JPH0781205B2 - Polyimide fiber - Google Patents
Polyimide fiberInfo
- Publication number
- JPH0781205B2 JPH0781205B2 JP62040013A JP4001387A JPH0781205B2 JP H0781205 B2 JPH0781205 B2 JP H0781205B2 JP 62040013 A JP62040013 A JP 62040013A JP 4001387 A JP4001387 A JP 4001387A JP H0781205 B2 JPH0781205 B2 JP H0781205B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- fiber
- polyamic acid
- polyimide fiber
- bis
- 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.)
- Expired - Lifetime
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規なポリイミドからなるポリイミド繊維に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a polyimide fiber made of a novel polyimide.
芳香族ポリイミドは有機ポリマーの中で最高級の耐熱性
に加え、優れた機械物性、耐溶剤性を有しており、例え
ばビス（４−アミノフェニル）エーテルとピロメリット
酸二無水物とからなるポリイミド（Dupont社製；商標KA
PTON,Vespel）は、それらの特徴を生かしてフィルムや
成形物の形態で実用化されている。これらポリイミドの
うちでも芳香族ジアミンとピロメリット酸二無水物とか
らなるポリピロメリットイミドはポリマー構造が直鎖状
であり高結晶性であるため高強度、高弾性率繊維素材と
しての可能性を有しているにもかゝわらずポリピロメリ
ットイミドからなるポリイミド繊維の研究は、M.M.Koto
n,Polym.Sci.USS.21.2756（1980）に見られるにすぎな
い。しかも得られたポリイミド繊維のうち、比較的高強
度であるポリ（4,4′−ビフェニレンピロメリットイミ
ド）繊維でもその強度は6.9g/dにすぎない。これは従来
のポリピロメリットイミドは加工性にとぼしいために溶
融紡糸できず、またほとんどの薬品に不溶であり、その
ために乾式紡糸もできず、ポリイミドの前駆体である不
安定なポリアミド酸の形態で湿式紡糸をして、ついで熱
水延伸後、熱環化させてポリイミド繊維を製造する湿式
紡糸法でしか繊維化することができなかったためであ
る。Aromatic polyimide has not only the highest heat resistance among organic polymers but also excellent mechanical properties and solvent resistance, and is composed of, for example, bis (4-aminophenyl) ether and pyromellitic dianhydride. Polyimide (made by Dupont; trademark KA
PTON, Vespel) has been put into practical use in the form of films and molded products by taking advantage of these characteristics. Among these polyimides, polypyromellitic imide consisting of aromatic diamine and pyromellitic dianhydride has high strength because of its linear polymer structure and high crystallinity, and its potential as a high elastic modulus fiber material. MMKoto is researching polyimide fibers made of polypyromellitimide despite having it.
n, not only to be seen in Polym.Sci.USS. 21 .2756 (1980). Moreover, among the obtained polyimide fibers, the strength of poly (4,4'-biphenylenepyromellitimide) fiber, which has a relatively high strength, is only 6.9 g / d. This is because conventional polypyromellitimide cannot be melt-spun because it has poor processability, and it is insoluble in most chemicals, and therefore cannot be dry-spun, and the form of unstable polyamic acid that is a precursor of polyimide is unstable. This is because the fiber can be formed only by the wet spinning method in which the polyimide fiber is produced by wet spinning, then hot water drawing, and then thermal cyclization.
また最近、神田ら〔繊学誌，40,T−480（1980）〕は、
ポリピロメリットイミドの高結晶性を犠牲にして、ポリ
イミドの延伸性の向上をはかり、テトラカルボン酸二無
水物成分として酸無水物中にエーテル結合や、カルボニ
ル結合の屈曲性の基を導入したビス（3,4−ジカルボキ
シフェニル）エーテル二無水物や3,3′,4,4′−ベンゾ
フェノンテトラカルボン酸二無水物を用い、またジアミ
ン成分として２−クロロベンジジンや２−クロロ−ｐ−
フェニレンジアミンを用いた低結晶性のポリイミドによ
る繊維化を検討して、強度19.7g/dのポリイミド繊維を
作成している。In addition, recently, Kanda et al. [Journal of Science, 40 , T-480 (1980)]
At the expense of the high crystallinity of polypyromellitimide, the stretchability of the polyimide is improved, and an ether bond or a carbonyl bond-flexible group is introduced into the acid anhydride as a tetracarboxylic dianhydride component. (3,4-dicarboxyphenyl) ether dianhydride or 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride is used, and 2-chlorobenzidine or 2-chloro-p- is used as a diamine component.
