹ and Q² are as previously defined; each R¹ is independently hydrogen or alkyl, with the proviso that the total number of carbon atoms in both R¹ radicals is 6 or less; and each R² is independently hydrogen or a C₁₋₆ primary alkyl radical. Preferably, each R¹ is hydrogen and each R² is alkyl, especially methyl or n-butyl. Polymers containing the aminoalkyl-substituted end groups of formula II 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-butylamine and dimethylamine, frequently become chemically bound to the polyphenylene ether, most often by replacing one of the α-hydrogen atoms on one or more Q¹ radicals. The principal site of reaction is the Q¹ radical adjacent to the hydroxy group on the terminal unit of the polymer chain. During further processing and/or blending, the aminoalkyl-substituted end groups may undergo various reactions, probably involving a quinone methide-type intermediate of the formula with numerous beneficial effects often including an increase in impact strength and compatibilization with other blend components. Reference is made to U.S- A - 4,054,553, 4,092,294, 4,477,649, 4,477,651 and 4,517,341. Polymers with 4-hydroxybiphenyl end groups of formula III are typically obtained from reaction mixtures in which a by-product diphenoquinone of the formula is present, especially in a copper-halide-secondary or tertiary amine system. In this regard, the disclosure of U.S - A -4,477,649 is again pertinent as are those of U.S.-A-4,234,706 and 4,482,697. In mixtures of this type, the diphenoquinone is ultimately incorporated into the polymer in substantial proportions, largely as an end group. In many polyphenylene ethers obtained under the above-described conditions, a substantial proportion of the polymer molecules, typically constituting as much as 90% by weight of the polymer, contain end groups having one or frequently both of formulas II and III. It should be understood, however, that other end groups may be present and that the invention in its broadest sense may not be dependent on the molecular structures of the polyphenylene ether end groups. It will be apparent to those skilled in the art from the foregoing that the polyphenylene ethers contemplated for use in the present invention include all those presently known, irrespective of variations in structural units or ancillary chemical features. As previously described, the functionalizing compound employed according to the present invention is at least one trialkylammonium or tribenzylammonium maleate or fumarate. The identity of the trialkylamine is not critical but it generally contains primary alkyl groups having from 1 to about 12 carbon atoms. Aryl-substituted alkyl groups such as benzyl and phenethyl are included. The preferred trialkylamines, by reason of their availability and particular suitability, are triethylamine, tri-n-butylamine and tribenzylamine. Fumarates are particularly preferred. Functionalized polyphenylene ethers may be conveniently prepared according to the invention by merely blending the two reagents under conditions adapted for the formation of an intimate blend, and at temperatures high enough to prepare a melt. Typical temperatures are within the range of 230-390°C. It is preferred that mixing be in the absence of free radical initiators. The fact that some type of interaction takes place under these conditions, and that the product is useful for compatibilizing blends as described hereinafter, is quite unexpected in view of the aforementioned Japanese Kokai 84/66452, which explicitly states by way of comparative test results that similar products prepared from the free acids are of little or no utility for this purpose. The proportions of polyphenylene ether and functionalizing compound are not critical, provided the functionalizing compound is used in minor proportions compared to the polyphenylene ether. Most often, 0.1-10 parts and preferably 1.0-5 parts of functionalizing agent are present per 100 parts of polyphenylene ether. Suitable mixing conditions often include extrusion, which may be conveniently effected in a screw-type or similar extruder which supplies a substantial shearing force to the composition. In certain instances, it may be advantageous to vacuum vent the extruder by connecting the vent thereof to a vacuum pump capable of drawing a vacuum of about 2.66 kPa (20 torr) or less. It is also sometimes found advantageous to extrude the mixture more than once, thereby ensuring effective blending. The precise chemical nature of the functionalization which takes place upon practice of the method of this invention is not known with certainty. The principal reaction (if any) may be a thermally initiated free radical interaction of the carbon-carbon double bond with the aromatic rings or the substituents thereon, especially the latter, to produce a product which may include single moieties and/or grafted side chains derived from the functionalizing agent. However, the invention is in no way dependent on theory. As more fully described hereinafter, a principal utility of the functionalized polyphenylene ethers of this invention is in the preparation of polyphenylene ether-polyamide compositions. Such compositions typically also contain impact modifying resins, and it is frequently preferred to melt-blend