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WO1994009071A1 - Melanges de copoly(sulfure d'arylene) et d'ether polyphenylenique - Google Patents

Melanges de copoly(sulfure d'arylene) et d'ether polyphenylenique Download PDF

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Publication number
WO1994009071A1
WO1994009071A1 PCT/US1993/009451 US9309451W WO9409071A1 WO 1994009071 A1 WO1994009071 A1 WO 1994009071A1 US 9309451 W US9309451 W US 9309451W WO 9409071 A1 WO9409071 A1 WO 9409071A1
Authority
WO
WIPO (PCT)
Prior art keywords
admixture
copoly
weight percent
polyphenylene ether
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1993/009451
Other languages
English (en)
Inventor
Shriram Bagrodia
David Richard Fagerburg
Joseph John Watkins
Paul Blakney Lawrence
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.)
Eastman Kodak Co
Eastman Chemical Co
Original Assignee
Eastman Kodak Co
Eastman 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 Eastman Kodak Co, Eastman Chemical Co filed Critical Eastman Kodak Co
Publication of WO1994009071A1 publication Critical patent/WO1994009071A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • 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 relates to blends of a copoly(arylene sulfide) and a polyphenylene ether.
  • Poly(arylene sulfide) resins are thermoplastic polymeric materials with good thermal stability, unusual insolubility, resistance to chemical environments and inherent flame resistance.
  • Poly(arylene sulfide) resins additionally have good electrical insulative properties which make them ideal for electrical and electronic applications. Their excellent resistance to chemical degradation makes them ideal for use in chemical environments which involve organic solvents and strong mineral acids, such as coatings for pipes, tanks, pumps and other equipment.
  • polymers can be prepared by reacting p—dichloro—benzene with sodium sulfide in a polar organic solvent to produce poly(phenylene sulfide) and the by ⁇ product sodium chloride in accordance with U.S. 2,513,188 and U.S. 2,538,941.
  • An improvement on this procedure involves adding N—haloamides as catalysts.
  • x is in the range of 0.5 to 0.001
  • A is a divalent aromatic radical and n is at least 200 and is preferably in the range of 500 to 5,000.
  • this copoly(arylene sulfide) can be blended with a polyphenylene ether.
  • This blend can be broadly described as an admixture of (A) from 99 to l weight percent, based on the weight of the admixture, of a copoly(arylene sulfide) corresponding to the structure
  • A is a divalent substituted or unsubstituted aromatic radical
  • x is in the range of 0.5 to 0.001 and n is at least 25, and
  • copoly(arylene sulfide) polymers useful in this invention are identical to the copoly(arylene sulfide) polymers disclosed in U.S. 4,786,713 and U.S. 4,855,393, herein incorporated by reference, except that the minimum value of n of the copoly(arylene sulfide) polymers useful in this invention is lower than the minimum value of n for the copoly(arylene sulfide) polymers which is disclosed in these references.
  • copoly(arylene sulfide) polymers useful in this invention are therefore inherent in the disclosure of these references because as the molecular weight builds up toward the minimum value of n of at least 200 which is disclosed in these references the molecular weight passes through a molecular weight associated with the lower minimum value of n of 25 of the copoly(arylene sulfide) polymers of this invention.
  • the copoly(arylene sulfide) polymers useful in this invention can be prepared by those skilled in the art by following the teachings of these references and controlling the stoichiometry, time, temperature and other variables of the reaction to achieve a molecular weight associated with a value of n which is at least 25.
  • diiodoaro atic compounds which can be utilized to prepare the copoly(arylene sulfide) useful in this invention, include unsubstituted or substituted aromatics which have two iodine substituents.
  • Preferred diiodoaromatic compounds are the diiodobenzenes, diiodonaphthalenes and diiodobiphenyls which may be unsubstituted or substituted.
  • the diiodoaromatic compounds suitable for the present invention include p—diiodobenzene, m—diiodobenzene, p,p'— diiodobiphenyl, p,p , -diiodobiphenyl, p,p'-diiododiphenyl ether and 2,6-diiodonaphthalene.
  • the diiodo compound is p—diiodobenzene.
  • polyphenylene ethers useful in this invention and the method of their preparation are well known in the art.
  • the polyphenylene ethers correspond to the structure
  • R lf R 2 , R 3 and R are selected from the group consisting of a hydrogen atom, a halogen atom, an aryl group containing 6 to 12 carbons, an alkyl group containing 1 to 4 carbons, an alkoxy group containing 1 to 6 carbons, a haloalkyl group containing 1 to 6 carbons in which at least 2 carbon atoms are present between a halogen atom and the phenyl ring and a haloalkoxy group containing 1 to 6 carbons in which at least 2 carbon atoms are present between a halogen atom.
  • the intrinsic viscosity of the polyphenylene ether is at least 0.35 dl/g as measured in chloroform at 25°C.
