JPS61221229A - Production of aromatic poly(thio)ether ketone - Google Patents
Production of aromatic poly(thio)ether ketoneInfo
- Publication number
- JPS61221229A JPS61221229A JP6428685A JP6428685A JPS61221229A JP S61221229 A JPS61221229 A JP S61221229A JP 6428685 A JP6428685 A JP 6428685A JP 6428685 A JP6428685 A JP 6428685A JP S61221229 A JPS61221229 A JP S61221229A
- Authority
- JP
- Japan
- Prior art keywords
- thio
- solvent
- ether
- aromatic
- aromatic poly
- 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.)
- Pending
Links
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は結晶性熱可塑性芳香族ポリ（チオ）エーテルケ
トンの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing crystalline thermoplastic aromatic poly(thio)etherketones.
一般式（ｎ）
（〔■〕式中、Ｒ１、９１２は水素原子、ノ・ロゲン原
子、炭化水素基、又はアルコキシ基を示し、Ｘは直接結
合、酸素原子、又は硫黄原子を示し、ｎはＯ−２の整数
を示す）の構造を持つ芳香族ポリ（チオ）エーテルケト
ン、特に構造式ＣＩＩＩ）及び（ＩＶ）
ノ構造を持つ芳香族ポリ（チオ）エーテルケトンは高融
点（〔■〕、Ｔｍ＝ｊ Ａ ｚ℃； （ｆＶ）、Ｔｍ＝
３３≠℃）且つ高ガラス転移点（〔■〕、Ｔｆ＝／！≠
Ｃ； （ＩＶ）、Ｔｙ ＝ ／ ４ｔ４ｔ ”Ｑ ）を
有し、耐熱性、機械的性質、電気的性質及び寸法安定性
に優れ、且つ吸水率が低く、物理的に非常に優れたポリ
マーである事が知られている。又、濃硫酸以外の溶剤に
は不溶であり、耐薬品性も非常に優れたポリマーである
。General formula (n) ([■] In the formula, R1 and 912 represent a hydrogen atom, a hydrogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond, an oxygen atom, or a sulfur atom, and n represents a Aromatic poly(thio)etherketones having the structure (indicating the integer of O-2), especially aromatic poly(thio)etherketones having the structure of structural formulas CIII) and (IV) have high melting points ([■], Tm=j A z℃; (fV), Tm=
33≠℃) and high glass transition point ([■], Tf=/!≠
C; (IV), Ty=/4t4t"Q), has excellent heat resistance, mechanical properties, electrical properties, and dimensional stability, and has low water absorption, and is a physically excellent polymer. It is also known that it is insoluble in solvents other than concentrated sulfuric acid, and has excellent chemical resistance.
一方その反面、これらのポリマーの製造方法トシてハ、
ｇ、ｐ’−ジフルオロベンゾフェノンとび、参′−ジ
ヒドロキシベンゾフェノン又はジヒドロキノンのアルカ
リ金属塩をジフェニルスルホン中で反応させる方法が知
られているが、反応温度を３００℃以上にする必要があ
る事や≠、仏Ｉ−ジフルオロベンゾフェノンが高価な事
等、その製造方法には欠点が多い。On the other hand, the manufacturing method of these polymers is
A method is known in which an alkali metal salt of g, p'-difluorobenzophenone, p'-dihydroxybenzophenone, or dihydroquinone is reacted in diphenylsulfone, but the reaction temperature needs to be 300°C or higher and ≠ There are many drawbacks to the production method, such as the fact that I-difluorobenzophenone is expensive.
