JPH01321915A - Production of aromatic heterocyclic polyimide fiber - Google Patents
Production of aromatic heterocyclic polyimide fiberInfo
- Publication number
- JPH01321915A JPH01321915A JP6562688A JP6562688A JPH01321915A JP H01321915 A JPH01321915 A JP H01321915A JP 6562688 A JP6562688 A JP 6562688A JP 6562688 A JP6562688 A JP 6562688A JP H01321915 A JPH01321915 A JP H01321915A
- Authority
- JP
- Japan
- Prior art keywords
- tables
- formulas
- aromatic heterocyclic
- group
- chemical formulas
- 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.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 29
- 239000004642 Polyimide Substances 0.000 title claims abstract description 23
- 229920001721 polyimide Polymers 0.000 title claims abstract description 23
- 125000006615 aromatic heterocyclic group Chemical group 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 13
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 229920005575 poly(amic acid) Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000005605 benzo group Chemical group 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 150000003949 imides Chemical group 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 structure (II)' Chemical compound 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 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 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N ortho-methyl aniline Natural products CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- JFEXPVDGVLNUSC-UHFFFAOYSA-N 3-(3-aminophenyl)sulfanylaniline Chemical compound NC1=CC=CC(SC=2C=C(N)C=CC=2)=C1 JFEXPVDGVLNUSC-UHFFFAOYSA-N 0.000 description 1
- TYIXLWWCOSKKNX-UHFFFAOYSA-N 3-(benzotriazol-1-yloxy)-n,n-dimethylpropan-1-amine;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.C1=CC=C2N(OCCCN(C)C)N=NC2=C1 TYIXLWWCOSKKNX-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JJYPMNFTHPTTDI-UHFFFAOYSA-N meta-toluidine Natural products CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は芳香族複素環ポリイミド繊維の製造法に関する
ものである。詳しくは、高弾性率で、かつ、耐熱性に優
れた、主鎖中にベンゾビスアゾール骨格を含有する新規
含芳香族複素環ポリイミド繊維を製造する方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing aromatic heterocyclic polyimide fibers. Specifically, the present invention relates to a method for producing a novel aromatic heterocyclic polyimide fiber containing a benzobisazole skeleton in the main chain, which has a high modulus of elasticity and excellent heat resistance.
（従来の技術）
芳香族複素環ポリマーは、高強度、高弾性率及び高耐熱
性素材として期待されているが、ポリイミド、ポリベン
ツイミダゾール以外のものヱン
が得られるとされる、ポリ−ｐ−フェニレンベンゾビス
チアゾール（ＰＢＴ）は１．２．ｊ−ジアミノベンゼン
−／、ｔＩ−ジチオールニ塩酸塩とテレフタル酸とをポ
リリン酸中で７６０〜コθ０℃の高温下に長時間反応さ
せて得られる、剛直鎖高分子であシ、全芳香族ポリアミ
ドの一種であるポリ−ｐ−フェニレンテレフタルアミド
・−一■
（ＰＰＴＡ）（ケフフ ）の２倍以上の引張弾性率（
３１０ＧＰａ）を与える。(Prior art) Aromatic heterocyclic polymers are expected to be materials with high strength, high modulus of elasticity, and high heat resistance. -Phenylenebenzobisthiazole (PBT) is 1.2. A fully aromatic polyamide made of a rigid linear chain polymer obtained by reacting j-diaminobenzene-/,tI-dithiol dihydrochloride and terephthalic acid in polyphosphoric acid at a high temperature of 760 to 0°C for a long period of time. It has a tensile modulus that is more than twice that of poly-p-phenylene terephthalamide (PPTA).
310 GPa).
しかしＰＢＴはメタンスルホン酸、クロルスルホン酸等
の強酸以外の溶媒には不溶であシ、しかもか＼る溶媒は
装置の腐蝕性が強くこの点においても工業上の不利益は
明らかである。However, PBT is insoluble in solvents other than strong acids such as methanesulfonic acid and chlorosulfonic acid, and furthermore, such solvents are highly corrosive to equipment, which is also an obvious industrial disadvantage.
（本発明が解決しようとする課題）
本発明は、かかる腐蝕性の強い溶媒を用いることなく、
高弾性率で且つ耐熱性に優れる繊維を製造することを目
的とする。(Problems to be Solved by the Present Invention) The present invention solves the problem without using such a highly corrosive solvent.
