[go: up one dir, main page]

EP1169389A1 - Compositions constituees d'un interpolymere et de resine d'ether de polyphenylene - Google Patents

Compositions constituees d'un interpolymere et de resine d'ether de polyphenylene

Info

Publication number
EP1169389A1
EP1169389A1 EP00910173A EP00910173A EP1169389A1 EP 1169389 A1 EP1169389 A1 EP 1169389A1 EP 00910173 A EP00910173 A EP 00910173A EP 00910173 A EP00910173 A EP 00910173A EP 1169389 A1 EP1169389 A1 EP 1169389A1
Authority
EP
European Patent Office
Prior art keywords
composition
polyphenylene ether
ether resin
ethylene
interpolymer
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.)
Withdrawn
Application number
EP00910173A
Other languages
German (de)
English (en)
Inventor
Adrianus J. F. M. Braat
Benny David
Juraj Liska
Glen D. Merfeld
John Bennie Yates, Iii
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.)
General Electric Co
Original Assignee
General Electric 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 General Electric Co filed Critical General Electric Co
Publication of EP1169389A1 publication Critical patent/EP1169389A1/fr
Withdrawn legal-status Critical Current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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • 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

Definitions

  • the invention generally relates to novel compositions comprising (i) at least one substantially random interpolymer containing (a) ethylene; (b) one or more aromatic vinylidene monomers or hindered aliphatic or cycloaliphatic vinylidene monomers, and (c) optionally, one or more polymerizable C 3 to C 20 olefinic monomers, and (ii) at least one polyphenylene ether resin having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.20 dl/g, more preferably within the range of about 0.08 dl/g to about 0.15 dl/g, as measured in chloroform at 25°C.
  • compositions are substantially free of elastomeric block copolymer resins, such as polystyrene- poly(butadiene)-polystyrene block copolymers, polystyrene- poly(ethylenebutylene)-polystyrene block copolymers and polystyrene- poly(ethylenepropylene) block copolymers and the like.
  • elastomeric block copolymer resins such as polystyrene- poly(butadiene)-polystyrene block copolymers, polystyrene- poly(ethylenebutylene)-polystyrene block copolymers and polystyrene- poly(ethylenepropylene) block copolymers and the like.
  • the invention also relates to processes to manufacture the blends as well articles made from the blends.
  • PPE Polyphenylene ether resins
  • Blends of PPE and polyolefins are of great interest because they can potentially bring some of the chemical resistance of the polyolefins to the PPE.
  • PPE can potentially add improved temperature resistance, flame retardance, electrical properties, dimensional stability, surface adhesion, thermo-oxidative stability and flame retardance to polyolefin resins.
  • such blends very often suffer from limitations of their own, apart from the limitations of the individual resins, due to the relative incompatibility of the PPE and the polyolefin resin, especially in those blends where one of the resins is present in an amount of more than about 3% by weight, based on 100% by weight of the two combined. In such instances, the beneficial property aspects which one resin could possibly confer on the other may not be fully realized.
  • Elastomeric materials such as polystyrene-poly(butadiene)-polystyrene block copolymers and polystyrene-poly(ethylenebutylene)-polystyrene block copolymers as well as polystyrene-poly(ethylenepropylene) have been used to improve the compatibility of PPE and polyolefin resins and to increase morphological stability of the composition in the melt. These systems are relatively inefficient because they require high levels of the elastomeric materials to give a substantial effect. Additionally, the elastomeric materials typically dissolve into the PPE phase and reduce the many desirable attributes of the PPE.
  • compositions comprising (i) at least one substantially random interpolymer containing (a) ethylene; (b) one or more aromatic vinylidene monomers or hindered aliphatic or cycloaliphatic vinylidene monomers, and (c) optionally, one or more polymerizable C 3 to C 20 olefinic monomers, and (ii) at least one PPE having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.20 dl/g, more preferably within the range of about 0.08 dl/g to about 0.15 dl/g, as measured in chloroform at 25°C.
  • the PPE is preferably prepared by a process comprising oxidative coupling in a reaction solution at least one monovalent phenol species using an oxygen containing gas and a complex metal catalyst to produce a PPE having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.20 dl/g, more preferably within the range of about 0.08 dl/g to about 0.15 dl/g, as measured in chloroform at 25°C; removing at least a portion of the complex metal catalyst with an aqueous containing solution; and isolating the PPE through devolatilization of the reaction solvent.
  • terpolymer is used herein to indicate a polymer wherein three different monomers are polymerized to make the terpolymer.
  • interpolymer is used herein to indicate a polymer wherein two or more, preferably three or more different monomers are polymerized to make the interpolymer.
  • substantially random in the substantially random interpolymer comprising ethylene, one or more vinylidene aromatic monomers or hindered aliphatic vinylidene monomers, and preferably one or more C 3 to C 20 olefinic monomers as used herein means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEQUENCE DETERMINATION, Carbon-13 NMR Method, Academic Press New York, 1977, pp. 71-78.
  • the substantially random interpolymer does not contain more than 15 percent of the total amount of vinylidene aromatic monomer in blocks of vinylidene aromatic monomer of more than 3 units. More preferably, the interpolymer is not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the Carbon-13 NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51 , 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001 , 0.001 , 0.01 or 0.1 as appropriate.
  • the substantially random interpolymers of the present invention preferably comprise at least three different monomers.
  • the substantially random interpolymers of the present invention comprise (1 ) from about 19.5 to about 98.5, preferably from about 25 to about 95, more preferably from about 30 to about 94 mole percent of ethylene; (2) from about 0.5 to about 60, preferably from about 1 to about 55, more preferably from about 1 to about 50 mole percent of one or more aromatic vinylidene monomers or hindered aliphatic vinylidene monomers, and (3) from about 1 to about 80, preferably from about 4 to about 65, more preferably from about 5 to about 50 mole percent of one or more C 3 to C 20 olefin monomers. It is to be understood that the total amount of (1 ), (2) and (3) is 100 mole percent.
