JPS63256624A - Aromatic-heterocyclic ring-containing polyimide - Google Patents
Aromatic-heterocyclic ring-containing polyimideInfo
- Publication number
- JPS63256624A JPS63256624A JP8975887A JP8975887A JPS63256624A JP S63256624 A JPS63256624 A JP S63256624A JP 8975887 A JP8975887 A JP 8975887A JP 8975887 A JP8975887 A JP 8975887A JP S63256624 A JPS63256624 A JP S63256624A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- tables
- aromatic
- formula
- mathematical
- 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
- 229920001721 polyimide Polymers 0.000 title claims abstract description 14
- 239000004642 Polyimide Substances 0.000 title claims abstract description 13
- 125000006615 aromatic heterocyclic group Chemical group 0.000 title claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 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 abstract description 10
- 150000004984 aromatic diamines Chemical class 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001408 amides Chemical class 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- -1 e.g. Chemical compound 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 125000006158 tetracarboxylic acid group Chemical group 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract 2
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 abstract 1
- JWLNXHODHNBWPR-UHFFFAOYSA-N [1,3]thiazolo[5,4-f][1,3]benzothiazole Chemical compound C1=C2SC=NC2=CC2=C1N=CS2 JWLNXHODHNBWPR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229940018564 m-phenylenediamine Drugs 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 16
- 229920005575 poly(amic acid) Polymers 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HSAOVLDFJCYOPX-UHFFFAOYSA-N 2-[4-(1,3-benzothiazol-2-yl)phenyl]-1,3-benzothiazole Chemical compound C1=CC=C2SC(C3=CC=C(C=C3)C=3SC4=CC=CC=C4N=3)=NC2=C1 HSAOVLDFJCYOPX-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-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
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical group C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高弾性率、かつ耐熱性に優れた、溶液成形可能
な新規含芳香族複素環ポリイミドに関する。特には主鎖
中にベンゾビスチアゾール骨格を含有することを特徴と
する、芳香族複素環ポリイミドに関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel aromatic heterocyclic polyimide which has a high elastic modulus and excellent heat resistance and is solution moldable. In particular, it relates to an aromatic heterocyclic polyimide characterized by containing a benzobisthiazole skeleton in its main chain.
（従来の技術）
主鎖中に対称性が良く、屈曲部のない芳香族の骨格を導
入したポリマーは、高弾性率かつ高耐熱性となる。現在
公知のポリマー中では、ポリ−ｐ−フェニレンベンゾビ
スチアゾール（ＰＰ Ｂ Ｔ ）（Ｍａｃｒｏｍ
ｏｘｅｃｕｘｅｓ ｆｆ＋ ９／！ｒ（／９１／）
）で非常に高弾性率な繊維が得られている。その理由は
、主鎖中にベンゾビスチアゾール骨格を含むためと考え
られる。しかしＰＰＢＴは不融であシ、かつ一般的な有
機溶媒には不溶であるため成形の困難なポリマーである
。一般に主鎖方向に対称性の良いポリマーはど高弾性率
かつ高耐熱性となるが、不溶、不融でありたシ、超強酸
、強酸等の特殊な溶媒にしか溶けず、成形性は必ずしも
良好ではない。(Prior Art) A polymer in which an aromatic skeleton with good symmetry and no bent portions is introduced into the main chain has a high elastic modulus and high heat resistance. Among currently known polymers, poly-p-phenylenebenzobisthiazole (PPBT) (Macrom
oxecuxes ff+ 9/! r(/91/)
), fibers with extremely high modulus of elasticity have been obtained. The reason for this is thought to be that the main chain contains a benzobistiazole skeleton. However, PPBT is a polymer that is difficult to mold because it is infusible and insoluble in common organic solvents. In general, polymers with good symmetry in the main chain direction have a high modulus of elasticity and high heat resistance, but they only dissolve in special solvents such as insoluble or infusible materials, super strong acids, and strong acids, and their moldability is not necessarily high. Not good.