We investigated the fiberization of low crystallinity polyimide using phenylenediamine and made polyimide fiber with a strength of 19.7g / d.
しかしながら、延伸性向上のために、結晶性を低下させ
る構造を導入し、弾性率が1380g/dと低いために、耐熱
性繊維としての総合的な性能は充分満足のゆくものでは
ない。またポリマー構造から、さらに高弾性の期待でき
るベンジジンとピロメリット酸二無水物とからなる高結
晶性のポリピロメリットイミドから得られるポリイミド
繊維は強度7.7g/d、弾性率は880g/dと低いものであっ
た。これも従来のポリピロメリットイミドの加工性が劣
るために前駆重合体であるポリアミド酸を一部化学イミ
ド化した後に紡糸して、その後熱処理延伸しポリイミド
繊維化を行なう乾湿式法でしか繊維化できなかったため
である。However, in order to improve the drawability, a structure that reduces the crystallinity is introduced, and the elastic modulus is low at 1380 g / d, so that the overall performance as a heat resistant fiber is not sufficiently satisfactory. In addition, from the polymer structure, the polyimide fiber obtained from highly crystalline polypyromellitimide composed of benzidine and pyromellitic dianhydride, which can be expected to have higher elasticity, has a low strength of 7.7 g / d and an elastic modulus of 880 g / d. It was a thing. This is also because the processability of conventional polypyromellitimide is inferior, so the polyamic acid, which is the precursor polymer, is partially chemically imidized, then spun, and then heat-treated and stretched to form a polyimide fiber. Because I couldn't.
本発明者らは、ポリピロメリットイミドの高結晶性をそ
こなうことなく、しかも、溶融紡糸可能な加工性良好な
新規ポリイミドを見い出し、高強度、高弾性率のポリイ
ミド繊維を得ることに成功し、本発明に至った。The present inventors, without impairing the high crystallinity of polypyromellitimide, yet, found a novel polyimide processability good melt spinning, high strength, succeeded in obtaining a polyimide fiber of high elastic modulus, The present invention has been completed.
本発明の目的は、高結晶性の新規なピロメリットイミド
からなる高強度、高弾性率のポリイミド繊維を提供する
ことにある。An object of the present invention is to provide a polyimide fiber having a high strength and a high elastic modulus, which is made of a novel highly crystalline pyromellitic imide.
本発明者らは前記目的を達成するために鋭意検討した結
果、下式（Ｉ）で表わされるポリイミドから高強度、高
弾性率のポリイミド繊維が得られることを見い出した。As a result of intensive studies to achieve the above object, the present inventors have found that a polyimide fiber having high strength and high elastic modulus can be obtained from the polyimide represented by the following formula (I).
すなわち、本発明は 式（Ｉ） で表わされる繰り返し単位を有するポリイミドからなる
ポリイミド繊維である。That is, the present invention has the formula (I) A polyimide fiber made of a polyimide having a repeating unit represented by
本発明におけるポリイミドは、ジアミン成分として4,
4′−ビス（３−アミノフェノキシ）ビフェニルを、ま
たテトラカルボン酸二無水物成分としてピロメリット酸
二無水物を用い、これらを重合させて得られるポリアミ
ド酸を、さらに脱水環化させて得られるポリイミドであ
る。Polyimide in the present invention, as a diamine component 4,
4'-bis (3-aminophenoxy) biphenyl and pyromellitic dianhydride as tetracarboxylic dianhydride components are used, and polyamic acid obtained by polymerizing these is further dehydrated and cyclized. It is polyimide.
かつまた本発明のポリイミドは従来のポリイミドと同様
な耐熱性を有していながら、結晶性であり、しかも熱可
塑性であるという特色を有している。そのため、溶融紡
糸可能な、高結晶性のポリイミドである。In addition, the polyimide of the present invention has the same heat resistance as conventional polyimides, but is also characterized by being crystalline and thermoplastic. Therefore, it is a highly crystalline polyimide that can be melt-spun.
