Kureha Kagaku Kogyo Kabushiki Kaisha

Kureha Kagaku Kogyo K.k.

Polyplastics Co., Ltd.

Kureha Kabaku Kogyo K.k.

Yo Iizuka

Takayuki Katto

Zenya Shiiki

Toshitaka Kouyama

Yoshikatsu Satake

Takao Iwasaki

Toshiya Mizuno

Toshio Hosokawa

Takashi Kaneko

Yukichika Kawakami

Yutaka Kobayashi

Ken Kashiwadate

Makoto Fukuda

Shunzo Endo

Kenichi Katase

Shinji Yamamoto

Teruo Sakagami

Naohiro Murayama

Yukio Ichikawa

Yasuo Sakaguchi

Hiroyuki Endo

Haruhiko Yusa

Toshio Enoki

Takao Ichii

Kazuo Kusida

Yoshinobu Itoh

Susumu Midorikawa, Deceased

Masahito Tada

Masaki Ohya

Akio Kobayashi

Tsuneo Okamoto

Hideyuki Yasumi

Humio Akutsu

Susumu Midorikawa

Kiyoshi Midorikawa, Heir

Sirou Suzuki

Yumi Midorikawa, Heir

By Taeko Midorikawa, Heir

Harunobu Egawa

The present invention discloses a process for producing a granular polyarylene sulfide which has a high melt viscosity and a high degree of cross-linkage, becomes gel under melting and is easy to handle in the production and the fabrication thereof. The process disclosed herein comprises (1) a step (A) an initial-stage polymerization step for obtaining a polyarylene sulfide by reacting an alkali metal sulfide, a dihaloaromatic compound and a polyhaloaromatic compound, having three or more halogen substituents in a molecule, in the presence of water in an amount of 0.5 to 2.9 moles per mol of said alkali metal sulfide at a temperature in the range of 180.degree. to 235.degree. C. until the total conversion ratio of said dihalo- and polyhaloaromatic compounds reaches 50 to 98% and the melt viscosity of a polyarylene sulfide obtained at the end of the step becomes 5 to 5,000 poise, measured at 310.degree. C. and a shear rate of 1,200/second; (2) a step (B) a temperature raising step in which while adjusting an amount of water to be 2.5 to 7 moles per mol of fed alkali metal sulfide, a temperature raising condition from the temperature of step (A) to 240.degree. C. is controlled so that the melt viscosity of a polymer obtained at 240.degree. C. reaches 300 to 10,000 poise, measured at 310.degree. C. and a shear rate of 1,200/second and the temperature raising rate between 240.degree. C. and a temperature of the following step (C) is further controlled to be within the range of 10.degree. to 100.degree. C./hour; and (3) a step (C) a second-stage polymerization step for further continuing the reaction at a temperature of 245.degree. to 290.degree. C. until a melt viscosity of the final product reaches not lower than 1.times.10.sup.5 poise, measured at 330.degree. C. and a shear rate of 2/second. The present invention also discloses a granular cross-linked polyarylene sulfide produced by the process described above.

Process for the preparation of cross-linked polyarylene sulfide

The present invention discloses a process for producing a granular polyarylene sulfide which has a high melt viscosity and a high degree of cross-linkage, becomes gel under melting and is easy to handle in the production and the fabrication thereof. The process disclosed herein comprises (1) a step (A) an initial-stage polymerization step for obtaining a polyarylene sulfide by reacting an alkali metal sulfide, a dihaloaromatic compound and a polyhaloaromatic compound, having three or more halogen substituents in a molecule, in the presence of water in an amount of 0.5 to 2.9 moles per mol of said alkali metal sulfide at a temperature in the range of 180.degree. to 235.degree. C. until the total conversion ratio of said dihalo- and polyhaloaromatic compounds reaches 50 to 98% and the melt viscosity of a polyarylene sulfide obtained at the end of the step becomes 5 to 5,000 poise, measured at 310.degree. C. and a shear rate of 1,200/second; (2) a step (B) a temperature raising step in which while adjusting an amount of water to be 2.5 to 7 moles per mol of fed alkali metal sulfide, a temperature raising condition from the temperature of step (A) to 240.degree. C. is controlled so that the melt viscosity of a polymer obtained at 240.degree. C. reaches 300 to 10,000 poise, measured at 310.degree. C. and a shear rate of 1,200/second and the temperature raising rate between 240.degree. C. and a temperature of the following step (C) is further controlled to be within the range of 10.degree. to 100.degree. C./hour; and (3) a step (C) a second -stage polymerization step for further continuing the reaction at a temperature of 245.degree. to 290.degree. C. until a melt viscosity of the final product reaches not lower than 1.times.10.sup.5 poise, measured at 330.degree. C. and a shear rate of 2/second. The present invention also discloses a granular cross-linked polyarylene sulfide produced by the process described above.

