JPH055862B2 - - Google Patents

Description

Claim 1 (a) polyphenylene ether resin, (b) polyamide resin and (c) 1,2- and 1,4-benzoquinone; 2,6-diphenylquinone; tetramethyldiquinone; 2,2'- and 4,4'-diphenoquinone;
1,2-, 1,4- and 2,6-naphthoquinone;
Chloranils, 2-chloro-1,4-benzoquinone; 2,3-dichloro-5,6-dicyano-1,
(a)
and (b) in an amount of 5 to 95% by weight and 95 to 5% by weight, respectively, based on the total weight of (c), and an amount of (c) based on the weight of the total composition. 0.05-20% by weight of the resin composition. 2 Quinones range from 0.1 to 4 based on the weight of the total composition
A composition according to claim 1, used in an amount of % by weight. 3. A composition according to claim 1, wherein the ratio of polyphenylene ether to polyamide is 30-70% by weight of the former and 70-30% by weight of the latter. 4 Polyphenylene ether has a repeating structural formula: (wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjacent unit, and n is a positive integer and is at least 50, and each Q is hydrogen, halogen, tertiary α−
Hydrocarbons having no carbon atoms and hydrocarbonoxy groups and halohydrocarbons and halohydrocarbons having no tertiary α-carbon atoms and having at least 2 carbon atoms between the halogen atom and the phenyl nucleus 2. The composition according to claim 1, which is a homopolymer or copolymer having units having a monovalent substituent selected from the group consisting of oxy groups. 5. The composition of claim 1, wherein the polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene) ether. Description The present invention relates to modified polyphenylene ether-polyamide compositions that have improved chemical resistance, processability, elongation properties and/or impact strength compared to unmodified compositions. More particularly, the invention comprises a blend and/or reaction product of a) one or more polyphenylene ether resins, b) one or more polyamide resins and c) at least one quinone compound. The present invention relates to a resin composition. Polyphenylene ether resins are characterized by a unique combination of chemical, physical and electrical properties over a temperature range of over 600° ranging from a embrittlement point of about -275° to a heat deflection temperature of about 375°.
This combination of properties makes polyphenylene ethers suitable for a wide range of applications. however,
Despite the advantageous properties mentioned above, the usefulness of polyphenylene ether resins is limited as a result of poor processability, impact resistance, and chemical resistance. Finholt (U.S. Pat. No. 3,379,792) discloses polymer formulations in which the processability of polyphenylene ether resins is improved by incorporating 0.1 to 25 weight percent polyamide. however,
The advantages of Finholt's invention are limited by the fact that polyamide concentrations above 20% by weight result in significant reductions in other physical properties. Specifically, polyphenylene ethers and polyamides are either incompatible or, in the best case, may cause phase separation of these resins during molding or result in molded articles with poor mechanical properties. Shows poor compatibility. Ueno et al. (U.S. Pat. No. 4,315,086) used a polyphenylene ether with a polyamide and A) a liquid diene polymer, B) an epoxy compound, and C) in the molecule).