The purpose is to produce fibers with high elastic modulus and excellent heat resistance.
ポリイミド繊維を製造する際に、該ポリイミドに対し、
１０〜１００θＭＰａの張力を与えながら最終熱処理温
度乞１Ｉ−２０〜５５０℃とする、緊張熱処理を施こす
ことを特徴とする芳香族複素環ポリイミド繊維の製造法
を要旨とするものである。When producing polyimide fiber, for the polyimide,
The gist of the present invention is a method for producing an aromatic heterocyclic polyimide fiber, which is characterized by carrying out tension heat treatment at a final heat treatment temperature of 1I-20 to 550° C. while applying a tension of 10 to 100 θ MPa.
ベンゾビスアゾール骨格を含有する芳香族複素環ポリイ
ミド：
甲群と乙群より選ばれる構造単位のそれぞれの総量が実
質的に半量であり、甲群中で以下に示す構造ＣＩ）が３
０〜１００モル％、構造（ＩＩ）が７０−０モル係であ
り、乙群中で構造（ＩＩＩ）が７０〜７００モル％、構
造（ＩＶ）及び／又は（Ｖ）が３０〜０モルチの構造を
有する。Aromatic heterocyclic polyimide containing a benzobisazole skeleton: The total amount of each of the structural units selected from Group A and Group O is substantially half, and in Group A, the structure CI) shown below is 3
0 to 100 mol%, structure (II) is 70-0 mol%, structure (III) is 70 to 700 mol%, structure (IV) and/or (V) is 30 to 0 mol% in group O Has a structure.
＼ ／
ｚＮ−Ａｒ’−Ｎ、 （ＩＩ）乙群
：
（式中Ｘは、Ｓ、ＯまたはＮＨを表わし、Ａｒ’及びＹ
３は、Ｈ１アルキル基、アルコキシ基又はハロゲン原子
を衣わし、そして、ｚ１ｚ’及びＺ２は単結合、−０−
１−ＣＨ２−１−Ｓ−１−Ｃ−１
しては、具体的には次の様な化合物を挙げることが出来
る。すなわち、芳香族ジアミンとしては、構造（１）を
与える、コ、乙−（グｔｌｌ−ジアミノ−ジフェニル）
ベンゾ〔／、コーｄニゲ、ｓ−ｄ’）ビスチアゾール、
ユ、６− （ｑ、ｔＩ’−ジアミノ−ジフェニル）ベン
ゾ〔／、コーｄ： ｌｌ、ｓ −ａ”）ビスオキサゾー
ル、ｊ、Ａ−（＜＜、Ｆ’−ジアミノ−ジフェニル）ベ
ンゾ［／、、２−ｄニゲ、ｓ−ｄ’］ビスイミダゾール
、構造（ＩＩ） ’に与える、ｍ−およびｐ−フェニレ
ンジアミン、コツ５−ジアミノトルエン、ｕ、＜”−お
よび３，３′−ジアミノジフェニルエーテル、Ｆ、Ｆ’
−および３．３′−ジアミノジフェニルメタン、＋４’
−および３，３′−チオジアニリン、ｕ、ｕ’−および
３，３′−ジアミノビフェニル、グ４’−および３．３
′−ジアミノジフェニルスルホン、ビス（クーアミノフ
ェニル）イソプロパン、ビス−（クーアミノフェニル）
ビス（） ＋）フルオロメチル）メタン、＜ｚ、ｔＩ’
−ジアミノベンゾフェノン、９４’−メチレンビス−（
ｏ−クロロアニリン）、ｕ４’−メチレンビス−（３−
メチルアニリン） 、＜ｚ、ｐ’−メチレンビス−（，
２−メトキンアニリン）、ｖ、ｖ’−メチレンビス−（
２−メチルアニリン）、ｐ、ｔＩ’−オキンビスー（ｘ
−メトキンアニリン）、＜ｚ、ｒ−オキンビスー（２−
クロロアニリン）、＜ｚ、ｔＩ’−チオビス−（−一メ
チルアニリン）、り、ｌｌ′−チオビス−（コーメトキ
シアニリン）、ｇ、ｐ’−チオビス−（２−クロロアニ
リン）、＆、’％’−スルホニルビス−（２−メチルア
ニリン）、ｙ、ｔｔ’−スルホニルビス−（２−エトキ
シアニリン） 、＆４’−スルホニルビスー（，２−ク
ロロアニリン）１．？、、？−ジメチルー’４４’−ジ
アミノベンゾフェノン、３．３’−ジメトキシーク、り
′−ジアミノベンゾフェノン、３．３′−ジクロロ−＜
７．＆’−ジアミノベンゾフェノン、３．３’−ジメチ
ルベンジジン、３．３’−ジメトキンベンジジン、３，
３′−ジクロロベンジジン、ユ、コ′−ビス［ｑ−（ｙ
−アミノフェノキン）フェニル〕プロパン、ビス（ｑ
−（ｑ−アミノフェノキシ）フェニル〕スルホン、／、
クビス（クーアミノフェノキシ）ベンゼン、／、３−ビ
ス（グーアミノンエノキシ）ベンゼン、／、３−ビス（
３−アミノフェノキシ）ベンゼン等である。\ / zN-Ar'-N, (II) Otsu group: (In the formula, X represents S, O or NH, and Ar' and Y
