EP0301003B1 - Modifizierte polyphenylenäther-polyamidzusammensetzungen - Google Patents
Modifizierte polyphenylenäther-polyamidzusammensetzungenInfo
- Publication number
- EP0301003B1 EP0301003B1 EP19870901840 EP87901840A EP0301003B1 EP 0301003 B1 EP0301003 B1 EP 0301003B1 EP 19870901840 EP19870901840 EP 19870901840 EP 87901840 A EP87901840 A EP 87901840A EP 0301003 B1 EP0301003 B1 EP 0301003B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- polyamide
- ether
- quinone
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
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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
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
Definitions
- the present invention relates to modified poly ⁇ phenylene ether-polyamide compositions having improved chemical resistance, processability, elongation proper ⁇ ties and/or impact strength as compared to unmodified compositions. More specifically, it relates to a resin composition which comprises a combination and/or the reaction product of a) one or more polyphenylene ether resins, b) one or more polyamide resins and c) at least, one quinone compound.
- the polyphenylene ether resins are characterized by a unique combination of chemical, physical and elec ⁇ trical properties over a temperature range of more than 600 ⁇ F., extending from a brittle point of about -275 ⁇ F. to a heat distortion temperature of about 375 ⁇ F.
- Ueno et al discloses polyphenyl ⁇ ene ether blends having improved chemical resistance without a loss of other mechanical properties by blend ⁇ ing therewith a polyamide and a specific compound selected from the group consisting essentially of A) liquid diene polymers, B) epoxy compounds and C) com ⁇ pounds having in the molecule both of i) a carbon- carbon double bond or carbon-carbon triple bond and ii) a carboxylic acid, acid anhydride, acid amide, imide, carboxylic acid ester, a ino or hydroxyl group.
- Kasahara et al discloses the_ use of a copolymer comprising units of a vinyl aromatic compound and either an alpha, beta-unsaturated dicar- boxylic acid anhydride or an imide compound thereof as a modifier to an impact resistant polyphenylene ether- -polyamide blend for improved heat resistance and oil resistance.
- novel polyphenylene ether polyamide blends having improved impact strength, elongation, chemical resistance, processability and/or heat resistance as compared to unmodified polyphenyl ⁇ ene ether-polyamide compositions as well as reduced water absorption as compared to polyamide alone.
- novel resin com- positions having the aforementioned properties compris ⁇ ing a combination of and/or the reaction product of a polyphenylene ether, a polyamide and a property improv ⁇ ing amount of a ⁇ uinone compuond.
- these comp ⁇ ositions may contain stabilizing and/or property improving amounts of primary or secondary amines.
- compositions of the present inven ⁇ tion may further comprise fillers as well as other property enhancing additives such as polymeric impact modifiers and/or inorganic reinforcing additives and/or other polymers including alkenyl aromatic polymers such as the styrenic polymers.
- other property enhancing additives such as polymeric impact modifiers and/or inorganic reinforcing additives and/or other polymers including alkenyl aromatic polymers such as the styrenic polymers.
- the exact physical configuration of the compositions of the present invention is not known, it is generally believed that the compositions comprise a dispersion of one polymer in the other. Applicants believe the likely configuration is wherein the polyphenylene ether is dispersed in a polyamide matrix, however, the inverse may also be possible particularly where the polyamide is present in only a minor amount.
- Applicants also contemplate that there may be present in the products produced hereby some graft polyphenylene ether-polyamide products.
- grafting if present, may be such that the quinone compound may, at least in part, promote grafting and/or act as a graft-linking agent itself.
- all such dispersions as well as graft, partially grafted and non-grafted products are within the full intended scope of the invention.
- polyphenylene ethers suitable for use in the practice of the present invention are well known in the art and may be prepared by any of a number of catalytic and non-catalytic processes from corresponding phenols or reactive derivatives thereof.
- Examples of poly ⁇ phenylene ethers and methods for their production are disclosed in U.S. Patent Nos. 3,306,874; 3,306,875; 3,257,357; 3,257,358; 3,337,501 and 3,787,361, all incorporated herein by reference.
