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WO1992001749A1 - Compositions d'ether de polyphenylene-sulfure de polyarylene - Google Patents

Compositions d'ether de polyphenylene-sulfure de polyarylene Download PDF

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Publication number
WO1992001749A1
WO1992001749A1 PCT/US1991/002139 US9102139W WO9201749A1 WO 1992001749 A1 WO1992001749 A1 WO 1992001749A1 US 9102139 W US9102139 W US 9102139W WO 9201749 A1 WO9201749 A1 WO 9201749A1
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Prior art keywords
polyphenylene ether
polyarylene sulfide
prepared
composition
reaction
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PCT/US1991/002139
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English (en)
Inventor
Timothy Mark Sivavec
Sharon Mccormick Fukuyama
Andrew James Caruson
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General Electric Company
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Publication of WO1992001749A1 publication Critical patent/WO1992001749A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0245—Block or graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0286—Chemical after-treatment
    • C08G75/0295—Modification with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L81/02—Polythioethers; Polythioether-ethers
    • 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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; 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

  • This invention relates to the preparation of compatible polyarylene sulfide-polyphenylene ether compositions, and more particularly to the preparation of copolymer-containing compositions.
  • the polyphenylene ethers are a widely used class of thermoplastic engineering resins characterized by excellent hydrolytic stability, dimensional stability, toughness, heat resistance and dielectric properties. However, they are . deficient in certain other properties such as solvent resistance.
  • polyarylene sulfides are crystalline engineering thermoplastics with high crystalline melting temperatures, typically on the order of 285 * C, and are characterized by low flammability, high modulus and excellent resistance to aggressive chemicals and solvents.
  • glass transition temperatures are very low, typically as low as 85'C; as a consequence, heat distortion temperatures are low in the absence of reinforcement with fillers such as glass fiber.
  • polyarylene sulfides are very brittle, as evidenced by a tensile elongation for polyphenylene sulfide usually no greater than about 2.5% and frequently below 1%.
  • polyarylene sulfide- polyphenylene ether blends could be prepared which would have such properties as high solvent resistance, high heat distortion temperature, good ductility and resistance to flammability.
  • blends of this type are incompatible and undergo phase separation and delamination, as a result of little or no phase interaction between the two resin phases. Molded parts made from such blends are typically characterized by low tensile and impact strength.
  • polyarylene sulfide- polyphenylene ether blends can be compatibilized by incorporating therein a copolymer of the two resins, prepared from polymers in which various functional groups have been incorporated.
  • This method of compatibilization is disclosed, for example, in Example 1 of EP-A-0341422, which is directed to a composition prepared from poly(2, 6-dimethyl-l,4- phenylene ether) , a polyphenylene sulfide and the product obtained by melt blending the aforesaid polyphenylene ether with trimellitic anhydride acid chloride.
  • compositions of that application are prepared from a polyhaloaromatic compound, an alkali metal sulfide, an organic amide and, optionally, an alkali metal carboxylate.
  • the present invention provides a method for preparing a composition comprising polyphenylene ether- polyarylene sulfide copolymer molecules which comprises melt blending a polyarylene sulfide containing amine groups with a capped polyphenylene ether prepared by the reaction of a polyphenylene ether with at least one trimellitic anhydride salicylate ester of the formula
  • R 1 is a C ⁇ -6 alkyl or a C ⁇ -io aromatic hydrocarbon
  • the polyarylene sulfides employed in the present invention are known polymers containing arylene groups separated by sulfur atoms . They include polyphenylene sulfides (hereinafter "PPS") and substituted polyphenylene sulfides .
  • PPS is often preferred.
  • PPS is typically prepared by the reaction of p-dichlorobenzene with sodium sulfide, optionally with the use of a minor proportion of 1,3,5- trichlorobenzene as a branching agent.
  • melt flow characteristics of the polyarylene sulfides used according to this invention are not critical; values in the range of 20-1000 g./lO min. (315'C, 5 kg. load) are typical.