  • the number average molecular weight (Mn) of the interpolymers of the present invention is usually greater than about 1 ,000, preferably from about 5,000 to about 1 ,000,000, more preferably from about 10,000 to about 500,000.
  • the present invention particularly concerns the following terpolymers: ethylene/styrene/propylene; ethylene/styrene/4-methyl-1 -pentene; ethylene/styrene/hexene-1 ; ethylene/styrene/octene-1 ; and ethylene/styrene/norbornene as well as terpolymers of ethylene/styrene/butene-1 and ethylene/styrene/vinylbenzocyclobutene.
  • Suitable alpha -olefins, or combinations of alpha -olefins, which can be employed as olefinic monomer(s) (3) include for example, those containing from 3 to about 20, preferably from 3 to about 12, more preferably from 3 to about 8 carbon atoms.
  • Suitable olefinic monomers which can be employed as olefinic monomer(s) (3) include strained ring olefins such as norbornene.
  • Particularly suitable as olefinic monomer(s) (3) include propylene, 4-methyl-1- pentene, pentene-1 , hexene-1 and octene-1.
  • Butene-1 or vinylbenzocyclobutene can be utilized in combination with other alpha -olefins or olefinic monomers such as, for example, propylene, hexene-1 , octene-1, or norbornene, or any other combination except for the above noted combination of ethylene/styrene/butene-1 or ethylene/styrene/vinylbenzocyclobutene.
  • Suitable vinylidene aromatic monomers for use as component (2) include, for example, those represented by the following formula I:
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C -alkyl, and C -haloalkyl; and n has a value from zero to about 6, preferably from zero to about 2, more preferably zero.
  • Exemplary monovinylidene aromatic monomers include styrene, vinyl toluene, alpha- methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, and the like.
  • Particulariy suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
  • Preferred monomers include styrene, alpha -methyl styrene, the lower alkyl- or phenyl- ring substituted derivatives of styrene, such as ortho-, meta-, and para- methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof, and the like.
  • a more preferred monovinylidene aromatic monomer is styrene.
  • Suitable "hindered aliphatic or cycloaliphatic vinylidene monomers" for use as components (2) include addition polymerizable vinylidene monomers corresponding to the following formula II:
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; and R 3 is a sterically bulky, aliphatic substituent of up to 20 carbons; or alternatively R 1 and R 3 together form a ring system.
  • sterically bulky it is meant that the monomer bearing this substituent is normally incapable of addition polymerization by standard Ziegler-Natta polymerization catalysts at a rate comparable with ethylene polymerizations.
  • Preferred hindered aliphatic or cycloaliphatic vinylidene monomers are those in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted.
  • substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyi, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert-butyl, norbomyl, and the like.
  • hindered aliphatic or cycloaliphatic vinylidene compounds are vinyl cyclohexane and the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene.
  • vinyl cyclohexane is especially suitable.
  • the substantially random interpolymers of the present invention may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art.
  • the polymers may be readily sulfonated or chlorinated to provide functionalized derivatives according to established techniques.
  • the substantially random interpolymers of the present invention can be prepared as described in U.S. application Ser. No. 545,403 filed Jul. 3, 1990 (corresponding to EP-A-0,416,815) by James C. Stevens et al., both of which are incorporated herein by reference in their entirety.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from - 30°C. to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization. While preparing the.
  • an amount of atactic vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinylidene aromatic monomer.
  • the presence of vinylidene aromatic homopolymer is in general not detrimental for the purposes of the present invention and may be tolerated.
  • the vinylidene aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from solution with a non- solvent for either the interpolymer or the vinylidene aromatic homopolymer.
  • the substantially random interpolymers of the present invention can also be prepared by the methods described by John G. Bradfute et al. (W. R. Grace & Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500; and in Plastics Technology, p. 25 (September 1992), all of which are incorporated herein by reference in their entirety. Further preparative methods which may be applicable for the interpolymers of the present invention have been described in the literature. Longo and Grassi (Makromol. Chem., Volume 191 , pages 2387 to 2396 [1990]) and D'Anniello et al.
  • Lu et al Journal of Applied Polymer Science, Volume 53, pages 1453 to 1460 [1994] have described the copolymerization of ethylene and styrene using a TiCI4/NdCI3/MgCI2 /AI(Et)3 catalyst.
  • Sernetz et al. (Macromol. Chem. Phys., v 197, pp 1071-1083, 1996) have described copolymerization of styrene with ethylene using Me 2 Si(Me 4 C) (N-tert- butylJTiClz/methylaluminoxane.
  • Another suitable method includes the method disclosed for the manufacture of alpha-olefin/vinyl aromatic monomer interpolymers such as propylene/styrene and butene/styrene described in U.S. Pat. No. 5,244,996, assigned to Mitsui Petrochemical Industries Ltd. All of the above are incorporated herein by reference.
  • the PPE employed in the present invention are known polymers comprising a plurality of structural units of the formula III
  • each structural unit may be the same or different, and in each structural unit, 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 . Most often, each Q 1 is alkyl or phenyl, especially C 1-4 alkyl, and each Q 2 is hydrogen.
  • each Q 1 is alkyl or phenyl, especially C 1-4 alkyl
  • each Q 2 is hydrogen.
  • Both homopolymer and copolymer PPE are included.
  • the preferred homopolymers are those containing 2,6-dimethyl-1 ,4-phenylene ether units.
  • Suitable copolymers include random copolymers containing such units in combination with (for example) 2, 3, 6-trimethyl-1 ,4-phenylene ether units.
  • PPE containing moieties prepared by grafting vinyl monomers or polymers such as polystyrenes and elastomers, as well as coupled PPE in which coupling agents such as low molecular weight polycarbonates, quinones, heterocycles and formals undergo reaction in known manner with the hydroxy groups of two poly(phenylene ether) chains to produce a higher molecular weight polymer, provided a substantial proportion of free OH groups remains.
  • PPE 's containing a functional endgroup obtained, for example, from reaction with a reactive compound having the functional endgroup.
