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WO1992019682A1 - Melanges de copoly (arylene sulfure) et de polyamide - Google Patents

Melanges de copoly (arylene sulfure) et de polyamide Download PDF

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Publication number
WO1992019682A1
WO1992019682A1 PCT/US1992/003671 US9203671W WO9219682A1 WO 1992019682 A1 WO1992019682 A1 WO 1992019682A1 US 9203671 W US9203671 W US 9203671W WO 9219682 A1 WO9219682 A1 WO 9219682A1
Authority
WO
WIPO (PCT)
Prior art keywords
copoly
range
weight
admixture
polyamide
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/US1992/003671
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
Original Assignee
Eastman Kodak 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 filed Critical Eastman Kodak Co
Priority to JP4511978A priority Critical patent/JPH06507440A/ja
Publication of WO1992019682A1 publication Critical patent/WO1992019682A1/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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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

Definitions

  • the invention relates to blends of a copoly(arylene sulfide) and a polyamide.
  • 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
  • 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
  • n is at least 200 and is preferably in the range of 500 to 5,000.
  • 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
  • (B) from 0.5 to 50 weight percent, based on the weight of the admixture, of two particular types of pol amides.
  • the copol (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 copol (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 miminu 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 stoichiometery, time, temperature and other variables of the reaction to achiefe a molecular weight associated with a value of n which is at least 25.
  • diiodoaromatic 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.
  • polyamides useful in this invention and the method of their preparation are well known in the art.
  • One polyamide useful in this invention corresponds to the structure
  • a is an integer in the range of 4 to 12 and is preferably 4,
  • R corresponds to the structure (-CH 2 -) b wherein b is an integer in the range of 4 to 13 and is preferably 6 or to the structure
  • a 4 and b is 6
  • the polyamide is often called poly(hexamethylene adipamide)
  • the polyamide is often called poly(cyclohexylene adipamide) .
  • Another polyamide useful in this invention corresponds to the structure
  • d is an integer in the range of 5 to 11, and is preferably 5,
  • m is at least 50 and preferably is at least 75.
  • poly(e— caprolactam) examples include poly(e— caprolactam); poly(enantholactam) , poly(w—undecaneamide) , poly(capryllactu ) , and poly(w-pelargonamide) .
  • d is 5 the polyamide is often called poly(e—caprolactam) .
  • 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 99.5 to 50 weight percent, preferably 98 to 75 weight percent, based on the weight of the admixture.
  • the amount of polyamide is in the range of 0.5 to 50 weight percent, preferably 2 to 25 weight percent, based on the weight of the admixture.
  • 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 enhanced rate of crystallization of the composition of this invention is extremely significant. High rates of crystallization enables crystalline-shaped articles, such as molded parts, extruded fibers or drawn film, to be more easily prepared because processing time is saved, thereby increasing production efficiency.
  • the crystallization rate of the composition of the invention is measured by the difference in the DSC transitions of Tec — Teh, often referred to by those skilled in the art as the quantity "delta". If two polymers were blended together one would expect the delta value of the blend to be the linear weighted average of the two component polymers. This relationship can be expressed by the equation
  • delta blend delta- L x weight fraction ! + delta 2 x weight fraction 2
  • the resultant delta blend would be expected to be the average of elta and delta 2 .
  • the transitions Tec and Teh are defined by heating the polymer sample in a Differential Scanning Calorimeter (DSC) instrument at a scan rate of 20°C/ ⁇ in.
  • the Tec is determined by heating the polymer to a molten state, usually 300°c and then cooling at 20°C/min.
  • the peak of the exotherm observed is defined as the Tec.
  • the Teh is determined by heating a sample of polymer to the melt again and quenching the sample onto a metal block cooled in dry ice. The thus produced glassy sample is then heated from room temperature up to a melt.
  • the peak of the exotherm observed in this heating sequence is defined as the Teh.
  • DSC differential scanning calorimetry
  • Copoly(phenylene sulfide) This example illustrates the slow crystallization rate of copoly(phenylene sulfide) .
  • Copoly(phenylene—sulfide) was prepared according to the procedure described in U.S. Patent No. 4,786,713.
  • the copoly(phenylene sulfide) had a melt viscosity of about 74,000 poise at 320°C at a shear rate of 25 sec -1 .
  • the value of x for the copoly(phenylene sulfide) was estimated to be about 0.094 based on elemental analysis.
  • the polymer had a glass transition temperature of about 94°C as measured by Differential Scanning Calorimetry.
  • the glass transition temperature were determined as follows: the sample was first heated from room temperature to 330° at a heating rage of 20°C/min (first heating cycle) . The sample was held at 330°C for one minute and subsequently quenched to room temperature at 320°C/min. In the second reheat cycle, it was heated at 20°CHiin to 330°C, held for one minute at 330°C, and then cooled at 20°C/min. The temperature of crystallization, Teh, was obtained from the exothermic peak temperature during the second reheat cycle. The temperature of crystallization upon cooling. Tec was obtained during the cooling scan from the melt.
  • the copoly(phenylene sulfide) has a melting point of 265°C as measured by 1st cycle heating scan on DSC.
  • the copoly(phenylene sulfide) did not show any significant crystallization exotherm during second heating scan or subsequent cooling scan from the melt, thus establishing that the copoly(phenylene sulfide) has a very slow crystallizing material.
  • compositions of this invention composed of copoly(phenylene sulfide) and poly(hexamethylene adipamide) .
  • Powder of the copoly(phenylene sulfide) prepared in Example 1 was admixed with powdered poly(hexamethylene adipamide) , to make a blend containing 80% by weight copoly(phenylene sulfide) and 20% by weight of poly(hexamethylene adipamide) .
  • the admixture was dried at 90° for 12 hours in a forced air-circulated oven.
  • the polymer admixture was extruded thru an extruder.
  • the temperature at the end of the die was kept at about 300°C and the rpm of the screw was about 90.
  • the extruded material was analyzed by DSC for thermal transitions.
  • the blended material had a Teh (temperature of crystallization during second heating) of about 112°C.
  • DSC experiment was performed as follows. The sample was first heated from room temperature to 330°C at a heating rate of (first heating cycle) . The sample was held at 330°C for one minute and subsequently quenched to room temperature at 320°Cmin. In the second reheat cycle, it was heated at 20°C/min to 330°C, held for one minute at 330°C, and then cooled at 20°C/min. The temperature of crystallization, Teh, was obtained from the exothermic peak temperature during the second reheat cycle. The temperature of crystallization upon cooling. Tec was obtained during the cooling scan from the melt. Tec for the blend was about 222°C. These data illustrate that the compositions of this invention exhibits an enhanced rate of crystallization composed to that of only copoly(phenylene sulfide) .
  • This example illustrates the faster crystallization rate of the composition of this invention.
  • Example 2 was repeated except that the amount of poly(hexamethylene adipamide) was 5% by weight.
  • the melt blended material had a Teh of 130.3°C and Tec of 202.5°C.
  • the crystallization rate is much higher as compared to 100% copoly(phenylene sulfide) of Example 1.
  • This example illustrates the faster crystallization rate of the composition of this invention.
  • Example 2 is repeated except that the amount of poly(hexamethylene adipamide) is reduced to 1% by weight.
  • the melt blended material had a Teh of 134°C and tec of 208°C.
  • This example illustrates the faster crystallization rate of the composition of this invention.
  • Example 2 is repeated except that the amount of poly(hexamethylene adipamide) is reduced to 0.5% by weight.
  • the melt blended material had a Teh of 167°C and Tec of 153.4°C.
  • This example illustrates the faster crystallization rate of the composition of this invention comprises copoly(phenylene sulfide) and poly(e-caprolactam) .
  • Five weight % poly(e—caprolactam) was melt blended with 95 weight % of the copoly(phenylene sulfide) used in Example 1.
  • DSC transitions showed a Teh of 123°C and Tec of 195.7°C.
  • This example illustrates the faster rate of crystallization of the composition of this invention.