  • polyarylene sulfides can be "cured" by heating in contact with an oxygen-containing gas (usually air) at temperatures above about 200 * C, resulting in a substantial decrease in melt flow and, apparently, a concomitant increase in molecular weight. While the exact nature of the curing reaction is not known, it appears to involve branching and/or chain extension, which probably occurs thermally or by oxidation of some type. It is frequently preferred to employ cured polyarylene sulfides in the present invention. Curing may be performed either before or after amine functionalization; it is often especially preferred to cure at both times, in order to counteract the decrease in molecular weight as a result of polymer chain scission during the reaction with an amine group-containing disulfide.
  • an oxygen-containing gas usually air
  • Curing is typically conducted in the solid or liquid state at temperatures in the range of 225-350"C for time periods of 2-6 hours.
  • the polyarylene sulfide contain amine groups, preferably primary amine groups. They may be provided in a number of ways .
  • One of these comprises the reaction of a dihalodiaryl sulfide with an alkali metal sulfide to form a halogen- terminated polyarylene sulfide, which then undergoes further reaction with an aminothiophenol with elimination of hydrogen halide to form a polyarylene sulfide having the required amine substituents on the end groups .
  • the polyarylene sulfide is prepared by the reaction of an alkali metal sulfide with a mixture of dichloroaromatic compounds and/or monochloroaromatic compounds (used as chain termination agents) , including at least one such compound which contains the required amine group.
  • a third method is the reaction of a polyarylene sulfide with a disulfide containing amine groups, typically at temperatures in the range of about 225-375"C, in the melt or in solution in a suitable high boiling solvent such as 1- chloronaphthalene.
  • Three reactively capped PPS compositions were prepared from the PPS employed in Preparation I, using 1.52%, 0.5% and 0.1%, respectively, of bis (4-aminophenyl) disulfide. Preparation was by melt blending in a counterrotating twin screw extruder at 400 rpm., at temperatures in the range of 135-302 * C. The compositions prepared from 0.5% and 0.1% disulfide were easily stranded, affording somewhat brittle, wire-like strands. The composition prepared from 1.52% disulfide was stranded with difficulty.
  • Samples comprising about 100 mg. of each uncured and cured composition were placed between two pieces of polytetrafluoroethylene-coated foil held between two stainless steel plates, placed in a Carver press preheated to 300-310"C, equilibrated for 1 minute and pressed at 1050 kg./cm. 2 .
  • the pressure was released and the polymer and foil sheets were immediately quenched in a water bath to prevent crystallization of the PPS chains, after which they were subjected to quantitative infrared analysis which showed, in each instance, the presence of amine groups. It is thus apparent that the amine functionality was not lost upon curing, although the proportion thereof decreased slightly.
  • polyarylene sulfides prepared by conventional methods contain a measurable proportion of amine groups even if one of the above-described methods of preparation is not employed. This is probably a result of incorporation in the molecule of moieties derived from nitrogen-containing solvents such as N- methy1-2-pyrrolidone.
  • the precise proportion of amine groups which must be present on the polyarylene sulfide can readily be determined by simple experimentation. All that is required is the preparation and analysis of a reaction product with a polyphenylene ether containing amine-reactive (e.g., epoxy or carboxy) groups . If a substantial proportion of copolymer formation is detected, it may be assumed that the required amine groups were present in the necessary proportion on the polyarylene sulfide. In general, some degree of copolymer formation in accordance with the invention is observed if the nitrogen content of the polyarylene sulfide is above about 800 ppm., even if no detectable proportion of amino nitrogen is present. The reasons for this are not fully understood. Preferable nitrogen proportions are in the range of about 1200-3000 ppm., since a favorable tendency toward copolymer formation is often observed in that range.
  • the other reactant employed in the method of this invention is chosen from a specific class of capped polyphenylene ethers .
  • the polyphenylene ethers from which they are prepared are a well known class of polymers widely used in industry, especially as engineering plastics in applications requiring toughness and heat resistance. Since their discovery, they have given rise to numerous variations and modifications all of which are applicable to the present invention, including but not limited to those described hereinafter.
  • the polyphenylene ethers comprise a plurality of structural units having the formula
  • each Q 1 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 Q 2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q 1 .
  • 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.
  • any alkyl radicals are straight chain rather than branched.
  • each Q 1 is alkyl or phenyl, especially C ⁇ - 4 alkyl
