WO1992013015A1 - Preparation et utilisation de compositions polymeres fonctionnalisees - Google Patents

Preparation et utilisation de compositions polymeres fonctionnalisees Download PDF

Info

Publication number
WO1992013015A1
WO1992013015A1 PCT/US1991/000474 US9100474W WO9213015A1 WO 1992013015 A1 WO1992013015 A1 WO 1992013015A1 US 9100474 W US9100474 W US 9100474W WO 9213015 A1 WO9213015 A1 WO 9213015A1
Authority
WO
WIPO (PCT)
Prior art keywords
phase
copolymer
weight
weight percent
monomer
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.)
Ceased
Application number
PCT/US1991/000474
Other languages
English (en)
Inventor
David E. Henton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to JP3506387A priority Critical patent/JPH06504296A/ja
Priority to EP9191905558A priority patent/EP0568528A4/fr
Priority to PCT/US1991/000474 priority patent/WO1992013015A1/fr
Publication of WO1992013015A1 publication Critical patent/WO1992013015A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Definitions

  • This invention relates to preparation and use of a functionalized polymeric composition comprising two normally incompatible polymers. Specifically, it relates to a polymeric composition having functional groups, said polymeric composition comprising a first phase which comprises a copolymer having a reactive functional group, and a second phase comprising a copolymer having a reactive functionality capable Of reacting with the functional groups of the first copolymer, the second phase being dispersed with the first phase.
  • the compatibility of the resulting copolymers is dependent upon the amount of copolymerizable comonomer incorporated into the copolymer matrix.
  • a copolymer of styrene and glycidyl methacrylate (GMA) may be compatible with a preformed polymer, whereas a different copolymer containing a greater amount or different type of comonomer may be incompatible with the same preformed polymer. In the latter event, blending of the preformed polymer and the comonomer does not result in an improved polymeric composition.
  • manufacturers who desire to blend two normally incompatible polymers generally polymerize the monomers of one polymer in the presence of the preformed second polymer. During this process, chain transfer, or reaction, with the preformed polymer occurs and some of
  • the first polymer is polymerized from a site on the preformed polymer.
  • the prior art technique is limited to preformed polymers which have active hydrogens capable of being extracted by radicals or reactive - i- groups that can copolymerize with the growing polymer. Most polymers can not be used in this process because of the lack of reactivity. This technique also requires that the preformed polymer be soluble or dispersible in a solvent or monomer system suitable for polymerization 0 of the first monomer.
  • a first broad aspect of the invention is a method for making a polymeric composition that is capable of being formed into an article having good impact and/or ductility properties, which method includes the step of melt blending a first polymeric phase with at least a second polymeric phase, in a weight ratio within the range of 1:9 to 9:1, characterized by the steps of:
  • the first phase comprising a first copolymer being formed from a first monomer mixture which comprises at least 70 weight percent of a monovinylidene monomer, and up to 30 weight percent of an ethylenically unsaturated comonomer copolymerizable with the monovinylidene monomer and additionally comprising at least one reactive epoxide functionality capable of reacting after the first copolymer is formed, said weight percents being based on the total weight of the first monomer mixture, wherein the first copolymer has a melt index, as determined by ASTM D-1238 Condition G, of between 0.1 g/10 minutes to 40 g/10 minutes, and a number average molecular weight, as determined by gel permeation, of between 20,000 to 150,000;
  • the second phase comprising a second copolymer being formed from a second monomer mixture which comprises at least 20 weight percent of an olefin monomer, and up to 80 weight percent of one or more ethylenically unsaturated monomers copolymerizable with the olefin monomer, wherein at least one of the ethylenically unsaturated monomers copolymerizable with the olefin monomer comprises a reactive functionality after the second copolymer is formed which is capable of reacting with one or more of the reactive epoxide functionalities of the first copolymer, said weight percents being based on the total weight of the second monomer mixture, wherein the second copolymer has a melt index, as determined by ASTM-1238 Condition I, of between 0.1 grams/10 minutes and 100 grams/10 minutes
