JP2013117015A - Polyimide, polyimide fiber, and methods for producing the same - Google Patents
Polyimide, polyimide fiber, and methods for producing the same Download PDFInfo
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本発明は、ポリイミド、ポリイミド繊維、及びそれらの製造方法に関し、より詳細には、溶媒可溶ポリイミド、及びこの溶媒可溶ポリイミドを使用して製造される高性能ポリイミド繊維、並びにそれらの製造方法に関する。 More particularly, the present invention relates to a solvent-soluble polyimide, a high-performance polyimide fiber produced using the solvent-soluble polyimide, and a production method thereof. .
衣料やタイヤや漁網などに用いられる繊維はナイロンやポリエステルの繊維が主として使用されている。その２倍以上の強度や高融点や高分解温度を示す繊維は高機能繊維といわれる。 Nylon and polyester fibers are mainly used for clothing, tires and fishing nets. A fiber exhibiting twice or more strength, a high melting point, and a high decomposition temperature is called a highly functional fiber.
デュポン社はピロメリット酸二無水物（ＰＭＤＡ）と４，４’−ジアミノジフェニルエーテル（ＤＡＤＥ）とからなるポリイミド繊条を提案している（特許文献１）。しかし、このポリイミド繊条は溶媒難溶であるため、その前駆体のポリアミック酸の紡糸溶液を合成し、加工してポリイミド繊維を得ている。 DuPont has proposed a polyimide filament composed of pyromellitic dianhydride (PMDA) and 4,4'-diaminodiphenyl ether (DADE) (Patent Document 1). However, since this polyimide fiber is hardly soluble in a solvent, a spinning solution of the precursor polyamic acid is synthesized and processed to obtain a polyimide fiber.
東レ株式会社もピロメリット酸二無水物（ＰＭＤＡ）と４，４’−ジアミノジフェニルエーテル（ＤＡＤＥ）とからなるポリイミド繊維を提案している（特許文献２）。このポリイミド繊維はＰＭＤＡとＤＡＤＥからなるポリアミド酸の溶媒溶液に脂肪族の二塩基酸無水物を加えてアミド酸の一部をイミド基に環化させ、得られた部分環化ポリアミド酸の溶液を水系凝固浴中に湿式紡糸し、さらに残りのアミド酸をイミド化させて得られる。 Toray Industries, Ltd. has also proposed a polyimide fiber composed of pyromellitic dianhydride (PMDA) and 4,4'-diaminodiphenyl ether (DADE) (Patent Document 2). This polyimide fiber is obtained by adding an aliphatic dibasic acid anhydride to a polyamic acid solvent solution composed of PMDA and DADE to cyclize a part of the amic acid to an imide group, and the resulting partially cyclized polyamic acid solution. It is obtained by wet spinning in an aqueous coagulation bath and imidizing the remaining amic acid.
繊維状ポリイミド「Ｐ−８４」はオーストリアのＩｎｓｐｅｃ Ｆｉｂｅｒ社の製品であって、従来の高機能繊維と異なる組成であり、ＢＴＤＡ(３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物)と芳香族イソシアネートから合成される（特許文献３）。 Fibrous polyimide “P-84” is a product of Inspec Fiber, Austria, and has a composition different from that of conventional high-performance fibers. BTDA (3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride ) And an aromatic isocyanate (Patent Document 3).
Ｎ−メチルピロリドン（ＮＭＰ）などの溶媒に可溶のポリイミドは、バレロラクトン−ピリジンの触媒の存在下にＮＭＰ溶液中で、芳香族酸ジ無水物と芳香族ジアミンの縮合によって溶媒可溶のポリイミドが合成される。 A polyimide soluble in a solvent such as N-methylpyrrolidone (NMP) is a polyimide soluble in a solvent by condensation of an aromatic dianhydride and an aromatic diamine in an NMP solution in the presence of a valerolactone-pyridine catalyst. Is synthesized.
ポリイミド溶液をガラス又は金属板上に流延され、加熱−脱溶媒することによってポリイミドフィルムが作製される。他方、ポリイミド溶液を水又は水−アルコール溶液中に糸状に流延することによってポリイミド繊維が合成される。この繊維は、乾燥中２００〜３００℃に加熱されて、強じんなポリイミド繊維となる。 A polyimide film is produced by casting a polyimide solution on a glass or metal plate and heating and removing the solvent. On the other hand, a polyimide fiber is synthesized by casting a polyimide solution into water or a water-alcohol solution in a thread form. This fiber is heated to 200-300 ° C. during drying to become a strong polyimide fiber.
しかし、ポリイミドの中でも耐熱性に優れたポリイミドはＮＭＰ等の溶媒に難溶である。このため耐熱性に優れるポリイミドからなるフィルムや繊維を製造することはこれまで行われていなかった。 However, among polyimides, polyimides having excellent heat resistance are hardly soluble in solvents such as NMP. For this reason, production of a film or fiber made of polyimide having excellent heat resistance has not been performed so far.
本発明者は、近年、ポリイミドの性質を改良するために、ポリイミドの製造工程を二段重合や三段重合にすることによって、容易にＮＭＰ等の溶媒に可溶する耐熱性に優れたポリイミドの製造に成功している（非特許文献１）。 In recent years, in order to improve the properties of polyimide, the present inventor has made the production process of polyimide a two-stage polymerization or a three-stage polymerization, so that a polyimide having excellent heat resistance that can be easily dissolved in a solvent such as NMP. It has been successfully manufactured (Non-Patent Document 1).