3 is H1 alkyl group, alkoxy group or halogen atom, and z1z' and Z2 are single bonds, -0-
Specific examples of 1-CH2-1-S-1-C-1 include the following compounds. That is, as the aromatic diamine, co-(gtll-diamino-diphenyl) giving the structure (1)
benzo [/, kodnige, s-d') bisthiazole,
U, 6- (q, tI'-diamino-diphenyl)benzo [/, code: ll, s -a'') bisoxazole, j, A- (<<, F'-diamino-diphenyl) benzo [/, , 2-dnige, s-d']bisimidazole, structure (II)', m- and p-phenylenediamine, 5-diaminotoluene, u,<''- and 3,3'-diaminodiphenyl ether, F, F'
- and 3,3'-diaminodiphenylmethane, +4'
- and 3,3'-thiodianiline, u, u'- and 3,3'-diaminobiphenyl, g4'- and 3.3
'-Diamino diphenyl sulfone, bis(couaminophenyl) isopropane, bis(couaminophenyl)
bis() +)fluoromethyl)methane, <z, tI'
-diaminobenzophenone, 94'-methylenebis-(
o-chloroaniline), u4'-methylenebis-(3-
methylaniline), <z, p'-methylenebis-(,
2-methquinaniline), v,v'-methylenebis-(
2-methylaniline), p,tI'-okinbisu (x
- metquinaniline), <z, r-okinbisu (2-
chloroaniline), <z, tI'-thiobis-(-monomethylaniline), ll'-thiobis-(comethoxyaniline), g, p'-thiobis-(2-chloroaniline), &, '% '-Sulfonylbis-(2-methylaniline), y,tt'-sulfonylbis-(2-ethoxyaniline), &4'-sulfonylbis(,2-chloroaniline)1. ? ,,? -dimethyl-'44'-diaminobenzophenone, 3,3'-dimethoxyk, ri'-diaminobenzophenone, 3,3'-dichloro-<
7. &'-Diaminobenzophenone, 3.3'-dimethylbenzidine, 3.3'-dimethquine benzidine, 3,
3'-dichlorobenzidine, u, co'-bis[q-(y
-aminophenoquine)phenyl]propane, bis(q
-(q-aminophenoxy)phenyl]sulfone, /,
Kubis(guaminophenoxy)benzene, /, 3-bis(guaminoenoxy)benzene, /, 3-bis(
3-aminophenoxy)benzene, etc.
又芳香族テトラカルボン酸二無水物としては構造（ｌｉ
ｔ）を与えるピロメリット酸無水物、構造（ｌＶｌｅ与
する。 ３． ｅ、 ３’、 ’ｌ’ −ベンゾフェノ
ンテトラカルボン酸二無水物、３．３’％Ｉ、’ｌ’−
ジフェニルテトラカルボン酸二無水物、ユ、、２’、３
．３’ −ジフェニルテトラカルボン酸二無水物、２．
２’−ビス（３，ｌｌ−ジカルボキシフェニル）プロパ
ン二無水物、ビス（３，ｐ−ジカルボキシフェニル）ビ
ス（トリフルオロメチル）メクンニ無水物、ビス（３４
−ジカルボキシフェニル）スルホン二無水物、ビス（、
ｙ４−ジカルボキシフェニル）エーテルニ無水物、ビス
（３，＜ｚ−ジカルボキシフェニル）メタンニ無水物等
が挙げられ、又構造（Ｖ） ’（ｒ与えるものとしてト
リメリット酸無水物、トリメリット酸無水物クロライド
等が挙げられる。In addition, the aromatic tetracarboxylic dianhydride has the structure (li
t), pyromellitic anhydride, giving structure (lVle. 3. e, 3', 'l' -benzophenonetetracarboxylic dianhydride, 3.3'% I, 'l'-
diphenyltetracarboxylic dianhydride, 2', 3
．． 3'-diphenyltetracarboxylic dianhydride, 2.