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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)

Abstract

Composition comprenant un mélange de: (A) un copoly (arylène sulfure) correspondant à la structure [(-A-S-)1-x(-A-S-S-)x]n où (A) représente un radical aromatique bivalent substitué ou non substitué, x se situe dans une plage comprise entre 0,5 et 0,001, et n vaut au moins 25, et (B) un polyamide correspondant à la structure générale (I) ou à la structure générale (II).
PCT/US1992/003671 1991-05-06 1992-05-04 Melanges de copoly (arylene sulfure) et de polyamide Ceased WO1992019682A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4511978A JPH06507440A (ja) 1991-05-06 1992-05-04 コポリ（アリーレンスルフィド）及びポリアミドのブレンド

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69637891A 1991-05-06 1991-05-06
US696,378 1991-05-06

Publications (1)

Publication Number Publication Date
WO1992019682A1 true WO1992019682A1 (fr) 1992-11-12

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PCT/US1992/003671 Ceased WO1992019682A1 (fr) 1991-05-06 1992-05-04 Melanges de copoly (arylene sulfure) et de polyamide

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EP (1) EP0588885A1 (fr)
JP (1) JPH06507440A (fr)
CA (1) CA2109079A1 (fr)
WO (1) WO1992019682A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101183780B1 (ko) * 2006-08-24 2012-09-17 에스케이케미칼주식회사 폴리아릴렌 설파이드의 제조방법
WO2014046483A1 (fr) 2012-09-19 2014-03-27 에스케이케미칼주식회사 Composition de résine de poly(sulfure d'arylène) et article formé

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4528335A (en) * 1984-05-18 1985-07-09 Phillips Petroleum Company Polymer blends
EP0440429A2 (fr) * 1990-02-02 1991-08-07 Tosoh Corporation Composition de poly(sulfure de phénylène)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4528335A (en) * 1984-05-18 1985-07-09 Phillips Petroleum Company Polymer blends
EP0440429A2 (fr) * 1990-02-02 1991-08-07 Tosoh Corporation Composition de poly(sulfure de phénylène)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX LATEST Derwent Publications Ltd., London, GB; AN 91-123014 & JP,A,3 064 358 (ASAHI CHEMICAL IND) 19 March 1991 *

Also Published As

Publication number Publication date
CA2109079A1 (fr) 1992-11-07
JPH06507440A (ja) 1994-08-25
EP0588885A1 (fr) 1994-03-30

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