carbon-carbon double bond or carbon-carbon triple bond and) carboxylic acid, acid anhydride, acid amide, imide,
Improved chemical resistance without deterioration of other mechanical properties by incorporating specific compounds selected from the group consisting essentially of carboxylic acid esters, compounds having both amino or hydroxyl groups It is disclosed that polyphenylene ether formulations are obtained. Finally, Kasahara et al. (European Patent No. 46040) added units of vinyl aromatics and α,β-unsaturated dicarboxylic compounds to high-impact polyphenylene ether-polyamide blends to improve their heat and oil resistance. It discloses the use of a copolymer consisting of units of acid anhydride or its imide compound as a modifier. Now, a polyphenylene ether-polyamide composition has improved impact strength, elongation, chemical resistance, processability and/or heat resistance compared to unmodified polyphenylene ether-polyamide compositions and reduced water absorption compared to polyamide alone. We have discovered a new polyphenylene ether-polyamide blend having the following properties. Specifically, we have discovered novel resin compositions having the properties described above, which consist of a blend and/or reaction product of a polyphenylene ether, a polyamide, and a property-improving effective amount of a quinone compound. Additionally, these compositions may contain stabilizing and/or property-improving amounts of primary or secondary amines. Optionally, the compositions of the present invention may further include fillers and other property-enhancing additives such as polymeric impact modifiers and/or inorganic reinforcing additives and/or alkenyls such as styrenic polymers. Other polymers may be included, including aromatic polymers. Although the exact physical makeup of the compositions of the present invention is not known, it is generally believed that the compositions consist of a dispersion of one polymer in another. A likely configuration would be one in which polyphenylene ether is dispersed in a polyamide matrix, but the opposite configuration is also possible, especially if the polyamide is only present in small amounts. be. Additionally, it is believed that some grafted polyphenylene ether-polyamide product may be present in the product thus produced. Furthermore, it is believed that when grafting is present, the quinone compound may facilitate grafting, at least to some extent, and/or itself act as a graft binding agent. Accordingly, all such dispersions as well as grafted, partially grafted and non-grafted products are within the broad contemplation of this invention. Polyphenylene ethers suitable for use in the practice of this invention and which are well known in the art and which can be prepared from the corresponding phenols or reactive derivatives thereof by any one of a number of catalytic and non-catalytic methods. can do. Examples of polyphenylene ethers and methods of making them are provided in U.S. Pat.
It is disclosed in the specifications of No. 3306874, No. 3306875, No. 3257357, No. 3257358, No. 3337501, and No. 3787361. For simplicity, the term "polyphenylene ether" as used throughout this specification and appended claims refers to unsubstituted polyphenylene ethers (made from phenols) as well as substituted polyphenylene ethers with various substituents. It also includes polyphenylene ethers. The term also includes copolymers, graft copolymers, and block copolymers of alnickel aromatics, particularly vinyl aromatics, and polyphenylene ethers, as described below. Phenol compounds suitable for the production of polyphenylene ethers have the general formula: (In the formula, each Q is hydrogen, halogen,
Aliphatic and aromatic hydrocarbons and hydrocarbon oxy groups that do not contain a tertiary α-carbon atom and halogen compounds that do not contain a tertiary α-carbon atom and have at least two carbon atoms between the halogen atom and the phenyl nucleus. a monovalent substituent selected from the group consisting of hydrocarbon and halohydrocarbonoxy groups and at least one Q is hydrogen. Specific examples of phenolic compounds represented by the above formula include phenols; o-, m- and p-cresols; 2,6-, 2,5-, 2,4-
and 3,5-dimethylphenol; 2-methyl-
6-phenylphenol; 2,6-diphenylphenol; 2,6-diethylphenol; 2-methyl-6-ethylphenol; and 2,3,5