  • the intrinsic viscosity (hereinafter "I.V.”) of the PPE is most often in the range of about 0.05-0.60 dl./g., preferably about 0.08-0.20 dl./g., more preferably in the range of about 0.10-0.14 dl./g., as measured in chloroform at 25°C.
  • I.V. a measure of molecular weight
  • compositions wherein the PPE has an I.V. in the range of about 0.10-0.14 dl./g. typically exhibit a higher heat resistance than compositions wherein the PPE has an I.V.
  • Preferred low molecular weight PPE include generally those that have a number average molecular weight within the range of about 1250 to about 7000 and a weight average molecular weight within the range of about 2500 to about 15,000, as determined by gel permeation chromatography, with a preferred number average molecular weight within the range of about 1750 to about 4000 and a weight average molecular weight within the range of about 3500 to about 9,000, as determined by gel permeation chromatography.
  • Correlation of PPE's Tg and molecular weight is very specific and related to PPE structure. For illustration, Tg drops only 35% at ten fold drop of molecular weight. That means, the retention of heat properties is extraordinary and beneficial for the application where a high flow is important (low IV PPE) while retaining heat properties.
  • the PPE are typically prepared by the oxidative coupling of at least one monohydroxyaromatic compound such as 2,6-xylenol, 2,3,6-trimethylphenol, or mixtures of the foregoing.
  • Catalyst systems are generally employed for such coupling and they typically contain at least one heavy metal compound such as a copper, manganese, or cobalt compound, usually in combination with various other materials.
  • the polymerization of the phenolic monomer may be carried out by adding the phenolic monomer or monomers to a suitable reaction solvent and preferably, a copper-amine catalyst. It is preferred to carry out the polymerization in the presence of a cupric or cuprous salt-secondary amine catalyst such as, for example, cupric chloride and di-n-butylamine.
  • a cupric or cuprous salt-secondary amine catalyst such as, for example, cupric chloride and di-n-butylamine.
  • the polymerizations are advantageously carried out in the presence of an inorganic alkali metal bromide or an alkaline earth metal bromide.
  • the inorganic bromides may be used at a level of from about 0.1 mole to about 150 moles per 100 moles of phenolic monomer.
  • Tetraalkylammonium salts may also be employed as promoters if desired. These promoters are disclosed in U.S. Pat. No. 3,988,297 (Bennett et al.).
  • the primary, secondary or tertiary amine component of the catalyst complex generally correspond to those disclosed in U.S. Pat. Nos. 3,306,874 and 3,306,875 (Hay).
  • Illustrative members include aliphatic amines, including aliphatic mono- and di-amines, where the aliphatic group can be straight or branched chain hydrocarbon or cycloaliphatic.
  • Preferred are aliphatic primary, secondary and tertiary monoamines and tertiary diamines.
  • Especially preferred are mono-, di- and tri(lower) alkyl amines, the alkyl groups having from 1 to 6 carbon atoms.
  • amines there can be used mono-, di- and tri- methyl, ethyl, n-propyl i-propyl, n-butyl substituted amines, mono- and di- cyclohexylamine, ethylmethyl amine, morpholine, N-(lower) alkyl cycloaliphatic amines, such as N-methylcyclohexylamine, N.N'-dialkylethylenediamines, the N.N'-dialkylpropanediamines, the N.N.N.'-trialkylpentanediamines, and the like.
  • cyclic tertiary amines such as pyridine, alpha-collidine, gamma picoiine, and the like, can be used.
  • cyclic tertiary amines such as pyridine, alpha-collidine, gamma picoiine, and the like.
  • cyclic tertiary amines such as pyridine, alpha-collidine, gamma picoiine, and the like.
  • N,N,N ⁇ N'- tetraalkylethylenediamines, butane-diamines, and the like are especially useful.
  • a preferred mono alkyl amine is n-butyl amine; a preferred dialkyl amine is di-n- butyl amine; and a preferred trialkyl amine is triethylamine.
  • a preferred cyclic tertiary amine is pyridine.
  • the concentration of primary and secondary amine in the reaction mixture may vary within wide limits, but is desirably added in low concentrations.
  • a preferred range of non-tertiary amines comprises from about 2.0 to about 25.0 moles per 100 moles of monovalent phenol.
  • a tertiary amine In the case of a tertiary amine, the preferred range is considerably broader, and comprises from about 0.2 to about 1500 moles per 100 moles of monovalent phenol. With tertiary amines, if water is not removed from the reaction mixture, it is preferred to use from about 500 to about 1500 moles of amine per 100 moles of phenol. If water is removed from the reaction, then only about 10 moles of tertiary amine, e.g., triethylamine or triethylamine, per 100 moles of phenol need be used as a lower limit. Even smaller amounts of tertiary diamines, such as N.N.N'N'-tetramethylbutanediamine can be used, down to as low as about 0.2 mole per 100 moles of phenol.
  • tertiary diamines such as N.N.N'N'-tetramethylbutanediamine
  • the level of amine incorporation is relatively low when made by the methods as described herein.
  • DBA dibutylamine
  • the level of DBA incorporated into high molecular weight (e.g., 0.48 I.V.) PPE is generally between about 0.9 to about 1.0% by weight based on the weight of the PPE.
  • the level of DBA incorporated into low molecular weight (e.g., 0.11 I.V.) PPE is generally between about 0.15 to about 0.28% by weight based on the weight of the PPE.
  • the present invention includes compositions of at least one interpolymer and a PPE having an incorporated amine level of less than about 0.3% by weight based on the weight of the PPE. Also included are compositions of at least one interpolymer and a low I.V. PPE having enhanced branching as compared to high molecular weight PPE.
  • cuprous salts and cupric salts suitable for the process are shown in the Hay patents. These salts include, for example, cuprous chloride, cuprous bromide, cuprous sulfate, cuprous azide, cuprous tetramine sulfate, cuprous acetate, cuprous butyrate, cuprous toluate, cupric chloride, cupric bromide, cupric sulfate, cupric azide, cupric tetramine sulfate, cupric acetate, cupric butyrate, cupric toluate, and the like.
  • cuprous and cupric salts include the halides, alkanoates or sulfates, e.g., cuprous bromide and cuprous chloride, cupric bromide and cupric chloride, cupric sulfate, cupric fluoride, cuprous acetate and cupric acetate.
  • concentration of the copper salts is desirable maintained low and preferably varies from about 0.2 to 2.5 moles per 100 moles of monovalent phenol.
  • the copper salt is preferable used in an amount providing from about 0.2 to about 15 moles per 100 moles of the monovalent phenol.
  • Cupric halides are generally preferred over cuprous halides for the preparation of the copper amine catalyst because of their lower cost.