  • each Q 2 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-dimethy1-1, 4-phenylene ether units. Suitable copolymers include random copolymers containing such units in combination with (for example) 2,3, 6-trimethyl-l, 4- phenylene ether units. Many suitable random copolymers, as well as homopolymers, are disclosed in the patent literature.
  • 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 .
  • 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, provided substantial proportions of free hydroxy groups remain present .
  • 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 Q 1 is methyl and each Q 2 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 Q 1 and one Q 2 is methyl and the other Q 2 is hydrogen) .
  • catalyst systems are known for the preparation of polyphenylene ethers by oxidative coupling. There is no particular limitation as to catalyst choice and any of the known catalysts can be used. For the most part, they contain at least one heavy metal compound such as a copper, manganese or cobalt compound, usually in combination with various other materials.
  • a first class of preferred catalyst systems consists of those containing a copper compound.
  • Such catalysts are disclosed, for example, in U.S. Patents 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 .
  • the manganese is present as a complex with one or more complexing and/or chelating agents such as dialkylamines, alkanola ines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds, ⁇ -hydroxyoximes (monomeric and polymeric), o-hydroxyaryl oximes and ⁇ -diketones .
  • complexing and/or chelating agents such as dialkylamines, alkanola ines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds, ⁇ -hydroxyoximes (monomeric and polymeric), o-hydroxyaryl oximes and ⁇ -diketones .
  • 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
  • each R 2 is independently hydrogen or alkyl, with the proviso that the total number of carbon atoms in both R 2 radicals is 6 or less; and each R 3 is independently hydrogen or a C - ⁇ primary alkyl radical.
  • each R 2 is hydrogen and each R 3 is alkyl, especially methyl or n-butyl.
  • Polymers containing the aminoalkyl-substituted end ' groups of formula III may be obtained by incorporating an appropriate primary or secondary monoamine as one of the constituents of the oxidative coupling reaction mixture, especially when a copper- or manganese-containing catalyst is used.
  • Such amines, especially the dialkylamines and preferably di-n-butylamine and dimethylamine frequently become chemically bound to the polyphenylene ether, most often by replacing one of the ⁇ -hydrogen atoms on one or more
  • the principal site of reaction is the Q 1 radical adjacent to the hydroxy groups on the terminal unit of the polymer chain.
  • the aminoalkyl-substituted end groups may undergo various reactions, probably involving a quinone methide-type intermediate of the formula
  • Polymers with 4-hydroxybiphenyl end groups of formula IV are typically obtained from reaction mixtures in which a by-product diphenoquinone of the formula
  • polyphenylene ethers contemplated for use in the present invention include all those presently known, irrespective of variations in structural units or ancillary chemical features .
  • the capped polyphenylene ether used in the method of this invention is prepared by the reaction of the above- described polyphenylene ether with at least one trimellitic anhydride salicylate ester of formula I.
  • R 1 may be C ⁇ -6 alkyl such as methyl, ethyl, 1-propyl, 2-propyl,
  • trimellitic anhydride ester is the 4- (phenyl salicylate) or 4-(o-carbophenoxyphenyl) ester. Trimellitic anhydride salicylate esters useful for capping may be prepared by conventional methods.
  • a particularly convenient method is the reaction of TAAC with an ester of salicylic acid, most often phenyl salicylate.
  • the reaction between the polyphenylene ether and the trimellitic anhydride ester may be conducted in solution or in the melt. Melt reactions are usually preferred; they may be performed in conventional melt blending apparatus of both the batch and continuous type. They are often preferably conducted continuously in an extruder, by reason of the excellent properties of extruded materials and the availability of extruders in commercial polymer processing facilities. Typical conditions include temperatures in the range of 225-350"C, preferably 275-325'C.
  • the proportion of trimellitic anhydride salicylate ester employed is not critical and will depend on the degree of dicarboxylate capping desired. It is most often about 3-5% but may be as high as about 10% by weight based on polyphenylene ether.
  • melt blending When melt blending is employed in the preparation of the capped polyphenylene ether, it is essential that it be conducted with application of vacuum. In general, blending processes involving pressures below about 20 torr for at least a portion of the process are desirable. Extrusion processes of this type may be conducted by means of vacuum venting, whereby a vacuum is drawn on at least one vent in the extruder.
  • the reaction between the polyphenylene ether and the trimellitic anhydride salicylate ester may be facilitated if the polyphenylene ether has also been melt processed under vacuum prior to formation of the blend with said ester.