本発明の目的は、新規なポリイミド、ポリイミド繊維、及びそれらの製造方法を提供することにある。
本発明の更なる目的は、溶媒可溶で耐熱性も備えたポリイミド、及びこの溶媒可溶ポリイミドを使用する高性能ポリイミド繊維、特に耐熱性ポリイミド繊維、並びにそれらの製造方法を提供することにある。
The objective of this invention is providing a novel polyimide, a polyimide fiber, and those manufacturing methods.
A further object of the present invention is to provide a solvent-soluble and heat-resistant polyimide, a high-performance polyimide fiber using the solvent-soluble polyimide, particularly a heat-resistant polyimide fiber, and a method for producing them. .
本発明によれば、以下の発明が提供される。
［１］ ビス（アミノフェノキシ）ビフェニルの両末端のアミノ基にテトラカルボン酸ジ無水物が付加したポリイミド構造単位を含むポリイミド。
［２］ 前記ビス（アミノフェノキシ）ビフェニルが、４，４’−ビス（４−アミノフェノキシ）ビフェニル（ＢＡＰＢ）である、［１］に記載のポリイミド。
［３］ 前記テトラカルボン酸ジ無水物が、３，３’，４，４’−ビフェニルテトラカルボン酸ジ無水物（ＢＰＤＡ）である［１］又は［２］に記載のポリイミド。
［４］ 前記ポリイミド構造単位が、下記式：
According to the present invention, the following inventions are provided.
[1] A polyimide comprising a polyimide structural unit in which tetracarboxylic dianhydride is added to the amino groups at both ends of bis (aminophenoxy) biphenyl.
[2] The polyimide according to [1], wherein the bis (aminophenoxy) biphenyl is 4,4′-bis (4-aminophenoxy) biphenyl (BAPB).
[3] The polyimide according to [1] or [2], wherein the tetracarboxylic dianhydride is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA).
[4] The polyimide structural unit has the following formula:
で表される［１］〜［３］のいずれかに記載のポリイミド。
［５］ テトラカルボン酸ジ無水物とビス（アミノフェノキシ）ビフェニルとを２：１のモル比で反応させ、ビス（アミノフェノキシ）ビフェニルの両末端のアミノ基にテトラカルボン酸ジ無水物が付加したイミドオリゴマーを調製する第一の重合工程、及び
前記イミドオリゴマーにテトラカルボン酸ジ無水物及びジアミンを反応させてイミドポリマーを調製する第二の重合工程
を含む［１］〜［４］のいずれかに記載のポリイミドの製造方法。
［６］ テトラカルボン酸ジ無水物及びジアミンを反応させイミドオリゴマーを調製する第一の重合工程、及び
前記イミドオリゴマーにテトラカルボン酸ジ無水物とビス（アミノフェノキシ）ビフェニルとを２：１のモル比で反応させ、ビス（アミノフェノキシ）ビフェニルの両末端のアミノ基にテトラカルボン酸ジ無水物が付加した構造を有するイミドポリマーを調製する第二の重合工程
を含む［１］〜［４］のいずれかに記載のポリイミドの製造方法。
［７］ 前記重合工程で使用するテトラカルボン酸ジ無水物が３，３’，４，４’−ビフェニルテトラカルボン酸ジ無水物（ＢＰＤＡ）及びピロメリット酸二無水物（ＰＭＤＡ）からなる群から選ばれる少なくとも１種であり、前記重合工程で使用するジアミンが４，４’−ジアミノジフェニルエーテル（ＤＡＤＥ）、ビス［３−アミノ−４−ヒドロキシフェニル］スルホン（ＨＯＡＢＳＯ２）及び４，４’−（９−フルオレニリデン）ジアニリン（ＦＤＡ）からなる群から選ばれる少なくとも１種である、［５］又は［６］に記載のポリイミドの製造方法。
［８］ ［５］〜［７］のいずれかに記載のポリイミドの製造方法により製造されるポリイミド。
［９］ ［１］〜［４］及び［８］のいずれかに記載のポリイミドを含んでなるポリイミド繊維。
［１０］ ［１］〜［４］及び［８］のいずれかに記載のポリイミドを含んでなるポリイミド溶液を溶媒中に射出して糸状に固化させる工程を含む［９］に記載のポリイミド繊維の製造方法。
The polyimide in any one of [1]-[3] represented by these.
[5] Tetracarboxylic dianhydride and bis (aminophenoxy) biphenyl were reacted at a molar ratio of 2: 1 to add tetracarboxylic dianhydride to the amino groups at both ends of bis (aminophenoxy) biphenyl. Any one of [1] to [4] including a first polymerization step for preparing an imide oligomer, and a second polymerization step for preparing an imide polymer by reacting the imide oligomer with a tetracarboxylic dianhydride and a diamine. The manufacturing method of the polyimide as described in.