  • the use of the copper (I) species also greatly increases the rate of oxygen utilization in the early stages of the polymerization reaction and the lower oxygen concentration in the head space of the reactor helps in reducing the risk of fire or explosion in the reactor.
  • a process for the preparation and use of suitable copper-amine catalysts is in U.S. Pat. No. 3,900,445 (Cooper et al.).
  • a faster initial reaction rate with the copper (I) based catalyst also results in less accumulation of unreacted monomer and a reduction in the amount of undesirable tetramethyldiphenylquinone produced.
  • the tetramethyldiphenylquinone, a backward dimer is believed to incorporate into the PPE through equilibration reactions.
  • the equilibration reactions lead to a drop in the intrinsic viscosity of the PPE due to the decrease in molecular weight of the PPE from the incorporation of the dimer.
  • tetramethyldiphenylquinone during the oxidation coupling is desirable so as to avoid the drop in molecular weight and the accompanying difficulties in having to build to a higher than desired molecular weight to offset the loss during equilibration of the backward dimer. Additionally, by minimizing the amount of tetramethyldiphenylquinone formed and consequently minimizing the amount of tetramethyldiphenylquinone incorporated into the backbone of the PPE, a PPE polymer change that is predominantly hydroxyl monofunctional is possible. By "hydroxyl monofunctional" is meant that one end of the polymer chain, i.e.
  • the "head end” is a 2,6-dimethyl phenol with the polymer chain extending from the 4-position.
  • the other end, i.e. the "tail end” has the hydroxyl on the 2,6-dimethyl phenol connected into the polymer and hence is non-functional.
  • the utilized PPE is at least 70%, preferably at least 85%, most preferably, at least 95% by weight hydroxyl monofunctional. Additionally, in another preferred embodiment, the utilized PPE had in the reaction mixture less than a 10% drop, preferably less than a 5% drop, most preferably less than a 3% drop in I.V. during an equilibration step after the oxidative polymerization of the phenolic monomers.
  • tetramethyldiphenylquinone during the reaction process is that it affords the possibility to redistribute various compounds into the PPE.
  • a wide range of functionalized phenolic compounds can be introduced to afford an equally wide range of functionalized PPE.
  • at least one phenolic compound may be added to the reaction mixture and allowed to circulate while maintaining the temperature preferably between about 20° and about 150°C, preferably between about 60° and 80°C.
  • the reaction mixture is maintained at temperature for about 30 to about 90 minutes, although longer times are possible.
  • the flow of oxygen has been preferably halted as the oxidative coupling has been completed.
  • higher redistribution conversions are obtained under air as opposed to nitrogen.
  • the functionalized phenolic compound may be chosen from the following illustrative list:
  • R 1 represents a hydrogen-atom or an alkyl group and X represents an allyl group, an amino group, a protected amino group (e.g., protected by a tertiary-butyl carbonate), a carboxyl group, a hydroxy group, an ester group or a thiol group, wherein R 1 is an alkyl group when X represents an hydroxy group or an ester group .
  • X may be separated from the phenol ring through an alkyl group and wherein the total number of carbon atoms in the alkyl groups attached to the phenol ring is not more than six;
  • each X independently of the other X represents a hydrogen atom, an allyl group, an amino group, a protected amino group (e.g., protected by a tertiary-butyl carbonate), a carboxyl group, a hydroxy group, an ester group or a thiol group, with the proviso that not more than one X group represents a hydrogen atom, R 2 and R 3 represent an hydrogen atom or an alkyl group with 1-6 carbon atoms and each R 4 represents independently of the other R 4 a hydrogen atom, a methyl group or an ethyl group;
  • n and n have values from 2-20;
  • x has a value of 12-20 and y has a value of 1-7 or a derivative thereof;
  • R 5 represents a hydrogen atom, an alkyl group, an allyl group, an amino group, a protected amino group (e.g., protected by a tert-butyl carbonate), a carboxyl group, a hydroxy group, an ester group or a thiol group; or
  • R 6 represents independently of one another a hydrogen atom, an alkyl group or a methylene phenol group.
  • the functionalized PPE has a lower intrinsic viscosity, and hence a lower molecular weight, than does the PPE at the end of the oxidative coupling reaction.
  • the degree of the decrease is determined at least in part by the amount of phenolic compound utilized and the amount of catalyst, e.g., tetramethyldiphenylquinone, present.
  • the functionalized PPE has a weight average molecular weight of at least 1000, preferably between about 3000 and about 70,000 as compared to polystyrene standards.
  • the functionalized PPE has an intrinsic viscosity of between about 0.05 dl/g and 0.50 dl/g, preferably between about 0.08 dl/g and 0.30 dl/g, more preferably between about 0.08 dl/g and about 0.15 dl/g as measured in chloroform at
  • the PPE may have a bi-modal distribution of molecular weights.
  • reaction products include, but are not limited to, random copolymers of PPE and the interpolymer and block copolymers of PPE and the interpolymer as well as variations of the foregoing. It is thought that even low levels of the copolymers can improve the compatibility between the resins. Improved compatibility can reduce delamination tendencies and improve the physical properties of the compositions.
  • compositions comprising PPE, the substantially random interpolymer, and copolymers of PPE and at least one polyolefin.
  • the polymerization reaction is preferably performed in a solvent.
  • Suitable solvents are disclosed in the above-noted Hay patents.
  • Aromatic solvents such as benzene, toluene, ethylbezene, xylene, and o-dichlorobenzene are especially preferred, although tetrachloromethane, trichloromethane, dichloromethane, 1 ,2-dichloroethane and trichloroethylene may also be used.
  • the weight ratio between solvent and monomer is normally in the range from 1:1 to 20:1 , ie. up to a maximum 20-fold excess of solvent.
  • the ratio between solvent and monomer is preferably in the range from 1 :1 to 10:1 by weight.
  • the process and reaction conditions for the polymerization are modified based on the exact target molecular weight desired.
  • the endpoint of the polymerization is conveniently determined with an in-line viscosity meter. Although other methods such as making molecular weight measurements, running to a predetermined reaction time, controlling to a specified endgroup concentration, or the oxygen concentration in solution may also be utilized.