- polyphenylene ether as used throughout this specification and the appended claims will include not only unsubstituted polyphenylene ether (made from phenol) but also polyphenylene ethers substituted with various substituents.
- the term also includes poly ⁇ phenylene ether copolymers, graft copolymers and block copolymers of alkenyl aromatic compounds, especially vinyl aromatic compounds, as disclosed below, and a polyphenylene ether.
- Suitable phenol compounds for the preparation of the polyphenylene ethers may be represented by the general formula:
- each Q is a monovalent substituent individually selected from the group consisting of hydrogen, halogen, aliphatic and aromatic hydrocarbon and hydrocarbonoxy radicals free of a tertiary alpha-carbon atom and halohydrocarbon and halohydrocarbonoxy radicals free of a tertiary alpha-carbon atom and having at least two carbon atoms between the halogen atom and the phenyl nucleus, and wherein at least one Q is hydrogen.
- phenol As specific examples of the phenol compound represented by the above formula, there may be given phenol; o-, m- and p- cresols; 2,6, 2,5, 2,4 and 3,5 dimethyIphenols; 2-methyl-6-phenyl-phenol; 2,6- diphenylphenol; 2,6-diethylphenol; 2-methyl-6-ethyl- phenol; and 2,3,5-, 2,3,6- and 2,4,6-trimethyIphenols. Two or more phenol compounds may be used in combination should copolymers be desired.
- copoly- phenylene ethers may also be prepared from a phenol compound of the above general formula with a phenol compound not represented by the above general formula including, for example, a dihydric phenol such as bis- phenol-A, tetrabromobisphenol-A, resorcinol or hydroquinione.
- a dihydric phenol such as bis- phenol-A, tetrabromobisphenol-A, resorcinol or hydroquinione.
- poly(2,6-dimethyl- 1,4-phenylene)ether for example, poly(2,6-dimethyl- 1,4-phenylene)ether; poly(2-methyl-l,4-phenylene) ether, poly(3-methyl-l,4-phenylene)ether; poly(2,6- diethyl-l,4-phenylene)ether; poly(2-methyl-6-allyl- 1,4-phenylene)ether; poly(2,6-dichloromethyl-l,4- phenylene)ether; poly(2,3,6-trimethyl-l,4-phenylene) ether; poly(2,3,5,6-tetramethyl-l,4-phenylene)ether; poly(2,6-dichloro-l,4-phenylene)ether; poly(2,6- diphenyl-1, -phenylene)ether; poly(2,5-dimethyl-l,4- phenylene)ether and the like.
- copolymers of the phenol compounds may also be used.
- Preferred polyphenylene ethers will have the formula:
- poly ⁇ phenylene ethers corresponding to the above formula can be found in the above referenced patents and include, among others: poly(2,6-dilauryl-l,4-phenylene)ether; poly(2,6-diphenyl-l,4-phenylene)ether; poly(2,6-dimethyoxy-l,4-phenylene)ether; poly(2,6-diethoxy-l,4-phenylene)ether; poly(2- methoxy-6-ethyoxy-l,4-phenylene)ether; poly(2-ethyl-6-stearyloxy-l,4-phenylene)ether; poly- (2,6-dichloro-l,4-phenylene)ether; poly(2-methyl-6- -phenyl-1,4-phenylene)ether poly(2,6-dibenzyl-l,4- -phenylene)ether; poly(2-eth
- an especially preferred family of polyphenylene ethers include those having a C 1 to C 4 alkyl substitution in the two positions ortho to the oxygen ether atom.
- Illustrative members of this class are: poly(2,6- dimethyl-1,4-phenylene)ether; poly(2,6-diethyl-l,4- phenylene)ether; poly(2-methyl-6-ethyl-l,4-phenyl- ene)ether; poly(2,6-dipropyl-l ,4-phenylene)ether; poly(2-ethyl-6-propy1-1,4-phenylene)ether; and the like; most preferably poly(2,6-dimethyl-l,4-phenyl- ene)ether.
- One method for the production of the above poly- phenylene ethers is by the oxidation of a phenol com ⁇ pound by oxygen or an oxygen-containing gas in the presence of a catalyst for oxidative coupling.