[6] A first polymerization step for preparing an imide oligomer by reacting a tetracarboxylic dianhydride and a diamine, and a 2: 1 mole of tetracarboxylic dianhydride and bis (aminophenoxy) biphenyl to the imide oligomer. A second polymerization step comprising preparing a imide polymer having a structure in which tetracarboxylic dianhydride is added to the amino groups at both ends of bis (aminophenoxy) biphenyl, which are reacted at a ratio. The manufacturing method of the polyimide in any one.
[7] The tetracarboxylic dianhydride used in the polymerization step is selected from the group consisting of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA). At least one selected from the group consisting of 4,4′-diaminodiphenyl ether (DADE), bis [3-amino-4-hydroxyphenyl] sulfone (HOABSO 2 ) and 4,4 ′-( [9] The method for producing a polyimide according to [6], which is at least one selected from the group consisting of 9-fluorenylidene) dianiline (FDA).
[8] A polyimide produced by the polyimide production method according to any one of [5] to [7].
[9] A polyimide fiber comprising the polyimide according to any one of [1] to [4] and [8].
[10] The polyimide fiber according to [9], which includes a step of injecting a polyimide solution containing the polyimide according to any one of [1] to [4] and [8] into a solvent to solidify it into a thread shape. Production method.
［ポリイミド及びその製造方法］
本発明のポリイミドは、ビス（アミノフェノキシ）ビフェニルの両末端のアミノ基にテトラカルボン酸ジ無水物が付加したポリイミド構造単位を有することを特徴とする。この構造単位を有することにより、耐熱性に優れるとともに溶媒に可溶であるポリイミドを形成することができる。本発明のポリイミドは、より具体的には、上記の構造単位を有するオリゴマーを調製し（一段目の重合）、そのオリゴマーに対してさらにテトラカルボン酸ジ無水物とジアミンとを反応させて（二段目の重合）所望の分子量を有するポリイミドとして形成される。重合工程は三段階以上行ってもよいし、重合工程の順番も限定されない。
[Polyimide and its production method]
The polyimide of the present invention is characterized by having a polyimide structural unit in which tetracarboxylic dianhydride is added to the amino groups at both ends of bis (aminophenoxy) biphenyl. By having this structural unit, it is possible to form a polyimide that has excellent heat resistance and is soluble in a solvent. More specifically, the polyimide of the present invention is prepared by preparing an oligomer having the above structural unit (first-stage polymerization), and further reacting the oligomer with tetracarboxylic dianhydride and diamine (2). Stage polymerization) It is formed as a polyimide having a desired molecular weight. The polymerization process may be performed in three or more stages, and the order of the polymerization process is not limited.
テトラカルボン酸ジ無水物としては、例えば、ピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、などの芳香族酸二無水物、１，２，３，４−ブタンテトラカルボン酸二無水物、１，２，３，４−シクロペンタンテトラカルボン酸二無水物、ビシクロ［２．２．オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物等の脂肪族酸二無水物などを挙げることができる。これらは単独でも２種類以上混合してもよい。 Examples of tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoro Aromatic acid dianhydrides such as propane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo [2 .2. Examples thereof include aliphatic acid dianhydrides such as octo-7-ene-2,3,5,6-tetracarboxylic dianhydride. These may be used alone or in combination of two or more.
ジアミンとしては、例えば、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、２，４−ジアミノトルエン、４，４’−ジアミノ−３，３’−ジメチル−１，１’−ビフェニル、４，４’−ジアミノ−３，３’−ジメトキシ−１，１’−ビフェニル、４，４’−ジアミノ−３，３’−ジヒドロキシ−１，１’−ビフェニル、４，４’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルスルホン、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スルフィド、２，２−ビス（４−アミノフェニル）プロパン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、３，５−ジアミノ安息香酸、２，５−ジアミノピリジン、２，６−ジアミノピリジン、２，６−ジアミノ−４−メチルピリジン、４，４’−（９−フルオレニリデン）ジアニリン、ジアミノシロキサン化合物、ビス［３−アミノ−４−ヒドロキシフェニル］スルホン（和歌山精化工業株式会社から製品番号ＢＰＳ−ＤＡとして、或いは日本純良薬品株式会社から製品番号３，３’−ＤＡＢＳとして入手可能）などが挙げられる。これらは単独でも２種類以上混合してもよい。 Examples of the diamine include m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 4,4′-diamino-3,3′-dimethyl-1,1′-biphenyl, and 4,4′-diamino. -3,3'-dimethoxy-1,1'-biphenyl, 4,4'-diamino-3,3'-dihydroxy-1,1'-biphenyl, 4,4'-diaminodiphenylmethane, 3,4'-diamino Diphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphene) E) hexafluoropropane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [ 4- (4-aminophenoxy) phenyl] sulfone, 3,5-diaminobenzoic acid, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4,4′- (9-Fluorenylidene) dianiline, diaminosiloxane compound, bis [3-amino-4-hydroxyphenyl] sulfone (Sei Wakayama) As a product number BPS-DA from Industry Co., Ltd., or available from Japan Junryo Pharmaceutical Co., Ltd. as a product number 3,3'-DABS) and the like. These may be used alone or in combination of two or more.