  • the temperature to carry out the polymerization stage of the invention generally ranges from about 0°C. to about 95°C. More preferably, the temperature range is from about 35°C. to about 45°C with the higher reaction temperature near the end of reaction. At substantially higher temperatures, side reactions can occur leading to reaction by-products and at temperatures substantially lower, ice crystals form in the solution.
  • extractants or chelating agents may be used in the practice of the invention to complex with the catalyst after the end of the polymerization reaction.
  • sulfuric acid, acetic acid, ammonium salts, bisulfate salts and various chelating agents may be used.
  • the copper-amine catalyst becomes poisoned and further oxidation does not take place.
  • Many different materials may be used but it is preferred to employ those chelating agents that are disclosed in U.S. Pat. No. 3,838,102 (Bennett et al.).
  • the useful chelating agents include polyfunctional carboxylic acid containing compounds such as, for example, sodium potassium tartrate, nitrilotriacetic acid (NTA), citric acid, glycine and especially preferably they will be selected from polyalkylenepolyamine polycarboxylic acids, aminopolycarboxylic acids, aminocarboxylic acids, aminopolycarboxylic acids, aminocarboxylic acids, polycarboxylic acids and their alkali metal, alkaline earth metal or mixed alkali metal-alkaline earth metal salts.
  • the preferred agents include ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid and their salts. Especially preferred are ethylenediaminotetraacetic acid or a mono-, di-, tri- and tetrasodium salt thereof and the resulting copper complex can be referred to as a copper carboxylate complex.
  • the chelated metallic catalyst component can be extracted with the water produced in the polymerization reaction by through the use of a liquid/liquid centrifuge.
  • the preferred extraction liquid for use in the process of the invention is an aqueous solution of lower alkanol, i.e., a mixture of water and an alkanol having from 1 to about 4 carbon atoms. Generally from about 1% to about 80% by volume of an alkanol or glycol may be employed. These ratios may vary from about 0.01 :1 to about 10:1 parts by volume of aqueous liquid extractant to discrete organic phase.
  • the reaction media generally comprises an aqueous environment.
  • Anti- solvents can also be utilized in combination with the aqueous media to help drive the precipitation of the copper (I) species.
  • the selection of an appropriate anti-solvent is based partially on the solubility co-efficient of the copper (I) species that is being precipitated.
  • the halides are highly insoluble in water, log K [spl values at 25°C. are - 4.49, - 8.23 and - 11.96 for CuCI, CuBr and Cul, respectively. Solubility in water is increased by the presence of excess of halide ions due to the formation of, e.g., CuCI 2 , CUCI 3 , and CuCI 4 and by other complexing species.
  • Non-limiting examples of anti-solvents would comprise low molecular weight alkyl and aromatic hydrocarbons, ketones, alcohols and the like which in themselves would have some solubility in the aqueous solution.
  • One skilled in the art would be able to select an appropriate type and amount of anti-solvent, if any was utilized.
  • the PPE containing solution is concentrated to a higher solids level as part of the isolation of the PPE.
  • the PPE can be readily functionalized prior to and/or during this solvent removal process by addition of at least one functionalizing agent, also known as compatibilizers or functionalizers.
  • the location of the addition of at least one functionalizing agent will depend on several factors such as the stability of the agent, the volatility of the agent to the isolation conditions, the flexibility of the equipment for addition points, and the like.
  • addition of the functionalizing agent prior to solvent removal is often preferred so as not to remove the functionalizing agent before it has functionalized the PPE. For less volatile functionalizing agents, greater flexibility in the location of the addition is possible.
  • the functionalizing agent includes compounds having both (i) a carbon-carbon double bond or a carbon-carbon triple bond and (ii) at least one species of the group consisting of carboxylic acids, acid anhydrides, acid amides, acid esters, imides, amines, ortho esters, hydroxyls and carboxylic acid ammonium salts.
  • Illustrative compounds useful to accomplish the functionalization of the PPE include maleic anhydride, fumaric acid, maleimides such as N-phenylmaleimide and 1 ,4-phenylene-bis-methylene- alpha , alpha '-bismaleimide, maleic hydrazide, methylnadic anhydride, fatty oils (e.g., soybean oil, tung oil, linseed oil, sesame oil), acrylate ortho esters and methacrylate ortho esters, unsaturated carboxylic acids such as acrylic, crotonic, methacrylic acid and oleic acid, unsaturated alcohols such as allyl alcohol and crotyl alcohol and unsaturated amines such as allylamine and trialkyl amine salts of unsaturated acids such as triethylammonium fumarate and tri-n-butylammonium fumarate. Examples of such typical reagents for preparing useful functionalized PPE are described in U.S. Pat.
  • Non-polymeric aliphatic polycarboxylic acids are also useful for preparing functionalized PPE. Included in the group of species, are, for example, the aliphatic polycarboxylic acids, and acid esters represented by the formula:
  • R is a linear or branched chain, saturated aliphatic hydrocarbon of from 2 to 20, preferably 2 to 10, carbon atoms;
  • R 1 is selected from the group consisting of hydrogen or an alkyl, aryl, acyl, or carbonyl dioxy group of 1 to 10, preferably 1 to 6, most preferably 1 to 4, carbon atoms, with hydrogen being especially preferred;
  • each R" is independently selected from the group consisting of hydrogen or an alkyl or aryl group of from 1 to 20 carbon atoms preferably from 1 to 10 carbon atoms;
  • each R'" and R ⁇ v is independently selected from the group consisting essentially of hydrogen or an alkyl or aryl group of from 1 to 10, preferably from 1 to 6, most preferably 1 to 4, carbon atoms;
  • m is equal to 1 and (n + s) is greater than or equal to 2, preferably equal to 2 or 3, and n and s are each greater than or equal to zero; and wherein (OR 1 ) is alpha or beta to a carbon
  • Suitable polycarboxylic acids are citric acid, malic acid, and agaricic acid; including the various commercial forms thereof, such as, for example, the anhydrous and hydrated acids.
  • Illustrative acid esters useful herein include, for example, acetyl citrate and mono- and/or di-stearyl citrates and the like.
  • Suitable acid amides useful herein include, for example, N,N'- diethyl citric acid amide; N,N'-dipropyl citric acid amide; N-phenyl citric acid amide; N-dodecyl citric acid amide; N,N'-didodecyl citric acid amide and N- dodecyl malic acid amide.
