EP0631595A1 - Polyphenylene ether coiffe ameliore destine a des melanges a haute resistance aux chocs et leur procede de preparation - Google Patents

Polyphenylene ether coiffe ameliore destine a des melanges a haute resistance aux chocs et leur procede de preparation

Info

Publication number
EP0631595A1
EP0631595A1 EP93903507A EP93903507A EP0631595A1 EP 0631595 A1 EP0631595 A1 EP 0631595A1 EP 93903507 A EP93903507 A EP 93903507A EP 93903507 A EP93903507 A EP 93903507A EP 0631595 A1 EP0631595 A1 EP 0631595A1
Authority
EP
European Patent Office
Prior art keywords
polyphenylene ether
capped
capped polyphenylene
reaction mixture
accordance
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Withdrawn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
EP93903507A
Other languages
German (de)
English (en)
Inventor
James Christopher Blubaugh
Sterling Bruce Brown
Patrick R. Dudley
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
Priority claimed from US07/634,578 external-priority patent/US5194517A/en
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP0631595A1 publication Critical patent/EP0631595A1/fr
Withdrawn legal-status Critical Current

Links

Definitions

  • removal of the salts during the isolation process affords a method to remove a substantial portion of the salts.
  • the isolation process may include precipitation of the capped polyphenylene ether by contact with a nonsolvent.
  • a nonsolvent used is an alcohol, as for example methanol, the preferred procedures include the following.
  • precipitation of the capped polyphenylene ether can be carried out with nonsolvent, followed by collection with a filtration or centrifugation step and washing with additional -6-
  • nonsolvent or with a mixture of nonsolvent for the capped polyphenylene ether and up to 10% water.
  • each Q 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; each Q2 i.s independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for
  • X is an alkyl, cycloalkyl or aromatic radical
  • R is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or substituted aromatic hydrocarbon radical.
  • compositions are prepared so as to have alkali metal ions and ammonium ions at a level no higher than 150 ppm and preferably about 20 ppm or less. This range includes the complete absence of such ions.
  • compositions prepared using chlorotriazines include but are not limited to phosphatetriazine capped polyphenylene ethers which can be obtained as set forth in U.S. Patent Application Serial No. 07/534,595, filed June 7, 1990, which is incorporated by reference herein.
  • blends of phosphatetriazine capped polyphenylene ethers can be prepared in accordance with U.S. Patent Application Serial No. 07/534,573, filed June 7, 1990, which is incorporated by reference herein.
  • the compositions of this invention may be prepared as described hereinafter from the polyphenylene ethers known in the art. The latter encompass numerous variations and modifications all of which are applicable to the present invention, including but not limited to those described hereinafter.
  • the polyphenylene ethers comprise a plurality of structural units having the formula
  • Suitable homopolymers are those containing, for example, 2,6-dimethyl-l,4-phenylene ether units.
  • Suitable copolymers include random copolymers containing such units in combination with (for example) 2,3,6-trimethyl-l,4-phenylene ether units.
  • Many suitable random copolymers, as well as homopolymers, are disclosed in the patent literature.
  • Suitable polymers are the coupled polyphenylene ethers in which the coupling agent is reacted in known manner with the hydroxy groups of two polyphenylene ether chains to produce a higher molecular weight polymer containing the reaction product of the hydroxy groups and the coupling agent, provided substantial proportions of free hydroxy groups remain present.
  • Illustrative coupling agents are low molecular weight polycarbonates, guinones, heterocycles and formals.
  • the polyphenylene ethers are typically prepared by the oxidative coupling of at least one corresponding monohydroxyaromatic compound.
  • each Q 1 is methyl and each Q2 is hydrogen
  • the polymer may be characterized as a poly(2,6-dimethyl-l,4-phenylene ether), and
  • a variety of catalyst systems are known for the preparation of polyphenylene ethers by oxidative coupling. There is no particular limitation as to catalyst choice and any of the known catalysts can be used. For the ' most part, they contain at least one heavy metal compound such as a copper, manganese or cobalt compound, usually in combination with various other materials.
  • a first class of preferred catalyst systems consists of those containing a copper compound. Such catalysts are disclosed, for example, in U.S. Patents 3,306,874, 3,306,875, 3,914,266 and 4,028,341. They are usually combinations of cuprous or cupric ions, halide (i.e., chloride, bromide or iodide) ions and at least one amine.
  • Catalyst systems containing manganese compounds constitute a second preferred class. They are generally alkaline systems in which divalent manganese is combined with such anions as halide, alkoxide or phenoxide. Most often, the manganese is present as a complex with one or more complexing and/or chelating agents such as dialkylamines, alkanolamines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds, -hydroxyoximes (monomeric and polymeric), o-hydroxyaryl oximes and ⁇ -diketones. Also useful are known cobalt-containing catalyst systems. Suitable manganese and cobalt-containing catalyst systems for polyphenylene ether preparation are known in the art by reason of disclosure in numerous patents and publications.