  • a second broad aspect of the invention is use of the polymeric composition formed by the first broad aspect of the invention in fabricating an article, wherein the article is fabricated using a method 5 selected from the group consisting of casting, blowing, extrusion, molding, injection molding, blow molding, coextrusion, laminating, or calendering.
  • the first phase of the polymeric composition of 0 the present invention comprises a first copolymer derived from (a) a monovinylidene monomer and optionally, an ethylenically unsaturated monomer copolymerizable therewith, and (b) a comonomer selected to have at least one reactive epoxide functionality, which epoxide functionality is available for reacting after the first copolymer is formed.
  • Monovinylidene monomers suitable for use in forming the first copolymer of the present invention are the acrylates and methacrylates of aliphatic alcohols selected from those alcohols having from 1 to 12 carbon atoms, (e.g., methylacrylate, ethylacrylate, methyl methacrylate, butylacrylate and nonylacrylate) ; monovinylidene aromatic monomers including those polymers based on styrene; ⁇ -alkyl monovinylidene monoaromatic compounds (such as . ⁇ -methylstyrene, ⁇ -ethylstyrene, ⁇ -methylvinyltoluene and ⁇ -methyldialkyl styrene); ring-substituted alkyl styrenes, (such as ortho-, meta-, and para-vinyl- toluene, ortho-ethylstyrene, para-ethylstyrene,
  • the first phase comprises one or more ethylenically unsaturated comonomers selected to have at least one reactive epoxide functionality, said ethylenically unsaturated comonomers being copolymerizable with the monovinylidene monomers.
  • the epoxide functionality is available for reacting after the first copolymer is formed.
  • Suitable epoxy- -containing comonomers include the glycidyl acrylates, glycidyl methacrylates and allyl glycidyl ether.
  • the ethylenically unsaturated comonomers copolymerizable with the monovinylidene monomer are selected to have one or more of the reactive epoxide functionalities of the first phase and are selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and mixtures thereof.
  • the balance of the monomer mixture used to form the first phase may additionally comprise minor amounts of suitably copolymerizable monomers which do not adversely affect the properties of the composition.
  • exemplary monomers include the unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, ethacrylonitrile) ; the anhydrides (e.g., maleic anhydride, citraconic anhydride, itaconic anhydride); vinyl halides (e.g., vinyl chloride, vinyl bromide etc.; vinylidene halides (e.g., vinylidene chloride and vinylidene bromide); vinyl esters (e.g., vinyl acetate and vinyl propionate); dialkyl maleate or fumurates (e.g., dimethyl maleate, diethyl maleate, dibutyl maleate and the corresponding fumurates); and ⁇ -olefin monomers having from 1 to 10 carbon atoms (e.g., ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene.
  • a particularly preferred monomer is acrylonitrile. These monomers may be present in an amount of up to 20 weight percent, preferably from up to 10 weight percent, most preferably from up to about 5 weight percent, based on total weight of the monomer mixture used to form the first phase.
  • the first copolymer which can be employed generally has a melt index as determined by ASTM D-1238 Condition G of between 0.1 g/10 minutes and 40 g/10 minutes, preferably between 0.5 g/10 minutes to 20 g/10 minutes.
  • X. first copolymer as determined by standard gel permeation is generally between 20,000 and 150,000, and preferably between 35,000 to 90,000. Ordinarily, the first copolymer is selected to have an intrinsic viscosity of 1Q between 0.2 and 1 dl/gram at 25°C in toluene.
  • the first copolymer may advantageously be grafted to rubber substrates, it being 0 understood that such grafting does not bind the reactive epoxide functionality.
  • Suitable rubbery substrate polymers include any polymer or copolymer which are selected to have a glass transition temperature (Tg) of less than about 0°C, preferably not higher than -20°C as 5 determined by American Society of Testing and Materials (ASTM) test Method D 746-52T.
  • Graftable rubber substrates suitable for use in the first phase of the present invention may be formed 0 from various elastomeric materials.
  • the elastomeric materials preferred for use in the present invention are diene rubbers, acrylate rubbers, ethylene propylene rubbers, hydrogenated diene rubbers, and EPDM rubbers, or mixtures thereof.