  • the polyphenylene ether corresponds to the structure
  • poly(2,6 dimethyl-1,4—phenylene) ether is..often.called poly(2,6 dimethyl-1,4—phenylene) ether.
  • the polyphenylene ether useful in this invention can be prepared by methods well know in the art such as disclosed in U.S. 3,306,874 and 3,236,807.
  • the blends of this invention can be prepared by known techniques for blending polymers.
  • the polymers can be coextruded in convention twin screw extrusion equipment.
  • polymers of both polymers may be admixed and the admixed powders extruded in a single screw extruder.
  • an admixture of powdered polymer is prepared and the admixture powder is extruded in a single screw extruder.
  • the amount of copoly(arylene sulfide) is in the range of 99 to 1 weight percent, preferably 95 to 5 weight percent, based on the weighty of the composition.
  • the amount of polyphenylene ether is in the range of 1 to 99 weight percent, preferably 5 to 95 weight percent, based on the weight of the composition.
  • compositions of this invention can be used for preparation of various shaped articles such as pellets, fibers and molded articles.
  • the polymer can be prepared into these shaped articles by conventional processes, such as injection molding, melt spinning, and melt extrusion.
  • the compositions of this invention can additionally contain fillers, nucleating agents and reinforcing materials in the form of fibers, minerals, powders or mats.
  • the compositions can contain glass fibers, aluminum oxide, calcium oxide, silicon dioxide, Titanium dioxide, copper, kaolin, and the like.
  • compositions of this invention are normally solid in the sense that at typical room temperatures and pressures the compositions are in a solid state as compared to a liquid state.
  • the solid character of the composition results from both polymers having a sufficiently high molecular weight to be a solid.
  • the blends of this invention are characterized by extremely desirable interfacial adhesion between the copoly(phenylene sulfide) and polyphenylene ether. Interfaced adhesion is an important property of a blend of two polymers because it governs the strength of the blended material. When the interfacial adhesion is high, the blends can withstand higher stress before failure for any given morphology.
  • Example 1 This example illustrates the enhanced interfacial adhesion associated with the admixtures of this invention.
  • a copoly(phenylene sulfide) was prepared by the melt phase reaction of sulfur and p-di—iodobenzene, as described in U.S. Patents 4,786,713 and 4,792,600.
  • the value of x was estimated to be 0.10 as determined by elemental analysis.
  • the melt viscosity of copoly(phenylene sulfide) at 300°C at 25 Sec -1 shear rate was 5000 poise.
  • Properties of the product included a melt viscosity of 5000 poise at 300°C and 25 rad/sec, a glass transition temperature of 89°C and an estimated disulfide content of 10 mol percent.
  • An admixture was prepared which contained 95 weight percent of the copoly(phenylene sulfide) and 5 weight percent of a poly(2,6—dimethyl—1,4—phenylene) ether having an intrinsic viscosity of 0.48 dl/g as measured at 25°C in chloroform.
  • the two polymers were cryogenically micropulverized to a particle size less than 1.0 mm.
  • a physical blend of 0.75 g of the polyphenylene ether and 14.25 g of copoly(phenylene sulfide) was made and well mixed.
  • the powdered mixture of the above two polymers 15 g by weight, was dried for at least 12 hours at 90°C in a vacuum oven.
  • the dried polymer mixture was melt extruded into a film at 615°F.
  • the film was cryogenically fractured in liquid nitrogen and the fracture surface morphology was determined using a scanning electron microscope.
  • a scanning electron micrograph of the cryogenically fractured surface clearly shows good interfacial adhesion between the two phases. The particle sizes are quite small and only a few particles are seen separate from the polyphenylene ether matrix.
  • Example 1 illustrates the composition of the invention containing different amounts of copoly(phenylene sulfide) and polyphenylene ether.
  • Example 1 is repeated except that the amount of copoly(phenylene sulfide) is 90 weight percent and the amount of polyphenylene ether is 10 weight percent.
  • the scanning electron micrograph of the cryogenically fractured surface clearly shows good interfacial adhesion between the two phases.
  • Example 1 illustrates the poor interfacial adhesion associated with admixtures of poly(phenylene sulfide) and polyphenylene ether.
  • Example 1 was repeated except that a poly(phenylene sulfide) was used instead of the copoly(phenylene sulfide) .
  • the poly(phenylene sulfide) had a melt shear viscosity of 11,700 poise at 300°C and 25 sec -1 shear rate.
  • the admixture of 95 percent poly(phenylene sulfide) and 5 percent polyphenylene ether was prepared the same way as in Example l.
  • a scanning electron photomicrograph of the fractured surface of the admixture clearly indicates very poor interfacial adhesion between the two phases.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