2'-bis(3,ll-dicarboxyphenyl)propane dianhydride, bis(3,p-dicarboxyphenyl)bis(trifluoromethyl)mecunnihydride, bis(34
-dicarboxyphenyl)sulfone dianhydride, bis(,
Examples include y4-dicarboxyphenyl)ether dianhydride, bis(3,<z-dicarboxyphenyl)methane dianhydride, and structures (V)'(r) such as trimellitic anhydride and trimellitic anhydride. Examples include monochloride.
重合に使用されるアミド溶媒としては、Ｎ−メチルーコ
ーピロリド７（ＭＭＰ ） 、／、３−ジメチルーコー
イミダゾリジノン（ＤＭＩ）、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
（ＤＭＡ ｃ ） 、ヘキサメチルホスホルトリアミド
（ＨＭ Ｐ Ａ ） 、及びそれらの混合溶媒等が挙げ
られる。Amide solvents used in the polymerization include N-methyl-copyrrolid 7 (MMP), 3-dimethyl-coimidazolidinone (DMI), N,N'-dimethylformamide (DMF), N,N Examples include '-dimethylacetamide (DMAc), hexamethylphosphortriamide (HMPA), and mixed solvents thereof.
以上のよりなアミド溶媒中で上記芳香族ジアミンと芳香
族カルボン酸誘導体とを反応させることによシボリアミ
ド酸溶液が得られる。A ciboriamic acid solution is obtained by reacting the aromatic diamine and the aromatic carboxylic acid derivative in the above-mentioned amide solvent.
本発明はポリイミドがその前、躯体としてポリアミド酸
を経由することに着目している。本発明で使用されるポ
リアミド酸は上記甲群、乙群に示された構造を有する芳
香族ジアミン、芳香族テトラカルボン酸無水物及び／又
は芳香族ジカルボン酸無水物、モノカルボン酸ヲアミド
系溶媒中で反応させて製造する事が出来るが、これらは
いづれも最終的に得られるポリイミド構造に対しより柔
軟性を有していることから、アミド系溶媒に代表される
極性有機溶剤に対する溶解性に優れており、か＼る溶液
よシ極めて容易に繊維状物を紡出することが出来る。The present invention focuses on the fact that polyimide is first passed through polyamic acid as a building block. The polyamic acids used in the present invention are aromatic diamines, aromatic tetracarboxylic acid anhydrides and/or aromatic dicarboxylic acid anhydrides, and monocarboxylic acid amide solvents having the structures shown in Group A and Group B above. However, since all of these have more flexibility with respect to the final polyimide structure, they have excellent solubility in polar organic solvents such as amide solvents. Therefore, it is possible to spin out a fibrous material very easily from such a solution.
本発明においては、か＼る特定構造を有する、ポリアミ
ド酸紡出繊維をイミド化させるとともに、特定の処理を
施こすことにより、高弾性率で、かつ、耐熱性に優れる
ポリイミド繊維を製造する。In the present invention, polyimide fibers having a high elastic modulus and excellent heat resistance are produced by imidizing polyamic acid-spun fibers having such a specific structure and subjecting them to specific treatments.
即ち、紡出繊維に緊張昇温熱処理を施こすに際し、／
０〜／ ０００ＭＰａ、好ましくは、ｓ。That is, when subjecting spun fibers to tension heating heat treatment, /
0~/000MPa, preferably s.
〜７００１’ｖＰａの張力を与えながら最終熱処理温度
をグユｏ−５ｓｏ℃、好ましくは、グｇθ〜ｓｉｏ℃に
保つ事を特徴とするものである。It is characterized in that the final heat treatment temperature is maintained at 0-5so°C, preferably at 0-50°C, while applying a tension of 7001'vPa to 7001'vPa.
本発明方法においては、かＸる緊張処理と熱的処理が互
いに不可欠であり、そのいづれか−方が満足されない場
合は、本発明の目的を達成することは出来ない。In the method of the present invention, the tension treatment and the heat treatment are essential to each other, and if either one of them is not satisfied, the object of the present invention cannot be achieved.