本発明者等は上記の点を鑑み、鋭意検討を行った結果、
先に、芳香族ポリエーテルケトン（ＩＩＩ）及び（ＩＶ
）さらに芳香族ポリチオエーテルケト ン （Ｖ）
を芳香族（チオ）エーテルとホスゲンとの反応により、
ルイス酸存在下、非プロトン性有機溶媒中で室温付近の
温和な条件下で、しかも、著しく安価に製造する方法を
見出した。しかし、この方法に於ても改良すべき点が残
されていた。In view of the above points, the present inventors conducted intensive studies and found that
First, aromatic polyetherketones (III) and (IV
) Further, aromatic polythioetherketone (V) is reacted with aromatic (thio)ether and phosgene,
We have found a method for producing it under mild conditions around room temperature in the presence of a Lewis acid in an aprotic organic solvent and at a significantly low cost. However, even in this method, there were still points to be improved.
すなわち、溶媒と生成ポリマー及び未反応モノマーとの
分離、さらに溶媒の回収及び精製等の工業的なプロセス
上の問題が残されていた。That is, there remain problems in industrial processes such as separation of the solvent from the produced polymer and unreacted monomers, and recovery and purification of the solvent.
本発明者等は、上記の点を改良すべくさらに鋭意検討を
重ねた結果、比変、実質的に溶媒を用いずに、上記ポリ
（チオ）エーテルケトンを製造する方法を発明するに到
った。As a result of further intensive studies aimed at improving the above points, the present inventors have now invented a method for producing the above poly(thio)etherketone without changing the ratio or using substantially no solvent. Ta.
すなわち、本発明の要旨は一般式ＣＩ）（〔１３式中、
Ｒ１〜Ｒ１！は水素原子、ハロゲン原子、炭化水素基、
又はアルコキシ基を示し、Ｘは直接結合、酸素原子又は
硫黄原子を示し、ｎは０−２の整数を示す）で表わされ
る芳香族（チオ）エーテルとホスゲンをルイス酸の存在
下で反応させて芳香族ポリ（チオ）エーテルケトンを製
造する際に、実質的に溶媒を用いずに反応を行う事を特
徴とする製造方法に存する。That is, the gist of the present invention is general formula CI) ([in formula 13,
R1~R1! is a hydrogen atom, a halogen atom, a hydrocarbon group,
or an alkoxy group, X represents a direct bond, an oxygen atom or a sulfur atom, and n represents an integer of 0-2) and phosgene are reacted in the presence of a Lewis acid. The present invention resides in a manufacturing method characterized in that the reaction is carried out substantially without using a solvent when manufacturing an aromatic poly(thio)etherketone.
本発明をさらに詳細に説明するに、本発明に用いられる
前記一般式（１）で表わされる芳香族（チオ）エーテル
としては、ジフェニルエーテル、ｌ、≠−ジフェノキシ
ベンゼン、ビフェニル、ビス（弘−フェノキシフェニル
）エーテル、弘、参′−ビス（≠−フェノキシフェニル
）ジフェニルエーテル、 ｉ、３’−ジメチルフェニル
エーテル、／、４Ｃ−ビス（３−メチルフェノキシ）ベ
ンゼン、Ｊ、Ｊ’−ジメトキシフェニルエーテル、／、
４Ｃ−ビス（３−メトキシフェノキシ）ベンゼン、ｌ、
≠−ビス（コークロロフエノキシ）ベンゼン、ジフェニ
ルサルファイド、≠−フェノキシジフェニルサルファイ
ド、／、！−ビス（フェニルメルカフ））ベンゼン、タ
ーフェニル、φ−フェノキシビフェニル、≠、４ｃ′−
ジフェノ中クビフェりルなどが挙げられるが、一般式（
１）で表わされるものはいずれも使用可能であり、必ず
しもこれらに限定されるものではない。又、これらの芳
香族（チオ）エーテルは単独もしくは混合して使用して
もよい。To explain the present invention in more detail, the aromatic (thio)ether represented by the general formula (1) used in the present invention includes diphenyl ether, l,≠-diphenoxybenzene, biphenyl, bis(Hiro-phenoxybenzene), phenyl) ether, Hiroshi, 3'-bis(≠-phenoxyphenyl) diphenyl ether, i, 3'-dimethylphenyl ether, /, 4C-bis(3-methylphenoxy)benzene, J, J'-dimethoxyphenyl ether, / ,
4C-bis(3-methoxyphenoxy)benzene, l,
≠-bis(cochlorophenoxy)benzene, diphenyl sulfide, ≠-phenoxydiphenyl sulfide, /,! -bis(phenylmercaf))benzene, terphenyl, φ-phenoxybiphenyl, ≠, 4c'-
Examples of diphenols include Kubiferil, but the general formula (
Any of those represented by 1) can be used, and the invention is not necessarily limited to these. Further, these aromatic (thio)ethers may be used alone or in combination.