  • R is independently hydrogen or alkyl, with the proviso that the total number of carbon atoms in both
  • Polymers with 4-hydroxybiphenyl end groups of formula V are often especially useful in the present invention. They are typically obtained from reaction mixtures in which a by-product diphenoquinone of the formula
  • polyphenylene ethers containing substantial amounts of unneutralized amino nitrogen may afford compositions with undesirably low impact strengths.
  • the possible reasons for this are explained hereinafter.
  • the amino compounds include, in addition to the aforementioned aminoalkyl end groups, traces of amine (particularly secondary amine) in the catalyst used to form the polyphenylene ether.
  • the present invention therefore includes the use of polyphenylene ethers in which a substantial proportion of amino compounds has been removed or inactivated.
  • Polymers so treated contain unneutralized amino nitrogen, if any, in amounts no greater than 800 ppm and more preferably in the range of about 100-800 ppm. -18-
  • polyphenylene ethers contemplated for use in the present invention include all those presently known, irrespective of variations in structural units or ancillary chemical features.
  • the end groups on the epoxytriazine-capped polyphenylene ethers in the compositions of this invention have formula I, in which Q 1 and Q2 are as previously defined.
  • X may be an alkyl or cycloalkyl radical, typically lower alkyl and especially primary or secondary lower alkyl; an aromatic radical, typically monocyclic and containing
  • R may be aliphatic, alicyclic, aromatic (including aromatic radicals containing art-recognized substituents) or heterocyclic. It is usually lower alkylene and especially methylene.
  • Methods for preparing the above-described epoxytriazine-capped polyphenylene ether compositions comprise contacting under reactive conditions, in the presence of a basic reagent, at least one polyphenylene ether with an epoxychlorotriazine of the formula
  • epoxychlorotriazines of formula VIII include 2-chloro- ,6-diglycidoxy-l,3,5-triazine (hereinafter "DGCC”),
  • Typical phosphatetriazines include 2-chloro- (2-diethylphosphatoethoxy)-6-(2,4,6- trimethylphenoxy)-l,3,5-triazine,2-chloro-4-(2- dibutylphosphatoethoxy)-6-(2,4,6-trimethylphenoxy)- 1,3,5-triazine, and
  • the reaction is conducted in solution in a non-polar organic liquid such as toluene, typically at a temperature in the range of about 80-150 ⁇ C and preferably about 100-125°C.
  • a non-polar organic liquid such as toluene
  • the basic reagent employed in this method should be soluble in the organic liquid and is generally a tertiary amine. Its identity is not otherwise critical, provided it is sufficiently non-volatile to remain in the reaction mixture at the temperatures employed. Pyridine is often preferred.
  • the triazine-capped polyphenylene ether may be isolated by conventional methods, typically by precipitation with a non-solvent.
  • non-solvents which may be employed are methanol, 1-propanol, acetone, acetonitrile and mixtures thereof.
  • polyphenylene ethers are among those which can be employed in this invention:
  • PPE - a poly(2,6-dimethyl-l,4-phenylene ether) having an intrinsic viscosity in chloroform at 25°C of 0.40 dl./g.
  • Percentages of epoxytriazine in the capped polymer can be determined from the relative areas of peaks in the nuclear magnetic resonance spectrum attributable to hydrogen atoms in the epoxy and aromatic moieties. Chlorine percentages can be determined by quantitative x-ray fluorescence.
  • Epoxytriazine-capped polyphenylene ethers of this invention differ from those of prior disclosures in that the alkali metal ion concentration and ammonium ion concentration are kept at a level below 150 ppm, which includes complete absence of such ions, which usually, if present, are present in salt form.
  • alkali metal hydroxide such as sodium hydroxide
  • alkali metal chlorides can be produced as by-products of the capping reaction. If neutralization of excess alkali metal hydroxide is employed, other salts will also be produced, depending upon the exact stoichiometry employed in the capping reaction.
  • water can be added to the precipitation reaction mixture, followed by separation of ' the liquid phases, collection of the precipitated triazine-capped polyphenylene ether material by filtration, centrifugation, or settling and decanting steps and washing the collected material with additional nonsolvents such as methanol.
  • additional nonsolvents such as methanol.
  • the low alkali metal salt and ammonium ion capped polyphenylene ethers of this invention can be mixed with polyesters or polyamides in conventional blending steps and proportions to obtain high impact materials.
  • the polyesters or polyamides are mixed with the capped polyphenylene ethers of this invention in amounts of 20-80% by weight of the polyester, polyamide, or mixtures thereof, to the capped polyphenylene ether, although mixtures outside of these ranges may also be useful and have improved impact strength.
  • each R is independently a divalent aliphatic, alicyclic or aromatic hydrocarbon or polyoxyalkylene radical and A is a divalent aromatic radical.