  • Other useful functionalizing agents useful in the process of the invention for preparing functionalized PPE include compounds containing an acyl functional group and at least one species of the group consisting of carboxylic acids, acid anhydrides, acid esters, acid amides, imides, amines, ortho esters, hydroxyls and carboxylic acid ammonium salts.
  • Non-limiting examples include chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride acid chloride, 1-acetoxy-acetyl-3,4-dibenzoic acid anhydride, terephthalic acid acid chloride, and reactive triazines including epoxyalkyl chlorocyanurates and chloroaryloxytriazines. Additional examples can be found in U.S. Pat. Nos. 4,600,741 and 4,642,358.
  • the amount of the above mentioned functionalizing agents that is required to appropriately functionalize the PPE is that which is sufficient to improve the compatibility between the various components in the final composition.
  • indications of improved compatibility include resistance to lamination, improved physical properties such as increased tensile and impact properties and a stabilized morphology between the blend component phases under static or low shear conditions.
  • an effective amount of the above mentioned functionalizers is generally up to about 8% by weight, and is preferably from about 0.05% to about 4% by weight.
  • the amount of functionalizing agent is in the range of about 0.1 % to about 2.0% by weight based on the amount of the PPE.
  • the actual amount utilized will also depend on the molecular weight of the functionalizing agent, the number and type of reactive species per molecule of functionalizing agent and the degree of compatibility that is desired in the final resin blend composition.
  • various techniques for isolating the PPE are useful.
  • the final I.V. of the PPE to utilized is greater than about 0.28 dl/g
  • standard solvent based techniques e.g., precipitation of the PPE containing reaction solution into a non-solvent followed by collection and drying of the PPE are useful.
  • using standard non-solvent techniques typical for PPE having I.V.'s greater than 0.28 dl/g are not generally useful for isolation of lower molecular weight PPE due to the small PPE particle size and friability of the particles. Very low yields are often obtained with undesirable fractionation of oligomeric species.
  • a total isolation process is preferred for isolating the PPE. As part of the total isolation, a portion of the solvent is preferably removed in order to reduce the solvent load on the total isolation equipment.
  • Concentration of the PPE containing solution is accomplished by reducing the pressure in a solvent flash vessel while preferably increasing the temperature of the PPE containing solution. Pressures of about 35 to 50 bar are desirable with solution temperatures increased to at least 200°C, preferably of at least 230°C. A solids level of PPE of at least 55%, preferably of at least 65% or higher is desirable.
  • the isolation of the PPE is typically carried out in a devolatilizing extruder although other methods involving spray drying, wiped film evaporators, flake evaporators, and flash vessels with melt pumps, including various combinations involving these methods are also useful and in some instances preferred.
  • total isolation is preferably from the viewpoint that oligomeric species are not removed to the same degree as with precipitation.
  • isolation yields are extremely high and are near quantitative.
  • Devolatilizing extruders and processes are known in the art and typically involve a twin-screw extruder equipped with multiple venting sections for solvent removal.
  • the resultant solvent level is reduced to less than about 1200 ppm, preferably less than about 600 ppm, and most preferably less than about 400 ppm.
  • the present process preferably comprises PPE obtained through a devolatilization process to remove the solvent.
  • a devolatilizing extruder typically affords a method to prepare low molecular weight polyphenylene ether resin, typically within the intrinsic viscosity range of about 0.08 dl/g to about 0.20 dl/g, in a yield of over 90%, preferably over 95%, more preferably over 98% and most preferably over 99%, based upon the amount of monovalent phenol utilized in the oxidative coupling.
  • Underwater pelletization also results in a significantly lower color in the PPE as compared to the standard stranding with water/air cooling followed by pelletization techniques.
  • Yellowness index (Yl) numbers of less than 30, and even less than 25 are achievable as compared to Yl > 50 achieved with the standard stranding technique.
  • the present invention includes compositions comprising (i) at least one interpolymer and (ii) at least one polyphenylene ether resin having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.20 dl/g, as measured in chloroform at 25°C. wherein the PPE was made by a process that affords a method of preparing a PPE with a Yl of less than about 30, preferably less than about 25.
  • the present invention includes a method to reduce the number of fines having a particle size less than about 850 micron in polyphenylene ether wherein the method comprises underwater pelletization of the polyphenylene ether resin.
  • a preferred embodiment includes a method to prepare the compositions of the invention wherein the method comprises reducing the number of PPE fines having a particle size less than about 850 micron to less than about 3%, preferably less than about 1.5% by weight based on the total weight of the pellets and mixing the PPE with at least one interpolymer.
  • the relative amounts of PPE and interpolymer in the composition can vary widely from 1-99 parts by weight PPE to 99-1 parts by weight interpolymer. For many commercial applications, it is preferred that the level of PPE be adjusted such that the PPE remains a dispersed phase within the interpolymer as a continuous phase. In other preferred embodiments, it is preferred to use a relatively minor proportion of PPE, e.g., up to about 20% by weight.
  • compositions of the present invention can be prepared by a variety of methods involving intimate admixing of the materials with any additional additives desired in the formulation. Suitable procedures include solution blending and melt blending. Because of the availability of melt blending equipment in commercial polymer processing facilities, melt processing procedures are generally preferred. Examples of equipment used in such melt compounding methods include: co-rotating and counter-rotating extruders, single screw extruders, disc-pack processors and various other types of extrusion equipment. In some instances, the compounded material exits the extruder through small exit holes in a die and the resulting strands of molten resin are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets for packaging and further handling.