本発明に用いられるホスゲンの量は、用いられる芳香族
（チオ）エーテルの０．／〜ｚｏｏ倍量（モル比）、好
ましくは１〜ｉｏｏ倍量（モル比）である。The amount of phosgene used in the present invention is 0.0% of the aromatic (thio)ether used. /~zoo times the amount (molar ratio), preferably 1~ioo times the amount (mole ratio).
本発明に用いられるルイス酸としては三塩化アルミニウ
ム、三臭化アルミニウム、三弗化硼素、塩化第二鉄、塩
化第二錫、四塩化チタン、三塩化硼素、五塩化アンチモ
ン、塩化亜鉛、三塩化ガリウム、六塩化アンチモン、三
塩化リン、五塩化リン、五塩化テルル、三弗化硼素エチ
ルエーテル錯化物な・どの無水物が挙げられるが必ずし
もこれらに限定されるものではない。又、これらの中で
コストの点から三塩化アルミニウムを用いる事が最も好
ましい。これらのルイス酸の使用量はジフェニルエーテ
ルに対してモル比で０．０／ Ａ−１００，好ましくは
０．１〜／ ０，０である。Lewis acids used in the present invention include aluminum trichloride, aluminum tribromide, boron trifluoride, ferric chloride, stannic chloride, titanium tetrachloride, boron trichloride, antimony pentachloride, zinc chloride, and trichloride. Examples include, but are not limited to, anhydrides such as gallium, antimony hexachloride, phosphorus trichloride, phosphorus pentachloride, tellurium pentachloride, and boron trifluoride ethyl ether complex. Moreover, among these, it is most preferable to use aluminum trichloride from the viewpoint of cost. The molar ratio of these Lewis acids to diphenyl ether is 0.0/A-100, preferably 0.1 to 0.0/A-100.
本発明に於ける反応は０〜３００℃の温度範囲で可能で
あるが、７５０℃以下の比較的温和な温度条件下でも高
重合度ポリマーが得られる。Although the reaction in the present invention is possible at a temperature range of 0 to 300°C, a highly polymerized polymer can be obtained even under relatively mild temperature conditions of 750°C or lower.
又、加圧下で反応を行ってもよい。Alternatively, the reaction may be carried out under pressure.
本発明による芳香族ポリ（チオ）エーテルケトンの無溶
媒重合の達成は多くの利点をもたらす。すなわち、重合
後の溶媒とポリマー及び未反応モノマーとの分離、さら
に溶媒の回収、精製等の操作が省かれ、プロセス上有利
である。Achieving solvent-free polymerization of aromatic poly(thio)etherketones according to the present invention provides many advantages. That is, operations such as separation of the solvent from the polymer and unreacted monomers after polymerization, and recovery and purification of the solvent can be omitted, which is advantageous in terms of the process.
又、耐熱性に優れ、引張強度、曲げ強度、引張弾性率、
曲げ弾性率等の機械的性質、電気的性質、及び寸法安定
性が良好で、且つ低吸水性であり、さらに耐薬品性にも
優れた芳香族ポリ（チオ）エーテルケトンが著しく安価
に製造できる。In addition, it has excellent heat resistance, tensile strength, bending strength, tensile modulus,
Aromatic poly(thio)etherketone with good mechanical properties such as flexural modulus, electrical properties, and dimensional stability, low water absorption, and excellent chemical resistance can be produced at a significantly low cost. .