-, 2,3,6- and 2,4,6-trimethylphenol. If a copolymer is desired, two or more phenolic compounds may be used in combination. Copolyphenylene ethers also include phenolic compounds of the above general formula and phenols not represented by the above general formula, including dihydric phenols such as bisphenol-A, tetrabromobisphenol-A, resorcinol or hydroquinone. It can be produced from a compound. Examples of suitable polyphenylene ethers include:
For example, poly(2,6-dimethyl-1,4-phenylene) ether; poly(2-methyl-1,4-
phenylene) ether; poly(3-methyl-1,
4-phenylene) ether; poly(2,6-diethyl-1,4-phenylene) ether; poly(2
-Methyl-6-allyl-1,4-phenylene) ether; poly(2,6-dichloromethyl-1,4
-phenylene) ether; poly(2,3,6-trimethyl-1,4-phenylene) ether; poly(2,3,5,6-tetramethyl-1,4-phenylene) ether; poly(2,6- Dichlor-
1,4-phenylene)ether; poly(2,6-
Diphenyl-1,4-phenylene) ether; poly(2,5-dimethyl-1,4-phenylene) ether and the like can be mentioned. Furthermore, as mentioned above, copolymers of phenolic compounds can also be used. Preferred polyphenylene ethers have the formula: where Q is as defined above and n is at least 50, preferably from 50 to about 200. Examples of polyphenylene ethers corresponding to the above formula can be found in the patent documents cited above and they include, inter alia, poly(2,6-dilauryl-1,4-phenylene) ether; poly(2,6-diphenyl -1,4-phenylene)ether; poly(2,6-dimethyloxy-1,4
-phenylene) ether; poly(2,6-diethoxy-1,4-phenylene) ether; poly(2
-methoxy-6-ethoxy-1,4-phenylene)ether; poly(2,6-dichloro-1,4
-phenylene)ether; poly(2-methyl-6)
-Phenyl-1,4-phenylene) ether; poly(2,6-dibenzyl-1,4-phenylene)
Ether; poly(2-ethoxy-1,4-phenylene) ether; poly(2-chloro-1,4-phenylene) ether; poly(2,6-dibromo-
1,4-phenylene) ether; and the like. A particularly preferred group of polyphenylene ethers for the purposes of this invention includes those having _C1 - _C4 alkyl substituents in the two positions ortho to the oxygen ether atom. Representative examples of this group are poly(2,6-dimethyl-1,4-phenylene) ether; poly(2,6-diethyl-1,4-phenylene) ether; poly(2-methyl-6-ethyl-1, 4-phenylene) ether; poly(2,6-
dipropyl-1,4-phenylene) ether; poly(2-ethyl-6-propyl-1,4-phenylene) ether; etc., most preferably poly(2,6-dimethyl-1,4-phenylene)
It is ether. One method for producing the polyphenylene ethers described above is by oxidizing the phenolic compound with oxygen or an oxygen-containing gas in the presence of an oxidative coupling catalyst. There are no particular restrictions regarding the choice of catalyst; any catalyst for oxidative polymerization can be used. Typical examples of catalysts include cuprous salts such as cuprous chloride-trimethylamine and dibutylamine, cuprous acetate-triethylamine or cuprous chloride-pyridine,
a catalyst consisting of a primary amine and/or a secondary amine;
A catalyst consisting of a cupric salt such as cupric chloride-pyridine-potassium hydroxide, a tertiary amine and an alkali metal hydroxide; a manganese salt such as manganese chloride-ethanolamine or manganese acetate-ethylenediamine; catalysts consisting of manganese salts and alcoholates or phenolates, such as manganese chloride-sodium methylate or manganese chloride-sodium phenolate; and catalysts consisting of cobalt salts and tertiary amines. The polyamides suitable for preparing the compositions of the invention can be prepared by polymerizing monoamino-monocarboxylic acids or lactams thereof having at least 2 carbon atoms between the amino and carboxylic acid groups; By polymerizing a diamine having at least two carbon atoms between the groups and a dicarboxylic acid in substantially equimolar proportions; or by polymerizing a diamine having at least two carbon atoms between the groups in substantially equimolar proportions; It can be obtained by polymerization with molar proportions of diamine and dicarboxylic acid. Dicarboxylic acids can be used in the form of their functional derivatives, such as esters or acid chlorides. The term "substantially equimolar" proportions (diamine and dicarboxylic acid) refers to the difference between strictly equimolar proportions and proportions that deviate slightly from the equimolar proportions practiced in conventional techniques for stabilizing the viscosity of the resulting polyamides. , is used in a meaning that includes both. Examples of the aforementioned monoamino-monocarboxylic acids or lactams thereof useful in making polyamides include such compounds containing from 2 to 16 carbon atoms between the amino group and the carboxylic acid group, where the carbon atoms are In the case of , it forms a ring together with the -CONH- group. Specific examples of aminocarboxylic acids and lactams include 6-aminocaproic acid, butyrolactam, bivalolactam, caprolactam, capryl-lactam, enantholactam, undecanolactam, dodecanolactam and 3- and 4-aminobenzoic acid. can. Diamines suitable for use in making polyamides include alkyl, aryl and alkyl-aryl diamines. Such diamines are, for example, those of the general formula: H ₂ N(CH ₂ ) _o NH ₂ , where n is an integer from 2 to 16, such as trimethylene diamine,