  • All of the ingredients may be added initially to the processing system, or else certain additives may be pre-compounded with each other. It is also sometimes advantageous to employ at least one vent port in each section between the feed ports to allow venting (either atmospheric or vacuum) of the melt.
  • vent port in each section between the feed ports to allow venting (either atmospheric or vacuum) of the melt.
  • concentrates containing relatively high levels of PPE in the interpolymer may be used that are let down to the desired lower level of PPE with additional interpolymer by, for example, a converter manufacturing sheet products or articles are also contemplated.
  • relatively high level of PPE is meant a concentrate that contains at least 20%, preferably at least 30% by weight, more preferably at least 40% by weight PPE based on the weight of the concentrate.
  • Such concentrates may be primarily composed of the polyphenylene ether resin and the interpolymer or may be composed of another resin such as, for example, a polystyrene resin.
  • the concentrate may also contain one or more of the additives and/or stabilizers as follows.
  • Additives such as antioxidants (e.g., hindered phenols such as, for example, IRGANOX Registered TM 1010), phosphites (e.g., IRGAFOS Registered TM 168)), U.V. stabilizers, cling additives (e.g., polyisobutylene ), antiblock additives, colorants, pigments, fillers, carbon fibers, carbon fibrils, and the like can also be included in the compositions of the present invention, to the extent that they do not interfere with the enhanced properties of the compositions.
  • antioxidants e.g., hindered phenols such as, for example, IRGANOX Registered TM 1010
  • phosphites e.g., IRGAFOS Registered TM 168
  • U.V. stabilizers e.g., polyisobutylene
  • antiblock additives e.g., colorants, pigments, fillers, carbon fibers, carbon fibrils, and the like
  • the additives are employed in functionally equivalent amounts known to those skilled in the art.
  • the amount of antioxidant employed is that amount which prevents the polymer from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers.
  • Such amounts of antioxidants is usually in the range of from about 0.01 to about 10, preferably from about 0.05 to about 5, more preferably from about 0.1 to about 2 percent by weight based upon the weight of the polymer.
  • the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer antiblocking, to produce the desired amount of filler loading to produce the desired result, to provide the desired color from the colorant or pigment.
  • Such additives can suitably be employed in the range of from about 0.05 to about 50, preferably from about 0.1 to about 35 more preferably from about 0.2 to about 20 percent by weight based upon the total weight of the polymers. However, in the instance of fillers, they could be employed up to about 90 percent by weight based on the total weight of the polymers.
  • compositions may further comprise at least of the following optional thermoplastic resins such as, for example, polyolefins, polyetherimides, polyethersulfones, polysulfones, , polyphenylsulfone, syndiotactic or isotactic polystyrenes, polyamides, polyesters, styrenic resins, polsiloxanes, ABS, polyvinyl chloride, polyurethanes, thermoplastic elastomers, and polyarylene sulfides.
  • compositions further comprising polyolefins such as, for example, polyethylene and polypropylene produced by either Ziegler-Natta or metallocene type catalysts.
  • compositions that are substantially free of the aforementioned resins are substantially free of the aforementioned resins.
  • substantially free of is meant compositions that contain less than about 5% by weight, preferably less than 3% by weight, most preferably essentially none of the aforementioned resins based on the total weight of the composition.
  • compositions of the present invention can be utilized to produce a wide range of fabricated articles such as, for example but not limited to, films, sheets or as a components of a multilayered structure resulting from calendering, blowing, casting or (co-)extrusion operations.
  • compositions can find utility in the form of fabricated articles produced, for example, by rotation molding, compression molding, injection molding, blow molding, calendering, sheet extrusion, profile extrusion, or thermoforming operations.
  • compositions can also be used in the manufacture of fibers, foams and lattices.
  • compositions of the present invention can also be utilized in adhesives, adhesive formulations and adhesive/sealant applications.
  • Ethylene/styrene/propylene interpolymers may be prepared by methods known in the art such as found in U.S. 5,872,201.
  • a twin-screw extruder or a single screw extruder may be utilized to melt compound the PPE with the interpolymer. It is important to control the temperature and shear of the molten compositions so as to minimize the degradation of the interpolymer.
  • Concentrates of PPE and another material, preferably interpolymer may also be used directly in calendering, injection molding, blowing, casting, or (co)extrusion operations. Addition of PPE to the interpolymers improves the heat resistance of the interpolymers as well as altering the rheological characteristics. For example flow properties can be enhanced and viscosity matching can be used to control blend morphology.
  • the present invention includes a method for improving the compatibility between PPE and a substantially random interpolymer wherein the method comprises at least one of varying the molecular weight and/or styrene content of the interpolymer and/or varying the molecular weight of the PPE and/or varying the weight ratio of the interpolymer and PPE.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne, d'une manière générale, des nouvelles compositions comprenant: (i) au moins un interpolymère sensiblement aléatoire contenant (a) de l'éthylène; (b) un ou plusieurs monomères de vinylidène aromatiques ou monomères de vinylidène aliphatiques ou cycloaliphatiques; et (c) éventuellement, un ou plusieurs monomères oléfiniques C3 à C20 polymérisables, et (ii) au moins une résine d'éther de polyphénylène présentant une viscosité intrinsèque de l'ordre de 0,05 dl/g à 0,60 dl/g, de préférence de l'ordre de 0,08 dl/g à 0,15 dl/g, mesurée dans du chloroforme à 25 °C. Dans un mode de réalisation préféré, les compositions sont sensiblement exemptes de résines de copolymère bloc élastomère. L'invention concerne également des procédés de fabrication des mélanges ainsi que des articles fabriqués à partir desdits mélanges.
EP00910173A 1999-04-02 2000-02-14 Compositions constituees d'un interpolymere et de resine d'ether de polyphenylene Withdrawn EP1169389A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US285561 1994-08-03
US28556199A 1999-04-02 1999-04-02
PCT/US2000/003763 WO2000060002A1 (fr) 1999-04-02 2000-02-14 Compositions constituees d'un interpolymere et de resine d'ether de polyphenylene