- a catalyst for oxidative coupling There is no particular limitation as to the choice of cataly ⁇ sts and any catalysts for oxidation polymerization can be employed.
- a catalyst comprising a cuprous salt and a tertiary amine and/or secondary amine, such as * cuprous chloride-trimethylamine and dibutylamine, cuprous acetate-triethylamine or cuprous chloride- -pyridine; a catalyst comprising a curpic salt, a tertiary amine, and an alkali metal hydroxide, such as cupric chloride-pyridine-potassium hydroxide; a cata ⁇ lyst comprising a manganese salt and a primary amine, such as manganese chloride-ethanolamine or manganese acetate-ethylenediamine; a catalyst comprising a mang ⁇ anese salt and an alcoholate or phenolate, such as manganese chloride-sodium methylate or manganese chloride-sodium phenolate; and a catalyst comprising a cobalt salt and a tertiary amine.
- a curpic salt such as cupric chloride-pyridine
- Polyamides suitable for the preparation of the compositions of the present invention may be obtained by polymerizing a monoamino- onocarboxylic acid or a lactam thereof having at least 2 carbon atoms between the amino and carboxylic acid group; or by polymerizing substantially equimolar proportions of a diamine which contains at least 2 carbon atoms between the amino groups and a dicarboxylic acid; or by polymerizing a monoaminocarboxylic acid or a lactam thereof as defined above together with substantially equimolecular propor- tions of a diamine and a dicarboxylic acid.
- the dicar ⁇ boxylic acid may be used in the form of a functional derivative thereof, for example an ester or acid chloride.
- substantially equimolecular proportions (of the diamine and of the dicarboxylic acid) is used to cover both strict equimolecular proportions and slight departures therefrom which are involved in conventional techniques for stabilizing the viscosity of the resultant polyamides.
- Examples of the aforementioned monoamino-mono- carboxylic acids or lactams thereof which are useful in preparing the polyamides include those compounds corf- taining 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 6-aminocaproic acid, butyrolactam, pivalolactam, caprolactam, capryl-lactam, enantholactam, undecanolactam, dodecanolactam and 3- and 4- aminobenzoic acids.
- Diamines suitable for use in the preparation of the polyamides include alkyl, aryl and alkyl-aryl diamines. Such diamines include, for example, those represented by the general formula:
- n is an integer of from 2 to 16, such as tri- methylenediamine, tetramethylenediamine, pentamethyl- enediamine, octamethylenediamine and especially hexa- methylenediamine, as well as trimethyl hexamethylene diamine, eta-phenylene diamine, meta-xylylene diamine and the like.
- the dicarboxylic acids may be aromatic, for example isophthalic and terephthalic acids or aliphatic, wherein the aliphatic dicarboxylic acids are of the formula: HOOC-Y-COOH wherein Y represents a divalent aliphatic group con ⁇ taining at least 2 carbon atoms, and examples of such acids are sebacic acid, octadecanedoic acid, suberic acid, glutaric acid, pimelic acid and adipic acid.
- polystyrene resin polystyrene resin
- nylons polystyrene resin
- polypyrrolidone polycaprolactam
- nylon 6 polycapryllactam
- nylon 8 polyhexamethylene adipamide
- nylon 11 polyundecanolactam
- nylon 12 polyhexamethylene azelaiamide
- nylon sebacamide polyhexamethylene sebacamide
- nylon 610 polyhexamethylene isophthalimide (nylon 6,1) polyhexamethylene terephthalamide (nylon 6,T) poiyamide of hexamethylene diamine (nylon 6,12) and n-dodeinedinic acid as well as polyamides resulting from terephthalic acid and/or isophthalic acid and trimethyl hexamethylene diamine, polyamides resulting from adipic acid and meta xylylenediamines, polyamides resulting from adipic acid,
- Copolymers of the foregoing polyamides or prepolymers thereof are also suitable for use in the practice of the present invention.