Tetramethylene diamine, pentamethylene diamine, octamethylene diamine and especially hexamethylene diamine, as well as trimethylhexamethylene diamine, meta-phenylene diamine, meta-
Including xylylene diamine and the like. The dicarboxylic acids can be aromatic, such as isophthalic acid and terephthalic acid, or aliphatic, with aliphatic dicarboxylic acids having the formula: HOOC-Y-COOH, where Y is a divalent fatty acid containing at least 2 carbon atoms. Examples of such acids are sebacic acid, octadecanedioic acid, suberic acid, glutaric acid, pimelic acid and adipic acid. Typical examples of these polyamides or nylons (i.e. they are often referred to as nylons) are:
For example, polypyrrolidone (nylon 4), polycaprolactam (nylon 6), polycapryllactam (nylon 8), polyhexamethyleneadipamide (nylon 6,
6) Polyundecanolactam (Nylon 11) Polydodecanolactam (Nylon 12) Polyhexamethylene azelaamide (Nylon 6,9) Polyhexamethylene sebacamide (Nylon 6,
10) Polyhexamethylene isophthalamide (nylon 6, I) Polyhexamethylene terephthalamide (nylon 6, T) Polyamide of hexamethylene diamine and n-dodecanedioic acid (nylon 6, 12) and terephthalic acid and/or isophthalic acid and trimethyl Polyamide obtained from hexamethylene diamine, polyamide obtained from adipic acid and metaxylylene diamine, adipic acid,
Includes polyamides obtained from azelaic acid and 2,2-bis-(p-aminocyclohexyl)pyropane and polyamides obtained from terephthalic acid and 4,4'-diamino-dicyclohexylmethane. Copolymers of the aforementioned polyamides or prepolymers thereof are also suitable for use in the practice of this invention. Such copolymers include the following copolymers: Hexamethylene adipamide/caprolactam (nylon 6,6/6) Hexamethylene adipamide/hexamethylene-isophthalamide (nylon 6,6/6I) Pamid/hexamethylene-terephthalamide (nylon 6,6/6T) hexamethyleneadipamide/hexamethylene-azelayamide (nylon 6,6/6,9) hexamethyleneadipamide/hexamethylene-azelayamide/caprolactam (nylon 6,
6/6, 9/6) Mixtures and/or copolymers of two or more of the aforementioned polyamides or their initial polymers are also within the scope of the present invention. Preferred polyamides are nylon 6; 6,6; 11 and 12, most preferably nylon 6,6. It should also be understood that the use of the term "polyamide" herein and in the appended claims is intended to encompass reinforced or ultra-tough polyamides. Ultra-tough polyamides, or ultra-tough nylons (as they are more commonly known), are commercially available, such as from EI DuPont (registered trademark Zytel ST resin), Wilson
Fiberfill (NY resin), Vadeitushi (registered trademark ULTRAMID resin), Allied (registered trademark CARPION) and Celanese (7000 series resin)
available from or inter alia
It can be made in accordance with a number of US patents including Epstein US Pat. No. 4,174,358; Novak US Pat. No. 4,474,927; Roura US Pat. No. 4,346,194 and Joffrion US Pat. No. 4,251,644. These ultra-tough nylons are made by incorporating one or more polyamides with one or more polymeric or copolymeric elastomeric reinforcements. Suitable toughening agents are described in more detail in the above-referenced U.S. patents and below.
Caywood, Jr. U.S. Pat. No. 3,884,882 and
U.S. Patent No. 4,147,740 to Swinger and “Preparation and Reactions of Epoxy” to Gallucci et al.
Modified Polyethylene”, J.APPL.POLY.SCI.
27, pp. 425-437 (1982). Typically, these elastomeric polymers and copolymers can be linear or branched, and can be graft polymers and copolymers, including core-shell graft copolymers, and have copolymerization in their structure. Monomers with functional and/or active or highly polar groups capable of interacting with or attaching to the polyamide matrix by incorporation or by grafting onto preformed polymers. It is characterized in that the toughness of the polyamide polymer is increased by bonding. The blending ratio of polyphenylene ether to polyamide is 5 to 95% by weight, preferably 30 to 70% by weight of the former.