  • This melt processing operation may also be conveniently effected via extrusion with vacuum venting.
  • polyphenylene ether- polyamide compositions prepared from the dicarboxylate-capped polyphenylene ethers of the invention may be improved by repeated extrusion of the capped polyphenylene ether.
  • Optimum conditions are often provided if the capped polyphenylene ether is again melt processed (e.g., reextruded) at least once, also under vacuum.
  • the preparation of the dicarboxylate-capped polyphenylene ethers is illustrated by the following examples. All parts are by weight.
  • the polyphenylene ether employed was a commercially available poly(2, 6-dimethyl-l,4- phenylene ether) having an intrinsic viscosity in chloroform at 25 * C of 0.42 dl./g.
  • Sample 1 was subjected to no treatment following precipitatio and.drying, sample 2 was extruded once with vacuum venting, and sample 3 was extruded twice with vacuum venting.
  • Copolymer formation according to the present invention is believed to be the result of reaction between the dicarboxylate end groups of the polyphenylene ether and amine groups in the polyarylene sulfide, forming imide linkages.
  • the dicarboxylate-capped polyphenylene ether and polyarylene sulfide are heated together in solution or, preferably, in the melt.
  • melt processing under vacuum is especially preferred and extrusion with vacuum venting is most preferred.
  • the reaction temperature is typically within the range of about 100-350'C.
  • the proportions of functionalized polyphenylene ether and polyarylene sulfide are not critical and may be adjusted over a wide range to yield copolymer compositions having the desired properties.
  • the polyphenylene ether- polyarylene sulfide compositions generally contain about 5-75% by weight polyphenylene ether and about 25-95% polyarylene sulfide.
  • the copolymer compositions comprise only partially copolymer, with the balance being a polyphenylene ether-polyarylene sulfide blend. It is also within the scope of the invention to incorporate in the composition uncapped polyphenylene ether and/or non-amine- functionalized polyarylene sulfide, said uncapped and/or unfunctionalized polymers frequently comprising up to about 50% by weight of total polyphenylene ether and polyarylene sulfide. Optimum properties are usually obtained when no uncapped polyphenylene ether is separately added; the opposite may be true, however, in regard to unfunctionalized polyarylene sulfide.
  • the polyphenylene ether-polyarylene sulfide compositions may also contain ingredients other than the copolymer, polyphenylene ether and polyarylene sulfide.
  • a particularly useful other ingredient in many instances is at least one elastomeric impact modifier which is compatible with the polyphenylene ether. It is generally present in the amount of about 5-25% by weight of resinous components.
  • Impact modifiers for polyphenylene ether 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 poly(1-butene) , poly(4-methyl-l- pentene) , propylene-ethylene copolymers and the like.
  • Additional olefin copolymers include copolymers of one or more ⁇ -olefins with copolymerizable monomers including, for example, acrylic acids and alkylacrylic acids as well as the ester derivatives thereof including, for example, ethylacrylic acid, ethyl acrylate, ethacrylic acid, methyl methacrylate and the like.
  • the ionomer resins which may be wholly or partially neutralized with metal ions .
  • a particularly useful class of impact modifiers are those derived from the vinyl aromatic monomers . • These include, for example, modified and unmodified polystyrenes, ABS type graft copolymers, AB and ABA type block and radial block copolymers and vinyl aromatic conjugated diene core- shell graft copolymers .
  • Modified and unmodified polystyrenes include homopolystyrenes and rubber modified polystyrenes, such as butadiene rubber-modified polystyrene (otherwise referred to as high impact polystyrene or HIPS) .
  • Additional useful polystyrenes include copolymers of styrene and various monomers, including, for example, poly (styrene-acrylonitrile) (SAN) , styrene-butadiene copolymers as well as the modified alpha- and para-substituted styrenes and any of the styrene resins disclosed in U.S. Patent 3,383,435, herein incorporated by reference.
  • SAN poly (styrene-acrylonitrile)
  • styrene-butadiene copolymers as well as the modified alpha- and para-substituted styrenes and any of the styrene resins disclosed in U.S. Patent 3,383,435, herein incorporated by reference.
  • ABS types of graft copolymers are typified as comprising a rubbery polymeric backbone derived from a conjugated diene alone or in 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) blocks and represented as AB and ABA block copolymers .
  • the conjugated diene blocks may be selectively hydrogenated.
  • Suitable AB type block copolymers are disclosed in, for example, U.S. Patents 3,078,254; 3,402,159; 3,297,793; 3,265,765 and 3,594,452 and UK Patent 1,264,741, all incorporated herein by reference.
  • Examples of typical species of AB block copolymers are 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 Petroleum under the trademark SOLPRENE.