本発明のポリイミドは、耐熱性ポリイミドにおいて問題となっていた溶媒可溶性の欠点を解決するものである。このような溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、ジメチルスルホキシド（ＤＭＳＯ）、Ｎ−メチルピロリドン（ＮＭＰ）、γ−ブチロラクトン（γＢＬ）、アニソール、シクロヘキサノン、テトラメチル尿素、スルホランなどが挙げられる。これらの中でもＮＭＰやγＢＬが好ましい。これら溶媒は、後述するようにポリイミドを調製する際の重合反応に使用する溶媒や、ポリイミド繊維を調製する際に使用するポリイミド溶液を構成する溶媒成分としても使用できる。上記の溶媒は単独でも２種類以上混合してもよい。 The polyimide of the present invention solves the solvent-soluble defect that has been a problem in heat-resistant polyimide. Examples of such solvents include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), γ-butyrolactone (γBL), anisole, Examples include cyclohexanone, tetramethylurea, sulfolane and the like. Among these, NMP and γBL are preferable. These solvents can be used also as a solvent component which comprises the solvent used for the polymerization reaction at the time of preparing a polyimide and the polyimide solution used when preparing a polyimide fiber so that it may mention later. The above solvents may be used alone or in combination of two or more.
本発明のポリイミド繊維を調製するためのポリイミドは、例えば、二段重合方法によって調製される。
一段目の重合反応は、テトラカルボン酸ジ無水物とビス（アミノフェノキシ）ビフェニルとを２：１のモル比で反応させて、ビス（アミノフェノキシ）ビフェニルの両末端にテトラカルボン酸ジ無水物が付加した溶媒に可溶なイミドオリゴマーを調製する。
The polyimide for preparing the polyimide fiber of the present invention is prepared, for example, by a two-stage polymerization method.
In the first stage polymerization reaction, tetracarboxylic dianhydride and bis (aminophenoxy) biphenyl are reacted at a molar ratio of 2: 1, and tetracarboxylic dianhydride is added to both ends of bis (aminophenoxy) biphenyl. An imide oligomer soluble in the added solvent is prepared.
以下の反応式で具体的に説明すると、３，３’，４，４’−ビフェニルテトラカルボン酸ジ無水物（ＢＰＤＡ）と４，４’−ビス（４−アミノフェノキシ）ビフェニル（ＢＡＰＢ）とを２：１のモル比で触媒存在下で加熱して脱水イミド化反応させて、ＮＭＰに可溶なオリゴマー（ＢＰＤＡ−ＢＡＰＢ−ＢＰＤＡ）を調製する（一段目の重合）。 Specifically, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-bis (4-aminophenoxy) biphenyl (BAPB) are represented by the following reaction formula. An oligomer (BPDA-BAPB-BPDA) soluble in NMP is prepared by heating in the presence of a catalyst at a molar ratio of 2: 1 to cause dehydration imidization (first stage polymerization).
上記のオリゴマーに、ＢＰＤＡ、４，４’−ジアミノジフェニルエーテル（ＤＡＤＥ）、下記式： To the above oligomer, BPDA, 4,4'-diaminodiphenyl ether (DADE), the following formula:
で表されるビス［３−アミノ−４−ヒドロキシフェニル］スルホン（ＨＯＡＢＳＯ２）を加えて１８０℃に加熱すると（二段目の重合）、下記式（１）： When the bis [3-amino-4-hydroxyphenyl] sulfone (HOABSO 2 ) represented by the formula ( II ) is added and heated to 180 ° C. (second stage polymerization), the following formula (1):
(実施例における試料33-79に含まれるポリイミド)
で表される本発明の溶媒可溶ポリイミドが生成し、このポリイミドを含む溶液が得られる。
(Polyimide contained in Sample 33-79 in Examples)
The solvent-soluble polyimide of this invention represented by this is produced | generated, and the solution containing this polyimide is obtained.
同様に、二段目の重合において、ＢＰＤＡに代えてピロメリット酸二無水物（ＰＭＤＡ）を使用すると下記式（２）： Similarly, in the second-stage polymerization, when pyromellitic dianhydride (PMDA) is used instead of BPDA, the following formula (2):
(実施例における試料33-80に含まれるポリイミド)
で表される本発明の溶媒可溶ポリイミドが生成し、このポリイミドを含む溶液が得られる。
(Polyimide contained in Sample 33-80 in Examples)
The solvent-soluble polyimide of this invention represented by this is produced | generated, and the solution containing this polyimide is obtained.
上記の説明は例示的なものであり、重合工程の順番は限定されない。即ち、上記の第二の重合工程の反応を先に行い、そこで得られたオリゴマーに対して第一の重合工程を行うこともできる。 The above description is exemplary and the order of the polymerization steps is not limited. That is, the reaction in the second polymerization step is performed first, and the first polymerization step can be performed on the oligomer obtained there.
本発明のポリイミドは溶媒に可溶なので、ポリイミド溶液として使用することが可能である。この溶液を、例えば、水などの非溶解性の溶媒中に射出することによりポリイミド繊維とすることができ、ガラス板、金属板などの上に流延することによりポリイミドフィルムとすることができる。 Since the polyimide of the present invention is soluble in a solvent, it can be used as a polyimide solution. For example, this solution can be made into a polyimide fiber by being injected into a non-soluble solvent such as water, and can be made into a polyimide film by being cast on a glass plate, a metal plate or the like.
