JPH01500112A - aryl-diether - Google Patents

aryl-diether

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JPH01500112A
JPH01500112A JP61503758A JP50375886A JPH01500112A JP H01500112 A JPH01500112 A JP H01500112A JP 61503758 A JP61503758 A JP 61503758A JP 50375886 A JP50375886 A JP 50375886A JP H01500112 A JPH01500112 A JP H01500112A
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セラ，ジェームズ・アンソニイ
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General Electric Co
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/275—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings having all ether-oxygen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 アリール−ジエーテル 本発明はビスフェノール化合物の塩から誘導されたアリール−ジエーテル類、及 びそれからポリエーテルイミド類を製造する方法に関する。特に本発明は式：の アリール−ジエーテル類、及びこれらのアリール−ジエーテル類を酸化しそして 酸化生成物を存機ジアミンとともに重合させることによってポリエーテルイミド 類を製造する方法に関するものである。ポリエーテルイミド類は高温に耐性であ るフィルム及び線材被覆用エナメルの製造に有用である。式Ｉの二価の基Ｒは一 般式 Ｈ３ Ｒ′ 一〇−１及び−Ｎ−の二価の基からなる群の一員であり、ｍは０又は１であり、 ｙは１〜５の整数でありそしてＲ′は１〜５個の炭素原子をもつアルキル基から 選ばれる）の有機基である。[Detailed description of the invention] aryl-diether The present invention relates to aryl-diethers derived from salts of bisphenol compounds, and and a method for producing polyetherimides therefrom. In particular, the present invention provides the formula: aryl-diethers, and oxidizing these aryl-diethers and Polyetherimide is produced by polymerizing the oxidation product with the remaining diamine. This relates to a method for producing a class of products. Polyetherimides are resistant to high temperatures. It is useful in the production of films and wire coating enamels. The divalent radical R of formula I is one general ceremony H3 R' A member of the group consisting of divalent groups 10-1 and -N-, m is 0 or 1, y is an integer from 1 to 5 and R' is an alkyl group having 1 to 5 carbon atoms. (selected) organic group.

式Ｉに包含されるアリール−ジエーテル類の［：Ｌい一部はＲが Ｈ３ である型のものである。この群の好ましいアリールジエーテル類の範囲内には次 式のアリール−ジエーテル類が包含される。Some of the aryl-diethers included in Formula I are H3 It is of a type. Within this group of preferred aryl diethers are: Included are aryl-diethers of the formula.

ハロゲン什キシレン＾ビ又フェノールの性、Ｌｌ−ＪＪｊｆｌｒＴ）塩のような 銅触媒の存在下で好ましくは１００℃以上の温度で反応させる。一般に反応剤は 等モル割合で使用するのが好ましいが、いずれか一方の反応剤を過剰に使用して もに参考文献として引用する米国特許第４，４９２．８０６号明細書に記載され ている。典型的なビスフェノール化合物はつぎのちのを包含する。halogen xylene ^ bimataphenol, Ll-JJjflrT) salt-like The reaction is preferably carried out in the presence of a copper catalyst at a temperature of 100° C. or higher. Generally, the reactant is It is preferable to use them in equimolar proportions, but if one of the reactants is used in excess, No. 4,492,806, which is also incorporated by reference. ing. Typical bisphenol compounds include:

２．２−ビス−（２−ヒドロキシフェニル）プロパン：２．４′−ジヒドロキシ ジフェニルメタン；ビス−（２−ヒドロキシフェニル）−メタン；２．２−ビス −（４−ヒドロキシフェニル）−プロパン、以下“ビスフェノールＡ２又は”Ｂ ＰＡ”と称する；１．１−ビス−（４−ヒドロキシフェニル）−エタン：１．１ −ビス−（４−ヒドロキシフェニル）−プロパン；２．２−ビス−（４−ヒドロ キシフェニル）−ペンタン：３．３−ビス−（４−ヒドロキシフェニル）−ペン タン；４．４′−ジヒドロキシビフェニル： ４．４′−ジヒドロキシ−３，３’　、５．５’　−テトラメチルビフェニル； ２．４′−ジヒドロキシベンゾフェノン；４．４′−ジヒドロキシジフェニルス ルホン；２．４′−ジヒドロキシジフェニルスルホン；４．４′−ジヒドロキシ ジフェニルスルホキシド：４．４′−ジヒドロキシジフェニルスルフィド：等。2.2-bis-(2-hydroxyphenyl)propane: 2.4'-dihydroxy diphenylmethane; bis-(2-hydroxyphenyl)-methane; 2,2-bis -(4-hydroxyphenyl)-propane, hereinafter "bisphenol A2 or" B 1.1-bis-(4-hydroxyphenyl)-ethane: 1.1 -bis-(4-hydroxyphenyl)-propane; 2,2-bis-(4-hydro xyphenyl)-pentane: 3.3-bis-(4-hydroxyphenyl)-pentane Tan; 4,4'-dihydroxybiphenyl: 4.4'-dihydroxy-3,3',5.5'-tetramethylbiphenyl; 2.4'-dihydroxybenzophenone; 4.4'-dihydroxydiphenyl 2,4'-dihydroxydiphenylsulfone; 4,4'-dihydroxy Diphenylsulfoxide: 4,4'-dihydroxydiphenylsulfide: etc.

式Ｉのアリール−ジエーテル類を使用してポリエーテルイミド類を製造する方法 も本発明の範囲内に包含される。Methods of making polyetherimides using aryl-diethers of formula I are also included within the scope of the present invention.

末端アリール基上のメチル基は酸化されてテトラ酸又は芳香族（エーテル無水物 ）を形成し得る。式■の好ましいアリール−ジエーテルから得られるテトラ酸の 一例は式Ｖによって表わされる。式Ｉのアリール−ジエーテル類の酸化によって 得られる芳香族ビス（エーテル無水物）は式■（式中、Ｒは前記定義したとおり である）によって表わされる。The methyl group on the terminal aryl group is oxidized to form a tetraacid or an aromatic (ether anhydride) ) can be formed. of the tetraacid obtained from the preferred aryl-diether of formula An example is represented by formula V. By oxidation of aryl-diethers of formula I The resulting aromatic bis(ether anhydride) has the formula ■ (wherein R is as defined above) ).

末端アリール基の酸化は当業者に既知のアルアルキル酸化法によって達成し得る 。か−る酸化法はマンガン又はコバルトのような金属イオン触媒の存在下におい て酸素を使用する反応を包含する。Ｈａｙの米国特許第３，１３９．４５２号明 細書にはアルアルキル化合物のアルキル基と酸素とをコバルト、臭素及びカルボ ン酸から本質的になる触媒の存在下、８０℃以上の温度で液相反応させる方法が 開示されている。このＨａｙの特許明細書の内容をニーに参考とされたい。この 酸化反応によって、Ｒがビスフェノール−Ａから誘導される好ましい種類におけ るごとく、特に二価有機基Ｒがその芳香族核に結合されたアルキル基を有する場 合に、生成物の混合物を得ることができる。酸化はこれらのアルキル基上にも同 様に生起し得る。Oxidation of the terminal aryl group may be accomplished by aralkyl oxidation methods known to those skilled in the art. . Such oxidation methods are carried out in the presence of metal ion catalysts such as manganese or cobalt. This includes reactions using oxygen. Hay U.S. Pat. No. 3,139.452 The specifications state that the alkyl group and oxygen of the aralkyl compound are There is a method in which a liquid phase reaction is carried out at a temperature of 80°C or higher in the presence of a catalyst consisting essentially of carbonic acid. Disclosed. Please refer to the contents of Hay's patent specification. this In a preferred type, R is derived from bisphenol-A by an oxidation reaction. In particular, when the divalent organic group R has an alkyl group bonded to its aromatic nucleus, In some cases, mixtures of products can be obtained. Oxidation also occurs on these alkyl groups. It can occur in many ways.