以下、実施例により、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
容量１００−の特殊合金１ハステロイ−〇”（商標）製
オートクレーブにジフェニルエーテ＃ ７．／ ＩＩ
ｔ （０，ＯＨ２ｍｏｌ ）、ホスゲンコλ、りｔ （
Ｏ８ａコ４ ｍｏｊ ）、と無水三塩化アルミニウＡ
／ ／、２ ｔ （０，／ Ａ ｒ ｍｏｊ ）を仕込
む。誘導回転装置により内容物を攪拌しながら、内温２
０℃で３．５時間反応させた所、内圧は７ｋｌ／−にな
った。続いて、オートクレーブを油浴で加熱して内温を
φＯ′ｃＫして、３時間反応させた。Example 1 Diphenyl ether #7./II was placed in an autoclave made of special alloy 1 Hastelloy 〇” (trademark) with a capacity of 100 mm.
t (0,OH2mol), phosgenco λ, rit (
O8a co4 moj), and anhydrous aluminum trichloride A
/ /, 2 t (0, / A r moj ) is prepared. While stirring the contents using an induction rotation device, the internal temperature
After reacting at 0°C for 3.5 hours, the internal pressure became 7 kl/-. Subsequently, the autoclave was heated in an oil bath to bring the internal temperature to φO'cK, and the reaction was allowed to proceed for 3 hours.
内圧はり辞／−に上昇した。３０分かけて内温を１ｉｏ
ｃに昇温した後、反応を、さらに％昼時間続けた。内圧
はｘｔＨ７−であった。室温まで冷却した後、残余圧を
パージした後、未反応のホスゲンを窒素ガスで置換した
。内容物を取出し、３ｏｏＩＬ／のメタノールで三塩化
アルミニウムを分解した後、得られたポリマーを沸騰メ
タノール、沸騰よチ塩醗水溶液で２回、沸騰水で２回（
各３００１Ｒ１）で洗浄後、１２０℃で一晩真空乾燥し
た。ポリマーの収率は定量的であった。り７％硫酸中の
ηｉｎｈ ＃ｉ０． ｊりｄｔ／ｌテアった。工Ｒスペ
クトルの測定により、／４１／−０σ−１に芳香族ケト
ン、ｌコ≠ｏｃｍ−”に芳香族エーテルの伸縮振動が確
認された。The internal pressure rose to /-. Reduce internal temperature to 1io over 30 minutes
After increasing the temperature to c., the reaction was continued for an additional % day time. The internal pressure was xtH7-. After cooling to room temperature, residual pressure was purged, and unreacted phosgene was replaced with nitrogen gas. After taking out the contents and decomposing aluminum trichloride with 3ooIL/methanol, the obtained polymer was dissolved twice in boiling methanol, twice in boiling salt solution, and twice in boiling water (
After washing with 3001R1), vacuum drying was performed at 120° C. overnight. The yield of polymer was quantitative. ηinh #i0. in 7% sulfuric acid. jri dt/l tear. By measuring the engineering R spectrum, stretching vibration of an aromatic ketone was confirmed at /41/-0σ-1, and stretching vibration of an aromatic ether was confirmed at lco≠ocm-''.
実施例２
実施例１と同様のオートクレーブにジフェニルエーテｈ
３．３７９ （０，０２／ｍｏＬ）、ホスゲン２コ、４
４９ （０，２２ｊ ｎｏｔ） 、無水三塩化アルミニ
ラＡ ／ ／、２ ｔ （０，／ ｔ Ｉ ｍｏｔ）を
仕込み、内温４′ｏ℃で／７時間反応させた。最終圧は
７ｋｌ／Ｉ：ＬＬ！であった。重合終了後の処理は実施
例１と同様の方法で行った。Example 2 Diphenyl ether h was placed in an autoclave similar to Example 1.