- Such copolyamides include copolymers of the following: hexamethylene adipamide/ (nylon 6,6/6) caprolactam hexamethylene adipamide/hexa- (nylon 6,6/61) methylene-isophthalamide hexamethylene adipamide/hexa- (nylon 6,6/6T) methylene-terephthalamide hexamethylene adipamide/hexa- (nylon 6,6/6,9) methylene-azelaiamide hexamethylene adipamide/hexa- (nylon 6,6/6,9 methylene-azelaiamide/caprolactam /6)
- Mixtures and/or copolymers of two or more of the foregoing polyamides or prepolymers thereof, respect ⁇ ively, are also within the scope of the present inven ⁇ tion.
- Preferred polyamides are the Nylons 6; 6,6; 11 and 12, most preferably Nylon 6,6. It is also to be understood that the use of the term "polyamides" herein and in the appended claims ⁇ s intended to include the toughened or super tough poly ⁇ amides.
- Super tough polyamides, or super tough nylons, as they are more commonly known, are available commer- cially, e.g. from E.I. duPont (Zytel® ST resins), Wilson Fiberfill (NY resins) , Badische (ULTRAMID® resins) , Allied (CARPION® resins) and Celanese (7000 series resins) , among others, or may be prepared in accordance with a number of U.S. Patents including, among others, Epstein - U.S. 4,174,358; Novak - U.S.
- these elastomeric polymers and co ⁇ polymers may be straight chain or branched as well as graft polymers and copolymers, including core-shell graft copolymers, and are characterized as having in ⁇ corporated therein either by copolymerization or by grafting on the preformed polymer, a monomer having functional and/or active or highly polar groupings capable of interacting with or adhering to the poly ⁇ amide matrix so as to enhance the toughness of the polyamide polymer.
- the blending ratio of polyphenylene ether to poly ⁇ amide is 5 to 95% by wt. preferably 30 to 70% by wt. of the former to 95 to 5% by wt., preferably 70 to 30% by wt. of the latter.
- polyamide is less than 5 wt. percent, its effect to improve solvent resistance is small, while when it exceeds 95 wt. percent, thermal properties such as heat distortion temperature and dimensional stability tend to become poor.
- the quinones employable in the prac ⁇ tice of the present invention may be substituted or non-substituted.
- the degree of substitution on the basic quinone structure is dependent upon the number of available sites, i.e. replaceable hydrogen atoms.
- Exemplary of the various substituents that may be pre ⁇ sent on the basic unsubstituted quinone structure in ⁇ clude halogen, e.g.
- hydrocarbon substituents including saturated and unsat- urated, branched and unbranched radicals of 1 to 40, preferably 1 to 8 carbon atoms selected from alkyl, aryl, arylalkyl, cycloalkyl, and the like, including halogenated derivatives thereof, and similar hydro- carbon radicals connected to the basic unsubstituted quinone structure through an oxygen, sulfur, phosphor ⁇ us, or other hetero atom bridge.
- Suitable quinones useful in the practice of the present invention include, 1,2- and 1,4-benzoquinone; 2,6-diphenylquinone; tetramethyl diquinone; 2,2' and
- the quinone compatibilizer will be employed in an amount suitable to enhance compatibility of the polyphenylene ether polyamide composition, particularly as evidenced by higher impact strength, as well as improve process- ability and/or other stress-strength characteristics including tensile elongation.
- the amount of quinone employed will be from about 0.05 to about 20, preferably from about 0.1 to about 4 percent by weight based on the weight of the total composition. Obviously, greater or lesser amounts may be employed; however, too high an amount may cause loss of certain properties and too small an amount may not be suffi ⁇ cient to produce any benefit.
- the specific amount of quinone compatibilizer to be employed to achieve optimum results for a qiven composition is dependent in part on the specific quinone compatibil ⁇ izer employed, the specific resinous polymers in the v composition and the weight ratio thereof as well as the process conditions and sequence employed in making the final compositions. In addition to the improved processability, impact strength and elongation, many of the compositions pre ⁇ pared in accordance with the present invention manifest improvements in other physical properties and characteristics including for example, reduced water absorption.