酸化された形のアリール−ジエーテル類は式％式％ ［式中、Ｒ１は（ａ）６〜２０個の炭素原子をもつ芳香族炭化水素基及びそれら のハロゲン化誘導体、（ｂ）２〜２０個の炭素原子をもつアルキレン基及びシク ロアルキレン基、及び（ｃ）式 （式中、Ｚ及びｍは前記定義したとおりである）によって前記に定義したＲの範 囲内に包含される二値の基、からなる群から選んだ二価有機基である］の有機ジ アミンとの反応によって重合されてポリエーテルイミドを与え得る。式■の有機 ジアミンの範囲内に包含される化合物の例はっぎのごとくである。Aryl-diethers in their oxidized form have the formula %formula% [In the formula, R1 represents (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms; (b) an alkylene group having 2 to 20 carbon atoms and a halogenated derivative of loalkylene group, and formula (c) (wherein Z and m are as defined above) is a divalent organic group selected from the group consisting of the binary groups contained within It can be polymerized to give polyetherimides by reaction with amines. Formula ■Organic Examples of compounds included within the scope of diamines are as follows.

ｍ−フェニレンジアミン； ｐ−フェニレンジアミン； ４．４′−ジアミノジフェニルプロパン；４．４′−ジアミノジフェニルメタン ；ベンチジン； ４．４′−ジアミノジフェニルスルフィド；４．４′−ジアミノジフェニルスル ホン；４．４′−ジアミノジフェニルエーテル；１．５−ジアミノナフタリン； ３．３′−ジメチルベンチジン； ３．３′−ジメトキシベンチジン； ２．４−ジアミノトルエン；２．６−ジアミツトルエン；２．４−ビス（β−ア ミノ−ｔ−ブチル）トルエン；ビス（ｐ−β−メチル−〇−アミノペンチル）ベ ンゼン；１．３−ジアミノ−４−イソプロピルベンゼン；１．２−ビス（３−ア ミノプロポキシ）エタン；ｍ−キシリレンジアミン； ｐ−キシリレンジアミン； ビス（４−アミノシクロヘキシル）メタン；デカメチレンジアミン； ３−メチルへブタメチレンジアミン； ４．４−ジメチルへブタメチレンジアミン；２．１１−ドデカンジアミン； ２．２−ジメチルプロピレンジアミン：オクタメチレンジアミン； ３−メトキシヘキサメチレンジアミン；２．５−ジメチルへキサメチレンジアミ ン；２．５−ジメチルへブタメチレンジアミン；３−メチルへブタメチレンジア ミン： ５−メチルノナメチレンジアミン： １．４−シクロヘキサンジアミン。m-phenylenediamine; p-phenylenediamine; 4.4'-diaminodiphenylpropane; 4.4'-diaminodiphenylmethane ;Benzidine; 4.4'-diaminodiphenylsulfide; 4.4'-diaminodiphenylsulfide Hon; 4,4'-diaminodiphenyl ether; 1,5-diaminonaphthalene; 3.3'-dimethylbenzidine; 3.3'-dimethoxybenzidine; 2.4-diaminotoluene; 2.6-diamittoluene; 2.4-bis(β-aminotoluene) mino-t-butyl)toluene; bis(p-β-methyl-〇-aminopentyl)beta 1,3-diamino-4-isopropylbenzene; 1,2-bis(3-albenzene) minopropoxy)ethane; m-xylylenediamine; p-xylylenediamine; Bis(4-aminocyclohexyl)methane; decamethylene diamine; 3-methylhebutamethylenediamine; 4.4-dimethylhebutamethylenediamine; 2.11-dodecanediamine; 2.2-dimethylpropylenediamine: octamethylenediamine; 3-methoxyhexamethylenediamine; 2,5-dimethylhexamethylenediamine 2,5-dimethyl hebutamethylene diamine; 3-methyl hebutamethylene diamine Min: 5-Methylnonamethylenediamine: 1.4-Cyclohexanediamine.