Disclosed herein is a process for the production of a polyarylenesulfide, wherein an alkali metal sulfide is reacted with a dihalo-aromatic compound in an organic amide solvent. The process comprises causing at least one compound selected from the oxides and hydroxides of alkaline earth metals to exist in a proportion not less than 0.01 mole but less than 0.1 mole per mole of the alkali metal sulfide charged in the reaction system, and performing the reaction of the alkali metal sulfide and dihalo-aromatic compound while raising the temperature by at least two stages in the presence of water in an amount defined in a specific range. A high-molecular weight linear polyarylenesulfide can be provided without use of a crosslinking agent or a polymerization aid.

Process for production of polyarylenesulfides

Disclosed herein are a polymer alloy prepared by polymerizing 0.1 to 100 parts by weight of at least one radically polymerizable monomer to 100 parts by weight of polyarylene thioether having a repeating unit of ##STR1## as a main constituent and at least a part of said radically polymerizable monomers is polymerized within inner pores of the polyarylene thioether particles and a process for producing the polymer alloy. The polymer alloy of polyarylene thioether according to the present invention has the fine particles of the radically polymerized monomer uniformly dispersed in the said polymer alloy, and accordingly, the polymer alloy of polyarylene thioether according to the present invention is excellent in various physical properties, such as, good impact strength and improved anti-flash property.

Polymer alloy of polyarylene thioether and a process for producing the

Heat-resistant resin composition including (A) 100 parts by weight of a poly(arylene sulfide) of a substantially linear structure containing 50% by weight or higher or recurring units of the formula ##STR1## and a logarithmic viscosity number of 0.1 to 1.0 dl/g; (B) from 0.01 to less than 25 parts by weight of a melt-stable poly(arylene thioether-ketone) having predominant recurring units of the formula ##STR2## wherein the --CO-- and --S-- are in the para position to each other, and having a melting point of 310.degree.-380.degree. C., a residual melt crystallization enthalpy of at least 10 J/g, a melt crystallization temperature of at least 210.degree. C. and a reduced viscosity of 0.2 to 2 dl/g; and (C) at least one of fibrous fibers and/or at least one of inorganic fillers in a proportion of 0 to 400 parts by weight per 100 parts by weight of the resin component including said poly(arylene sulfide) and said poly(arylene thioether-ketone). Heat-resistant articles obtained by melt-molding or forming said resin compositions and a method for the production of such articles are also described.

Heat-resistant resin compositions, and heat-resistant molded or formed

A film having high lubricity and excellent dielectric strength characteristics and containing few fish eyes is obtained by biaxially-stretching a resin composition which has been obtained by radical polymerization of 0.5-80 parts by weight of a monomer component composed principally of a styrene monomer in the presence of 100 parts by weight of particles of a substantially straight-chain poly(arylene sulfide) having a melt viscosity of at least 1,000 poises.

High-lubricity film

Disclosed herein are (1) a composition which is prepared by combining 0.2 to 90 parts by weight of a cross-linked polyarylene thioether having a melt viscosity of 5.times.10.sup.5 to 1.times.10.sup.9 poise, which becomes gel under melting, with 100 parts by weight of a resin consisting of polyarylene thioether, which has a repeating unit of ##STR1## as the main constituent, having a melt viscosity of 10 to 5.times.10.sup.4 poise and (2) a composition of polyarylene thioether for molding, which is prepared by combining not more than 400 parts by weight of a fibrous filler and/or an inorganic filler with 100 parts by weight of the above-mentioned composition (1), is excellent in an antiflash property, is high in a mechanical strength and a thermal stability and is easily processed on melt molding and can easily recycle its molded scraps.

Polyarylene thioether composition for molding

Disclosed herein is a process for producing a medium- or high-molecular-weight polyarylene sulfide which comprises subjecting an alkali metal sulfide, a dihalo aromatic compound and optionally, small amount of tri- or higher polyhalo aromatic compound to dehalogenation and sulfidation reaction at a temperature of from 240.degree. to 270.degree. C. in the presence of a water in amount of from 0.5 to 5 mol per 1 kg of an aprotic organic polar solvent until the conversion of said dihalo aromatic compound reaches from 70 to 98 mol %, thereby forming a polyarylene sulfide prepolymer having a melt viscosity of from 5 to 300 poise (as measured at 310.degree. C. under a shear rate of 200 sec.sup.-1), adding water to the resultant reaction mixture containing the polyarylene sulfide prepolymer so that from 6 to 15 mol of water is present per 1 kg of said solvent, and then continuing the reaction at a temperature of from 240.degree.-290.degree. C., in which the reaction comprising said two steps is conducted for from 2 to 6 hours.