  • They include thermoplastic polyesters illustrated by poly(alkylene dicarboxylates) , elastomeric polyesters, polyarylates, and polyester copolymers such as copolyestercarbonates. Because the principal reaction which occurs with the epoxy groups in the capped polyphenylene ether involves a carboxylic acid group of the polyester, it is highly preferred that said polyester have a relatively high carboxylic end group concentration. Concentrations in the range of about 5-250 microequivalents per gram are generally suitable, with 10-100 microequivalents per gram being preferable, 30-100 being more preferable and 40-80 being particularly desirable.
  • the polyester generally has a number average molecular weight in the range of about 20,000-70,000, as determined by intrinsic viscosity (IV) at 30 ⁇ C in a mixture of 60% (by weight) phenol and 40% 1,1,2,2-tetrachloroethane.
  • polyamides and polyamide precursor materials are provided in U.S. Patent 4,755,566, issued to J. Yates, III, the entire contents of which are incorporated herein by reference.
  • suitable polyamides are provided in U.S. Patents 4,732,938 (Grant et al.), 4,659,760 (van der Meer), and 4,315,086 (Ueno et al.), each also incorporated herein by reference.
  • the polyamide used may also be one or more of those referred to as "toughened nylons", which are often prepared by blending one or more polyamides with one or more polymeric or copolymeric elastomeric toughening agents.
  • examples of these types of materials are given in U.S. Patents 4,174,358; 4,474,927; 4,346,194; 4,251,644; 3,884,882; 4,147,740; all incorporated herein by reference, as well as in a publication by Gallucci et al, "Preparation and Reactions of Epoxy-Modified Polyethylene", J.APPL.POLY.SCI. , V.27, PP. 425-437 (1982) .
  • Additional suitable impact modifiers include various elastomeric copolymers, of which examples are ethylene-propylene-diene polymers (EPDM's), both unfunctionalized and functionalized with (for example) sulfonate or phosphonate groups; carboxylated ethylene-propylene rubbers; polymerized cycloalkenes; and block copolymers of alkenylaromatic compounds such as styrene with polymerizable olefins or dienes, including butadiene, isoprene, chloroprene, ethylene, propylene and butylene.
  • core-shell polymers including those containing a poly(alkyl acrylate) core attached to a polystyrene shell via interpenetrating network, and more fully disclosed in U.S. Patent 4,681,915.
  • tapeered linear block copolymers may also be included in the compositions of the present invention, usually at levels of about 1% by weight to about 20% by weight, based on the weight of the entire composition. These materials are also generally described in the above-referenced application serial number 589,871. Tapered styrene-butadiene-styrene (SBS) linear copolymers are especially preferred, such as FINACLEAR 520, also available from Fina Company.
  • SBS Tapered styrene-butadiene-styrene
  • polyepoxide epoxide moieties
  • Illustrative compounds of this type are homopolymers of such compounds as glycidyl acrylate and glycidyl methacrylate, as well as copolymers thereof, preferred comonomers being lower alkyl acrylates, methyl methacrylate, acrylonitrile and styrene. Also useful are epoxy-substituted cyanurates and isocyanurates such as triglycidyl isocyanurate.
  • the other polyepoxide may be introduced by blending with the other components in a single operation. However, its effectiveness may be maximized by preblending with the polyester, typically by dry mixing followed by extrusion. Such preblending frequently increases the impact strength of the composition. While the reason for the effectiveness of the other polyepoxide is not entirely understood, it is believed to increase molecular weight, melt viscosity and degree of branching of the polyester by reaction with carboxylic acid end groups of a portion of the polyester molecules.
  • ingredients such as fillers, reinforcing agents, drip retardants, plasticizers, flame retardants, pigments, dyes, ultraviolet light stabilizers, heat stabilizers, anti-static agents, crystallization aids, mold release agents and the like, as well as resinous components not previously discussed.
  • Polyesters and impact modifiers useful in this invention include but are not limited to the following:
  • PET various poly(ethylene terephthalates).
  • PBT - a poly(butylene terephthalate) having a number average molecular weight of about 50,000, as determined by gel permeation chromatography.
  • PATME a commercially available elastomeric polyterephthalate from a mixture of tetramethylene glycol, hexamethylene glycol and poly(tetramethylene ether) glycol.
  • PTME(50,000) and PTME(54,000) - commercially available elastomeric polyterephthalates from mixtures of tetramethylene glycol and poly(tetramethylene ether) glycol, having the designated number average molecular weights and about 20% and 50% by weight, respectively, of poly(tetramethylene ether) glycol units.
  • PIE - a copolyester prepared from 1,4-butanediol and a 0.91:1 (by weight) mixture of dimethyl terephthalate and the diimide-diacid reaction product of trimellitic acid and a polyoxypropylenediamine having an average molecular weight of about 2000.
  • Resin blends can be prepared by drying, mixing and extruding on a twin-screw extruder, as for example at 400 rpm and 190-255°C. Extrudates can be quenched in water, pelletized, oven dried and then molded, as for example at 280°C into test specimens which can be tested for notched Izod impact strength.
  • a capped polyphenylene ether made in accordance with Examples 2-4 is blended with polymers, as shown in the Examples below:
  • Table 2 of Example 6 illustrates the value of washing as in Example 2, using the blend proportions described in Example 5. The samples show higher impact values with low sodium levels in the final blend.