本発明におけるポリイミドは次のごとき方法で得られ
る。The polyimide in the present invention can be obtained by the following method.
すなわちまず4,4′−ビス（３−アミノフェノキシ）ビ
フェニルとピロメリット酸二無水物とを有機溶媒中で重
合させてポリアミド酸を得る。That is, first, 4,4'-bis (3-aminophenoxy) biphenyl and pyromellitic dianhydride are polymerized in an organic solvent to obtain a polyamic acid.
このポリアミド酸の生成反応は通常、有機溶媒中で実施
する。この反応に用いる有機溶媒としては、例えばN,N
−ジメチルホルムアミド、N,N−ジメチルアセトアミ
ド、N,N−ジエチルアセトアミド、N,N−ジメチルメトキ
シアセトアミド、Ｎ−メチル−２−ピロリドン、1,3−
ジメチル−２−イミダゾリジノン、Ｎ−メチルカプロラ
クタム、1,2−ジメトキシエタン、ビス（２−メトキシ
エチル）エーテル、1,2−ビス（２−メトキシエトキ
シ）エタン、ビス｛２−（２−メトキシエトキシ）エチ
ル｝エーテル、テトラヒドロフラン、1,3−ジオキサ
ン、1,4−ジオキサン、ピリジン、ピコリン、ジメチル
スルホキシド、ジメチルスルホン、テトラメチル尿素、
ヘキサメチルホスホルアミド、ｍ−クレゾール、Ｐ−ク
ロロフェノール、アニソールなどが挙げられる。またこ
れらの有機溶剤は単独でも或いは２種以上混合して用い
ても差し支えない。The reaction for producing this polyamic acid is usually carried out in an organic solvent. Examples of the organic solvent used in this reaction include N, N
-Dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-
Dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis {2- (2-methoxy Ethoxy) ethyl} ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea,
Hexamethylphosphoramide, m-cresol, P-chlorophenol, anisole and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.
反応温度は通常200℃以下、好ましくは50℃以下であ
る。The reaction temperature is usually 200 ° C or lower, preferably 50 ° C or lower.
反応圧力は特に限定されず、常圧で十分実施できる。The reaction pressure is not particularly limited and can be carried out at normal pressure.
反応時間は溶剤の種類および反応温度により異なり、通
常、下記式（II）で表わされるポリアミド酸の生成が完
了するに十分な時間反応させる。The reaction time varies depending on the type of solvent and the reaction temperature, and usually the reaction is performed for a time sufficient to complete the production of the polyamic acid represented by the following formula (II).
通常４〜24時間で十分である。4-24 hours is usually sufficient.
このような反応により、下記式（II）の繰り返し単位を
有するポリアミド酸が得られる。By such a reaction, a polyamic acid having a repeating unit of the following formula (II) is obtained.
さらに得られたポリアミド酸を100〜400℃に加熱してイ
ミド化するか、または無水酢酸などのイミド化剤を用い
て化学イミド化することにより下記式（Ｉ）の繰り返し
単位を有する対応するポリイミドが得られる。 Further, the obtained polyamic acid is heated to 100 to 400 ° C. for imidization, or is chemically imidized with an imidizing agent such as acetic anhydride to obtain a corresponding polyimide having a repeating unit of the following formula (I). Is obtained.
また、4,4′−ビス（３−アミノフェノキシ）ビフェニ
ルとピロメリット酸二無水物とを有機溶媒中に懸濁また
は溶解させた後加熱し、ポリイミドの前駆体であるポリ
アミド酸の生成と脱水イミド化とを同時に行なうことに
より上記式（Ｉ）の繰り返し単位を有するポリイミドを
得ることも可能である。すなわち、従来公知の手法を用
いて上記（Ｉ）の繰り返し単位を有するポリイミドを得
ることができる。 Further, 4,4′-bis (3-aminophenoxy) biphenyl and pyromellitic dianhydride are suspended or dissolved in an organic solvent and then heated to generate and dehydrate a polyamic acid which is a precursor of polyimide. It is also possible to obtain a polyimide having a repeating unit of the above formula (I) by simultaneously performing imidization. That is, a polyimide having the repeating unit (I) can be obtained by using a conventionally known method.