１，１２−オクタデカンジアミン； ビス（３−アミノプロピル）スルフィド；Ｎ−メチル−ビス（３−アミノプロピ ル）アミン；ヘキサメチレンジアミン； ヘプタメチレンジアミン；２，４−ジアミノトルエン；ノナメチレンジアミン； ２．６−ジアミツトルエン：ビス−（３−アミノプロピル）テトラメチルジシロ キサン；等。1,12-octadecanediamine; Bis(3-aminopropyl) sulfide; N-methyl-bis(3-aminopropyl) ) amine; hexamethylene diamine; Heptamethylene diamine; 2,4-diaminotoluene; nonamethylene diamine; 2.6-Diamitsutoluene: bis-(3-aminopropyl)tetramethyldisilo Kisan; etc.

酸化されたアリール−ジエーテル及びジアミンの重合は溶剤を使用し又は使用す ることなしに達成され得る。有機ジアミンとの溶融重合は約２００℃以上でかつ 好ましくは３５０℃より低い温度で達成され得る。タケコシ（Ｔａｋｅｋ。Polymerization of oxidized aryl-diethers and diamines can be carried out with or without the use of solvents. can be achieved without any Melt polymerization with organic diamine is carried out at approximately 200°C or higher and Preferably it can be achieved at temperatures below 350°C. Takekoshi.

ｓｈｌ　）は特にこ〜に参考文献として引用する米国特許第３゜８３３．５４６ 号明細書において適当な溶融重合方法を記載している。No. 3,833,546, which is specifically incorporated herein by reference. A suitable melt polymerization method is described in the specification.

溶液重合はより低い温度を使用し得るので溶融重合よりもしばしばより好都合で ある。非酸性の窒素及び／又は酸素含有溶剤であるジメチルスルホキシド、Ｎ、 Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、Ｎ、Ｎ−ジメチルホルムア ミド、Ｎ、Ｎ−ジエチルホルムアミド等のごとき両性非プロトン性溶剤が好まし い。用語“両性非プロトン性溶剤”はニーに記載した反応を妨害し得る活性プロ トンをもたない任意の有機溶剤を意味することを意図するものである。両性非プ ロトン溶剤とベンゼン、トルエン、キシレン及び塩化メチレンのような他の不活 性有機溶剤の混合物も使用し得る。溶液重合のためには約１００℃以上の温度が 好ましく、３００℃より低い温度がもつとも好ましい。Solution polymerization is often more convenient than melt polymerization because lower temperatures can be used. be. dimethyl sulfoxide, N, which is a non-acidic nitrogen- and/or oxygen-containing solvent; N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylformua Amphoteric aprotic solvents such as amide, N,N-diethylformamide are preferred. stomach. The term "ampholytic aprotic solvent" refers to active protons that can interfere with the reactions described in Ni. is intended to mean any organic solvent that does not contain a ton. bisexual Roton solvents and other inerts such as benzene, toluene, xylene and methylene chloride Mixtures of organic solvents may also be used. For solution polymerization, a temperature of approximately 100°C or higher is required. Preferably, a temperature below 300°C is also preferred.

当業者に本発明をよりよ〈実施せしめるために、つぎの実施例を例証の目的で示 すが、これらは本発明を限定するものではない。すべての部は重量によるもので ある。To enable those skilled in the art to better practice the invention, the following examples are presented for illustrative purposes. However, these are not intended to limit the invention. All parts are by weight be.

実　施　例　Ｉ Ｎ−メチル−２−ピロリドン中のビスフェノール−Ａのジカリウム塩（０，７６ ｇ、２．５ミリモル）、４−ブロム−オルト−キシレン（１，１１ｍｇ、６．０ ミリモル）及び塩化銅塩ＣｕＣ１（３７，１ｍｇ、０．　３８ミリモル）の溶液 を油浴中に浸漬したフラスコ中で撹拌しつつ約１７５℃に３時間加熱した。冷却 した混合物をエーテル（約６０ｍ１）及び水（約３０ｍ１）で稀釈しそして分液 ロートに移した。Implementation example I Dipotassium salt of bisphenol-A in N-methyl-2-pyrrolidone (0,76 g, 2.5 mmol), 4-bromo-ortho-xylene (1.11 mg, 6.0 solution of the copper chloride salt CuC1 (37.1 mg, 0.38 mmol) was heated to about 175° C. for 3 hours with stirring in a flask immersed in an oil bath. cooling The mixture was diluted with ether (approximately 60 ml) and water (approximately 30 ml) and separated. Transferred to funnel.

