JPH03287815A - Production of polyimide fiber - Google Patents
Production of polyimide fiberInfo
- Publication number
- JPH03287815A JPH03287815A JP8911390A JP8911390A JPH03287815A JP H03287815 A JPH03287815 A JP H03287815A JP 8911390 A JP8911390 A JP 8911390A JP 8911390 A JP8911390 A JP 8911390A JP H03287815 A JPH03287815 A JP H03287815A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- spinning
- solvent
- polyamic acid
- polar solvent
- 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
- 239000000835 fiber Substances 0.000 title claims abstract description 53
- 239000004642 Polyimide Substances 0.000 title claims abstract description 30
- 229920001721 polyimide Polymers 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000009987 spinning Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- 229920006240 drawn fiber Polymers 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 13
- 238000007363 ring formation reaction Methods 0.000 abstract description 9
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 230000001112 coagulating effect Effects 0.000 abstract description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 abstract description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract description 2
- 229940018564 m-phenylenediamine Drugs 0.000 abstract description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 2
- 230000015271 coagulation Effects 0.000 description 28
- 238000005345 coagulation Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- -1 NN-dimethylacetamide Chemical compound 0.000 description 1
- 101100074998 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) nmp-2 gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、宇宙、航空分野及び産業資材分野等において
有用な、高強度、高弾性率を有し、かつ耐熱性の優れた
ポリイミド繊維の製造法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a polyimide fiber having high strength, high modulus of elasticity, and excellent heat resistance, which is useful in the fields of space, aviation, industrial materials, etc. Regarding manufacturing methods.
更に詳しくは、糸条体への形成過程において剛直骨格ポ
リイミドの分子配向を促進せしめ、剛直骨格ポリイミド
の力学特性に関る潜在能力をいかんなく発現させること
のできるポリイミド繊維の製造法に関するものである。More specifically, the present invention relates to a method for producing polyimide fibers that promotes the molecular orientation of rigid skeleton polyimide during the process of forming filaments, thereby fully expressing the potential of the rigid skeleton polyimide regarding its mechanical properties. .
（従来の技術〕
全芳香族ポリイミド繊維は高耐熱、高モジュラス繊維を
目的に種々研究がされている。(Prior Art) Various studies have been conducted on wholly aromatic polyimide fibers with the aim of producing highly heat resistant and high modulus fibers.
全芳香族ポリイミド繊維は、該ポリマーをとかす溶剤が
ないためポリイミドの前駆体である可溶性のポリアミド
酸溶液を用いて紡糸して繊維化し、ついで熱環化又は化
学環化方法を用いてイミド化させる製法でつくられてい
る。Since there is no solvent to melt the polymer, fully aromatic polyimide fibers are spun into fibers using a soluble polyamic acid solution, which is a precursor of polyimide, and then imidized using a thermal cyclization or chemical cyclization method. It is made using a manufacturing method.
イミド化の方法としては、熱環化の方が化学環化よりコ
スト的には有利であるが、繊維の物性面で劣る場合が多
いとされていた。As for the imidization method, thermal cyclization is more cost-effective than chemical cyclization, but it has often been thought that the physical properties of the fibers are inferior.
しかし、いずれのイミド化方法を採用するにしてもポリ
イミドの前駆体であるポリアミド酸繊維の段階から予め
その分子配向を高めておがなけれは、その潜在性能を発
現させることが極めて難しかった。However, no matter which imidization method is adopted, it is extremely difficult to realize its latent performance unless the molecular orientation of the polyamic acid fiber, which is a precursor of polyimide, is enhanced in advance.
そこで、ポリイミドの前駆体を湿式紡糸する際紡糸原液
を一旦不活性雰囲気中に吐出した後、凝固浴中に導く、
いわゆる、乾湿式紡糸法によりポリアミド酸繊維の配向
を高める方法が、特開平１−２６００１５号公報に提案
されている。しかしながら、上記乾湿式方法は、紡糸口
金から糸を立てることが難しいこと、また紡糸安定性も
悪いため工業化は難しい等の問題があり、また得られる
繊維も充分に高い機械的物性を有するものではなかった
。Therefore, when wet spinning a polyimide precursor, the spinning stock solution is once discharged into an inert atmosphere and then introduced into a coagulation bath.