かくして得られたポリイミドを380℃から450℃で溶融
し、押し出し、繊維化する。その後200〜550℃、好まし
くは220〜250℃において３〜４倍に熱延伸することによ
り高強度、高弾性率のポリイミド繊維を得ることができ
る。The polyimide thus obtained is melted at 380 ° C to 450 ° C, extruded and made into fibers. Then, by heat drawing at 3 to 4 times at 200 to 550 ° C, preferably 220 to 250 ° C, a polyimide fiber having high strength and high elastic modulus can be obtained.
また、ポリイミドの前駆体である前記式（II）で表され
るポリアミド酸を有機溶剤に溶解した溶液を用いて、湿
式紡糸法によりポリアミド酸繊維を製造し、次いで熱処
理してイミドに環化させるか、または必要に応じて熱延
伸することによってもポリイミド繊維が得られる。さら
にはまたポリアミド酸繊維を化学的手段によってイミド
に環化させ、ついで熱延伸を行なうことによっても、も
ちろんポリイミド繊維を得ることは可能である。Further, using a solution prepared by dissolving a polyamic acid represented by the above formula (II), which is a precursor of polyimide, in an organic solvent, polyamic acid fibers are produced by a wet spinning method, and then heat treated to cyclize to an imide. Alternatively, the polyimide fiber can be obtained by hot stretching if necessary. Furthermore, it is also possible to obtain a polyimide fiber, of course, by cyclizing a polyamic acid fiber into an imide by a chemical means and then performing heat drawing.
たとえば濃度約20％のポリアミド酸のＮ−メチルピロリ
ドン溶液をＮ−メチルピロリドンと水の混合溶液からな
る凝固浴中へ、吐出量0.1〜5.0ml/分で吐出し、紡糸速
度１〜20m/分で巻き取り、ついで10〜90℃の水中で１〜
３倍に延伸することによりポリアミド酸繊維を得ること
ができる。かくして得られたポリアミド酸繊維を200〜5
50℃において熱処理してイミドに環化させることにより
ポリイミド繊維を得ることができる。また湿式紡糸によ
り得られたポリアミド酸繊維を、無水酢酸などの脱水環
化剤およびピリジン、トリエチルアミンなどのイミド化
触媒とからなる混合溶液に浸せきし、化学的手法により
あらかじめイミド化し、次いでイミド化剤を抽出した
後、真空乾燥し、さらに400〜550℃で1.01〜3.0倍に熱
延伸することにより高強度、高弾性のポリイミド繊維を
得ることができる。For example, a N-methylpyrrolidone solution of polyamic acid having a concentration of about 20% is discharged into a coagulation bath consisting of a mixed solution of N-methylpyrrolidone and water at a discharge rate of 0.1 to 5.0 ml / min, and a spinning speed of 1 to 20 m / min. And then in water at 10-90 ° C
A polyamic acid fiber can be obtained by stretching 3 times. 200 ~ 5 polyamic acid fiber thus obtained
A polyimide fiber can be obtained by heat treatment at 50 ° C. to cyclize the imide. Further, the polyamic acid fiber obtained by wet spinning is dipped in a mixed solution consisting of a cyclodehydrating agent such as acetic anhydride and an imidization catalyst such as pyridine and triethylamine, preliminarily imidized by a chemical method, and then an imidizing agent. After being extracted, the polyimide fiber having high strength and high elasticity can be obtained by vacuum drying and further heat stretching 1.01 to 3.0 times at 400 to 550 ° C.
すなわち、本発明におけるポリイミド繊維は、溶融紡糸
法においても、またポリイミドの前駆体であるポリアミ
ド酸の段階で湿式紡糸法により繊維化しその後、熱的ま
たは化学的にイミド化する方法においても製造すること
が可能である。That is, the polyimide fiber in the present invention can be produced not only by the melt spinning method but also by the method of fiberizing by the wet spinning method at the stage of the polyamic acid which is the precursor of the polyimide, and then thermally or chemically imidizing. Is possible.