  • a diene rubber is any rubbery polymer of one or more conjugated 1,3-diene, e.g., butadiene, isoprene, piperylene, chlor ⁇ prene.
  • An acrylate rubber is any rubbery polymer of one or more acrylate monomers, e.g., 2-ethylhexyl acrylate, butylacrylate.
  • An EPDM rubber is an interpolymer formed from ethylene, propylene and one or more dienes.
  • Such rubbery polymers include homopolymers, interpolymers, and block copolymers of conjugated 1,3-dienes and/or acrylate monomers with up to an equal amount by weight of one or more copolymerizable monoethylenically unsaturated monomers, such as monovinylidene aromatic hydrocarbons (e.q., styrene; a ring-substituted alkylstyrene, such as o-, m-, and p-vinyl toluene, 2,4-diethylstyrene, the ring- -substituted ethylstyrenes, p-tert-butylstyrene; an alpha-alkylstyrene, such as alpha-methylstyrene, alpha- ethylstyrene, alpha-methyl-p-methylstyrene; vinyl naphthalene); ring-substitute
  • a most preferred group of elastomeric polymers for use in the first phase of the present invention includes those polymers derived from 75 to 100 percent by weight of butadiene and/or isoprene and the balance substantially being one or more of the monomers selected from the group consisting of monovinylidene aromatic hydrocarbons (e.g., styrene) and unsaturated nitriles (e.g., acrylonitrile).
  • Particularly advantageous elastomeric materials for the preparation of the graftable rubber substrates of the present invention are butadiene homopolymers or an interpolymer of 80 to 96 percent by weight butadiene and the balance substantially being acrylonitrile and/or styrene and/or methyl methacrylate.
  • the graftable rubber substrate suitably is selected to have a volume average particle diameter within the range of from 300 Angstroms to 25,000 Angstroms.
  • the particles have a diameter within the range of from 800 Angstroms to 20,000 Angstroms.
  • the graftable rubber substrates of the present invention may contain up to about 2 percent of a cross- linking agent based on the weight of the elastomeric polymer-forming monomer or monomers.
  • the cross-linking agent can be any of the agents conventionally used for cross-linking acrylate rubbers. Suitable examples include divinylbenzene, diallyl maleate, diallyl fumurate, diallyl adipate, allyl acrylate, allyl methacrylate, diacrylates, and dimethylacrylates of polyhydric alcohols (e.g., ethylene glycol dimethacrylate) .
  • the graftable rubber substrates of the present invention are well-known in the prior art.
  • the graftable rubber substrates are formed through an emulsion polymerization process, anionic polymerization process, or Ziegler-Nata polymerization process. Exemplary processes are described in The Kirk-Othmer Encyclopedia of Chemical Technology at Vol 8, Pages 549-559 and ' Vol 18, Pages 740-744.
  • the graftable rubber substrates may be desirable to select the graftable rubber substrates to have a broad particle diameter range or which comprise two or more distinct groups having different average particle diameters. For example, it is sometimes desirable to select the graftable rubber substrates to have an average particle diameter within the range of from 800 Angstroms to 2000 Angstroms and a second group of graftable rubber substrates having an average particle diameter within the range of from 4000 Angstroms to 20,000 Angstroms.
  • the first copolymer is free-radically grafted to the graftable rubber substrate, by processes well-known in the prior art.
  • Examples of known polymerization processes suitable for use in the present invention include mass, mass-solution, mass-suspension, suspension, and emulsion polymerization processes as well as other modifications and/or combinations of such processes. See, for example, U.S. Patent Nos. 4,430.478 which teach such processes.
  • the graft polymerization process involves combining the graftable rubber substrate with the monomers from which the first copolymer is to be formed. The monomers are then polymerized to chemically combine or graft at least a portion of the graft-forming polymer on the graftable rubber substrate.
  • the graftable rubber substrates may have a first layer of a first copolymer grafted thereto.
  • a second layer of first copolymer may be formed wherein the second layer comprises reactive epoxide functionalities capable of reacting with the one or more of the reactive functionalities of the second phase.
  • the process used to graft the first copolymer onto the graftable rubber substrate inherently produces an amount of free first copolymer, that is, an amount of free first copolymer which is not grafted to the graftable rubber substrate.