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  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On a préparé des polyphénylène éthers coiffés en faisant réagir un polyphénylène éther avec des matières époxydiques dans des procédés qui permettent d'obtenir de faibles niveaux d'ions de métaux alcalins et d'ions ammonium dans le produit final. Ces polyphénylène éthers coiffés d'ions de métaux alcalins et d'ions ammonium de faible niveau sont particulièrement utiles pour former des mélanges à haute résistance aux chocs avec des polyesters et des polyamides, lesquels sont des compositions de moulage très utiles.
EP93903507A 1990-12-27 1993-01-15 Polyphenylene ether coiffe ameliore destine a des melanges a haute resistance aux chocs et leur procede de preparation Withdrawn EP0631595A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/634,578 US5194517A (en) 1990-12-27 1990-12-27 Capped polyphenylene ether for high impact blends and method of preparation
PCT/US1993/000359 WO1994015992A1 (fr) 1990-12-27 1993-01-15 Polyphenylene ether coiffe ameliore destine a des melanges a haute resistance aux chocs et leur procede de preparation

Publications (1)

Publication Number Publication Date
EP0631595A1 true EP0631595A1 (fr) 1995-01-04

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EP93903507A Withdrawn EP0631595A1 (fr) 1990-12-27 1993-01-15 Polyphenylene ether coiffe ameliore destine a des melanges a haute resistance aux chocs et leur procede de preparation

Country Status (2)

Country Link
EP (1) EP0631595A1 (fr)
JP (1) JPH07504941A (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9415992A1 *

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