本発明を実施例および合成例により具体的に説明する。 The present invention will be specifically described with reference to examples and synthetic examples.
合成例 ３ガラス製反応容器に4,4′−ジヒドロキシビフェニ
ル186g（1.0モル）、ｍ−ジニトロベンゼン438g（2.6モ
ル）、炭酸カリウム363gおよびN,N−ジメチルホルムア
ミド2000mlを装入し145〜150℃で16時間反応させる。反
応終了後、冷却、無機塩をろ別し、次にろ液の溶剤を減
圧蒸留により留去したのち65℃に冷却し、メタノール20
00mlを装入し１時間かきまぜる。結晶をろ別、水洗、メ
タノール洗浄、乾燥して4,4′−ビス（３−ニトロフェ
ノキシ）ビフェニルの茶褐色結晶を得た。収量426g（収
率99.5％）。ついで、１のガラス製密閉容器に、得ら
れた粗4,4′−ビス（３−ニトロフェノキシ）ビフェニ
ル100g（0.23モル）を５％Pd/C（日本エンゲルハルト社
製）1g、メチルセロソルブ350mlとともに装入した。60
〜65℃で激しくかきまぜながら水素を導入すると８時間
でそれ以上水素を吸収しなくなり反応が完了した。冷却
後、ろ過して触媒を除去し、これを水500mlに排出し、
結晶をろ別する。これに35％塩酸48gと50％イソプロパ
ノール540mlを加えて加熱溶解し、放冷すると4,4′−ビ
ス（３−アミノフェノキシ）ビフェニルの塩酸塩が析出
した。これをろ過後、50％イソプロパノール540mlを加
えて加熱溶解し、活性炭5gを加えてろ過後、アンモニア
水で中和し、結晶をろ別、水洗、乾燥して4,4′−ビス
（３−アミノフェノキシ）ビフェニルを得た。Synthesis Example 3 A glass reaction vessel was charged with 186 g (1.0 mol) of 4,4′-dihydroxybiphenyl, 438 g (2.6 mol) of m-dinitrobenzene, 363 g of potassium carbonate and 2000 ml of N, N-dimethylformamide, and 145 to 150 ° C. React for 16 hours. After completion of the reaction, cooling, the inorganic salt was filtered off, the solvent of the filtrate was distilled off under reduced pressure and then cooled to 65 ° C., and methanol 20
Charge 00 ml and stir for 1 hour. The crystals were separated by filtration, washed with water, washed with methanol, and dried to obtain 4,4'-bis (3-nitrophenoxy) biphenyl brown brown crystals. Yield 426g (99.5% yield). Then, 100 g (0.23 mol) of the obtained crude 4,4′-bis (3-nitrophenoxy) biphenyl was added to 1 g of a glass closed container, 5 g of Pd / C (manufactured by Engelhardt Japan) 1 g, and methyl cellosolve 350 ml. Charged with. 60
When hydrogen was introduced with vigorous stirring at ˜65 ° C., hydrogen was not absorbed any more in 8 hours and the reaction was completed. After cooling, the catalyst was removed by filtration, and this was discharged into 500 ml of water,
The crystals are filtered off. To this, 48 g of 35% hydrochloric acid and 540 ml of 50% isopropanol were added, and the mixture was heated and dissolved, and when left to cool, 4,4'-bis (3-aminophenoxy) biphenyl hydrochloride was precipitated. After filtering this, 540 ml of 50% isopropanol was added and dissolved by heating, 5 g of activated carbon was added, the mixture was filtered, neutralized with aqueous ammonia, the crystals were separated by filtration, washed with water and dried to obtain 4,4'-bis (3- Aminophenoxy) biphenyl was obtained.
収量72.0g（収率85％）、無色結晶、融点144〜146℃、
純度99.6％（高速液体クロマトグラフィーによる）。Yield 72.0 g (85% yield), colorless crystals, melting point 144-146 ° C,
Purity 99.6% (by high performance liquid chromatography).