  • triblock copolymers examples include polystyrene-polybutadiene-polystyrene (SBS) , polystyrene- polyisoprene-polystyrene (SIS), pol ( ⁇ -methylstyrene) - polybutadiene-poly- ( ⁇ -methylstyrene) and poly(CC— methylstyrene) -polyisoprene-poly- (OC— ⁇ meth lstyrene) .
  • triblock copolymers are available commercially as CARIFLEX®, KRATON D® and KRATON G® from Shell.
  • conjugated dienes Another class of impact modifiers is derived from conjugated dienes . While many copolymers containing 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, butadiene-glycidyl methacrylate copolymers, isoprene-isobutylene copolymers, chlorobutadiene polymers, butadiene-acrylonitrile copolymers, polyisoprene, and the like. Ethylene-propylene-diene monomer rubbers may also be used.
  • EPDM's are typified as comprising predominantly ethylene units, a moderate amount of propylene units and up to about 20 mole percent of non-conjugated diene monomer units.
  • Many such EPDM's and processes for the production thereof are disclosed in U.S. Patents 2,933,480; 3,000,866; 3,407,158; 3,093,621 and 3,379,701, incorporated herein by reference .
  • Other suitable impact modifiers are the core-shell type graft copolymers.
  • these have a predominantly conjugated diene rubbery core or a predominantly cross-linked acrylate rubbery core and one or more shells polymerized thereon and derived from monoalkenylarene and/or acrylic monomers alone or, preferably, in combination with other vinyl monomers.
  • core-shell copolymers are widely available commercially, for example, from Rohm and Haas Company under the trade names KM- 611, KM-653 and KM-330, and are described in U.S. Patents 3,808,180; 4,034,013; 4,096,202; 4,180,494 and 4,292,233.
  • core-shell copolymers wherein an interpenetrating network of the resins employed characterizes the interface between the core and shell.
  • ASA type copolymers available from General Electric Company and sold as GELOYTM resin and described in U.S. Patent 3,944,631.
  • GELOYTM resin available from General Electric Company and sold as GELOYTM resin and described in U.S. Patent 3,944,631.
  • Suitable impact modifiers include Thiokol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (e.g., polypropylene oxide) , epichlorohydrin rubber, ethylene- propylene rubber, thermoplastic polyester elastomers and thermoplastic etherester elastomers.
  • the preferred impact modifiers are block (typically diblock, triblock or radial teleblock) copolymers of alkenylaromatic compounds and olefins or dienes .
  • at least one block is derived from styrene and at least one other block from at least one of butadiene, isoprene, ethylene and butylene.
  • the triblock copolymers with polystyrene end blocks and olefin- or diene- derived midblocks .
  • the weight average molecular weights of the impact modifiers are typically in e range of about 50,000-300,000.
  • Block copolymers of this type are commercially available from Shell Chemical Company under the trademark KRATON, and include KRATON D1101, G1650, G1651, G1652, G1657 and G1702.
  • copolymer-containing compositions include fillers, flame retardants, colorants, stabilizers, antistatic agents, mold release agents and the like, used in conventional amounts. The presence of other resinous components is also contemplated.
  • the invention is illustrated by the following examples. All parts and percentages are by weight.
  • the polyphenylene ether employed was a poly(2, 6-dimethyl-l, 4- phenylene ether) having an intrinsic viscosity of 0.41 dl/g. in chloroform at 25 * C.
  • Dry blends of capped polyphenylene ethers similar to those obtained in Preparations IV to X, the amine- functionlized PPS of Preparation II and a commercially available triblock copolymer with polystyrene endblocks having weight average molecular weights of 29,000 and hydrogenated butadiene midblock having a weight average molecular weight of 116,000 were prepared and extruded on a twin-screw extruder at temperatures from 130-280"C, with vacuum venting.
  • the extrudates were quenched in water, peiletized and molded into test specimens which were tested for tensile properties (ASTM method D638) , flexural properties (ASTM method D790) and heat distortion temperature at 1.8 MPa. (ASTM method D648) .
  • the results are given in Table II, in comparison with a control employing uncapped vacuum-vented polyphenylene ether .
  • Solutions were prepared from 50 grams of various capped polyphenylene ethers similar to those obtained in Preparations IV to X and 50 grams of the product of Preparation II in 133 ml. of 1-chloronaphthalene. Said solutions were heated at 250"C for 12 hours, after which the polymers were precipitated by pouring into acetone in a blender, slurried repeatedly in acetone and extracted in a Soxhlet extractor with acetone for 24 hours to remove traces of 1-chloronaphthalene. The resulting solids were weighed and extracted with chloroform for 3 days in a Soxhlet extractor to remove uncopolymerized polyphenylene ether.
  • Polyphenylene ether % capping agent 8 6 Copolymerized polyphenylene ether 75 25.2