A method of increasing the orientation of polyamic acid fibers by a so-called dry-wet spinning method is proposed in JP-A-1-260015. However, the dry-wet method described above has problems such as difficulty in preparing yarn from the spinneret and poor spinning stability, making it difficult to industrialize, and the resulting fibers do not have sufficiently high mechanical properties. There wasn't.
また、ポリイミドの前駆体を湿式紡糸する際、紡糸原液
を凝固浴に直接導く紡糸方法（以下ドブ浸は紡糸と略す
。）が−船釣であるが、従来の方法はいずれも凝固浴に
少量の非凝固性溶剤を混ぜた溶液を用いるものであるた
め、湿式凝固に際し、重合体が析出する沈澱凝固を伴う
ものであった。In addition, when wet-spinning a polyimide precursor, the spinning method in which the spinning stock solution is directly introduced into the coagulation bath (hereinafter referred to as "spinning") is the spinning method, but in all conventional methods, a small amount is added to the coagulation bath. Since a solution containing a non-coagulable solvent is used, wet coagulation is accompanied by precipitation coagulation in which the polymer precipitates.
その結果、凝固繊維は、表面が緻密な構造を形成し、内
部が析出重合体間に多量の凝固浴の溶媒を含む疏な構造
を形成し、紡糸ドラフトがかけられると欠陥部を生成し
ながら引き延ばされ、現実には満足すべき繊維性能を発
現するには至っていない。As a result, the coagulated fibers form a dense structure on the surface and a rough structure containing a large amount of coagulation bath solvent between the precipitated polymers, and when the spinning draft is applied, defects are generated. In reality, it has not yet reached the point where it has achieved satisfactory fiber performance.
（発明が解決しようとする課題）
本発明の課題は、ドブ浸は紡糸における上述の問題点を
解決し、成形初期における分子配向を促進し、更には繊
維の構造を緻密化し、欠陥を減少する製造法を開発する
ことにある。そして複合材料等に極めて有用な高弾性を
与える繊維の製造法を提供することにある。(Problems to be Solved by the Invention) The problems of the present invention are to solve the above-mentioned problems in spinning, promote molecular orientation at the initial stage of forming, and further densify the fiber structure and reduce defects. The goal is to develop manufacturing methods. Another object of the present invention is to provide a method for producing fibers that exhibit high elasticity and are extremely useful for composite materials.
本発明者らは、上記課題について鋭意検討した結果、ド
ブ漬は紡糸においても、ポリイミドの前駆体の紡糸原液
を特定組成の凝固浴中で凝固させ、かつ延伸し、ポリイ
ミドの成形過程の初期においてその分子配向を高めてお
くことにより、前記課題が解決できることを見出し、本
発明を完成した。As a result of intensive studies on the above-mentioned problems, the present inventors have found that dobu dipping is also used in spinning, by coagulating the spinning dope of the polyimide precursor in a coagulation bath with a specific composition, and then stretching it, in the early stage of the polyimide forming process. The inventors have discovered that the above problem can be solved by increasing the molecular orientation, and have completed the present invention.
すなわち、本発明は、芳香族ジアミンと芳香族テトラカ
ルボン酸二無水物とを重合させたポリアミド酸重合体と
、有機極性溶媒とからなる紡糸原液を、口金を通して臨
界濃度以上の非凝固性有機溶媒を含む凝固浴中に押出し
た後、有機極性溶媒を含む水溶液中又は水浴中で少なく
とも１．１倍延伸した後、該延伸繊維を湿式法又は乾式
法で脱水環化することを特徴とするポリイミド繊維の製
造法、である。That is, in the present invention, a spinning stock solution consisting of a polyamic acid polymer obtained by polymerizing an aromatic diamine and an aromatic tetracarboxylic dianhydride and an organic polar solvent is passed through a spinneret into a non-coagulable organic solvent having a critical concentration or more. The polyimide is extruded into a coagulation bath containing a polyimide, stretched by at least 1.1 times in an aqueous solution containing an organic polar solvent or in a water bath, and then dehydrated and cyclized by a wet method or a dry method. This is a method for producing fibers.