元 素 分 析（C24H20N2O2） Ｃ Ｈ Ｎ 計算値（％） 78.26 5.43 7.61 分析値（％） 78.56 5.21 7.66 MS:368（M+）、340、184 IR（KBr、cm-1）:3400と3310（NH2基）、1240（エーテ
ル結合） 実施例−１ かきまぜ機、還流冷却器および窒素導入管を備えた反応
容器に、4,4′−ビス（３−アミノフェノキシ）ビフェ
ニル368g（１モル）と、N,N−ジメチルアセトアミド234
4gを装入し、窒素雰囲気下に、ピロメリット酸二無水物
218g（１モル）を溶液温度の上昇に注意しながら分割し
て加え、室温で約20時間かきまぜた。かくして得られた
ポリアミド酸の対数粘度は3.21dl/gであった。こゝに対
数粘度は、N,N−ジメチルアセトアミドを溶媒とし、濃
度0.5g/100ml溶媒、35℃で測定した値である。Elemental analysis (C 24 H 20 N 2 O 2) C H N calc (%) 78.26 5.43 7.61 Analytical values (%) 78.56 5.21 7.66 MS: 368 (M +), 340,184 IR (KBr, cm - 1 ): 3400 and 3310 (NH 2 group), 1240 (ether bond) Example-1 In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 4,4′-bis (3-aminophenoxy) was added. Biphenyl 368g (1 mol) and N, N-dimethylacetamide 234
Charge 4 g, and in a nitrogen atmosphere, pyromellitic dianhydride
218 g (1 mol) was added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours. The polyamic acid thus obtained had an inherent viscosity of 3.21 dl / g. Here, the logarithmic viscosity is a value measured by using N, N-dimethylacetamide as a solvent at a concentration of 0.5 g / 100 ml solvent at 35 ° C.
かくして得られたポリアミド酸溶液に30.3g（0.3モル）
のトリエチルアミンおよび30.6g（0.3モル）の無水酢酸
を約30分かけて添加し、その後約30分かきまぜた。かく
して得られた溶液を0.08mmφ×20ホールの口金から吐出
量0.7ml/分で、室温のN,N−ジメチルアセトアミド／水
（容積比25/75）の凝固浴に吐出し、紡糸速度10m/分で
巻きとり、ついで室温の水中において1.4倍に延伸し
た。かくして得られた凝固糸をガラスボビンにまいたま
ま、ただちに室温の無水酢酸／トリエチルアミン（容積
比70/30）に12時間浸漬した。ついで室温のジメチルア
セトアミド中に１時間浸漬したのち、90℃の熱水中で1.
2倍に延伸後90℃で２時間真空乾燥した。かくして得ら
れたポリイミド繊維を窒素雰囲気下500℃において1.1倍
に延伸した。30.3g (0.3mol) in the polyamic acid solution thus obtained
Of triethylamine and 30.6 g (0.3 mol) of acetic anhydride were added over about 30 minutes, followed by stirring for about 30 minutes. The solution thus obtained was discharged from a 0.08 mmφ × 20 hole spinneret at a discharge rate of 0.7 ml / min into a room temperature N, N-dimethylacetamide / water (volume ratio 25/75) coagulation bath, and the spinning speed was 10 m / min. It was wound up in minutes and then stretched 1.4 times in water at room temperature. The coagulated yarn thus obtained was immediately dipped in acetic anhydride / triethylamine (volume ratio 70/30) at room temperature for 12 hours while being spread on a glass bobbin. Then, after immersing in dimethylacetamide at room temperature for 1 hour, in hot water at 90 ° C for 1.
After stretching twice, it was vacuum dried at 90 ° C. for 2 hours. The polyimide fiber thus obtained was stretched 1.1 times at 500 ° C. in a nitrogen atmosphere.
得られたポリイミド繊維の強度は19.8g/d、弾性率は170
0g/dであった。The strength of the obtained polyimide fiber is 19.8 g / d, and the elastic modulus is 170.
It was 0 g / d.