3.379 (0.02/mol), 2 phosgenes, 4
49 (0,22j not), anhydrous aluminum trichloride A / /, 2 t (0, / t I mot) were charged and reacted at an internal temperature of 4'oC for /7 hours. Final pressure is 7kl/I:LL! Met. The treatment after completion of the polymerization was carried out in the same manner as in Example 1.
収率は２７％、ηｉｎｈはｏ、３ｒｔｕ７ｔ （実施
例／と同様に測定）であった。The yield was 27%, and ηinh was o, 3rtu7t (measured in the same manner as in Example).
実施例３
ジフェニルエーテルの代９に、／、弘−ジフェノキシベ
ンゼン／ ／、０．２ ｆ （０，０ｕ２ ｍｏｌ ）
を用いて、実施例２と同様のオートクレーブ中で、内温
／１０℃で２時間反応させた。内圧は一２ｇ貯／−にな
った。重合後の処理は実施例１と同様の方法で行った。Example 3 To the base 9 of diphenyl ether, /, Hiro-diphenoxybenzene /, 0.2 f (0,0u2 mol)
Using this, the reaction was carried out in the same autoclave as in Example 2 at an internal temperature of 10° C. for 2 hours. The internal pressure became -2g/-. The treatment after polymerization was carried out in the same manner as in Example 1.
収率は定量的であった。ηｉｎｈは０，１ｊｄｔ／ｌ（
実施例１と同様に測定）であった。The yield was quantitative. ηinh is 0,1jdt/l(
(measured in the same manner as in Example 1).
実施例１
ジフェニルエーテルの代りに、ジフェニルサルファイド
７３コｆ （０，０４Ａ２ｒｎｏＬ ）を用いる以外は
実施例３と同様に行った。最終圧は２０ｋｆ／ｃｄであ
った。重合後の処理は実施例／と同様に行った。Example 1 The same procedure as in Example 3 was carried out except that diphenyl sulfide 73cof (0,04A2rnoL) was used instead of diphenyl ether. The final pressure was 20kf/cd. The treatment after polymerization was carried out in the same manner as in Example.
収率は♂２％で、η土ｎｈ ｌｄ ＯｏＪ ／ ｄｌ
／ ｆ （実施例／と同様に測定）であった。The yield was 2%, η soil nh ld OoJ / dl
/f (measured in the same manner as in Example/).
本発明方法によれば、第三成分である溶媒を用いないの
で、重合後の分離・精製工程において、きわめて有利な
プロセスを特徴する特許出願人 三菱化成工業株式会
社
代 理 人 弁理士 長谷用 −ほか１名According to the method of the present invention, since a solvent, which is a third component, is not used, the process is extremely advantageous in the separation and purification steps after polymerization. 1 other person
Claims (2)
ゲン原子、炭化水素基、又はアルコキシ基を示し、Ｘは
直接結合、酸素原子又は硫黄原子を示し、ｎは０〜２の
整数である）で表わされる芳香族（チオ）エーテルとホ
スゲンをルイス酸の存在下で反応させて芳香族ポリ（チ
オ）エーテルケトンを製造する際に、実質的に溶媒を用
いずに反応を行う事を特徴とする製造法。(1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the [I] formula, R^1 to R^1^2 are hydrogen atoms, halogen atoms, hydrocarbon groups , or an alkoxy group, X is a direct bond, an oxygen atom or a sulfur atom, and n is an integer of 0 to 2) is reacted with phosgene in the presence of a Lewis acid. A production method characterized in that the reaction is carried out substantially without using a solvent when producing an aromatic poly(thio)etherketone.