以下、本発明を更に説明する。The present invention will be further explained below.
本発明のポリイミド繊維を構成する芳香族ジアミンとし
て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エテル、３．４′−ジ
アミノジフェニルエーテル、ヘンジジン又はこれらの核
メチル若しくはハロゲン置換体である。As the aromatic diamine constituting the polyimide fiber of the present invention, m-phenylenediamine, P-phenylenediamine,
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, hendidine, or a nuclear methyl or halogen substituted product thereof.
また、本発明のポリイミド繊維を構成する芳香族テトラ
カルボン酸二無水物としては、無水ピロメリット酸、３
．３’、４．４’−ビフェニルテトラカルボン酸二無水
物、３．３’、４．４’−ベンゾフェノンテトラカルボ
ン酸二無水物、等である。In addition, the aromatic tetracarboxylic dianhydride constituting the polyimide fiber of the present invention includes pyromellitic anhydride, 3
．． 3',4.4'-biphenyltetracarboxylic dianhydride, 3.3',4.4'-benzophenonetetracarboxylic dianhydride, and the like.
これらのモノマーを単独で用いて重合したホモポリマー
、又は、いくつかの七ツマ−を組合せたランダムコポリ
マーであってもよい。It may be a homopolymer polymerized using these monomers alone, or a random copolymer obtained by combining several heptads.
本発明で用いられる有機極性溶媒としては、Ｎ−メチル
ピロリドン、Ｎ、Ｎ−ジメチルホルムアミド、ＮＮ−ジ
メチルアセトアミド、ジメチルスルホキシド、ヘキサメ
チルホスホルアミド等がある。Examples of the organic polar solvent used in the present invention include N-methylpyrrolidone, N,N-dimethylformamide, NN-dimethylacetamide, dimethylsulfoxide, and hexamethylphosphoramide.
湿式紡糸原液としては、通常の方法である溶液重合で得
たポリアミド酸溶液、又は、アミド酸単位の一部をイミ
ド化させた部分環化ポリアミド酸溶液が用いられるが、
上記重合ドープに非溶媒を混合等により、ポリマーを一
旦単Ｉｖｉ後、適当な溶媒に再溶解し、これを紡糸原液
とすることもできる。本発明ではいずれの方法も採用で
きるが、工業的には、前者の方法が好ましい。As the wet spinning stock solution, a polyamic acid solution obtained by solution polymerization, which is a normal method, or a partially cyclized polyamic acid solution, in which a part of the amic acid units are imidized, is used.
It is also possible to mix the polymer dope with a non-solvent, etc., and then re-dissolve the polymer in a suitable solvent to obtain a spinning dope. Although either method can be employed in the present invention, the former method is industrially preferred.
紡糸原液のポリマー濃度は通常５〜３０重量％、好まし
くは８〜２０重景％であり、紡糸に適した粘度となるよ
うに設定される。The polymer concentration of the spinning stock solution is usually 5 to 30% by weight, preferably 8 to 20% by weight, and is set to have a viscosity suitable for spinning.
本発明の繊維製造法においては、上記紡糸原液を、口金
を通して臨界濃度以上の非凝固性有機溶媒を含む凝固浴
中に押出すことが肝要である。In the fiber manufacturing method of the present invention, it is important to extrude the above-mentioned spinning dope through a spinneret into a coagulation bath containing a non-coagulable organic solvent at a critical concentration or higher.
ここでいう臨界濃度とは、最大紡糸速度が最小、又は全
く紡糸不可能となり、その両側の濃度においては紡糸可
能領域を有する凝固浴の溶媒温度をいう。The critical concentration here refers to the temperature of the solvent in the coagulation bath at which the maximum spinning speed becomes the minimum or no spinning is possible, and which has a spinnable region at concentrations on either side of the maximum spinning speed.