  • the amount of free first copolymer present in the polymeric compositions of the present invention will be within the range of from 1.0 to 80 weight percent based on total polymeric composition weight. It is to be understood that free first copolymer may be incorporated into the polymeric compositions of the present invention through the above process or by blending the graftable rubber substrate with a separately prepared first polymer.
  • the graftable rubber substrate has grafted thereto an amount of first copolymer such that the weight ratio of the chemically attached graft to the graftable rubber is within the range of from 0.05:1 to 1.5:1 (graft to rubber ratio), beneficially from 0:1 to 1.0:1.
  • the graft to rubber ' ratio is from 0.2:1 to 0.7: 1.
  • the second phase of the present invention comprises an olefin monomer and one or more ethylenically unsaturated comonomers copolymerizable with the olefin monomer, wherein at least one of the ethylenically unsaturated monomers copolymerizable with the olefin monomer comprises a reactive functionality capable of reacting with one or more of the reactive
  • the reactive functionality of the second copolymer is available for reacting with one or more of the reactive epoxide functionalities of the first copolymer after the -j- second copolymer is formed.
  • olefin monomer an aliphatic hydrocarbon having one or more double bonds or mixtures thereof.
  • Preferred monomers include the ⁇ -olefin 0 monomers having from 1 to 10 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1- pentene, 1-hexene, and 1-octene. Ethylene is particularly preferred.
  • ethylenically unsaturated comonomers copolymerizable with the olefin monomers include mono ⁇ basic carboxylic acids or polybasic carboxylic acids and partial esters and amides thereof (e.g., acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic 0 acid and itaconic acid; the corresponding partial esters, e.g., monomethyl fumarateand the corresponding partial amides, e.g., fumaric acid).
  • the reactive functionality of the ethylenically unsaturated comonomer will be available for reacting with the ' epoxide functionality of the first copolymer.
  • the balance of the monomer mixture used to form the second phase may additionally comprise an amount of suitably copolymerizable monomers which do not adversely affect the properties of the composition.
  • exemplary monomers include carbon monoxide and vinyl acetate. These non-hydrocarbon monomers may be present in an amount of up to 80 weight percent, beneficially up to 50 weight percent, preferably up to about 30 weight percent, based on total weight of the monomer mixture used to form the second phase.
  • the second copolymer which can be employed generally has a melt index as determined by ASTM-1238 Condition I of between 0.1 grams/10 minutes and 100 grams/10 minutes, preferably between 0.5 to 75.
  • the number average molecular weight of the second copolymer as determined by standard gel permeation is generally between 20,000 and 150,000, and preferably between 35,000 and 90,000.
  • the second phase of the present invention can be dispersed with the first phase of the present invention through methods well-known in the prior art. Typically, the second phase will be melt blended with the first phase under conditions sufficient to cause the reaction between one or more of the reactive epoxide functionalities of the first copolymer with the one or more reactive functionalities of the second copolymer.
  • the temperature at which the copolyme ⁇ zation occurs should be effective to melt and mix the polymers, and to induce a reaction.
  • the upper temperature is determined by the thermal stability of the polymers, and the point
  • the lower temperature is determined by the viscosity of the polymer mixture and the point prior to which the mixture components can react.
  • the temperature should be in a range from 177°C to 316°C, most preferably 5 from 204°C to 274°C.
  • Exemplary melt processing equipment includes heated two-roll compounding mills, Brabender mixers, Banbury mixers, single screw extruders and twin screw extruders.
  • the melt processing equipment is preferably a twin screw compounder operating between 50 RPM and 500 RPM. 5
  • An amount of the second phase is dispersed with the first phase such that the first phase comprises from 10 to 90 weight percent, and the second phase comprises from 10 to 90 weight percent, said weight percents being based on the total weight of the functionalized polymeric composition.
  • an amount of the second phase is dispersed with the first phase so that the resultant polymeric composition comprises from 50 to 90 weight percent of the first phase and 10 to 50 weight percent of the second phase.