Publications (1)

Publication Number Publication Date
EP1169389A1 true EP1169389A1 (fr) 2002-01-09

Family

ID=23094778

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00910173A Withdrawn EP1169389A1 (fr) 1999-04-02 2000-02-14 Compositions constituees d'un interpolymere et de resine d'ether de polyphenylene

Country Status (7)

Country Link
EP (1) EP1169389A1 (fr)
JP (1) JP2002541293A (fr)
KR (1) KR20010112375A (fr)
CN (1) CN1353739A (fr)
AR (1) AR032582A1 (fr)
AU (1) AU3231100A (fr)
WO (1) WO2000060002A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6894102B2 (en) 2002-05-20 2005-05-17 General Electric Syndiotactic polystyrene blends
US7244813B2 (en) * 2003-08-26 2007-07-17 General Electric Company Methods of purifying polymeric material
US7638566B2 (en) 2006-10-30 2009-12-29 Sabic Innovative Plastics Ip B.V. Poly(arylene ether) compositions
CN101928455A (zh) * 2010-06-30 2010-12-29 中国蓝星（集团）股份有限公司 一种聚苯醚组合物及其提高聚苯醚热稳定性的方法
US8703848B1 (en) * 2012-10-09 2014-04-22 Sabic Innovative Plastics Blends of micronized polyphenylene ether and thermoplastic polyurethanes blend
US20150028247A1 (en) 2013-07-23 2015-01-29 Sabic Innovative Plastics Ip B.V. Rigid foam and associated article and method
US9175160B2 (en) 2013-08-28 2015-11-03 Sabic Global Technologies B.V. Blend of poly(phenylene ether) particles and polyoxymethylene, article thereof, and method of preparation
US9447227B2 (en) 2013-10-03 2016-09-20 Sabic Global Technologies B.V. Flexible polyurethane foam and associated method and article
US9074086B1 (en) * 2013-12-18 2015-07-07 Sabic Global Technologies B.V. Polyolefin composition with poly(phenylene ether) filler and article thereof
CN104130513B (zh) * 2014-08-18 2017-02-08 重庆昆旺电子有限责任公司 一种高分子打包带材料及其制备方法
CN107429022B (zh) * 2015-03-31 2021-01-29 Sabic环球技术有限责任公司 变色发生率减少的光泽聚合物添加剂
EP3390491B1 (fr) 2015-12-16 2021-03-03 SHPP Global Technologies B.V. Procédé pour isoler une composition d'oligomère oxyde de phénylène et composition d'oligomère oxyde de phénylène
CN105860412B (zh) * 2016-04-27 2019-03-12 安徽中鼎橡塑制品有限公司 用于电线电缆的无卤阻燃热塑性弹性体材料及其制备方法
JP6149995B1 (ja) * 2016-09-28 2017-06-21 富士ゼロックス株式会社 非架橋樹脂組成物、及び非架橋樹脂成形体
CN115785603B (zh) * 2021-09-10 2025-10-14 台光电子材料(昆山)股份有限公司 一种树脂组合物及其制品

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS523427B1 (fr) * 1971-04-27 1977-01-27
JPS56104961A (en) * 1980-01-24 1981-08-21 Sumitomo Chem Co Ltd Novel polyphenylene-ether resin composition
US5247006A (en) * 1992-04-03 1993-09-21 General Electric Company Polyphenylene ether-graft-orthoester copolymer blends and method of preparation
ZA977907B (en) * 1996-09-04 1999-03-03 Dow Chemical Co Alpha-olefin/vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers
BR9712009A (pt) * 1996-09-04 2000-01-18 Dow Chemical Co Revestimento para piso, parede ou teto.
US5739200A (en) * 1996-12-17 1998-04-14 The Dow Chemical Company Plasticizied α-olefin/vinylidene aromatic monomer of hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers
AR014306A1 (es) * 1998-01-14 2001-02-07 Dow Chemical Co Mezclas termoplasticas de materiales polimericos, composiciones adhesivas o sellantes que contienen dichas mezclas y hojas, articulos, fibras, espumas olatex preparados utilizando dichas mezclas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0060002A1 *

Also Published As

Publication number Publication date
AR032582A1 (es) 2003-11-19
WO2000060002A1 (fr) 2000-10-12
JP2002541293A (ja) 2002-12-03
AU3231100A (en) 2000-10-23
CN1353739A (zh) 2002-06-12
KR20010112375A (ko) 2001-12-20

Similar Documents

Publication Publication Date Title
EP1169389A1 (fr) Compositions constituees d'un interpolymere et de resine d'ether de polyphenylene
EP0375937B1 (fr) Procédé pour éliminer des substances volatiles de résines polyphénylène-éther ou de compositions de résines polyphénylène-éther/styrène
US7056980B2 (en) Poly(arylene ether) compositions, articles thereof and methods of making them
EP0239347B1 (fr) Composition de résine thermoplastique
EP0048154B1 (fr) Composition de résine pour moulage par injection, méthode de préparation de cette composition et objets moulés de celle-ci
US5156920A (en) Polyphenylene ether resin compositions having improved adhesion for decorative and protective coatings
EP0435023A2 (fr) Procédé pour enlever les matières volatiles des compositions en polyphénylène-éther
US5204410A (en) Method for removing volatile substances from polyphenylene ether or polyphenylene ether/styrene resin compositions
JPH0314855A (ja) 熱可塑性樹脂組成物
EP0362660B1 (fr) Compositions modifiées de résines à base de polyphénylène-éther, qui sont très résistantes à la délamination
JPH0415260B2 (fr)
JPH05262933A (ja) 高分子量ポリエチレン樹脂を含有するポリフェニレンエーテル樹脂を基剤とする組成物
AU2003298788B2 (en) Polyphenylene ether compositions with improved die lip buildup performance
EP1969050A1 (fr) Procede de melange de polymeres, composition et article
WO2000064973A1 (fr) Compositions de resine de copolymere sequence styrenique et de resine de polyphenylene ether
US4740556A (en) Copolymers of alkenyl aromatics, unsaturated carboxylic acid polyphenylene ether resin and diene rubber
EP1431345B1 (fr) Composition des polyaryleneéthers
WO2000046274A1 (fr) Procede de production de polyphenylene ethers fonctionnalises
JP6480261B2 (ja) 樹脂組成物
EP0719832A2 (fr) Compositions thermoplastiques contenant des résines polyéther de phénylène et polyoléfines
CN110628201A (zh) 树脂组合物和成型品
US4826919A (en) Polyphenylene ether compositions having improved flow
JP6533456B2 (ja) 食品容器
EP0520146B1 (fr) Procédé de préparation d'une composition de résine thermoplastique
JP2001302900A (ja) ポリフェニレンエーテル樹脂組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20011102

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20030901

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20040113