臨界濃度以下では、充分に高い弾性率を有するポリイミ
ド繊維は得られない。この理由は、推定の域を脱しない
が、臨界濃度以下では繊維表面の固化が速いため内部ま
で紡糸張力が伝わらず、配向による繊維内部の緻密化が
進まないと考えられる。臨界濃度以上で凝固した繊維は
、紡糸ドラフトをかけることで析出重合体を流動化させ
ると同時に配向が促進され、更には、析出重合体が密着
し緻密な繊維構造が形成されるものと推定される。If the concentration is below the critical concentration, polyimide fibers with a sufficiently high modulus of elasticity cannot be obtained. The reason for this is speculation, but it is thought that below the critical concentration, the fiber surface solidifies quickly, so the spinning tension is not transmitted to the interior, and the interior of the fiber does not become densified due to orientation. It is assumed that the fibers coagulated above the critical concentration are subjected to spinning draft to fluidize the precipitated polymer and at the same time promote orientation, and furthermore, the precipitated polymer sticks together to form a dense fiber structure. Ru.
凝固浴濃度の上限は、単糸間の融着が起こらない濃度で
あり、具体的には繊度、凝固塔長、凝固浴の温度等によ
り決って（る。The upper limit of the coagulation bath concentration is the concentration at which fusion between single yarns does not occur, and is specifically determined by the fineness, coagulation tower length, coagulation bath temperature, etc.
一方、臨界濃度は、紡糸原液のポリマー濃度、繊度、凝
固塔長、凝固浴の温度、使用した溶剤等によって変動す
るが、Ｎ−メチルピロリドン（以下ＮＭＰと略す）を溶
剤とする場合は、おおよそ３５重量％を中心とする。Ｎ
ＭＰを溶剤とする紡糸は、ＮＭＰ濃度が４０〜４５重量
％の範囲に調整された凝固浴中に、紡糸原液を押出し、
０．５以上、好ましくは１以上、更に好ましくは２以上
の紡糸ドラフトで引取られる。ここでいう紡糸ドラフト
は、巻上げローラー速度をノズル孔からの紡糸原液吐出
線速度で割った値をいう。On the other hand, the critical concentration varies depending on the polymer concentration of the spinning dope, fineness, coagulation tower length, coagulation bath temperature, solvent used, etc., but when N-methylpyrrolidone (hereinafter abbreviated as NMP) is used as the solvent, approximately Mainly 35% by weight. N
Spinning using MP as a solvent involves extruding the spinning stock solution into a coagulation bath in which the NMP concentration is adjusted to a range of 40 to 45% by weight.
It is taken up with a spinning draft of 0.5 or more, preferably 1 or more, more preferably 2 or more. The spinning draft here refers to the value obtained by dividing the speed of the winding roller by the linear speed at which the spinning dope is discharged from the nozzle hole.
凝固浴濃度が臨界濃度をおおよそ１０重量％越えると繊
維間での接着、膠着が発生しやすくなる。If the coagulation bath concentration exceeds the critical concentration by approximately 10% by weight, adhesion and sticking between fibers will easily occur.
また浴の温度を上げるに伴い繊維間での接着、膠着が発
生しやすくなるため、凝固濃度と凝固温度とがバランス
する条件範囲が存在する。Furthermore, as the temperature of the bath increases, adhesion and sticking between fibers becomes more likely to occur, so there is a range of conditions in which the coagulation concentration and coagulation temperature are balanced.
凝固浴内での糸条の滞留時間は、通常０．１秒以上、好
ましくは０．３秒以上である。The residence time of the yarn in the coagulation bath is usually 0.1 seconds or more, preferably 0.3 seconds or more.
臨界濃度以上の凝固浴中で凝固した糸条は、更に有機極
性溶媒を含む水溶液中又は水浴中で少なくとも１．１倍
延伸することが必要であり、できる限り大きくとること
が好ましい。The thread coagulated in a coagulation bath having a concentration higher than the critical concentration needs to be further stretched by at least 1.1 times in an aqueous solution containing an organic polar solvent or in a water bath, and it is preferable to draw it as large as possible.
上記延伸浴の濃度は、通常、臨界濃度±１０重量％の範
囲が好ましいが、水浴を用いても本発明の効果は得られ
、特に制限されるものではない。The concentration of the above-mentioned stretching bath is usually preferably in the range of ±10% by weight of the critical concentration, but the effects of the present invention can be obtained even if a water bath is used, and there is no particular limitation.