の無水物を用いる特許請求の範囲第１項記載の製造法。(2) The production method according to claim 1, in which an anhydride of a Group III halide of the periodic table is used as the Lewis acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6428685A JPS61221229A (en) | 1985-03-28 | 1985-03-28 | Production of aromatic poly(thio)ether ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6428685A JPS61221229A (en) | 1985-03-28 | 1985-03-28 | Production of aromatic poly(thio)ether ketone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61221229A true JPS61221229A (en) | 1986-10-01 |
Family
ID=13253837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6428685A Pending JPS61221229A (en) | 1985-03-28 | 1985-03-28 | Production of aromatic poly(thio)ether ketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61221229A (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0293118A2 (en) | 1987-05-15 | 1988-11-30 | Kureha Kagaku Kogyo Kabushiki Kaisha | Molded or formed poly(arylene thioether-ketone) articles |
| EP0293113A2 (en) | 1987-05-15 | 1988-11-30 | Kureha Kagaku Kogyo Kabushiki Kaisha | Stretched poly(arylene thioether-ketone) films and production process thereof |
| EP0293117A2 (en) | 1987-05-15 | 1988-11-30 | Kureha Kagaku Kogyo Kabushiki Kaisha | Heat-resistant molded or formed articles and production process thereof |
| US4826906A (en) * | 1987-06-22 | 1989-05-02 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketone) compositions improved in both melt stability and crystallinity |
| US4873283A (en) * | 1987-05-15 | 1989-10-10 | Kureha Kagaku Kogyo K.K. | Molded or formed poly(arylene thioether-ketone) articles |
| US4886871A (en) * | 1987-05-15 | 1989-12-12 | Kureha Kagaku Kogyo K. K. | Melt-stable poly(arylene thioetherketone) and production process thereof |
| US4895924A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K. K. | Poly(arylene thioether-ketone) fibers and production process thereof |
| US4895892A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K.K. | Melt-stable poly(arylene thioether-ketone) compositions |
| US4895893A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K.K. | Heat-resistant resin compositions, and heat-resistant molded or formed articles and production process thereof |
| US4897238A (en) * | 1987-05-15 | 1990-01-30 | Kureha Kagaku Kogyo K.K. | Stretched poly(arylene thioether-ketone) films and production process thereof |
| US4910086A (en) * | 1987-12-25 | 1990-03-20 | Kureha Kagaku Kogyo K.K. | Resin coated metal body |
| US4960555A (en) * | 1988-10-25 | 1990-10-02 | Kureha Kagaku Kogho K.K. | Poly (arylene thioether) block copolymer fibers and production process thereof |
| US4960806A (en) * | 1988-10-25 | 1990-10-02 | Kureha Kagaku Kagyo K.K. | Stretched poly(arylene thioether) block copolymer films and production process thereof |
| US4975479A (en) * | 1988-10-25 | 1990-12-04 | Kureha Kagaku Kogyo K.K. | Heat-resistant thermoplastic resin composition |
| US5008370A (en) * | 1988-11-11 | 1991-04-16 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketones) improved in melt stability and preparation process thereof |
| US5045630A (en) * | 1988-11-11 | 1991-09-03 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketones) improved in melt stability and preparation process thereof |
| US5110681A (en) * | 1987-10-30 | 1992-05-05 | Kureha Kagaku Kogyo K. K. | Melt-stable poly(arylene thioether-ketone) prepregs and molded or formed products thereof |
| US5120808A (en) * | 1988-10-25 | 1992-06-09 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer and production process thereof |
| US5153279A (en) * | 1988-10-25 | 1992-10-06 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer and production process thereof |
| US5153264A (en) * | 1988-10-25 | 1992-10-06 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer and production process thereof |
| US5153278A (en) * | 1988-10-25 | 1992-10-06 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer and production process thereof |
| US5286814A (en) * | 1988-06-13 | 1994-02-15 | Kureha Kagaku Kogyo K. K. | Heat-resistant stretched film and production process thereof |