この稀釈溶液をＨＣｆ　（３０ｍｌ、１．　ＯＮ）で洗滌し、ついでＮａＯＨ（ ３０ｍｌ、Ｉ　Ｎ）で及びその後に食塩水で洗滌した。This diluted solution was washed with HCf (30 ml, 1. ON) and then with NaOH ( Washed with 30 ml IN) and then with saline.

このエーテル性溶液を無水Ｃａ５Ｏａのコーンに通ずることによって乾燥しそし て減圧蒸留によってエーテルを除去した。This ethereal solution was dried by passing it through a cone of anhydrous Ca5Oa. The ether was removed by vacuum distillation.

残渣（１，０９ｇ）を５％酢酸エチル／ヘキサンで稀釈されたシリコンゲル７５ ｇ上でクロマトグラフ処理して式Ｉのアリール−ジエーテル７７６ｍｇ（収率７ １．２％）を得た。ＣＤＣｆｚ中でのプロトンＮＭＲは６．９０（多重線）、２ ．０５（−重線）及び１．５１（−重線）　ｐｐｍにピークを与えた。強度はそ れぞれ１４．１２及び６でありだ。２．０５ｐｐ１１＋及び１．５１ｐｐｍにお けるピークはそれぞれメチル−芳香族核及びメチーｇａｍ核に合致した。Silicone gel 75 was prepared by diluting the residue (1,09 g) with 5% ethyl acetate/hexane. 776 mg aryl-diether of formula I (yield 7 1.2%) was obtained. Proton NMR in CDCfz is 6.90 (multiplet), 2 ．． Peaks were given at 05 (-double line) and 1.51 (-double line) ppm. Strength is that They are 14.12 and 6 respectively. 2.05pp11+ and 1.51ppm The peaks corresponded to the methyl-aromatic nucleus and the methyl-gam nucleus, respectively.

実　施　例　■ Ｎ−メチル−２−ピロリドン（約１００ｍ１）中のビスフェノール−Ａのジナト リウム塩（７５ミリモル）、４−ブロム−オルト−キシレン（８０ミリモル）及 び塩化銅塩ムＣｊ（２，５モル９６）の溶液を油浴中で撹拌しつつ約１５０℃に 約２〜４時間加熱した。冷却した混合物をエーテル（約６０ｍ１）で稀釈しそし て分液ロートに移し、そこで有機相を水（３０ｍｌ）、ＨＣｆ　（１，ＯＮ、３ ０ｍ１）及び食塩水で洗滌した。エーテル抽出物を無水Ｃａ　Ｓｏ　４のコーン に通ずることによって乾燥した。減圧蒸留によってエーテルを除去しモして残渣 をカラムクロマトグラフィーによって精製した。式ｌのアリール−ジエーテルの 単離された収率は４８．６％であった。Implementation example ■ Dinate of bisphenol-A in N-methyl-2-pyrrolidone (approximately 100 ml) salt (75 mmol), 4-bromo-ortho-xylene (80 mmol) and A solution of copper chloride and copper chloride Cj (2.5 mol 96) was heated to about 150°C with stirring in an oil bath. Heated for about 2-4 hours. Dilute the cooled mixture with ether (approximately 60 ml) and and transferred to a separatory funnel, where the organic phase was mixed with water (30 ml), HCf (1, ON, 3 0 ml) and saline. Cone of ether extract anhydrous Ca So 4 Dry by passing through. The ether was removed by vacuum distillation and the residue was purified by column chromatography. of the aryl-diether of formula l The isolated yield was 48.6%.