at least one such impact modifier with the polyphenylene ether and the functionalizing compound. Impact modifiers for polyphenylene ether-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 monomers, acrylic and alkylacrylic acids and their ester derivatives as well as conjugated dienes. Especially preferred impact modifiers are the rubbery high-molecular weight materials including natural and synthetic polymeric materials 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 α-olefins, particularly ethylene, with copolymerizable monomers including, for example, vinyl acetate, acrylic acids and alkylacrylic acids as well as the ester derivatives thereof including, for example, ethylene-acrylic acid, ethyl acrylate, methacrylic acid, methyl methacrylate and the like. Also suitable are 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(styreneacrylonitrile) (SAN), styrene-butadiene copolymers as well as the modified alpha- and para-substituted styrenes and any of the styrene resins disclosed in U.S- A - 3,383,435. ABS types of graft copolymers are typified as comprising a rubbery polymeric backbone derived from a conjugated diene alone or in combination 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., ethylene-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 - A - 3,078,254; 3,402,159; 3,297,793; 3,265,765 and 3,594,452 and G.B.-A- 1,264,741. Exemplary of typical species of AB block copolymers there may be given: polystyrene-polybutadiene (SBR) polystyrene-polyisoprene and poly(alpha-methylstyrene)-polybutadiene. Such AB block copolymers are available commercially from a number of sources, including Phillips Petroleum under the trademark SOLPRENE. Additionally, ABA triblock copolymers and processes for their production as well as hydrogenation, if desired, are disclosed in U.S - A -3,149,182; 3,231,635; 3,462,162; 3,287,333; 3,595,942; 3,694,523 and 3,842,029. Examples of triblock copolymers include: polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS), poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) and poly(α-methylstyrene)-polyisoprene-poly(α-methylstyrene). Particularly preferred triblock copolymers are available commercially as CARIFLEX®, KRATON D® and KRATON G® from Shell. Another class of impact modifiers is derived from conjugated dienes. While many copolymers containing conjugated dienes have been discussed above, additional conjugated diene modifier resins include, for example, homopolymers and copolymers of one or more conjugated dienes including, for example, polybutadiene, butadiene-styrene copolymers, isoprene-isobutylene copolymers, chlorobutadiene polymers, butadiene-acrylonitrile copolymers, polyisoprene and the like. Ethylene-propylene-diene monomer rubbers may also be used. These 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 ore disclosed in U.S- A -2,933,480; 3,000,866; 3,407,158; 3.093,621 and 3,379,701. Other suitable impact modifiers are the core-shell type graft copolymers. In general, these have a predominantly conjugated diene rubbery core or a predominantly cross-linked acrylate rubbery core and one or more shells polymerised thereon and derived from monoalkenylarene and/or acrylic monomers alone or, preferably, in combination with other vinyl monomers. Such core-shell copolymers are widely available commercially, for example, from Rohm and Haas Company under the trade names KM-611, KM-653 and KM-330, and are described in U.S - A - 3,808,180; 4,034,013; 4,096,202; 4,180,494 and 4,292,233. Also useful are the core-shell copolymers wherein an interpenetrating network of the resins employed characterizes the interface between the core and shell. Especially preferred in this regard are the ASA type copolymers available from General Electric Company and sold as GELOY™ resin and described in U.S - A - 3,944,631. In addition, there may be employed the above-described polymers and copolymers having copolymerized therewith or grafted thereon monomers having functional groups and/or polar or active groups. Finally, other suitable impact modifiers include Thiokol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (e.g., polypropylene oxide), epichlorohydrin rubber, ethylenepropylene rubber, thermoplastic polyester elastomers and thermoplastic ether-ester elastomers. The proportion of impact modifier is subject to wide variation. Generally, 1-150 parts by weight thereof are employed per 100 parts of polyphenylene ether. When the impact modifier is styrene-conjugated diene, a diblock or triblock copolymer, in particular olefin diblock or olefin-styrene triblock copolymer, it is usually present in an amount up to 50 parts per 100 parts of polyphenylene ether. The preparation of the functionalized polyphenylene ethers of this invention is illustrated by the following examples. All parts are by weight. The polyphenylene ether used in these examples was a poly-(2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight of about 20,000 and an intrinsic viscosity in chloroform at 25°C of 0.48-0.49 dl./g. Examples 1-5 Mixtures of 49 parts of polyphenylene ether, 10 parts of a partially hydrogenated styrene-butadiene-styrene copolymer having a styrene-butadiene ratio of 27:73 and a number average molecular weight of about 74,000, and various proportions of bis-trialkylammmonium