The latter accounts for 95 to 5% by weight, preferably 70 to 30% by weight. When the polyamide content is less than 5% by weight, the improvement effect on solvent resistance is small, while when the polyamide content exceeds 95% by weight, thermal properties such as heat deflection temperature and dimensional stability tend to be poor. There is. As mentioned above, such polyphenylene ether-polyamide blends suffer from poor compatibility, as evidenced by particularly poor impact strength. However, it has now surprisingly been found that cyclic diketones (more commonly known as quinones) with a high degree of conjugation can enhance the compatibility and other physical properties of these formulations. Ta. Almost any quinone is believed to provide improved properties within the range indicated above. Generally, quinones suitable for use in the present invention have at least one six-membered carbocyclic ring in the molecule, at least two carbonyl groups (C=
0), (provided that each of said carbonyl groups is present in the same or separate rings, e.g.

【formula】

[Formula] or

[Formula]) and at least two carbon-carbon double bonds in the ring structure (provided that each of the double bonds may exist in the same or different rings) ). When two or more rings are present in the quinone structure of a molecule, they can be fused or unfused structures, or the compound can have both fused and unfused rings. Unfused rings are directly bonded, especially carbon-
It may be bonded by a carbon double bond or by a hydrocarbon group with conjugated unsaturation, for example =CH-CH=. Additionally, quinones that can be used in the practice of this invention can be substituted or unsubstituted. The degree of substitution on the basic quinone structure is related to the number of substitutable sites, ie the number of hydrogen atoms that can be substituted. Examples of various substituents that may be present on the basic unsubstituted quinone structure are halogens, such as chlorine, bromine, fluorine, etc.; saturated and unsaturated, branched and hydrocarbon substituents selected from alkyl, aryl, arylalkyl, cycloalkyl, etc., including unbranched groups, and their halogenated derivatives, and basic non-substituents through acid, sulfur, phosphorus or other heteroatom bridges. Includes similar hydrocarbon groups linked to substituted quinone structures. Suitable quinones useful in the practice of this invention are 1,2-
and 1,4-benzoquinone; 2,6-diphenylquinone; tetramethyldiquinone; 2,2'- and 4,4'-diphenoquinone; 1,2-, 1,4- and 2,6-naphthoquinone; chloranils, 2-chloro-1,4-benzoquinone; 2,3-dichloro-; 5,6-dicyano-1,4-benzoquinone,
Includes 2,5-dimethylbenzoquinone, 2-methylbenzoquinone and 4,4'-stilbenequinone. In the practice of this invention, the quinone compatibilizer is
Adequate amounts that increase the compatibility of polyphenylene ether-polyamide compositions, particularly as evidenced by higher impact strength and other stress-strength properties including improved processability and/or tensile elongation. used. Generally, the amount of quinone used is from about 0.05 to about 20% by weight, preferably from about 0.1 to about 4% by weight, based on the weight of the total composition. Although it is clear that larger or smaller amounts can be used,
Too much may lead to deterioration of certain properties, while too little may be insufficient to produce any benefits. In general, the specific amount of quinone compatibilizer that should be used to achieve optimal results for a given composition will depend in part on the particular quinone compatibilizer used, the specific amount of quinone compatibilizer in the composition, etc. It concerns the resinous polymers and their weight ratios, as well as the processing conditions and sequence used to make the final composition. In addition to improved processability, impact strength and elongation, many of the compositions made in accordance with the present invention exhibit improvements in other physical properties and properties, including, for example, reduced water absorption. The aforementioned property-improving quinone compounds can be used alone or in combination with primary or secondary amines. The presence of amines has been found to increase the degree of improvement in certain physical properties, particularly gloss, when used in combination with various quinone compatibilizers. Suitable amines include 1 to about 20, preferably 1
Includes primary and secondary amines having ~10 carbon atoms. Examples of such suitable amines include methylethylamine, diethylamine, butylamine, dibutylamine, aniline, n-octadecylamine, and the like. The amount of primary or secondary amine used is generally up to about 3% by weight, preferably from about 0.35 to about 1% by weight. In the practice of this invention, it may be further desirable to add additional modifier resins or combinations of resins to further improve the physical properties of the composition, particularly impact strength and/or processability. Such modifier resins are well known in the art and typically include olefins, vinyl aromatic monomers,
It is derived from one or more monomers selected from the group consisting of acrylic acid or alkyl acrylic acid, their ester derivatives, and conjugated dienes.