［ポリイミド繊維及びその製造方法］
本発明はまた、上記溶媒可溶ポリイミドから製造される高機能ポリイミド繊維をも提供する。
[Polyimide fiber and manufacturing method thereof]
The present invention also provides a high-performance polyimide fiber produced from the solvent-soluble polyimide.
従来のポリイミド繊維は、その前駆体であるポリアミック酸を使用するためポリアミック酸溶液から一度ポリアミド繊維を製造し、そのポリアミド繊維を加熱などによりイミド化させることが必要である。 Since the conventional polyimide fiber uses the precursor polyamic acid, it is necessary to once produce a polyamide fiber from a polyamic acid solution and imidize the polyamide fiber by heating or the like.
一方、本発明の溶媒可溶性ポリイミドは、ポリイミドを調製した後のそのポリイミドの溶液をポリイミドが溶解しない溶媒中に糸状に射出し、固化させ、先ず繊維として巻き取り、例えば、１００℃−２００℃−３００℃と順次加熱して残留溶媒を蒸発除去させてポリイミド繊維にすることができる。このようにポリイミドを調製してから繊維状に成形することができるので、製造工程を簡易なものとすることができるという利点がある。 On the other hand, the solvent-soluble polyimide of the present invention is prepared by injecting the polyimide solution after preparing the polyimide into a solvent in which the polyimide does not dissolve, solidifying, and winding up as a fiber, for example, 100 ° C.-200 ° C.- Heating at 300 ° C. in order to evaporate and remove the residual solvent can yield polyimide fibers. Thus, since polyimide can be prepared and formed into a fiber shape, there is an advantage that the manufacturing process can be simplified.
ポリイミドが溶解しない溶媒としては、ポリイミドが溶解せずに除去が容易な溶媒であれば特に限定されるものではないが、例えば、水、水及びアルコールの混合溶媒などが挙げられる。 The solvent in which polyimide does not dissolve is not particularly limited as long as it is a solvent that does not dissolve polyimide and can be easily removed, and examples thereof include a mixed solvent of water, water, and alcohol.
本発明を以下の例で具体的に説明するが、本発明は以下の例に限定して解釈されるものではない。
［測定方法］
（１）熱分析
試料には、ポリイミド溶液をガラス板に流延し、乾燥し、生成したフイルムをガラス板からはぎ取り用いた。
The present invention will be specifically described with reference to the following examples, but the present invention should not be construed as being limited to the following examples.
[Measuring method]
(1) Thermal analysis As a sample, a polyimide solution was cast on a glass plate, dried, and the produced film was peeled off from the glass plate.
熱重量分析（ＴＧＡ）及び示差熱分析（ＤＴＡ）には、同時測定装置として島津製作所製ＤＴＧ−６０を使用した。
示差走査熱量分析（ＤＳＣ）には、測定装置として島津製作所製ＤＳＣ−６０を使用した。
For thermogravimetric analysis (TGA) and differential thermal analysis (DTA), DTG-60 manufactured by Shimadzu Corporation was used as a simultaneous measurement apparatus.
For differential scanning calorimetry (DSC), DSC-60 manufactured by Shimadzu Corporation was used as a measuring device.
動的熱機械測定（ＤＭＡ）には、エスアイアイ・ナノテクノロジー社の測定装置を使用した。
（２）ゲル浸透クロマトグラフ（ＧＰＣ）
試料には２段目の重合後の重合体溶液を使用した。
For dynamic thermomechanical measurement (DMA), a measuring device manufactured by SII Nanotechnology was used.
(2) Gel permeation chromatograph (GPC)
A polymer solution after the second stage polymerization was used as a sample.
測定装置として東ソー製ＨＬＣ−８３２０６ＰＣ Ｅｃｏ ＳＥＣを使用した。
標準ポリスチレンを基準として分子量を計算した。
（３）引張試験
試料には、以下の方法で調製したポリイミド繊維を用いた。
Tosoh HLC-83206PC Eco SEC was used as a measuring device.
The molecular weight was calculated based on standard polystyrene.
(3) Tensile test A polyimide fiber prepared by the following method was used as a sample.
ポリイミド繊維の繊維径をKEYENCE社製レーザー顕微鏡により500倍に拡大し求め、繊維断面積より強度を求めた。
引張試験機は、インストロン社製の万能材料試験機３３４４２測定装置を使用し、チャック間距離20mmで測定した。
（４）ポリイミド溶液の濃度及び粘度
試料には、２段目の重合後の重合体溶液を使用した。
The fiber diameter of the polyimide fiber was obtained by enlarging it 500 times with a KEYENCE laser microscope, and the strength was obtained from the fiber cross-sectional area.
As the tensile tester, a universal material tester 33442 measuring apparatus manufactured by Instron was used, and measurement was performed at a distance between chucks of 20 mm.
(4) Concentration and viscosity of polyimide solution A polymer solution after the second stage polymerization was used as a sample.
ポリイミド溶液の粘度は、BLOOK FIELD DV-E VISCOMETERを用い、25℃で測定した。
［ポリイミドの調製］
（試料No.33-39）(HOABSO2+BPDA+DADE)(2BPDA+BAPB)の合成
ステンレススチール製の碇型撹拌器を取り付けたガラス製のセパラブル３つ口フラスコに水分分離トラップを備えた玉付冷却管を取り付けた。窒素ガスを通しながら、上記フラスコをシリコンオイル浴につけ、加熱、撹拌した。
The viscosity of the polyimide solution was measured at 25 ° C. using a BLOOK FIELD DV-E VISCOMETER.