- the above-mentioned property improving quinone compound may be used alone or in combination with a primary or secondary amine.
- the presence of the amine is found to enhance the improvement of certain physical properties, especially brightness, when used in combin ⁇ ation with various quinone compatabilizers.
- Suitable amines include those primary and secondary amines having from 1 to about 20, preferably from 1 to about 10 carbon atoms. Illustrative of said suitable amines there may be given, methyl ethylamine, diethylamine, butylamine, dibutylamine, analine, n-octadecylamine and the like.
- the amount of the primary or secondary amine to be used is generally up to about 3% by wt., prefer ⁇ ably from about 0.35 to about 1% by wt..
- an additional modifier resin or resin combination to further improve the phys ⁇ ical properties, particularly the impact strength, and/or processability of the composition.
- modi ⁇ fier resins are well known in the art and are typically derived from one or more monomers selected from the group consisting of olefins, vinyl aromatic monomers, acrylic or alkyl acrylic acids and their ester deriva ⁇ tives as well as conjugated dienes.
- Suitable modifier resins include both homopolymers and copolymers, including random, block, radial block, graft and core-shell copolymers as well as combinations thereof.
- Polyolefins or olefin-based copolymer employable in the practice of the present invention include, among others, low density polyethylene, high density poly ⁇ ethylene, linear low density polyethylene, isotactic polypropylene, poly(1-butene) , poly(4-methyl-l-pen- tene) , propylene-ethylene copolymers, and the like.
- Additional olefin copolymers include copolymers of one or more alpha olefins, particularly ethylene, with co- polymerizeable monomers including for example vinyl acetate, acrylic acids and alkyl acrylic acids as well as the ester derivatives thereof including for example, ethylene acrylic acid, ethylacrylate, methacrylic acid, methyl methacrylate and the like.
- co- polymerizeable monomers including for example vinyl acetate, acrylic acids and alkyl acrylic acids as well as the ester derivatives thereof including for example, ethylene acrylic acid, ethylacrylate, methacrylic acid, methyl methacrylate and the like.
- an addi ⁇ tional class of olefin-based copolymers suitable for use herein include the ionomer resins, which may be wholly or partially neutralized with metal ions.
- a second class of modifier resins employable here ⁇ in 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 homopoly- styrenes 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 dis ⁇ closed in U.S. Patent Number 3,383,435, herein incor*- porated 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 dis ⁇ closed in U.S. Patent Number 3,383,435, herein incor*- porated by reference.
- ABS type 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, se ⁇ lected from the group consisting of monoalkenyl arene monomers and substituted derivatives thereof as well as acrylic monomers such as acrylonitriles and acrylic and alkyl acrylic acids and their esters.
- An especially preferred class of vinyl aromatic monomer derived polymer resins are the block copolymers comprising monoalkenyl arene blocks and hydrogenated, partially hydrogenated and non-hydrogenated conjugated diene blocks and represented as AB and ABA block co ⁇ polymers.
- Suitable AB type block copolymers are dis ⁇ closed in for example U.S. Patent Nos. 3,078,254; 3,402,159; 3,297,793; 3,265,765; and 3,594,452 and UK Patent No. 1,264,741, all herein incorporated by refer- ence.
- AB block copoly ⁇ mers there may be given: polystyrene-polybutadiene (SBR) polystyrene-polyisoprene and poly(alpha-methylstyrene)-polybutadiene.
- SBR polystyrene-polybutadiene
- Such AB block copolymers are available commercially from a number of sources including Phillips under the trademark Solprene.
- SBS polystyrene-polybutadiene-polystyrene
- SIS polystyrene-polyisoprene-polystyrene
- SBS polystyrene-polybutadiene-polystyrene
- SIS polystyrene-polyisoprene-polystyrene
- a particularly preferred class of such triblock copolymers are available commercially as CARIFLEX®, KRATON D® and KRATON G® from Shell.