  • the polymeric compo ⁇ sitions produced according to the method of the present invention possess improved physical properties when compared to compositions obtained by polymerizing the monomers of either the first or second phases alone, or polymerizing monomers of both the first or second phases
  • the polymeric compositions of the present invention possess an * t - improved combination of impact strength and ductility.
  • compositions of the present invention may be blended with thermoplastic resins to achieve modified physical properties.
  • exemplary thermoplastic resins 0 include polyolefins e.g., ultra-low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, poly 1-butene; and monovinylidene aromatic polymers e.g., styrene, ⁇ -methylstyrene, m-ethylstyrene, p-methoxy- ⁇ - 5 -methylstyrene, p-ethyl- ⁇ -methylstyrene, p-ethyl- ⁇ - -ethylstyrene, 2,4-diethylstyrene and m-isopropylstyrene.
  • polyolefins e.g., ultra-low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, poly 1-butene
  • monovinylidene aromatic polymers
  • the polyolefin employed will preferably be present in an amount of from 1 to 80 percent by weight 0 of polyblend.
  • the thermoplastic resin is a monovinylidene aromatic polymer
  • the monovinylidene aromatic polymer employed will preferably be present in an amount of from 1 to 30 percent by weight of polyblend.
  • the compositions of the present invention have a good balance of properties, rendering them suitable for formation into tool housings, automotive parts, sheets, films and containers.
  • the articles formed from the polymeric composition of the present invention possess a good balance of toughness and ductility, which render them suitable for use in applications previously unavailable to conventional articles.
  • Code Polymer S/GMA-1 A styrene/glycidal methacrylate copolymer having polymerized therein 90 weight percent styrene and 10 weight percent glycidyl methacrylate, said weight percentages being based upon the total weight of the copolymer.
  • the polymerization is carried out as follows: Into a one gallon glass reactor is loaded
  • the aqueous stream contains 0.3 55 sodium dodecyl benzene sulfonate (NDBS) soap and 0.21% sodium persulfate and is added at a rate of 153.8g/hr for 5 hours; the monomer stream consists of
  • S/GMA-2 A styrene/glycidyl methacrylate copolymer made similar to S/GMA-1, except that it contains S/GMA in a 90/10 weight ratio.
  • GMA A terpolymer of ⁇ -methylstyrene/ acrylonitrile/glycidyl methacrylate (65/25/10 weight ratio) made similar to S/GMA-1.
  • EAA-1 An ethylene/acrylic acid copolymer having polymerized therein 93.5 percent ethylene and 6.5 percent acrylic acid, both percentages being based upon copolymers weight.
  • the copolymer has a density (ASTM Test D-792) of 0.932 grams per cubic centimeter and a melt index (ASTM Test D-1238) of 5.5 grams per ten minutes.
  • the copolymer is commercially available from The Dow Chemical Company under the trade designation EAA Resin 459.
  • EAA-2 An ethylene/acrylic acid copolymer having polymerized therein 90.0 percent ethylene and 10.0 percent acrylic acid, both percentages being based upon copolymers weight.
  • the copolymer has a density (ASTM Test D-792) of 0.932 grams per cubic centimeter and a melt
  • the copolymer is commercially available from The Dow Chemical Company under the trade designation EAA Resin 455.
  • GRC-1 The polymerization of the grafted copolymer ] ,- (GRC) is carried out as follows: A relatively small (1400 Angstoms), monodisperse rubber particle is grafted with styrene/glycidyl methacrylate (95/5) in an emulsion process as follows: Into a one gallon glass reactor is placed 1645g of rubber latex (1400 Angstoms), styrene/butadiene/acrylonitrile (ABS), 5/93/2, 0 569g of rubber solids). The reactor is flushed with nitrogen and heated to 90°C while being agitated at 150 rpm. When the temperature reaches 85°C, two continuous addition (conadd) streams are started.
  • An aqueous stream containing 0.94% sodium dodecyl benzene sulfonate NDBS soap and 0.24% sodium g persulfate is added at a rate of 108g/hour for six hours.
  • a monomer steam containing 95.0% styrene, 5.0% glycidyl methacrylate and 0.05 parts (BOM) n-octyl mercaptan is added at a rate of 51.0g/hour for six hours.
  • the latex After stopping the conadd streams, the latex is heated an additional 0.25 hours at 90°C, steam stripped to remove residual monomers and stabilized with (1/3) mixture of T0PAN0L ® CA, commercially available from Canadian Industries, and dilauryl thiodipropinate (0.2%, based on rubber).