On décrit une composition obtenue par mélange de (A): 99 à 1 % en poids, rapporté au poids du mélange, d'un copoly(sulfure d'arylène) correspondant à la structure [(-A-S)1-x(-A-S-S-)x]n, où A est un radical aromatique divalent substitué ou non, x est compris entre 0,5 et 0,001 et n est au moins 25 et (B): 1 à 99 % en poids, rapporté au poids du mélange, d'un éther polyphénylénique correspondant à la structure (I), où R1, R2, R3 et R4 sont choisis dans le groupe composé d'un groupe alkyle, un groupe alcoxy, un groupe haloalkyle et un groupe haloalcoxy.
PCT/US1993/009451 1992-10-13 1993-10-01 Melanges de copoly(sulfure d'arylene) et d'ether polyphenylenique Ceased WO1994009071A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US96033192A 1992-10-13 1992-10-13
US960,331 1992-10-13

Publications (1)

Publication Number Publication Date
WO1994009071A1 true WO1994009071A1 (fr) 1994-04-28

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/009451 Ceased WO1994009071A1 (fr) 1992-10-13 1993-10-01 Melanges de copoly(sulfure d'arylene) et d'ether polyphenylenique

Country Status (1)

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WO (1) WO1994009071A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0222199A1 (fr) * 1985-10-17 1987-05-20 Kureha Kagaku Kogyo Kabushiki Kaisha Articles tubulaires extrudés et leur production
EP0341422A2 (fr) * 1988-05-09 1989-11-15 General Electric Company Mélange de polymères comprenant un poly(éther de phénylène) et un poly(sulfure d'arylène)
EP0472960A2 (fr) * 1990-08-14 1992-03-04 Mitsubishi Chemical Corporation Composition de résine thermoplastique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0222199A1 (fr) * 1985-10-17 1987-05-20 Kureha Kagaku Kogyo Kabushiki Kaisha Articles tubulaires extrudés et leur production
EP0341422A2 (fr) * 1988-05-09 1989-11-15 General Electric Company Mélange de polymères comprenant un poly(éther de phénylène) et un poly(sulfure d'arylène)
EP0472960A2 (fr) * 1990-08-14 1992-03-04 Mitsubishi Chemical Corporation Composition de résine thermoplastique

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