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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)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Abstract

On prépare des compositions compatibles contenant un copolymère, en faisant réagir un éther de polyphénylène recouvert de salicylate, préparé de préférence par la réaction d'un éther de polyphénylène avec un ester de salicylate phénylique anhydride trimellitique, avec un sulfure de polyarylène contenant des groupes amine, de préférence préparé par la réaction d'un sulfure de polyarylène avec un bisulfure contenant des groupes amine. Ces compositions peuvent également contenir des modificateurs d'impact compatibles avec l'éther de polyphénylène.
PCT/US1991/002139 1990-07-16 1991-03-28 Compositions d'ether de polyphenylene-sulfure de polyarylene WO1992001749A1 (fr)

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US553,035 1990-07-16

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0635548A1 (fr) * 1993-07-16 1995-01-25 Mitsubishi Chemical Corporation Composition de résine thermoplastique
US5504165A (en) * 1995-03-17 1996-04-02 General Electric Company Poly(phenylene ether)-poly(arylene sulfide)resin compositions.
EP0752449A3 (fr) * 1995-06-07 1997-01-22 General Electric Company Compositions à partir de polyphénylèneéther, polyarylènesulfide et un composé orthoester
US5612401A (en) * 1995-03-17 1997-03-18 General Electric Company Compositions of poly(phenylene ether) poly(arylene sulfide) polyester resins and compatibilizer compound
US6303708B1 (en) 1995-03-17 2001-10-16 General Electric Company Functional poly(phenylene ether)/poly(arylene sulfide)/epoxy function alpha olefin elastomer/elastomeric block copolymer/metal salt compositions and process for making thereof
WO2022023735A1 (fr) 2020-07-28 2022-02-03 Femtogenix Limited Agents cytotoxiques

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6714510B2 (ja) * 2013-08-27 2020-06-24 ティコナ・エルエルシー 炭化水素取り込みの低い熱可塑性組成物

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US4808671A (en) * 1988-04-21 1989-02-28 General Electric Company Catalytic method of preparing carboxy derivatives of polyphenylene ethers
EP0341422A2 (fr) * 1988-05-09 1989-11-15 General Electric Company Mélange de polymères comprenant un poly(éther de phénylène) et un poly(sulfure d'arylène)
JPH0280458A (ja) * 1988-09-16 1990-03-20 Mitsubishi Gas Chem Co Inc 新規な耐熱性樹脂組成物

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US4808671A (en) * 1988-04-21 1989-02-28 General Electric Company Catalytic method of preparing carboxy derivatives of polyphenylene ethers
EP0341422A2 (fr) * 1988-05-09 1989-11-15 General Electric Company Mélange de polymères comprenant un poly(éther de phénylène) et un poly(sulfure d'arylène)
JPH0280458A (ja) * 1988-09-16 1990-03-20 Mitsubishi Gas Chem Co Inc 新規な耐熱性樹脂組成物

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PATENT ABSTRACTS OF JAPAN vol. 014, no. 270 (C - 727)<4213> 12 June 1990 (1990-06-12) *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0635548A1 (fr) * 1993-07-16 1995-01-25 Mitsubishi Chemical Corporation Composition de résine thermoplastique
US5541243A (en) * 1993-07-16 1996-07-30 Mitsubishi Chemical Corporation Thermoplastic resin composition
US5504165A (en) * 1995-03-17 1996-04-02 General Electric Company Poly(phenylene ether)-poly(arylene sulfide)resin compositions.
EP0732367A3 (fr) * 1995-03-17 1997-01-22 Gen Electric Compositions de résines à partir de polyéther de phénylène et de polysulfure d'arylène
US5612401A (en) * 1995-03-17 1997-03-18 General Electric Company Compositions of poly(phenylene ether) poly(arylene sulfide) polyester resins and compatibilizer compound
US6303708B1 (en) 1995-03-17 2001-10-16 General Electric Company Functional poly(phenylene ether)/poly(arylene sulfide)/epoxy function alpha olefin elastomer/elastomeric block copolymer/metal salt compositions and process for making thereof
EP0752449A3 (fr) * 1995-06-07 1997-01-22 General Electric Company Compositions à partir de polyphénylèneéther, polyarylènesulfide et un composé orthoester
US5837758A (en) * 1995-06-07 1998-11-17 General Electric Company Compositions of poly (phenylene ether), poly (arylene sulfide) and ortho ester compounds
WO2022023735A1 (fr) 2020-07-28 2022-02-03 Femtogenix Limited Agents cytotoxiques

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JPH05500535A (ja) 1993-02-04

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