また、上記延伸比が１．１に満たないとポリアミド酸繊
維の延伸による繊維内部での濃厚相の再融着が起こらな
いためか、機械的物性が優れたポリイミド繊維は得られ
ない。Furthermore, if the above-mentioned drawing ratio is less than 1.1, polyimide fibers with excellent mechanical properties cannot be obtained, probably because refusion of the dense phase within the fibers does not occur due to drawing of the polyamic acid fibers.
延伸された糸条はその後、脱溶媒される湿式法又は乾式
法で脱水環化される。本発明でいう湿式法による脱水閉
環とは、化学環化剤を用いる化学環化法といい、乾式法
による脱水閉環とは、加熱による熱閉環法をいう。いず
れも公知の方法であり、本発明の製造法は両者のうちど
ちらを採用してもよい。The drawn yarn is then dehydrated and cyclized by a wet method or a dry method in which the solvent is removed. In the present invention, dehydration ring closure by a wet method refers to a chemical cyclization method using a chemical cyclizing agent, and dehydration ring closure by a dry method refers to a thermal ring closure method by heating. Both are known methods, and the production method of the present invention may employ either of them.
化学環化法は、無水酢酸等の脱水剤によりポリアミド酸
の閉環イミド化を進行させ、この際触媒としてピリジン
等の３級アミンを併用してイミド化速度を大きくするこ
ともできる、糸条のイミド化においては、具体的には凝
固後、−旦糸条をボビンに巻取ったのちボビンごと上記
の化学環化剤中に浸漬、又は凝固後の糸条を化学環化剤
を配した浴中を通過させる等の手法により糸条と化学環
化剤とを接触させればよく、その手法に関しては特に限
定されるものではない。浸漬時間は通常１０分以上１２
時間以下である。In the chemical cyclization method, ring-closing imidization of polyamic acid is proceeded with a dehydrating agent such as acetic anhydride, and at this time, a tertiary amine such as pyridine can be used as a catalyst to increase the imidization rate. In imidization, concretely, after coagulation, the yarn is wound onto a bobbin, and then the whole bobbin is immersed in the above chemical cyclizing agent, or the coagulated yarn is bathed in a chemical cyclizing agent. The yarn and the chemical cyclizing agent may be brought into contact by a method such as passing through the yarn, and the method is not particularly limited. Soaking time is usually 10 minutes or more12
less than an hour.
化学環化した糸条は緊張化で熱処理を実施されることが
好ましく、３００〜６００°Ｃで行われる。The chemically cyclized yarn is preferably subjected to a heat treatment under tension, which is carried out at 300 to 600°C.
一方、前記延伸されたポリアミド酸の糸条を化学環化を
することなく直接加熱による熱閉環することもでき、加
熱温度２００〜６００°Ｃで緊張下で行なうことが好ま
しい。On the other hand, it is also possible to thermally ring-close the drawn polyamic acid thread by direct heating without chemical cyclization, and it is preferable to carry out the thermal ring-closing by heating at a heating temperature of 200 to 600°C under tension.
以上のごとく得られた繊維は耐熱性に加え、高度の力学
特性を有している。The fibers obtained as described above have high mechanical properties in addition to heat resistance.
（実施例〕 以下、本発明を実施例を挙げて説明する。(Example〕 Hereinafter, the present invention will be explained by giving examples.
実施例中のポリアミド酸の固有粘度（ηｉｎｈ ）はポ
リマー濃度０．５．ｇ／ｄｆとなるように、重合溶媒を
ＮＭＰで希釈し、３５°Ｃで測定した。The intrinsic viscosity (ηinh) of the polyamic acid in the examples was determined at a polymer concentration of 0.5. The polymerization solvent was diluted with NMP to give g/df, and the measurement was performed at 35°C.
また、繊維の引張特性は、東洋ボールウィン■製テンシ
ロンを用い、糸長１００ａｎ、引張速度５０ ｍｍ／ｍ
ｉｎで繊維について測定した。In addition, the tensile properties of the fibers were determined using Tensilon manufactured by Toyo Ballwin ■, yarn length 100an, and tensile speed 50 mm/m.