[Preparation of polyimide]
(Sample No.33-39) Synthesis of (HOABSO 2 + BPDA + DADE) (2BPDA + BAPB) A glass separable three-necked flask equipped with a stainless steel vertical stirrer and a water separation trap An attached cooling pipe was attached. While passing nitrogen gas, the flask was placed in a silicon oil bath and heated and stirred.
１Ｌの容量の３つ口フラスコにＢＰＤＡ 5.84g、ＨＯＡＢＳＯ２ 5.60g、ＤＡＤＥ 4.00gを加え、ついでバレロラクトン 2.0g、ピリジン 3.0gを加えた後、ＮＭＰ（Ｎ−メチルピロリドン） 180g、トルエン 20gを加えた。窒素を通じながら、シリコン浴温度180℃、180rpm回転数で加熱、撹拌した（一段目の重合）。１時間経過後、反応器を空冷して、ＢＰＤＡ 11.76gとＢＡＰＢ 7.3g及びＮＭＰ 90gとを加えた。１０分後180℃、180rpmの回転数の撹拌をしながら１時間２０分加熱、撹拌した（二段目の重合）。反応液は容器に移す。 Add BPDA 5.84g, HOABSO 2 5.60g, DADE 4.00g to a 1L three-necked flask, then add valerolactone 2.0g, pyridine 3.0g, then add NMP (N-methylpyrrolidone) 180g, toluene 20g. added. While passing through nitrogen, the mixture was heated and stirred at a silicon bath temperature of 180 ° C. and a rotation speed of 180 rpm (first stage polymerization). After 1 hour, the reactor was air-cooled and 11.76 g BPDA, 7.3 g BAPB and 90 g NMP were added. After 10 minutes, the mixture was heated and stirred for 1 hour and 20 minutes while stirring at 180 ° C. and 180 rpm (second stage polymerization). Transfer the reaction mixture to a container.
（試料No.33-47）(BPDA+HOABSO2+DADE)(2BPDA+BAPB)
１Ｌの３つ口フラスコに、同様に加熱、撹拌して反応した。
(Sample No.33-47) (BPDA + HOABSO 2 + DADE) (2BPDA + BAPB)
In the same manner, the reaction was conducted by heating and stirring in a 1 L three-necked flask.
ＢＰＤＡ（5.84g）、ＨＯＡＢＳＯ２（5.60g）、ＤＡＤＥ（4.0g）、バレロラクトン（2.0g）、ピリジン（3.0g）を加え、ＮＭＰ（180g）とトルエン（20g）を加えた。室温で窒素を通じながら撹拌し、１０分後オイルバスに反応器をつけて180℃、180rpm（撹拌）で４０分間反応した（一段目の重合）後、空冷して、ＢＰＤＡ（11.76g）とＢＡＰＢ（7.36g）及びＮＭＰ（190g）を加え、180℃で反応した（二段目の重合）。３時間反応後、反応器をオイルバスから引き上げて反応を停止した。 BPDA (5.84 g), HOABSO 2 (5.60 g), DADE (4.0 g), valerolactone (2.0 g) and pyridine (3.0 g) were added, and NMP (180 g) and toluene (20 g) were added. The mixture was stirred at room temperature with nitrogen, and after 10 minutes, a reactor was attached to an oil bath and reacted at 180 ° C. and 180 rpm (stirring) for 40 minutes (first stage polymerization), then air-cooled, BPDA (11.76 g) and BAPB (7.36 g) and NMP (190 g) were added and reacted at 180 ° C. (second stage polymerization). After reacting for 3 hours, the reaction was stopped by lifting the reactor from the oil bath.
（試料No.33-49）(BPDA+HOABSO2+DADE)(2BPDA+BAPB)
各材料の使用量を変更して使用した以外は（試料No.33-39）及び（試料No.33-47）と同様にして行った。
(Sample No.33-49) (BPDA + HOABSO 2 + DADE) (2BPDA + BAPB)
The procedure was the same as (Sample No. 33-39) and (Sample No. 33-47) except that the amount used of each material was changed.
（試料No.33-77）(2BPDA+BAPB)(PMDA+DADE+HOABSO2)
前記と同様の３つ口フラスコを使用した。
(Sample No.33-77) (2BPDA + BAPB) (PMDA + DADE + HOABSO 2 )
A three-necked flask similar to the above was used.
ＢＰＤＡ（8.82g）、ＢＡＰＢ（5.52g）を反応器に加え、ＮＭＰ（150g）、バレロラクトン（1.5g）、ピリジン（2.25g）を加えつつ、トルエン（30g）を加えた。オイルバスに反応器を入れて180℃、180rpmで反応した（一段目の重合）。３０分後に反応を止め、空冷してＰＭＤＡ（4.41g）、ＤＡＤＥ（3.08g）、ＨＯＡＢＳＯ２（4.2g）を加え、ついでＮＭＰ（147g）を加えた。反応器をＮＭＰ浴に漬け180℃、180rpmで撹拌して５時間４０分反応して（二段目の重合）、冷却して反応を停止した。 BPDA (8.82 g) and BAPB (5.52 g) were added to the reactor, and toluene (30 g) was added while NMP (150 g), valerolactone (1.5 g) and pyridine (2.25 g) were added. The reactor was placed in an oil bath and reacted at 180 ° C. and 180 rpm (first stage polymerization). After 30 minutes, the reaction was stopped, air-cooled, PMDA (4.41 g), DADE (3.08 g) and HOABSO 2 (4.2 g) were added, and then NMP (147 g) was added. The reactor was immersed in an NMP bath, stirred at 180 ° C. and 180 rpm, reacted for 5 hours and 40 minutes (second stage polymerization), and cooled to stop the reaction.