国際調査報告 −惨鴫一一ム紳−沖−ＩＩ＠、ｐ（τ／ＵＳ　１１６１０１３８）ＡＮＮＥＸ　 Ｔｏ　Ｔ！：Ｅ　ＩＮＴＥＲＮＡＴ工０ＮＡＬ　５ＥＡＲＣＨＦＬＥ？ＯＲ丁Ｏ Ｎinternational search report -Kazushi Kazumu-Oki-II @, p (τ/US 11610138) ANNEX To T! :E INTERNAT 0NAL 5EARCHFLE? OR N

Claims (11)

【特許請求の範囲】[Claims] １．式 ▲数式、化学式、表等があります▼ ［式中、Ｒは一般式 ▲数式、化学式、表等があります▼ （式中、Ｚは式−ＣｙＨ２ｙ−，▲数式、化学式、表等があります▼，▲数式、 化学式、表等があります▼，−Ｓ−，−Ｏ−，及び▲数式、化学式、表等があり ます▼の二価の基からなる群の一員であり；ｍは０又は１であり；ｙは１〜５の 整数でありそしてＲ′は１〜５個の炭素原子をもつアルキル基から選ばれる）の 二価の有機基である］のアリール−ジエーテル。1. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R is a general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z is the formula -CyH2y-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼, -S-, -O-, and ▲ There are mathematical formulas, chemical formulas, tables, etc. is a member of the group consisting of divalent groups ▼; m is 0 or 1; y is 1 to 5; an integer and R' is selected from alkyl groups having 1 to 5 carbon atoms) aryl-diether of ] which is a divalent organic group. ２．式 ▲数式、化学式、表等があります▼ （式中、ｙは１〜５の整数である）のアリール−ジエーテル。2. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein y is an integer from 1 to 5). ３．式 ▲数式、化学式、表等があります▼ ▲数式、化学式、表等があります▼ 及び ▲数式、化学式、表等があります▼ からなる群から選んだ式のアリール−ジエーテル。3. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ as well as ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ An aryl-diether of the formula selected from the group consisting of. ４．式 ▲数式、化学式、表等があります▼及び▲数式、化学式、表等があります▼から なる群から選んだ式のハロゲン化キシレン及び式▲数式、化学式、表等がありま す▼ をもつビスフェノール−Ａのアルカリ金属塩（上式中、Ｑはハロゲンでありそし てＭはアルカリ金属である）を銅触媒の存在下で反応させることによって得られ る請求項３記載のアリール−ジエーテル。4. formula From ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ There are xylene halides and formulas selected from the group ▲mathematical formulas, chemical formulas, tables, etc. S▼ an alkali metal salt of bisphenol-A with (in the above formula, Q is a halogen) (M is an alkali metal) in the presence of a copper catalyst. The aryl-diether according to claim 3. ５．Ｑが塩素及び臭素からなる群から選ばれそしてＭがナトリウム及びカリウム からなる群から選ばれる請求項４記載のアリール−ジエーテル。5. Q is selected from the group consisting of chlorine and bromine and M is sodium and potassium The aryl-diether of claim 4 selected from the group consisting of. ６．ａ）式 ▲数式、化学式、表等があります▼及び▲数式、化学式、表等があります▼（式 中、Ｑはハロゲンである）からなる群から選んだ式をもつハロゲン化キシレン及 び式 ＋Ｍ−Ｏ−Ｒ−Ｏ−Ｍ＋ ［式中、Ｍはアルカリ金属でありそしてＲは一般式▲数式、化学式、表等があり ます▼ （式中、Ｚは式−ＣｙＨ２ｙ，▲数式、化学式、表等があります▼，▲数式、化 学式、表等があります▼，−Ｓ−，−Ｏ−，及び▲数式、化学式、表等がありま す▼の二価の基からなる群の一員であり、ｍは０又は１であり、ｙは１〜５の整 数でありそしてＲ′は１〜５個の炭素原子をもつアルキル基から選ばれる）の二 価の有機基である］をもつビスフェノール化合物のアルカリ金属塩を、銅触媒の 存在下、約１００℃以上の温度で反応させ、 ｂ）工程ａのアリール−ジエーテルを液相中で、カルボン酸及びマンガン及びコ バルトからなる群から選んだ触媒の存在下、約８０℃以上の温度で酸素と反応さ せることによって酸化させ、そして ｃ）工程ｂで形成されたジ無水物又はテトラ酸を両性非プロトン性溶剤の存在下 、１００〜３５０℃の範囲の温度で式Ｈ２Ｎ−Ｒ１−ＮＨ２（式中、Ｒ１は（ｉ ）６〜２０個の炭素原子をもつ芳香族炭化水素基及びそのハロゲン化誘導体、 （ｉｉ）２〜２０個の炭素原子をもつアルキレン基及びシクロアルキレン基、及 び （ｉｉｉ）前記定義したごときＲの範囲内に包含される二価の基、 からなる群から選んだ二価の有機基である）の有機ジアミンと反応させる、こと からなるポリエーテルイミドの製造法。