Particularly preferred modifier resins are rubbery high molecular weight materials including natural and synthetic polymeric materials that are elastic at room temperature. Suitable modifier resins include both homopolymers and copolymers, including random, block, radial block, graft and core-shell type copolymers, and combinations thereof. Polyolefins or olefin-based copolymers that may be used in the practice of this invention include, among others, low density polyethylene, high density polyethylene, linear low density polyethylene, isotactic polypropylene, poly(1-butene), poly(4-methyl-1 -pentene), propylene-ethylene copolymers, etc. Other olefin copolymers are copolymers of one or more α-olefins, especially ethylene, such as vinyl acetate, acrylic acid and alkyl acrylic acids and their ester derivatives, such as ethylene acrylic acid, ethyl acrylate, methacrylic acid, methyl methacrylate, etc. It includes copolymers with copolymerizable monomers including. Finally, another group of olefin-based copolymers suitable for use herein includes ionomeric resins, which may be fully or partially neutralized with metal ions. A second group of modifier resins that can be used in the present invention are those derived from vinyl aromatic monomers. These include, for example, modified or unmodified polystyrene, ABS type graft copolymers; AB and
Includes ABA type block and radial block copolymers and vinyl aromatic-conjugated diene core-shell type graft copolymers. Modified and unmodified polystyrene includes pure polystyrene and rubber modified polystyrene such as butadiene rubber modified polystyrene, also known as high impact polystyrene or HIPS. Other useful polystyrenes are, for example, poly(styrene-acrylonitrile) (SAN), styrene-butadiene copolymers and modified alpha- and p-substituted styrenes and U.S. Pat.
Copolymers of styrene and various monomers are included, including any of the styrene resins disclosed in No. 3,383,435. ABS-type graft copolymers typically include a rubbery polymeric backbone derived from a conjugated diene alone or in combination with a copolymerizable monomer and a monoalkenyl arene grafted onto the backbone. It is characterized as consisting of at least one, and preferably two, monomers selected from the group consisting of monomers and substituted derivatives thereof, acrylonitriles, acrylic acids and alkyl acrylic acids, and esters thereof. A particularly preferred group of polymeric resins derived from vinyl aromatic monomers consists of monoalkenyl arene blocks and hydrogenated, partially hydrogenated and non-hydrogenated conjugated diene blocks and AB and ABA.
It is a block copolymer labeled as a block copolymer. Suitable AB type block copolymers are disclosed, for example, in U.S. Pat.
Typical series of AB block copolymers include polystyrene-polybutadiene (SBR), polystyrene-polyisoprene and poly(α-methylstyrene)-polybutadiene. Such AB block copolymers are commercially available from a number of sources, including the Phillips trademark Solprene. Further, ABA triblock copolymers and their preparation and optional hydrogenation are all described in U.S. Pat.