- a third class of modifier resins suitable for use in the instant invention are those derived from conjugated dienes. While many copolymers containing conjugated dienes have been discussed above, additional conjugated diene modifier resins include for example ho opolymers and copolymers of one or more conjugated dienes including for example polybutadiene, butadiene- -styrene copolymers, isoprene-isobutylene copolymers, chlorobutadiene polymers, butadiene-acrylonitrile co ⁇ polymers, polyisoprene, and the like. Finally, ethyl- ene-propylene-diene monomer rubbers are also intended to be within the full scope of the present invention.
- EPDMs are typified as comprising predominately ethylene units, a moderate amount of propylene units and only a minor amount, up to about 20 mole % of diene monomer units.
- Many such EPDM's and processes for the production thereof are disclosed in U.S. Patent Numbers 2,933,480; 3,000,866; 3,407,158; 3,093,621 and 3,379,701, herein incorporated by reference.
- modifier resins employable in the instant invention are the core-shell type graft copolymers.
- these are characterized as having a predominately conjugated diene rubbery core or a predominately cross-linked acrylate rubbery core and one or more shells polymerized thereon and derived from monoalkenyl arene and/or acrylic monomers alone or, preferably, in combination with other vinyl monomers.
- Such core-shell copolymers are widely available commer ⁇ cially for example, from Rohm and Haas Company under the tradenames KM-611, KM-653 and KM-330, and are described in U.S. Patent Numbers 3,808,180; 4,034,013; 4,096,202; 4,180,494 and 4,292,233.
- the core-shell copolymers wherein an interpenetrating network of the resins employed characterizes the inter ⁇ face between the core and shell.
- the ASA type copolymers available from General Electric Company and sold as GELOYTM resin and described in U.S. Patent Number 3,944,631.
- All of such functionalized or activated polymers and copolymers may be directly blended with the ingredients to the present co posiions or, as described above, may be precompound with a polyamide or polyphenylene ether. It is especially preferred to precompounded the func- tionalized or activated rubbery polymer or copolymer with the polyamide to prepare a toughened or super tough polyamide which is then employed in preparing the polyphenylene ether-polyamide composition of the present invention.
- suitable modifier resins and high molecular weight rubbery materials which may be employed in the practice of the present invention in ⁇ clude for example thiokol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (e.g. polypropyl- ene oxide) , epichlorhydrin rubber, ethylene propylene rubber, thermoplastic polyester elastomers, thermo ⁇ plastic ether-ester elastomers and the like.
- the amount of the rubbery polymer used will be up to about 100 parts by weight, preferably from about 5 to about 50 parts by weight, most preferably from about 5 to about 25 parts by weight, based on 100 parts by weight of a mixture of polyphenylene ether and poly ⁇ amide. However, when the amount is less than 2 parts by weight, the effect of the rubbery polymer to improve impact resistance is poor. When the amount is more than 100 parts by weight, the impact resistance is much improved, however, some loss of other physical proper ⁇ ties may result. Thus, in the interest of balancing impact resistance and other physical properties, it is preferred to use less than 100 parts by weight of the rubbery polymer.
- poly ⁇ phenylene ether-polyamide resin compositions of the present invention may further comprise other reinforc ⁇ ing additives, including glass fibers, carbon fibers, mineral fillers and the like as well as various flame retardants, colorants, stabilizers and the like known to those skilled in the art.
- reinforcing additives When employed in the practice of the present invention, reinforcing additives should be used in an amount up to no more than about 50 wt. % based on the total composition, preferably no more than about 30 wt. %.
- Especially preferred reinforcing additives are the filamentous and chopped glass fibers. Such glass fibers may be untreated or, preferably, treated with a silane or titanate coupling agent, and are well known in the art and widely available from a number of manufacturers.
- Suitable stabilizers for use in the practice of the present invention generally include most any of the known thermal and oxidative stabilizers suitable for use with either polyamides or polyphenylene ethers. Especially preferred are those stabilizers suitable for use with polyamides. For example, liquid phosphates and hindered phenols may be employed as well as stabil ⁇ izer packages encompassing combinations of hindered phenols and potassium and cuprous salts.
- the method for producing the resin compositions of the present invention is not particularly limited, and the conventional methods are satisfactorily employed. Generally, however, melt blending methods are desir ⁇ able. The time and temperature required for melt- blending are not particularly limited, and they can properly be determined according to the composition of the material.