Process for producing polyarylene sulfide in titanium vessel with

Disclosed herein is a stretched poly(arylene thioether-ketone) film made of a thermoplastic material which comprises (A) 100 parts by weight of a melt-stable poly(arylene thioether-ketone) having predominant recurring units of the formula ##STR1## and having a melting point, Tm of 310.degree.-380.degree. C., a residual melt crystallization enthalpy, .DELTA.Hmc (420.degree. C./10 min) of at least 10 J/g and a melt crystallization temperature, Tmc (420.degree. C./10 min) of at least 210.degree. C., and a reduced viscosity of 0.3-2 dl/g as determined by viscosity measurement at 25.degree. C. and a polymer concentration of 0.5 g/dl in 98 percent by weight sulfuric acid; and optionally, (B) up to 100 parts by weight of at least one of thermoplastic resins and/or up to 15 parts by weight of at least one of fillers. Its production process is also disclosed.

Stretched poly(arylene thioether-ketone) films and production process

Heat-resistant resin composition comprising (A) 100 parts by weight of a poly(arylene sulfide) of a substantially linear structure containing 50% by weight or higher of recurring units of the formula ##STR1## and a logarithmic viscosity number of 0.1 to 1.0 dl/g; (B) from 0.01 to less than 25 parts by weight of a melt-stable poly(arylene thioether-ketone) having predominant recurring units of the formula ##STR2## wherein the --CO-- and --S-- are in the para position to each other, and having a melting point of 310.degree.-380.degree. C., a residual melt crystallization enthalpy of at least 10 J/g, a melt crystallization temperature of at least 210.degree. C. and a reduced viscosity of 0.2 to 2 dl/g; and (C) at least one of fibrous fibers and/or at least one of inorganic fillers in a proportion of 0 to 400 parts by weight per 100 parts by weight of the resin component comprising said poly(arylene sulfide) and said poly(arylene thioether-ketone). Heat-resistant articles obtained by melt-molding or forming said resin compositions and a method for the production of such articles are also described.

Disclosed herein are a melt-stable poly(arylene thioether-ketone) having predominant recurring units of the formula ##STR1## and having a melting point, Tm of 310.degree.-380.degree. C., a residual melt crystallization enthalpy, .DELTA.Hmc (420.degree. C./10 min) of at least 10 J/g, a melt crystallization temperature, Tmc (420.degree. C./10 min) of at least 210.degree. C., and a reduced viscosity of 0.2-2 dl/g as measured at 25.degree. C. and a polymer concentration of 0.5 g/dl in 98 wt. % sulfuric acid as well as a production process of the poly(arylene thioether-ketone). The poly(arylene thioether-ketone) has melt stability so that conventional melt processing techniques can be applied easily. The poly(arylene thioether-ketone) is a highly-crystalline polymer whose density is at least 1.34 g/cm.sup.3 when annealed at 280.degree. C. for 30 minutes.

Melt-stable poly(arylene thioether-ketone) and production process thereof

Disclosed herein is a melt-stable poly(arylene thioether-ketone) composition, which comprises:

Melt-stable poly(arylene thioether-ketone) compositions

Disclosed herein are poly(arylene thioether-ketone) fibers obtained by melt-spinning a thermoplastic material which comprises 100 parts by weight of a melt-stable poly(arylene thioether-ketone) (PTK) and optionally, up to 50 parts by weight of at least one of thermoplastic resins. The PTK has predominant recurring units of the formula ##STR1## wherein the --CO-- and --S-- are in the para position to each other, and has a melting point, Tm of 310.degree.-380.degree. C., a residual melt crystallization enthalpy, .DELTA.Hmc (420.degree. C./10 min) of at least 10 J/g, a melt crystallization temperature, Tmc (420.degree. C./10 min) of at least 210.degree. C., and a reduced viscosity of 0.3-2 dl/g as determined by viscosity measurement at 25.degree. C. and a polymer concentration of 0.5 g/dl in 98 percent by weight sulfuric acid. The PTK fibers of this invention have high heat resistance and strength.

Poly(arylene thioether-ketone) fibers and production process thereof

Disclosed herein are poly(arylene thioetherketone) fibers obtained by melt-spinning a thermoplastic material which comprises 100 parts by weight of a melt-stable poly(arylene thioether-ketone) (PTK) and optionally, up to 50 parts by weight of at least one of thermoplastic resins. The PTK has predominant recurring units of the formula ##STR1## wherein the --CO-- and --S-- are in the para position to each other, and has a melting point, Tm of 310-380.degree. C., a residual melt crystallization enthalpy, .DELTA.Hmc (420.degree. C./10 min) of at least 10 J/g, a melt crystallization temperature, Tmc (420.degree. C./10 min) of at least 210.degree. C., and a reduced viscosity of 0.3-2 dl/g as determined by viscosity measurement at 25.degree. C. and a polymer concentration of 0.5 g/dl in 98 percent by weight sulfuric acid. The PTK fibers of this invention have high heat resistance and strength.

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Iwaki, Japan

Yo Iizuka