  • the GRC is isolated by freeze coagulation.
  • a grafted rubber concentrate (GRC) of 66.8% styrene/butadiene/acrylonitrile rubber and 33.2% styrene/glycidylmethacrylate S/GMA (95/5) is obtained.
  • the GRC has grafted thereto 43% (weight of grafted phase divided by the weight of rubber X 100) of a styrene/glycidyl methacrylate copolymer having polymerized therein 95 percent styrene and 5 percent glycidyl methacrylate, both percentages being based upon the rigid phase graft copolymer weight.
  • GRC-1 A grafted rubber concentrate prepared similar to S/GMA-GRC-1, except that it does not contain the epoxy functional monomer.
  • GRC-2 A grafted rubber concentrate prepared similar to S/GMA-GRC-1, except that in place of styrene/glycidyl methacrylate copolymer (95/5) a styrene/acrylonitrile/glycidyl methacrylate copolymer (66/25.5/8.5 weight ratio) is used.
  • HDPE A high density polyethylene resin having a density (ASTM Test D-1505) of 0.965 grams per cubic centimeter and a melt index, (ASTM Test D-1238) of 0.8 decigrams per minute. The resin is commercially available from The Dow Chemical Company under the trade designation HDPE 12065.
  • HIPS A rubber-modified high impact polystyrene, commercially available from The Dow Chemical
  • Molded samples to test the physical properties of the compositions of this invention are prepared as follows. Various components from Table I are added to a plastic bag and tumble mixed. More sophisticated equipment could have been used but was not necessary. When the substituents have been thoroughly mixed, they are single passed through an 0.8 inch counter-rotating nonintermeshing twin screw extruder at a feed rate of about 10 lbs/hour while the screws rotate at 200 rpm. The extruder is heated (from back to front) with a temperature profile of 164°C to 204°C (from back to front) .
  • the pellets are air dried at 8 ⁇ °C for several hours before being injection molded.
  • a two-ounce Negri- Bossi reciprocating screw injection molding machine is preheated to 191°C (375°F) in zone 1 and 204°C (400°F) in zone 2 and the hydraulic injection pressure is 800/600 pounds per square inch with a 45 second cycle time.
  • Polymeric compositions are converted into samples for testing purposes.
  • the test samples are subjected to physical property tests which are described below and footnoted in the respective tables.
  • Notched Izod Impact Strength measures the toughness of the samples which contain a notch, in foot pounds per inch notch. Notched Izod Impact Strength is determined according to American Society of Testing and Materials Test Method D-256, Method A. • - Dart impact measures the toughness of the sample in inch pounds. Dart impact is determined using 3.63 kg drop weight and an opening of 3.2 cm on a test specimen having a thickness of 3.175 mm and a Dart of 1.59 cm with a radius of curvature of 0.795 cm.
  • T y Tensile yield
  • T r Tensile rupture
  • ⁇ m x ⁇ o 5 measures the modulus of the sample in pounds per square inch.
  • ⁇ m x ⁇ o 5 is determined according to American Society of Testing and Materials Test Method D-638 at 0.2 inches/min.
  • %E Percent Elongation
  • Vicat measures the heat distortion temperature of the sample in degrees Fahrenheit. Vicat is determined according to American Society of Testing and Materials Test Method D-1525-82.
  • Blends of these components previously described show an excellent combination of physical properties as seen in Table II. Specifically, the control samples, lacking functional groups in the first phase, have significantly poorer physical properties than the alloys of the present invention.
  • Blends of these components previously described show an excellent combination of physical properties as seen in Table III.
  • compositions according to the present invention having various comonomers in the first phase and grafted rubber modifiers possess very desirable physical properties.
  • the control samples, lacking functional groups in the first phase have significantly poorer physical properties than the alloys of the present invention.
  • ** Amounts are in percentages based upon weight of blend.
  • Blends of these components previously described, and mixtures of polyolefins or low levels of additional nonfunctional first phase polymers show an excellent combination of physical properties as seen in Table IV.
  • compositions according to the present invention possess very desirable physical properties.
  • the control samples, having high levels of first phase polymer have significantly poorer physical properties than the alloys of the present invention.