- the temperature varies somewhat with the blending ratio of the polyphenylene ether to polyamide, but it is generally within a range of 270° to 350°C.
- a prolonged time and/or a high shear rate is desirable for mixing, but the deterioration of the resin composi- tion advances. Consequently, the time needs to be de ⁇ termined taking into account these points.
- melt-blending methods may be used, if it can handle a molten viscous mass.
- the method may be applied in either a batchwise form or a continuous form. Specifically, extruders, Bambury mixers, roll ⁇ ers, kneaders and the like may be exemplified.
- sequence of processing steps in the prepar ⁇ ation of the present invention may also vary widely, with certain sequences, as follows, providing superior properties in the final product as compared to other.
- sequences for example, all ingredients may be initial ⁇ ly and directly added to the processing system. In this process the ingredients may be premixed by dry blending and subsequently fed to the extruder or melt- blending apparatus or the ingredients individually may be added to the melt-blending apparatus.
- the polyamide may be precompounded with the rubbery polymer or copolymer, particularly a functionalized rubbery polymer or copolymer, to create a toughened or supertough polyamide.
- the polyphenylene ether with the compatibilizer, alone or together with the rubbery polymer or copolymer.
- other precompounded materials may be prepared and subsequently compounded with the remaining ingredient(s) -to prepare the final composition.
- precompounding may be achieved in two steps whereby the precompounded material is recompounded together with the remaining ingredients or wherein an extruder having downstream feed port(s) is employed such that two or more ingredients are added at the throat of the screw and subsequently compounded and the remaining ingredients added to the melt via the downstream feed port. Finally, where an ingredient is to be precompounded, one can precompound all or only a portion of that ingredient. In essence, any sequence of precompounding may be employed in the practice of the present invention.
- polyphenylene ether 3 70 70 70 50 50 50 50 polyamide 6,6 30 30 30 50 50 50 1, -benzoquinone — 1. .0 2. 0 — 1. 0 — — tetramethyl diquinone 1.0 2,6-diphenylquinone 1.0
- poly(2,6-diemthy1-1, -phenylene)ether from General Electric Company
- polyamide 6,6 from E.I. duPont
- Styrene hydrogenated polybutadiene styrene triblock copolymer from Shell
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1987/000259 WO1988006172A1 (en) | 1987-02-12 | 1987-02-12 | Modified polyphenylene ether-polyamide compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0301003A1 EP0301003A1 (de) | 1989-02-01 |
EP0301003B1 true EP0301003B1 (de) | 1991-01-02 |
Family
ID=22202275
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19870901840 Expired EP0301003B1 (de) | 1987-02-12 | 1987-02-12 | Modifizierte polyphenylenäther-polyamidzusammensetzungen |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0301003B1 (de) |
JP (1) | JPH01500271A (de) |
DE (1) | DE3766960D1 (de) |
WO (1) | WO1988006172A1 (de) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1155583A (en) * | 1979-08-08 | 1983-10-18 | Katsuji Ueno | Impact resistant blends of polyphenylene oxide and polyamide resins |
NL8301284A (nl) * | 1983-04-12 | 1984-11-01 | Gen Electric | Polymeermengsel dat een polyfenyleenether en eventueel een polystyreen en/of een met rubber gemodificeerd polystyreen bevat en daaruit gevormde voorwerpen. |
-
1987
- 1987-02-12 DE DE8787901840T patent/DE3766960D1/de not_active Expired - Fee Related
- 1987-02-12 WO PCT/US1987/000259 patent/WO1988006172A1/en active IP Right Grant
- 1987-02-12 EP EP19870901840 patent/EP0301003B1/de not_active Expired
- 1987-02-12 JP JP50134187A patent/JPH01500271A/ja active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH01500271A (ja) | 1989-02-02 |
EP0301003A1 (de) | 1989-02-01 |
JPH055862B2 (de) | 1993-01-25 |
DE3766960D1 (de) | 1991-02-07 |
WO1988006172A1 (en) | 1988-08-25 |
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