6. a) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Formula halogenated xylenes and having formulas selected from the group consisting of Bi-style +M-O-R-O-M+ [In the formula, M is an alkali metal and R is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Masu▼ (In the formula, Z is the formula -CyH2y, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, etc. There are scientific formulas, tables, etc. ▼, -S-, -O-, and ▲ There are mathematical formulas, chemical formulas, tables, etc. It is a member of the group consisting of divalent groups of ▼, m is 0 or 1, and y is an integer from 1 to 5. and R' is selected from alkyl groups having 1 to 5 carbon atoms). An alkali metal salt of a bisphenol compound having a valent organic group] is treated with a copper catalyst. reacting at a temperature of about 100° C. or higher in the presence of b) The aryl-diether of step a is combined with the carboxylic acid and the manganese and copolymer in the liquid phase. reacts with oxygen at a temperature above about 80°C in the presence of a catalyst selected from the group consisting of oxidized by c) The dianhydride or tetraacid formed in step b in the presence of an amphoteric aprotic solvent , at a temperature in the range of 100-350°C with the formula H2N-R1-NH2, where R1 is (i ) aromatic hydrocarbon groups having 6 to 20 carbon atoms and their halogenated derivatives; (ii) alkylene groups and cycloalkylene groups having 2 to 20 carbon atoms, and Beauty (iii) a divalent group included within the scope of R as defined above; a divalent organic group selected from the group consisting of A method for producing polyetherimide consisting of ７．銅触媒はＣｕＣｌであり、Ｑは塩素及び臭素からなる群のハロゲンから選ば れ、Ｍはナトリウム及びカリウムからなる群のアルカリ金属から選ばれそしてカ ルボン酸は酢酸である請求項６記載の方法。7. The copper catalyst is CuCl and Q is selected from the group consisting of chlorine and bromine. , M is selected from the alkali metals of the group consisting of sodium and potassium; 7. The method according to claim 6, wherein the rubonic acid is acetic acid. ８．ＺはＣ３Ｈ６でありそしてｍは１である請求項７記載の方法。8. 8. The method of claim 7, wherein Z is C3H6 and m is 1. ９．有機ジアミン及びジ無水物又はテトラ酸の間の反応を溶剤の不存在下、２０ ０℃以上の温度で行なう請求項８記載の方法。9. The reaction between an organic diamine and a dianhydride or tetraacid is carried out in the absence of a solvent for 20 9. The method according to claim 8, which is carried out at a temperature of 0°C or higher. １０．両性非プロトン性溶剤はＮ，Ｎ−ジメチルホルムアミド、ジメチルスルホ キシド、Ｎ，Ｎ−ジメチルアセトアミド及びＮ−メチルピロリドンからなる群か ら選ばれる請求項８記載の方法。10. Amphoteric aprotic solvents include N,N-dimethylformamide and dimethylsulfonate. oxide, N,N-dimethylacetamide and N-methylpyrrolidone 9. The method according to claim 8, wherein the method is selected from: １１．酸化触媒は臭素を促進剤とするコバルトでありそして温度は８０℃〜１１ ５℃の範囲内である請求項１０記載の方法。11. The oxidation catalyst is cobalt with bromine as promoter and the temperature is between 80°C and 11°C. 11. The method according to claim 10, wherein the temperature is within the range of 5°C.
JP61503758A 1986-07-02 1986-07-02 aryl-diether Pending JPH01500112A (en)

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US3139452A (en) * 1957-02-25 1964-06-30 Gen Electric Oxidation of p-xylene to terephthalic acid
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US3699075A (en) * 1970-10-28 1972-10-17 Trw Inc Soluble high molecular weight polyimide
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