Landscapes

  • 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)
  • Graft Or Block Polymers (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

Préparation et utilisation d'une composition polymère fonctionnalisée comprenant des première et deuxième phases. La première phase comporte un premier copolymère d'un monomère de monovinylidène et un comonomère sélectionné pour avoir au moins une fonctionnalité époxyde réactive. La deuxième phase est dispersée avec la première phase. La deuxième phase comprend un copolymère d'un monomère d'oléfine et un ou plusieurs monomères non saturés par l'éthylène qui sont copolymérisables avec le monomère d'oléfine dont au moins un des monomères non saturés par l'éthylène et copolymérisables avec le monomère d'oléfine comprend une fonctionnalité de réaction capable de réagir avec une ou plusieurs des fonctionnalités époxydes réactives du premier copolymère.
PCT/US1991/000474 1991-01-23 1991-01-23 Preparation et utilisation de compositions polymeres fonctionnalisees Ceased WO1992013015A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP3506387A JPH06504296A (ja) 1991-01-23 1991-01-23 官能化ポリマー組成物の製造および使用
EP9191905558A EP0568528A4 (fr) 1991-01-23 1991-01-23 Preparation et utilisation de compositions polymeres fonctionnalisees.
PCT/US1991/000474 WO1992013015A1 (fr) 1991-01-23 1991-01-23 Preparation et utilisation de compositions polymeres fonctionnalisees

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1991/000474 WO1992013015A1 (fr) 1991-01-23 1991-01-23 Preparation et utilisation de compositions polymeres fonctionnalisees

Publications (1)

Publication Number Publication Date
WO1992013015A1 true WO1992013015A1 (fr) 1992-08-06

Family

ID=22225303

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/000474 Ceased WO1992013015A1 (fr) 1991-01-23 1991-01-23 Preparation et utilisation de compositions polymeres fonctionnalisees

Country Status (3)

Country Link
EP (1) EP0568528A4 (fr)
JP (1) JPH06504296A (fr)
WO (1) WO1992013015A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658741A (en) * 1966-09-19 1972-04-25 Allied Chem Homogeneous copolymers from ethylene
US3770848A (en) * 1971-08-16 1973-11-06 Ford Motor Co Self-crosslinking powder containing carboxy and epoxy groups admixed with a flow control agent
US3852236A (en) * 1970-12-21 1974-12-03 Gulf Research Development Co Homogeneous thermosettable composition of a polyanhydride and a polyepoxide
US4528329A (en) * 1982-05-17 1985-07-09 Toa Nenryo Kogyo Kabushiki Kaisha Production of polyolefin copolymer