Measured on fibers at in.
実施例１
ポリイミド前駆体の合成については脱水したＮＭＰ ２
００ｄにｐ−フェニレンジアミン６．４８ ｇ（６０，
０ｍｍｏｊ２ ） ）を溶解後、溶液を２°Ｃに冷却し
、激しく攪拌しつつ３．３ ’ 、 ４ 、４ ’−ビ
フェニルテトラカルボン酸二無水物（以下ＢＰＤＡと略
す） １７．６９ ｇ （６０，２＋ｎｍｏ１）を添加
した。引き続き重合を続け、溶液の粘度上昇とともに順
次ＮＭＰを添加し、最終的にポリマー濃度１０．５重量
％の高粘度溶液を得た。この間に要した重合時間は約２
時間であり、固有粘度は２．５に達した。Example 1 Dehydrated NMP 2 for synthesis of polyimide precursor
6.48 g of p-phenylenediamine (60,
After dissolving 3.3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA), the solution was cooled to 2°C and stirred vigorously. 2+nmol) was added. Subsequently, polymerization was continued, and as the viscosity of the solution increased, NMP was sequentially added to obtain a high viscosity solution with a polymer concentration of 10.5% by weight. The polymerization time required during this period was approximately 2
time and the intrinsic viscosity reached 2.5.
この溶液を０．０７ ｔｕｒｎφ、１０ホールの口金か
ら吐出線速１０ｏ＋／分でＮＭＰ４０重量％水溶液から
なる１５°Ｃの凝固浴中に押出し、ついで塔長２ｍの２
０重量％ＮＭＰ水溶液（１５°Ｃ）中で１．９倍に延長
した後、塔長２ｍの水浴（１５°Ｃ）中で１．３倍に延
長するとともに水洗を行なった。得られた糸条を室温で
２０分風乾後、６０°Ｃで２４時間真空乾燥しポリアミ
ド酸繊維とした。This solution was extruded into a 15°C coagulation bath consisting of a 40% by weight aqueous solution of NMP at a linear discharge speed of 10 o+/min through a 10-hole nozzle with a turnφ of 0.07, and then
After being extended 1.9 times in a 0% by weight NMP aqueous solution (15°C), it was extended 1.3 times in a 2 m water bath (15°C) and washed with water. The obtained yarn was air-dried at room temperature for 20 minutes and then vacuum-dried at 60°C for 24 hours to obtain polyamic acid fibers.
このポリアミド酸繊維は繊度２７デニール、強度１．７
ｇ／ｄ 、伸度５．１％、弾性率４５ｇ／ｄであった。This polyamic acid fiber has a fineness of 27 denier and a strength of 1.7
g/d, elongation 5.1%, and elastic modulus 45 g/d.
さらに、この糸条を窒素雰囲気下で２００°Ｃで１０分
間、次いで４００°Ｃで３０分間緊張下で１．６倍延伸
、熱処理して得たポリイミド繊維の物性は、繊度１５．
３デニール、強度１３．２ｇ／ｄ、伸度２．６％、弾性
率７８０ｇ／ｄであった。Furthermore, this yarn was stretched 1.6 times under tension at 200°C for 10 minutes in a nitrogen atmosphere, then 1.6 times under tension at 400°C for 30 minutes, and the physical properties of the polyimide fiber obtained were as follows: fineness: 15.
It had a denier of 3 denier, a strength of 13.2 g/d, an elongation of 2.6%, and a modulus of elasticity of 780 g/d.
比較例１
実施例１で得られたポリイミド前駆体溶液をそのまま紡
糸用ドープとして用い、凝固濃度が２５重量％のＮＭＰ
水溶液中で凝固させたことを除いては、すべて実施例１
と同様に実施した。その結果、ポリアミド酸繊維の物性
は繊度２９デニール、強度１．６ｇ／ｄ 、伸度１０％
、弾性率６８ｇ／ｄであった。Comparative Example 1 The polyimide precursor solution obtained in Example 1 was used as a spinning dope, and NMP with a coagulation concentration of 25% by weight was used.
All Example 1 except that they were coagulated in aqueous solution.