（試料No.33-79）(2BPDA+BAPB)(BPDA+DADE+HOABSO2)
５００ｍＬ容量の３つ口フラスコを使用した。
(Sample No.33-79) (2BPDA + BAPB) (BPDA + DADE + HOABSO 2 )
A 500 mL three-necked flask was used.
ＢＰＤＡ（5.88g）、ＢＡＰＢ（3.6g）を加え、ついでＮＭＰ（100g）、バレロラクトン（1.0g）、ピリジン（1.5g）、トルエン（20g）を加え、180℃、180rpmで反応した（一段目の重合）。空冷してＢＰＤＡ（4.41g）、ＤＡＤＥ（2.40g）、ＨＯＡＢＳＯ２（4.2g）を加え、次にＮＭＰ（47g）を加えて、180℃に加熱、撹拌して５時間反応した（二段目の重合）。 BPDA (5.88 g) and BAPB (3.6 g) were added, and then NMP (100 g), valerolactone (1.0 g), pyridine (1.5 g), and toluene (20 g) were added and reacted at 180 ° C. and 180 rpm (first stage) Polymerization). Air-cooled, BPDA (4.41 g), DADE (2.40 g), HOABSO 2 (4.2 g) were added, then NMP (47 g) was added, and the mixture was heated to 180 ° C. and stirred for 5 hours (second stage) Polymerization).
（試料No.33-80）(2BPDA+BAPB)(PMDA+DADE+HOABSO2)
各材料の使用量を変更して使用した以外は（試料No.33-77）と同様にして行った。
(Sample No.33-80) (2BPDA + BAPB) (PMDA + DADE + HOABSO 2 )
The procedure was the same as (Sample No. 33-77) except that the amount of each material used was changed.
（試料No.81-5）(2BPDA+BAPB)(PMDA+DADE+FDA)
HOABSO2に代えてFDAを使用した以外は（試料No.33-77）と同様にして行った。
(Sample No.81-5) (2BPDA + BAPB) (PMDA + DADE + FDA)
The procedure was the same as (Sample No. 33-77) except that FDA was used instead of HOABSO 2 .
［ポリイミドの熱分析の結果］
（１）試料３３−３９（ＢＰＤＡ型）は、分解開始が２００℃、一次分解が４０５℃、二次分解が５６８℃の耐熱性ポリイミドであった。
（２）試料３３−７７（ＰＭＤＡ型）は、分解開始温度３３６℃、一次分解が４０２℃、二次分解が５６３℃の耐熱性ポリイミドであった。
（３）ＤＳＣ測定の結果、試料３３−３９（ＢＰＤＡ型）のＴｇは３０２℃、試料３３−７７（ＰＭＤＡ型）のＴｇは３０７℃であった。
（４）熱分析の結果を表１にまとめる。
（５）参考までに、ＨＯＡＢＳＯ２の代わりにＦＤＡを用いた場合の熱分析を提出する（試料８１−５）。
[Results of thermal analysis of polyimide]
(1) Sample 33-39 (BPDA type) was a heat-resistant polyimide having an onset of decomposition at 200 ° C, a primary decomposition at 405 ° C, and a secondary decomposition at 568 ° C.
(2) Sample 33-77 (PMDA type) was a heat-resistant polyimide having a decomposition start temperature of 336 ° C, a primary decomposition of 402 ° C, and a secondary decomposition of 563 ° C.
(3) As a result of DSC measurement, Tg of Sample 33-39 (BPDA type) was 302 ° C., and Tg of Sample 33-77 (PMDA type) was 307 ° C.
(4) The results of thermal analysis are summarized in Table 1.
(5) For reference, submit a thermal analysis when using FDA instead of HOABSO 2 (Sample 81-5).
（表１の注釈）
（１）備考欄の「250°C後測定」は、ＤＳＣ測定において、一回の走査（one pass）で２５０℃まで試料を加熱し、その後試料を室温に戻した後測定を行ったことを意味する。
（２）81-5についてはＤＭＡの結果、Ｔｇは３３８℃（Ｅ’’）であった。軟化温度は３１４℃であった。
（３）表中の「不明」はＤＴＡ又はＤＳＣチャートからＴｇが検出されなかったことを意味する。
(Notes on Table 1)
(1) “Measurement after 250 ° C.” in the remarks column means that in DSC measurement, the sample was heated to 250 ° C. in one pass and then the sample was returned to room temperature and then measured. means.
(2) As for 81-5, Tg was 338 ° C. (E ″) as a result of DMA. The softening temperature was 314 ° C.
(3) “Unknown” in the table means that Tg was not detected from the DTA or DSC chart.