Disclosed in No. 3462162, No. 3287333, No. 3595942, No. 3694523, and No. 3842029. Typical series of triblock copolymers include: polystyrene-polybutadiene-polystyrene (SBS) polystyrene-polyisoprene-polystyrene (SIS) poly(α-methylstyrene)-polybutadiene-
Mention may be made of poly(α-methylstyrene) and poly(α-methylstyrene)-polyisoprene-poly(α-methylstyrene). A particularly preferred family of such triblock copolymers are commercially available from Siel Corporation under the trademarks CARIFLEX, KRATON D and KRATON G. A third group of modifier resins suitable for use in the present invention are those derived from conjugated dienes. Although a number of copolymers containing conjugated dienes have already been described above, other conjugated diene modifier resins include, for example, homopolymers and copolymers of one or more conjugated dienes, which include Examples include polybutadiene, butadiene-butylene copolymer, isoprene-isobutylene copolymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, polyisoprene, and the like. Finally, ethylene-propylene-diene rubbers are also intended to be within the scope of this invention. These EPDMs are typically predominantly ethylene units with moderate amounts of propylene units and approx.
It is expressed as containing small amounts of diene monomer units, up to 20 mol%. It takes a lot of money
EPDM and their manufacturing method is covered by U.S. Patent No. 2933480.
No. 3000866, No. 3407158, No. 3000866, No. 3407158, No.
Disclosed in No. 3093621 and No. 3379701. Another group of modifier resins that can be used in the present invention are core-shell graft copolymers. In general, these include a rubbery core based on a conjugated diene or a rubbery core based on a crosslinked acrylate and monoalkenyl arene and/or acrylic monomers alone or preferably other vinyl monomers polymerized onto the core. It is characterized as having one or more shells derived from combination with monomers. Such core-shell type copolymers are widely available commercially, for example from Rohm and Haas under the trade names KM-611, KM-653 and KM-330, and are disclosed in U.S. Pat. No. 3,808,180;
It is described in No. 4034013, No. 4096202, No. 4180494, and No. 4292233. Core-shell type copolymers in which the interpenetrating network structure of the resins used characterize the interface between the core and the shell are also within the scope of the present invention. Particularly preferred in this regard are the ASA type copolymers available from General Electric Co., sold under the trade name GELOY resin and described in U.S. Pat. No. 3,944,631. In addition to the linear polymers and copolymers mentioned above, such polymers and copolymers having monomers with functional groups and/or polar or active groups copolymerized therewith or grafted thereto are used. It should also be understood that obtaining. Such functional groups include epoxy, amine, amide, thio, ether, ester, carboxy, anhydride, carbonyl, carboxylic anhydride and other highly polar groups. Such functionalized or activated polymers and copolymers are described above in connection with the discussion of reinforced polyamides.
Epstein, Novak, Roura, Joffrion, Caywood;
It is described in the literature by Swiger and Gallucci.
All such functionalized or activated polymers and copolymers may be mixed directly with the components of the compositions of the present invention or may be premixed with the polyamide or polyphenylene ether as described above. A functionalized or activated rubbery polymer or copolymer can be premixed with a polyamide to produce a toughened or ultra-tough polyamide, which can then be used to make the polyphenylene ether-polyamide compositions of the present invention. Particularly preferred. Finally, other suitable modifier resins and high molecular weight rubbery materials that can be used in the practice of the invention include, for example, thiokol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (e.g. polypropylene oxide), epichlorohydrin rubber, ethylene propylene rubber, etc. Includes rubber, thermoplastic polyester elastomer, thermoplastic ether-ester elastomer, and the like. The amount of rubbery polymer used is up to about 100 parts by weight, preferably about 5/50 parts by weight, based on 100 parts by weight of the mixture of polyphenylene ether and polyamide;
Most preferably from about 5 to about 25 parts by weight. However, if this amount is less than 2 parts by weight, the effect of improving the impact resistance of the rubbery polymer is poor. If this amount is greater than 100 parts by weight, impact resistance is significantly improved but may result in some deterioration of other physical properties. Therefore, it is preferred to use less than 100 parts by weight of rubbery polymer to balance impact resistance and other physical properties. It is further to be understood that combinations of the aforementioned modifier resins may be used and are still within the broadly contemplated scope of the invention. Finally, in addition to the foregoing, the polyphenylene ether-polyamide resin compositions of the present invention may further contain other reinforcing additives including glass fibers, carbon fibers, inorganic fillers, etc., as well as various other reinforcing additives known to those skilled in the art. It may contain flame retardants, colorants, stabilizers, etc. When used in the practice of this invention, reinforcing additives should be used in amounts of no more than about 50% by weight, preferably no more than about 30% by weight, based on the total composition.