It was carried out in the same way. As a result, the physical properties of the polyamic acid fiber were as follows: fineness: 29 denier, strength: 1.6 g/d, elongation: 10%.
, the elastic modulus was 68 g/d.
さらに、この繊維を実施例１と同様に熱延伸、イミド化
してポリイミド繊維を得た。該繊維の物性は、繊度１６
デニール、強度３．５ ｇ／ｄ、伸度０．９％、弾性率
５２８ｇ／ｄであり、凝固浴濃度が４０重量％の実施例
１に比較して強度が２６％、弾性率が６７％と劣ってい
た。Furthermore, this fiber was hot-stretched and imidized in the same manner as in Example 1 to obtain a polyimide fiber. The physical properties of the fiber include a fineness of 16
Denier, strength 3.5 g/d, elongation 0.9%, elastic modulus 528 g/d, and compared to Example 1 where the coagulation bath concentration was 40% by weight, the strength was 26% and the elastic modulus was 67%. and was inferior.
実施例２
２−クロル−Ｐ−フェニレンジアミンと無水ピロメリッ
ト酸とを脱水したＮＭＰ中で実施例１と同様の方法でポ
リイミド前駆体を合成して、ポリマー濃度１２．３重量
％、固有粘度２．６のポリアミド酸溶液を得た。Example 2 A polyimide precursor was synthesized in the same manner as in Example 1 in NMP obtained by dehydrating 2-chloro-P-phenylenediamine and pyromellitic anhydride, and the polymer concentration was 12.3% by weight and the intrinsic viscosity was 2. A polyamic acid solution of .6 was obtained.
この溶液を０．０９ ｍｍφ、１０ホールの口金から吐
出線速１０ｍ／分で４３％のＮＭＰ水溶液からなる１５
°Ｃの凝固浴中に押出し、ついで塔長２ｍの水浴（１５
°Ｃ）中で１．３倍に延伸するとともに水洗を行なった
。得られた糸条を室温で２０分風乾後、６０°Ｃで２４
時間真空乾燥しポリアミド酸繊維とした。This solution was discharged from a nozzle with a diameter of 0.09 mm and 10 holes at a linear velocity of 10 m/min to a 15-mm tube consisting of a 43% NMP aqueous solution.
°C into a coagulation bath, followed by a water bath with a column length of 2 m (15
The film was stretched to 1.3 times in 100°C (°C) and washed with water. The obtained yarn was air-dried at room temperature for 20 minutes, then dried at 60°C for 24 minutes.
It was vacuum dried for hours to obtain polyamic acid fibers.
得られた繊維はパール色を呈していた。この繊維の物性
は繊度２０デニール、強度１．５ｇ／ｄ 、伸度１．０
％、弾性率１２０ｇ／ｄであった。この糸条を窒素雰囲
気下で２００°Ｃで１０分間熱処理し、更に５００ ’
Ｃにて緊張下で１．０３倍に熱延伸してポリイミド繊維
を得た。この繊維の物性は、繊度１６デニール、強度７
．８ ｇ／ｄ、伸度１．１％、弾性率８６５ ｇ／ｄで
あった。The obtained fibers had a pearl color. The physical properties of this fiber are fineness 20 denier, strength 1.5 g/d, and elongation 1.0.
%, and the elastic modulus was 120 g/d. This yarn was heat-treated at 200°C for 10 minutes in a nitrogen atmosphere, and then
Polyimide fibers were obtained by hot stretching the fibers to 1.03 times under tension at C. The physical properties of this fiber include a fineness of 16 denier and a strength of 7.
．． 8 g/d, elongation 1.1%, and elastic modulus 865 g/d.