実施例−２ かきまぜ機、還流冷却器および窒素導入管を備えた反応
容器に、4,4′−ビス（３−アミノフェノキシ）ビフェ
ニル184g（0.5モル）、ピロメリット酸二無水物104.64g
（0.48モル）とフェノール2600gを装入し、窒素雰囲気
下に加熱し、100℃で約４時間かきまぜると黄色のポリ
イミド粉が析出しはじめる。さらに100℃において約16
時間かきまぜた後、150℃に昇温し、さらに150℃で４時
間かきまぜた。その後60℃付近まで冷却した後、2600g
のメタノールを装入し、30℃においてポリイミド粉をろ
別した。得られたポリイミド粉をメタノールおよびアセ
トンで洗浄した後、窒素雰囲気下に、300℃で８時間乾
燥して265.2g（収率98％）のポリイミド粉を得た。この
ポリイミド粉のＸ線分析を行なったところ35.1％の結晶
化度を有していた。かくして得られたポリイミド粉を41
0℃に加熱し溶融させ、0.08mmφ×20ホールの口金から2
20℃の窒素雰囲気下に吐出し、ドラフト倍率10倍でまき
取った。得られたポリイミド繊維を窒素雰囲気下240℃
において、4.0倍に延伸した。かくして得られたポリイ
ミド繊維の強度は26.0g/d、弾性率は2100g/dであった。Example-2 In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 184 g (0.5 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and 104.64 g of pyromellitic dianhydride were placed.
(0.48 mol) and 2600 g of phenol are charged, heated under a nitrogen atmosphere and stirred at 100 ° C. for about 4 hours, and yellow polyimide powder begins to precipitate. About 16 at 100 ℃
After stirring for an hour, the temperature was raised to 150 ° C, and the mixture was further stirred at 150 ° C for 4 hours. Then, after cooling to around 60 ℃, 2600g
Was charged and the polyimide powder was filtered off at 30 ° C. The obtained polyimide powder was washed with methanol and acetone and then dried at 300 ° C. for 8 hours in a nitrogen atmosphere to obtain 265.2 g (yield 98%) of polyimide powder. An X-ray analysis of this polyimide powder showed that it had a crystallinity of 35.1%. 41 thus obtained polyimide powder
Heat it to 0 ℃ to melt it, and then use the 0.08mmφ × 20 hole base
It was discharged under a nitrogen atmosphere at 20 ° C. and wound up at a draft ratio of 10 times. The obtained polyimide fiber was placed in a nitrogen atmosphere at 240 ° C.
In, the film was stretched 4.0 times. The polyimide fiber thus obtained had a strength of 26.0 g / d and an elastic modulus of 2100 g / d.
本発明により新規なポリイミドからなる高強度、高弾性
率のポリイミド繊維が提供される。INDUSTRIAL APPLICABILITY The present invention provides a high-strength, high-modulus polyimide fiber made of a novel polyimide.
Claims (1)
ポリイミド繊維。1. A formula (I) A polyimide fiber comprising a polyimide having a repeating unit represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62040013A JPH0781205B2 (en) | 1987-02-25 | 1987-02-25 | Polyimide fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62040013A JPH0781205B2 (en) | 1987-02-25 | 1987-02-25 | Polyimide fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63211319A JPS63211319A (en) | 1988-09-02 |
| JPH0781205B2 true JPH0781205B2 (en) | 1995-08-30 |
Family
ID=12569023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62040013A Expired - Lifetime JPH0781205B2 (en) | 1987-02-25 | 1987-02-25 | Polyimide fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0781205B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2002147A1 (en) * | 1988-11-07 | 1990-05-07 | Shuichi Morikawa | Production process for polyimide fibers |
| JPH03103444A (en) * | 1989-09-16 | 1991-04-30 | Mitsui Toatsu Chem Inc | Production of polyimide molded article |
| DE69027595T2 (en) * | 1989-12-22 | 1997-01-23 | Mitsui Toatsu Chemicals | POLYIMID GIESSLING |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4640972A (en) | 1985-11-15 | 1987-02-03 | E. I. Du Pont De Nemours And Company | Filament of polyimide from pyromellitic acid dianhydride and 3,4'-oxydianiline |
-
1987
- 1987-02-25 JP JP62040013A patent/JPH0781205B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4640972A (en) | 1985-11-15 | 1987-02-03 | E. I. Du Pont De Nemours And Company | Filament of polyimide from pyromellitic acid dianhydride and 3,4'-oxydianiline |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63211319A (en) | 1988-09-02 |
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