Particularly preferred reinforcing additives are filamentary and chopped glass fibers. Such glass fibers may be untreated or preferably treated with silane or titanate coupling agents, which are well known in the art and widely available from a number of manufacturers. . Stabilizers suitable for use in the practice of this invention generally include nearly all known thermal and oxidative stabilizers suitable for use with polyamides or polyphenylene ethers. Particularly preferred are those stabilizers that are suitable for use with polyamides. For example, a stabilizer package containing a liquid phosphate and a hindered phenol, and a combination of a hindered phenol and a potassium salt and a cuprous salt may be used. The method for producing the resin composition of the present invention is not particularly limited, and conventional methods can be used satisfactorily. However, melt blending is generally preferred. The time and temperature required for melt blending are not particularly limited and can be appropriately determined according to the composition of the materials. The temperature varies somewhat with the polyphenylene ether to polyamide blend ratio, but is usually within the range of 270° to 350°C. Long periods of time and/or high shear rates are desirable for mixing, but promote degradation of the resin composition. Therefore, the time needs to be determined taking these points into consideration. Any melt blending method can be used so long as it can handle the molten consistency. This method can be applied either batchwise or continuously. Specifically, extruders, Banbury mixers, rollers, kneaders, etc. may be used. The order of the process steps in the process of the present invention can also vary widely, and certain orders, as shown below, may give better properties to the final product compared to other orders. For example, all components may be added initially and directly to the treatment system. In this method, the components may be premixed by dry blending and then fed to an extruder or melt blending device, or the components may be added to the melt blending device, respectively. Alternatively, it has often been found preferable to premix any two or more of the components. For example, polyamides can be premixed with rubbery polymers or copolymers, particularly functionalized rubbery polymers or copolymers, to form reinforced or ultra-tough polyamides. It is also possible to premix the polyphenylene ether with the compatibilizer alone or with the rubbery polymer or copolymer. It is clear that other premixed materials may be prepared and then combined with the remaining ingredients to form the final composition. Additionally, premixing can be accomplished in two steps, whereby the premixed materials can be remixed with the remaining components, or two or more components can be combined using an extruder with a downstream feed port. It should also be noted that it is possible to add and mix at the throat of the screw and add the remaining ingredients to the melt through a downstream feed port. Finally, if certain components are to be premixed, all or only some of the components can be premixed. Essentially any premix order can be used in the practice of the present invention. The following examples are provided so that those skilled in the art may better understand how to practice the invention. These examples are given for illustrative purposes only and are not intended to limit the invention in any way. Unless otherwise indicated, all dispositions are expressed in parts by weight. Examples E1-E5 and Comparative Examples CE1-CE2 A series of polyphenylene ether-polyamide compositions within and outside the scope of the present invention were prepared. All compositions were prepared by direct addition of ingredients on a single screw extruder and extruded at 300°C. The extrudates were pelletized and injection molded to form test members, which were tested for physical properties. Specific compositions and their physical properties are shown in Table 1.

Table 1 Clearly, from the results shown in Table 1, the use of various quinones in the preparation of polyphenylene ether-polyamide compositions provides significantly and unexpectedly increased impact strength. Furthermore, from Examples E1 and E2, it appears that higher amounts of quinone compatibilizer are preferred and give progressively increasing impact strength improvements. Examples E6-E8 and Comparative Examples CE3-CE4 A second series of examples were prepared by the same method as above, but with the addition of a rubbery copolymer to the composition. Specific dispositions and their physical properties are shown in Table 2. Again, it is clear from these examples that the use of quinones in the preparation of rubber-modified polyphenylene ether-polyamide compositions results in significantly and unexpectedly increased impact strength and % elongation in the compositions. .

【table】

Obviously, other modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that modifications may be made to the specific disclosed embodiments of the invention that are within the broad intended scope of the invention as defined by the appended claims. It is.