［ポリイミド繊維の調製］
上記で得られたポリイミドのＮＭＰ溶液（７〜１５重量％ポリイミド含有、約１５〜２０００ポイズ）をシリンダーに密閉し、先端の細孔から窒素の圧力で押し出し、水−メタノール（３：１）混合液に通され、ポリイミド繊維を得た。
[Preparation of polyimide fiber]
The NMP solution of polyimide obtained above (containing 7 to 15% by weight of polyimide, about 15 to 2000 poise) is sealed in a cylinder, extruded from the pores at the tip with nitrogen pressure, and mixed with water-methanol (3: 1). The solution was passed through the solution to obtain a polyimide fiber.
空気中に取り出されたＮＭＰで濡れたポリイミド繊維は回転する円筒の周りに巻き取られた。
巻き取られたポリイミド繊維は水中に３時間以上浸漬され、次いで空気中に５時間以上室温で乾燥した。
The polyimide fiber wetted with NMP taken out into the air was wound around a rotating cylinder.
The wound polyimide fiber was immersed in water for 3 hours or more and then dried in air at room temperature for 5 hours or more.
上記の乾燥したポリイミド繊維は加熱−乾燥器に入れられて、空気中で、１００℃で２〜３時間、ついで２００℃で２〜３時間、最後に、３００乃至３５０℃で２〜３時間加熱乾燥され、ポリイミド繊維を得た。 The dried polyimide fiber is placed in a heating-dryer and heated in air at 100 ° C for 2-3 hours, then at 200 ° C for 2-3 hours, and finally at 300-350 ° C for 2-3 hours. It dried and obtained the polyimide fiber.
［ＧＰＣの測定結果］
試料３３−７９及び３３−４９のＧＰＣ測定結果を図６及び図７に示す。
[GPC measurement results]
The GPC measurement results of Samples 33-79 and 33-49 are shown in FIGS.
分子量の計算結果は、
（１）試料３３−７９
Ｍｎ（数平均分子量）：５００３６
Ｍｗ（重量平均分子量）：２１２０５３
（２）試料３３−４９
Ｍｎ（数平均分子量）は１１７１２
Ｍｗ（重量平均分子量）は３１４６０
であった。
The calculation result of molecular weight is
(1) Sample 33-79
M n (number average molecular weight): 50036
M w (weight average molecular weight): 212053
(2) Sample 33-49
M n (number average molecular weight) is 11712
M w (weight average molecular weight) is 31460
Met.
［引張試験の測定結果］
測定結果を以下の表に示す。
[Measurement result of tensile test]
The measurement results are shown in the following table.
従来の耐熱性ポリイミドは溶媒に溶解しないために、ポリイミドフィルムやポリイミド繊維の製造工程が複雑になるという不利があった。 Since conventional heat-resistant polyimide is not dissolved in a solvent, there is a disadvantage that a manufacturing process of a polyimide film or a polyimide fiber becomes complicated.
本発明により提供されるポリイミドは、非常に優れた耐熱性を有しつつも溶媒、特に有機溶媒に可溶性であるという特徴を有する。このポリイミドの溶液を使用して容易に耐熱性のポリイミド繊維、ポリイミドフィルム、その他の成形品を製造することができる。よって、従来の耐熱性ポリイミドに比べて、本発明のポリイミドは、その成形品の製造プロセスが単純化でき、しかもその成形品は優れた耐熱性を備えているから、産業上極めて有用である。 The polyimide provided by the present invention is characterized by being extremely soluble in a solvent, particularly an organic solvent, while having excellent heat resistance. Heat-resistant polyimide fibers, polyimide films, and other molded products can be easily produced using this polyimide solution. Therefore, compared with the conventional heat resistant polyimide, the polyimide of this invention can simplify the manufacturing process of the molded product, and since the molded product has the excellent heat resistance, it is very useful industrially.
Claims (10)
前記イミドオリゴマーにテトラカルボン酸ジ無水物及びジアミンを反応させてイミドポリマーを調製する第二の重合工程
を含む請求項１〜４のいずれかに記載のポリイミドの製造方法。 An imide oligomer obtained by reacting tetracarboxylic dianhydride and bis (aminophenoxy) biphenyl at a molar ratio of 2: 1 and adding tetracarboxylic dianhydride to the amino groups at both ends of bis (aminophenoxy) biphenyl The first polymerization step to be prepared and the second polymerization step to prepare an imide polymer by reacting the imide oligomer with a tetracarboxylic dianhydride and a diamine. Production method.
前記イミドオリゴマーにテトラカルボン酸ジ無水物とビス（アミノフェノキシ）ビフェニルとを２：１のモル比で反応させ、ビス（アミノフェノキシ）ビフェニルの両末端のアミノ基にテトラカルボン酸ジ無水物が付加した構造を有するイミドポリマーを調製する第二の重合工程
を含む請求項１〜４のいずれかに記載のポリイミドの製造方法。 A first polymerization step of reacting tetracarboxylic dianhydride and diamine to prepare an imide oligomer, and reacting the imide oligomer with tetracarboxylic dianhydride and bis (aminophenoxy) biphenyl in a molar ratio of 2: 1 And a second polymerization step for preparing an imide polymer having a structure in which tetracarboxylic dianhydride is added to the amino groups at both ends of bis (aminophenoxy) biphenyl. A method for producing polyimide.
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