即ち、張力が／ Ｏｒ’ｖＰａ ｆ超えること、しかも
熱処理温度が１ｌａＯ０Ｃを超すことは高弾性率繊維を
得る上で必須の要件である。That is, it is essential to obtain a high elastic modulus fiber that the tension exceeds / Or'vPa f and that the heat treatment temperature exceeds 1 laO0C.
しかしながら、１０００ＭＰａを超す張力を繊維に施こ
すことは熱処理時の糸切れの原因とカリ、又５５０℃を
超す熱処理は繊維の熱劣化を顕著なものとする。However, applying a tension exceeding 1000 MPa to the fiber causes yarn breakage during heat treatment, and heat treatment exceeding 550° C. causes significant thermal deterioration of the fiber.
紡出繊維を得る方法としては、公知の湿式紡糸ン五に挙
げることができる。その後、イミド閉環を行うが、その
方法としては、凝固浴中に紡出させて得た繊維を、脱溶
媒乾燥させ、上記処理条件下で併わせイミド閉環させて
も良いし、又は、無水酢酸−ピリジンの様なイミド閉環
試薬を凝固浴ないしは凝固浴中に共存させることにより
、紡出及びイミド閉環を同時に行っても良い。Methods for obtaining spun fibers include five known wet spinning methods. Thereafter, imide ring closure is carried out, and the method may be to dry the fiber obtained by spinning it in a coagulation bath, remove the solvent, and combine it under the above treatment conditions, or to perform imide ring closure. - Spinning and imide ring-closing may be carried out simultaneously by coexisting an imide ring-closing reagent such as pyridine in the coagulation bath or coagulation bath.
（実施例）
以下実施例によりさらに本発明の詳細な説明するが、本
発明はこれらの実施例に限定されるものではない。(Examples) The present invention will be further explained in detail with reference to Examples below, but the present invention is not limited to these Examples.
ポリアミド酸の重合は窒素気流下、室温で行った。Polymerization of polyamic acid was performed at room temperature under a nitrogen stream.
またポリアミド酸の対数粘度ηｉｎｈは、ポリマー濃度
が０．２ ｇ／ｄｉとなる様にＮ−メチル−コーピロリ
ドンで希釈して３０℃で測定した。Further, the logarithmic viscosity ηinh of the polyamic acid was measured at 30°C after diluting with N-methyl-copyrrolidone so that the polymer concentration was 0.2 g/di.
なおユ、乙−（ｐ、ｇ’−ジアミノ−ジフェニル）ベン
ゾ［／、、２−ａニゲ、ｓ−ａ’）ビスチアゾール’（
ｉ−ＤＡＰＢＴ、 ピロメリット酸二無水物をＰＭＤ
Ａ。Furthermore, you, Otsu-(p,g'-diamino-diphenyl)benzo[/,,2-anige,sa')bisthiazole'(
i-DAPBT, PMD pyromellitic dianhydride
A.
Ｎ−メチルーコーピロリドンをＮＭＰＸ ／、３−ジメ
チルーコーイミダゾリジノン’ｉＤＭＩと略する。N-methyl-copyrrolidone is abbreviated as NMPX/3-dimethyl-coimidazolidinone'iDMI.
参考例／
ＤＡＰＢＴ ＩＩ−、ｅｑｔａ！！ （／ ２ミリモル
） ヲＮＭＰ’Ｉ左ｍｌにスラリー化させた。このスラ
リーにＰＭＤＡの粉末コ、３９２ｇ（／ ／、ｔ、ミリ
モル）をＮ Ｍ Ｐ ２０ ｍｌとともに加え重合を開
始させた。Reference example/DAPBT II-, eqta! ! (/2 mmol) was made into a slurry in the left ml of NMP'I. To this slurry, 392 g (//, t, mmol) of PMDA powder was added together with 20 ml of NMP to initiate polymerization.
溶液は徐々に粘稠になるとともに均一となった。The solution gradually became viscous and homogeneous.
重合開始７時間後に、ηｉｎｈ ３．ｓ ｄｉ／ｇのポ
リアミド酸溶液を得た。7 hours after the start of polymerization, ηinh 3. A polyamic acid solution of s di/g was obtained.