fumarates were tumble mixed on a roll mill for 30 minutes and extruded in a Welding Engineers twin screw extruder at 400 rpm. and 288°C, with full vacuum vent, to yield the desired functionalized polyphenylene ethers. The fumarates and proportions thereof were as follows: Example 1 - triethylammmonium fumarate, 0.7 part. Example 2 - triethylammmonium fumarate, 1.5 parts. Example 3 - tri-n-butylammmonium fumarate, 0.7 part. Example 4 - tri-n-butylammonium fumarate, 1.5 parts. Example 5 - tribenzylammonium fumarate, 0.7 part. As previously noted, the functionalized polyphenylene ethers of this invention are useful in the preparation of blends of polyphenylene ethers with polyamides and linear polyesters. For this purpose, functionalization may be effected before or during blending with the polyamide. Prior functionalization is generally preferred; that is, it is preferred that a functionalized polyphenylene ether as described hereinabove be subsequently blended with the polyamide. Other aspects of the invention, therefore, are a method for preparing a resin composition which comprises mixing in the melt at least one polyphenylene ether, at least one polyamide and at least one above-described functionalizing compound, and compositions so prepared. A preferred embodiment comprises: (A) mixing at least a portion of said polyphenylene ether in the melt, in the absence of free radical initiators, with said functionalizing compound, thereby producing a functionalized polyphenylene ether; and subsequently (B) melt-blending said functionalized polyphenylene ether with at least one polyamide; with the proviso that there is also blended into said composition at least one impact modifying resin for polyphenylene ether-polyamide compositions. Suitable polyamides may be made by any known method, including the polymerization of a monoamino-monocarboxylic acid or a lactam thereof having at least 2 carbon atoms between the amino and carboxylic 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 monoaminocarboxylic acid or a lactam thereof as defined above together with substantially equimolar proportions of a diamine and a dicarboxylic acid. (The term "substantially equimolar" proportions includes both strictly equimolar proportions and slight departures therefrom which are involved in conventional techniques for stabilizing the viscosity of the resultant polyamides.) 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 monoamino-monocarboxylic acids or lactams thereof which are useful in preparing 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. As particular examples of aminocarboxylic acids and lactams there may be mentioned ε-aminocaproic acid, butyrolactam, pivalolactam, ε-caprolactam, capryllactam, enantholactam, undecanolactam, dodecanolactam 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 H₂N(CH₂) n NH₂ wherein 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 HOOC-Y-COOH wherein Y is a divalent aliphatic or aromatic group containing at least 2 carbon atoms. Examples of aliphatic acids are sebacic acid, octadecanedioic acid, suberic acid, glutaric acid, pimelic acid and adipic acid. Aromatic acids, such as isophthalic and terephthalic acids, are preferred. Typical examples of the polyamides or nylons, as these are often called, include, for example, polyamide-6, 66, 11, 12, 63, 64, 6/10 and 6/12 as well as polyamides from terephthalic acid and/or isophthalic acid and trimethylhexamethylenediamine; from adipic acid and m-xylylenediamines; from adipic acid, azelaic acid and 2,2-bis-(p-aminocyclohexyl)propane and from terephthalic acid and 4,4'-diaminodicyclohexylmethane. 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. Linear polyesters which may be blended with the functionalized polyphenylene ethers include thermoplastic poly(alkylene dicarboxylates) and alicyclic analogs thereof. They typically comprise structural units of the formula wherein R³ is a saturated divalent aliphatic or alicyclic hydrocarbon radical containing 2-10 and usually 2-6 carbon atoms and A is a divalent aromatic radical containing 6-20 carbon atoms. They are ordinarily prepared by the reaction of at least one diol such as ethylene glycol, 1,4-butanediol or 1,4-cyclohexanedimethanol with at least one aromatic dicarboxylic acid such as isophthalic or terephthalic acid, or lower alkyl ester thereof. The polyalkylene terephthalates, particularly polyethylene and polybutylene terephthalate and especially the latter, are preferred. Such polyesters are known in the art as illustrated by the following US patents: 2,465,319 3,047,539 2,720,502 3,671,487 2,727,881 3,953,394 2,822,348 4,128,526. The polyphenylene ether which is blended with the polyamide or polyester may be solely functionalized polyphenylene ether prepared by the method of this invention. However, it is also contemplated to include both functionalized and unfunctionalized polyphenylene ether in the blend, the latter being present in an amount up to 90% by weight of total polyphenylene ether. The polyphenylene ether-polyamide or polyester blend generally contains 5-75% by weight polyphenylene ether and 25-95% polyamide or polyester. There is preferably also blended into the polyphenylene ether-polyamide composition at least one of the previously identified impact