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60240747A (ja) * 1984-05-15 1985-11-29 Showa Denko Kk 架橋性組成物及びエステル架橋型重合体
JPH0611836B2 (ja) * 1985-05-28 1994-02-16 昭和電工株式会社 熱可塑性樹脂組成物
US4886856A (en) * 1986-08-21 1989-12-12 The Dow Chemical Company Functionalized elastomers blended with polar copolymers of styrene and acrylic acid methacrylic acid or maleic anhydride

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658741A (en) * 1966-09-19 1972-04-25 Allied Chem Homogeneous copolymers from ethylene
US3852236A (en) * 1970-12-21 1974-12-03 Gulf Research Development Co Homogeneous thermosettable composition of a polyanhydride and a polyepoxide
US3770848A (en) * 1971-08-16 1973-11-06 Ford Motor Co Self-crosslinking powder containing carboxy and epoxy groups admixed with a flow control agent
US4528329A (en) * 1982-05-17 1985-07-09 Toa Nenryo Kogyo Kabushiki Kaisha Production of polyolefin copolymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0568528A4 *

Also Published As

Publication number Publication date
EP0568528A1 (fr) 1993-11-10
JPH06504296A (ja) 1994-05-19
EP0568528A4 (fr) 1994-11-30

Similar Documents

Publication Publication Date Title
JP2005534775A (ja) 低光沢の外観を有する熱可塑性組成物
US5001194A (en) Method of making functionalized polymeric compositions
US4524180A (en) Rubber-modified, impact-resistant polymeric compositions
EP0486914B1 (fr) Compositions thermoplastiques à base de polyoléfine et les polymères de vinyles aromatiques
CN101050299B (zh) 一种基于连续本体法的abs聚合物与聚碳酸酯合金的制备方法
WO2003027181A2 (fr) Resine asa a faible brillance
EP0568528A4 (fr) Preparation et utilisation de compositions polymeres fonctionnalisees.
CA2079794A1 (fr) Composition polymerique renforcee par des fibres
US6221969B1 (en) Method for producing rubber-modified styrenic resin having high gloss and high impact strength
AU640478B2 (en) High heat styrenic copolymer blends having improved tensile properties
EP0564242A1 (fr) Compositions de polycarbonate et d'ABS de faible brillance
US20030045634A1 (en) Graft copolymer composition and vinyl chloride resin composition containing the same
AU610091B2 (en) Toughened polyamide compositions
JP3862452B2 (ja) 熱可塑性樹脂組成物
JPH04505628A (ja) カーボネートポリマーとゴム改質ビニル芳香族ニトリルグラフトコポリマーとメチル（メタ）アクリレート―ブタジエン―スチレングラフトコポリマーとを含む成形用組成物及びこのような組成物を用いたブロー成形法と熱成形法
JPH10101887A (ja) ゴム変性スチレン系樹脂組成物及びその成形品
JPH0623294B2 (ja) 熱可塑性樹脂組成物
EP0824135A1 (fr) Composition thermoplastique à base d'une polyoléfine chlorée et un caoutchouc à greffage élevé
JPH0940838A (ja) 優れたフロー・インパクトバランスを有する低光沢・耐熱性樹脂組成物
EP1394208A1 (fr) Compositions de résine résistantes aux intempéries et ayant une faible brillance
JPH0517645A (ja) 熱可塑性樹脂組成物
JPH04356514A (ja) メッキ性、耐衝撃性及び大型成形性に優れた熱可塑性樹脂組成物
KR970004668B1 (ko) 열가소성 수지조성물
WO1986001218A1 (fr) Melanges de resine de chlorure de vinyle modifiee par du caoutchouc, d'une resine de chlorure de vinyle non modifiee, et d'un polymere d'un monomere vinylique aromatique et d'un monomere de l'anhydride de l'acide dicarboxylique insature
WO1989008683A1 (fr) Composition de resine thermoplastique

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1991905558

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1991905558

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

WWW Wipo information: withdrawn in national office

Ref document number: 1991905558

Country of ref document: EP