実施例／−３
参考例／で得られたポリアミド酸溶液を０．３φの単孔
ノズルより、無水酢酸／ピリジン＝’１０／３０（容積
比）から成る凝固浴中に紡出した。更に同じ組成の溶液
中で一昼夜浸漬して化学閉環させポリイミド繊維を得た
。Example/-3 The polyamic acid solution obtained in Reference Example/ was spun into a coagulation bath consisting of acetic anhydride/pyridine='10/30 (volume ratio) through a 0.3φ single-hole nozzle. Further, the fibers were immersed in a solution of the same composition for a day and night to chemically close the ring and obtain polyimide fibers.
次にこの繊維をトルエン中に移し３時間浸漬０Ｃを７０
秒、ユＳＯ°Ｃを１０秒、３ＳＯ℃を７０秒、り００℃
を１０秒、５ＯＯ０Ｃを１０秒。Next, this fiber was transferred to toluene and immersed for 3 hours at 70°C.
seconds, 10 seconds at 3SO°C, 70 seconds at 3SO°C, 00°C
for 10 seconds, and 5OO0C for 10 seconds.
この様にして得られたポリイミド繊維の動的弾性率を、
東洋ボルドウィン社製、バイプロンＤＯＶ ｎ型装置に
より測定した。得られた結果を第１表に示す。なお第７
表中の張力は荷重と最終繊維径から算出したものである
。The dynamic elastic modulus of the polyimide fiber obtained in this way is
Measurement was performed using a Biplon DOV n-type device manufactured by Toyo Baldwin. The results obtained are shown in Table 1. Furthermore, the seventh
The tension in the table was calculated from the load and final fiber diameter.
第 ／ 表
比較例１
張力を与えないこと以外は実施例／と同様の処決でポリ
イミド繊維を得た。この繊維の最終繊維径は／グＯμで
あった。又動的弾性率は乙０ＧＰａであった。Table 1 Comparative Example 1 Polyimide fibers were obtained in the same manner as in Example except that no tension was applied. The final fiber diameter of this fiber was /g Oμ. Moreover, the dynamic elastic modulus was 0 GPa.
（発明の効果）
本発明方法によれば、高弾性率で且つ耐熱性に優れる芳
香族複素環ポリイミド繊維を得ることが出来る。(Effects of the Invention) According to the method of the present invention, an aromatic heterocyclic polyimide fiber having a high elastic modulus and excellent heat resistance can be obtained.
Claims (1)
る芳香族複素環ポリイミドから、ポリイミド繊維を製造
する際に、該ポリイミドに対し、１０〜１０００ＭＰａ
の張力を与えながら最終熱処理温度を４２０〜５５０℃
とする、緊張熱処理を施こすことを特徴とする芳香族複
素環ポリイミド繊維の製造法。 ベンゾビスアゾール骨格を含有する芳香族複素環ポリイ
ミド： 甲群と乙群より選ばれる構造単位のそれぞれの総量が実
質的に当量であり、甲群中で以下に示す構造（ I ）が
３０〜１００モル％、構造（II）が７０〜０モル％であ
り、乙群中で構造（III）が７０〜１００モル％、構造
（IV）及び／又は（Ｖ）が３０〜０モル％の構造を有す
る。 甲群： ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） 乙群： ▲数式、化学式、表等があります▼（III） ▲数式、化学式、表等があります▼（IV） ▲数式、化学式、表等があります▼（Ｖ） （式中Ｘは、Ｓ、ＯまたはＮＨを表わし、Ａｒ＾１は▲
数式、化学式、表等があります▼、▲数式、化学式、表
等があります▼、▲数式、化学式、表等があります▼ または▲数式、化学式、表等があります▼を表わし、 Ａｒ＾２は▲数式、化学式、表等があります▼を表わし
、Ｙ、Ｙ＾１、Ｙ＾２及びＹ＾３は、Ｈ、アルキル基、
アルコキシ基又はハロゲン原子を表わし、そして、Ｚ、
Ｚ＾１及びＺ＾２は単結合、−Ｏ−、−ＣＨ＿２−、−
Ｓ−、▲数式、化学式、表等があります▼、−ＳＯ＿２
−、▲数式、化学式、表等があります▼又は▲数式、化
学式、表等があります▼を表わす。）(1) When producing polyimide fiber from an aromatic heterocyclic polyimide containing the following benzobisazole skeleton in the main chain, the pressure of 10 to 1000 MPa is applied to the polyimide.