modifiers. The impact modifier may be introduced at any time during the blending operation, or over an extended time period separate from or concurrent with the addition of other blend constituents. It is preferred, however, to complete addition of the impact modifier before beginning polyamide addition. More preferably, all of the impact modifier is blended with the polyphenylene ether concurrent with functionalization thereof as described hereinabove. Blending may be achieved by known methods, typically involving melt blending and extrusion. In one suitable method, the functionalized polyphenylene ether is prepared in a first extruder, preferably in the presence of the impact modifier as previously noted, and subsequently blended in a second extruder with the remaining constituents, including polyamide and any unfunctionalized polyphenylene ether. It is also possible to perform the entire blending operation in a lateral-feed extruder, in which it is possible to supply constituents at various points. Under these conditions, the polyphenylene ether, the functionalizing agent and preferably the impact modifier are supplied at the rear of the extruder, and any remaining constituents are supplied at one or more points nearer its outlet. The preparation of the polyphenylene ether-polyamide compositions of this invention is illustrated by the following examples. Examples 6-10 The compositions of Examples 1-5 (each prepared from 49 parts of polyphenylene ether, 10 parts of impact modifier and varying amount of trialkylammonium fumarate) were combined with 41 parts of a commercially available polyamide-66 and extruded under the conditions described in Examples 1-5. The extrudates were quenched in water, pelletized, dried for 3-4 hours at 95-105°C and injection molded into test specimens for the notched Izod impact test. The results of the test are given in the following table. Example Functionalized polyhenylene ether Impact strength, joules/m. 6 1 123 7 2 748 8 3 171 9 4 748 10 5 748

Claims: A method for functionalizing a polyphenylene ether which comprises mixing said polyphenylene ether in the melt with at least one functionalizing compound comprising a trialkylamine, or tribenzylamine salt of maleic or fumaric acid. A method according to claim 1 which is effected in the absence of free radical initiators, and wherein the polyphenylene ether comprises a plurality of structural units having the formula and in each of said units independently, each Q¹ is independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Q² is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹. A method according to claim 2 wherein polyphenylene ether in a poly(2,6-dimethyl-1,4-phenylene ether). A method according to claim 3 wherein the functionalizing compound is triethylammonium fumarate. A method according to claim 3 wherein the functionalizing compound is tri-n-butylammonium fumarate. A method according to claim 3 wherein the functionalizing compound is tribenzylammonium fumarate. A method for preparing a resin composition which comprises mixing in the melt at least one polyphenylene ether, at least one polyamide and at least one functionalizing compound comprising a trialkylamine or tribenzylamine salt of maleic or fumaric acid. A method according to claim 7 which comprises: (A) mixing at least a portion of said polyphenylene ether in the melt, in the absence of free radical initiators, with said functionalizing compound, thereby producing a functionalized polyphenylene ether; and subsequently (B) melt-blending said functionalized polyphenylene ether with at least one polyamide; with the proviso that there is also blended into said composition at least one impact modifying resin for polyphenylene ether- polyamide compositions. A method according to claim 8 wherein the polyamide is nylon-6 or nylon-66 and the polyphenylene ether comprises a plurality of structural units having the formula and in each of said units independently, each Q¹ is independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Q² is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹; and wherein the impact modifying resin is blended into the composition during step A. A method according to claim 9 wherein the polyphenylene ether is a poly(2,6-dimethyl-1,4-phenylene ether) and the functionalizing compound is a fumarate. A method according to claim 10 wherein the functionalizing compound is triethylammonium fumarate. A method according to claim 10 wherein the functionalizing compound is tri-n-butylammonium fumarate. A method according to claim 10 wherein the functionalizing compound is tribenzylammonium fumarate. A method according to claim 10 wherein an impact modifying resin is blended into the composition during step A, said impact modifying resin being selected from high impact polystyrene, styrene-conjugated diene or olefin diblock or olefin-styrene triblock copolymer and is present in an amount from 1 to 150 parts by weight per 100 parts of polyphenylene ether. A method according to claim 10 wherein the mixing temperature is within the range of 230-390°C.

Inventors: YATES III JOHN BENNIE, YATES III, JOHN BENNIE
Applicants: GEN ELECTRIC, GENERAL ELECTRIC COMPANY
Application year: 1987
Main classification: C08G65
IPC codes: C08L75, C08L81, C08L77, C08L67, C08L71, C08G65