-
1985
- 1985-03-28 JP JP6428685A patent/JPS61221229A/en active Pending
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897238A (en) * | 1987-05-15 | 1990-01-30 | Kureha Kagaku Kogyo K.K. | Stretched poly(arylene thioether-ketone) films and production process thereof |
| EP0293117A2 (en) | 1987-05-15 | 1988-11-30 | Kureha Kagaku Kogyo Kabushiki Kaisha | Heat-resistant molded or formed articles and production process thereof |
| EP0293118A2 (en) | 1987-05-15 | 1988-11-30 | Kureha Kagaku Kogyo Kabushiki Kaisha | Molded or formed poly(arylene thioether-ketone) articles |
| EP0293113A2 (en) | 1987-05-15 | 1988-11-30 | Kureha Kagaku Kogyo Kabushiki Kaisha | Stretched poly(arylene thioether-ketone) films and production process thereof |
| US4873283A (en) * | 1987-05-15 | 1989-10-10 | Kureha Kagaku Kogyo K.K. | Molded or formed poly(arylene thioether-ketone) articles |
| US4886871A (en) * | 1987-05-15 | 1989-12-12 | Kureha Kagaku Kogyo K. K. | Melt-stable poly(arylene thioetherketone) and production process thereof |
| US4895924A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K. K. | Poly(arylene thioether-ketone) fibers and production process thereof |
| US4895912A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K.K. | Stretched poly(arylene thioether-ketone) films and production process thereof |
| US4895691A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketone) fibers and production process thereof |
| US4895892A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K.K. | Melt-stable poly(arylene thioether-ketone) compositions |
| US4895925A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K.K. | Melt-stable poly(arylene thioether-ketone) and production process thereof |
| US4895893A (en) * | 1987-05-15 | 1990-01-23 | Kureha Kagaku Kogyo K.K. | Heat-resistant resin compositions, and heat-resistant molded or formed articles and production process thereof |
| US4826906A (en) * | 1987-06-22 | 1989-05-02 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketone) compositions improved in both melt stability and crystallinity |
| US5110681A (en) * | 1987-10-30 | 1992-05-05 | Kureha Kagaku Kogyo K. K. | Melt-stable poly(arylene thioether-ketone) prepregs and molded or formed products thereof |
| US4910086A (en) * | 1987-12-25 | 1990-03-20 | Kureha Kagaku Kogyo K.K. | Resin coated metal body |
| US5286814A (en) * | 1988-06-13 | 1994-02-15 | Kureha Kagaku Kogyo K. K. | Heat-resistant stretched film and production process thereof |
| US5120808A (en) * | 1988-10-25 | 1992-06-09 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer and production process thereof |
| US4962143A (en) * | 1988-10-25 | 1990-10-09 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer fibers and production process thereof |
| US4975479A (en) * | 1988-10-25 | 1990-12-04 | Kureha Kagaku Kogyo K.K. | Heat-resistant thermoplastic resin composition |
| US4960806A (en) * | 1988-10-25 | 1990-10-02 | Kureha Kagaku Kagyo K.K. | Stretched poly(arylene thioether) block copolymer films and production process thereof |
| US5153279A (en) * | 1988-10-25 | 1992-10-06 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer and production process thereof |
| US5153264A (en) * | 1988-10-25 | 1992-10-06 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer and production process thereof |
| US5153278A (en) * | 1988-10-25 | 1992-10-06 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether) block copolymer and production process thereof |
| US4960555A (en) * | 1988-10-25 | 1990-10-02 | Kureha Kagaku Kogho K.K. | Poly (arylene thioether) block copolymer fibers and production process thereof |
| US5045630A (en) * | 1988-11-11 | 1991-09-03 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketones) improved in melt stability and preparation process thereof |
| US5008370A (en) * | 1988-11-11 | 1991-04-16 | Kureha Kagaku Kogyo K.K. | Poly(arylene thioether-ketones) improved in melt stability and preparation process thereof |
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