The final heat treatment temperature was set at 420-550℃ while applying a tension of
A method for producing an aromatic heterocyclic polyimide fiber, characterized by subjecting it to tension heat treatment. Aromatic heterocyclic polyimide containing a benzobisazole skeleton: The total amount of each structural unit selected from Group A and Group O is substantially equivalent, and in Group A, the structure (I) shown below is 30 to 100 mol%, structure (II) is 70 to 0 mol%, structure (III) is 70 to 100 mol%, and structure (IV) and/or (V) is 30 to 0 mol%. have Group A: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) Group O: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲Mathematical formulas, chemical formulas, There are tables, etc.▼(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, X represents S, O or NH, and Ar^1 is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Ar^2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ represents Y, Y^1, Y^2 and Y^3 are H, alkyl group,
represents an alkoxy group or a halogen atom, and Z,
Z^1 and Z^2 are single bonds, -O-, -CH_2-, -
S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2
- Represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6562688A JPH01321915A (en) | 1988-03-22 | 1988-03-22 | Production of aromatic heterocyclic polyimide fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6562688A JPH01321915A (en) | 1988-03-22 | 1988-03-22 | Production of aromatic heterocyclic polyimide fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01321915A true JPH01321915A (en) | 1989-12-27 |
| JPH0429771B2 JPH0429771B2 (en) | 1992-05-19 |
Family
ID=13292419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6562688A Granted JPH01321915A (en) | 1988-03-22 | 1988-03-22 | Production of aromatic heterocyclic polyimide fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01321915A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5698135A (en) * | 1994-12-16 | 1997-12-16 | Japan Synthetic Rubber Co., Ltd., A Japanese Corporation | Liquid crystal-aligning agent |
| JP2006249186A (en) * | 2005-03-09 | 2006-09-21 | Teijin Ltd | Rigid heterocyclic polymer and method for producing the same |
| JP2013032507A (en) * | 2011-06-30 | 2013-02-14 | Jfe Chemical Corp | Polyamic acid composition and polyimide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365424A (en) * | 1976-11-22 | 1978-06-10 | Takamatsu Electric Works Ltd | Magnetic fiber |
| JPS59173312A (en) * | 1983-03-23 | 1984-10-01 | Chisso Corp | Hot-melt magnetic fiber and its manufacture |
| JPS60204309A (en) * | 1984-03-30 | 1985-10-15 | Minoru Hashimoto | Manufacture of film or fiber excellent in mechanical property |
| JPS611525A (en) * | 1984-06-14 | 1986-01-07 | Diesel Kiki Co Ltd | Air conditioner for automobile |
| JPS6279227A (en) * | 1985-10-02 | 1987-04-11 | Agency Of Ind Science & Technol | Wholly aromatic copolypyromellitic imide |
| JPS636028A (en) * | 1986-06-25 | 1988-01-12 | Teijin Ltd | Preparation of polyimide molding |
-
1988
- 1988-03-22 JP JP6562688A patent/JPH01321915A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365424A (en) * | 1976-11-22 | 1978-06-10 | Takamatsu Electric Works Ltd | Magnetic fiber |
| JPS59173312A (en) * | 1983-03-23 | 1984-10-01 | Chisso Corp | Hot-melt magnetic fiber and its manufacture |
| JPS60204309A (en) * | 1984-03-30 | 1985-10-15 | Minoru Hashimoto | Manufacture of film or fiber excellent in mechanical property |
| JPS611525A (en) * | 1984-06-14 | 1986-01-07 | Diesel Kiki Co Ltd | Air conditioner for automobile |
| JPS6279227A (en) * | 1985-10-02 | 1987-04-11 | Agency Of Ind Science & Technol | Wholly aromatic copolypyromellitic imide |
| JPS636028A (en) * | 1986-06-25 | 1988-01-12 | Teijin Ltd | Preparation of polyimide molding |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5698135A (en) * | 1994-12-16 | 1997-12-16 | Japan Synthetic Rubber Co., Ltd., A Japanese Corporation | Liquid crystal-aligning agent |
| JP2006249186A (en) * | 2005-03-09 | 2006-09-21 | Teijin Ltd | Rigid heterocyclic polymer and method for producing the same |
| JP4546854B2 (en) * | 2005-03-09 | 2010-09-22 | 帝人株式会社 | Rigid heterocyclic polymer and method for producing the same |
| JP2013032507A (en) * | 2011-06-30 | 2013-02-14 | Jfe Chemical Corp | Polyamic acid composition and polyimide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0429771B2 (en) | 1992-05-19 |
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