比較例２
実施例２で得られたポリイミド前駆体溶液をそのまま紡
糸用ドープとして用い、凝固浴濃度が２５重量％のＮＭ
Ｐ水溶液中で凝固させたことを除いては、すべて実施例
２と同様に実施した。ポリアミド酸繊維の物性は、繊度
１９デニール、強度１．６ｇ／ｄ 、伸度１．１％、弾
性率１０３ｇ／ｄであった。この繊維を実施例２と同様
の方法で熱処理、熱延伸すると、糸が跪すぎて物性を測
定することができなかった。そこで、３００°Ｃから５
００°Ｃまで昇温しつつ緊張下で熱延伸した。この糸の
物性は、繊度１６デニール、強度２．４８／ｄ 、伸度
０．８％、弾性率６４２ｇ／ｄであり、２−クロル−フ
ェニレンジアミンと無水ピロメリット酸との重合体の場
合も、凝固浴濃度が４３重量％の実施例２に比較して２
５重量％では強度が３１％、弾性率が７４％と劣ってい
た。Comparative Example 2 The polyimide precursor solution obtained in Example 2 was used directly as a spinning dope, and NM with a coagulation bath concentration of 25% by weight was used.
Everything was carried out in the same manner as in Example 2, except that it was coagulated in a P aqueous solution. The physical properties of the polyamic acid fiber were a fineness of 19 denier, a strength of 1.6 g/d, an elongation of 1.1%, and an elastic modulus of 103 g/d. When this fiber was heat-treated and hot-stretched in the same manner as in Example 2, the yarn was too loose to measure its physical properties. Therefore, from 300°C
Hot stretching was carried out under tension while raising the temperature to 00°C. The physical properties of this yarn are a fineness of 16 denier, a strength of 2.48/d, an elongation of 0.8%, and an elastic modulus of 642 g/d. , compared to Example 2 where the coagulation bath concentration was 43% by weight.
At 5% by weight, the strength was 31% and the elastic modulus was 74%.
本発明の方法で得られるポリイミド繊維は、高強度、高
弾性率を有し、更に耐熱性が高いため、電気絶縁材料、
防炎服、タイヤコード、ＦＲＰなどの各種産業資材用途
に広く利用できる。The polyimide fiber obtained by the method of the present invention has high strength, high modulus of elasticity, and high heat resistance, so it can be used as an electrical insulating material.
It can be widely used for various industrial materials such as flame-retardant clothing, tire cords, and FRP.
Claims (1)
とを重合させて得たポリアミド酸重合体と有機極性溶媒
とからなる紡糸原液を、口金を通して臨界濃度以上の非
凝固性有機溶媒を含む凝固浴中に押出した後、有機極性
溶媒を含む水溶液中又は水浴中で少なくとも１．１倍延
伸し、ついで該延伸繊維を湿式法又は乾式法で脱水環化
することを特徴とするポリイミド繊維の製造法。1. A spinning stock solution consisting of a polyamic acid polymer obtained by polymerizing an aromatic diamine and an aromatic tetracarboxylic dianhydride and an organic polar solvent is passed through a spinneret to coagulate it containing a non-coagulable organic solvent at a critical concentration or higher. Production of a polyimide fiber characterized by extruding it into a bath, drawing it at least 1.1 times in an aqueous solution containing an organic polar solvent or in a water bath, and then dehydrating and cyclizing the drawn fiber by a wet method or a dry method. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8911390A JPH03287815A (en) | 1990-04-05 | 1990-04-05 | Production of polyimide fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8911390A JPH03287815A (en) | 1990-04-05 | 1990-04-05 | Production of polyimide fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03287815A true JPH03287815A (en) | 1991-12-18 |
Family
ID=13961838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8911390A Pending JPH03287815A (en) | 1990-04-05 | 1990-04-05 | Production of polyimide fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03287815A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383299C (en) * | 2006-03-17 | 2008-04-23 | 东华大学 | Polyimide fiber and its preparing method |
| WO2013016892A1 (en) * | 2011-08-04 | 2013-02-07 | 北京化工大学 | High-strength and high-modulus polyimide fiber and preparation method therefor |
-
1990
- 1990-04-05 JP JP8911390A patent/JPH03287815A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383299C (en) * | 2006-03-17 | 2008-04-23 | 东华大学 | Polyimide fiber and its preparing method |
| WO2013016892A1 (en) * | 2011-08-04 | 2013-02-07 | 北京化工大学 | High-strength and high-modulus polyimide fiber and preparation method therefor |
| US9428614B2 (en) | 2011-08-04 | 2016-08-30 | Beijing University Of Chemical Technology | Polyimide fiber with high strength and high modulus and its preparation method |
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