−１、多くのポリイミドに見られるピロメリットイミド
環■は、非常に対称性が良い構造であシ、この構造を主
鎖に導入したポリマーは高弾性率となることが予想でき
る。しかもポリイミドは前駆体としてポリアミド酸を経
由して製造されることが多い。この場合、閉環後に非常
に剛直なポリマーとなシ、不溶、不融又は難溶性のポリ
マーになるものであっても、ポリアミド酸状態では、ア
ミド溶媒等の通常の有機溶媒に可溶となる。従って、ポ
リアミド酸の溶液状態で任意の形に成形し、成形後に閉
環させることによシ、高弾性率、高耐熱性材料を容易に
得ることができる。-1. The pyromellitimide ring (2) found in many polyimides has a very symmetrical structure, and it can be expected that a polymer with this structure introduced into the main chain will have a high elastic modulus. Furthermore, polyimide is often produced using polyamic acid as a precursor. In this case, even if the polymer becomes a very rigid polymer after ring closure, or becomes an insoluble, infusible or poorly soluble polymer, in the polyamic acid state, it becomes soluble in ordinary organic solvents such as amide solvents. Therefore, a material with high elastic modulus and high heat resistance can be easily obtained by molding the polyamic acid into an arbitrary shape in a solution state and then ring-closing it after molding.
（発明が解決しようとする問題点〕
ベンゾビスチアゾール構造を主鎖に持つポリマーは、Ｐ
ＰＢＴに見られるよ５に剛直で弾性率は高くなるが成形
性は悪い。しかしこの構造をポリアミド酸を経て製造さ
れるポリイミドに導入すれば、高弾性率でかつ成形性に
も優れたポリマーとなると考え、本発明に到達した。(Problem to be solved by the invention) A polymer having a benzobistiazole structure in its main chain is P
As seen in PBT, it is rigid and has a high elastic modulus, but its moldability is poor. However, if this structure is introduced into polyimide produced via polyamic acid, a polymer with high elastic modulus and excellent moldability can be obtained, and thus the present invention was achieved.
（問題点を解決するための手段）
すなわち本発明は、構造が実質的に下記構造単位（ｉＪ
、 （［７及び（ＩＩからなシ、構造単位（ＩＩが全体
のｌｊ〜５０モル％、構造単位（１）が全体のＪ、ｒ〜
θモル％、構造単位（ＩＩＩ）が全体の５０モル係であ
ることを特徴とする含芳香族複素環ポリイミドに関する
。(Means for Solving the Problems) That is, the present invention provides a structure having substantially the following structural units (iJ
, ([7 and (II), structural unit (II is lj ~ 50 mol% of the whole, structural unit (1) is J, r ~
The present invention relates to an aromatic heterocyclic polyimide characterized in that the structural unit (III) accounts for 50 mol% of the total θ mol%.
〉Ｎ−ムｒ、 −Ｎぐ ａｓ・１１１
１１１１１１１１１１１１１１１・（ＩＩＩ基、アルコ
キシ基又はハロゲン基、Ｙは、単結合、−〇−１−〇＆
−５−Ｓ−１−ｏｏ−，−８０１−。〉N-Mur, -Ngu as・111
111111111111111・(III group, alkoxy group or halogen group, Y is a single bond, -〇-1-〇&
-5-S-1-oo-, -801-.
本発明のポリマーの製造に必要な七ツマ−としては、構
造（１１及び（１１）を与える芳香族ジアミン。Aromatic diamines having structures (11 and (11)) are necessary for producing the polymer of the present invention.
構造（１）を与える芳香族テトラカルボン酸二無水物が
挙げられる。構造（１）を与える芳香族ジアミンはコ＋
ｂ （４’ｌ弘′−ジアミノジフェニルメタンゾ（’
＋２−ａ：ＩＩ、ｊ−ａ’：ｌビスチアゾールであ〕、
構造（ＩＩＩを与える芳香族ジアミンとしては。Examples include aromatic tetracarboxylic dianhydrides that give structure (1). The aromatic diamine giving structure (1) is co+
b (4'lhiro'-diaminodiphenylmethanezo('
+2-a:II, j-a':l bisthiazole],
As an aromatic diamine giving structure (III).
ｍ−およびｐ−フェニレンジアミン、コ、！−ジアミノ
トルエン、ｔ、４／−および、？、、？’−ジアミノジ
フェニルエーテル、亭、４／−およびｓ、ｓ’−ジアミ
ノジフェニルメタン、ｐ、＋’−およびＪ、３′−チオ
ジアニリン、！、４Ｌ’−および、７．．７’−ジアミ
ノビフェニル、４ｔ、＋’−および、７．、？’−ジア
ミノジフェニルスルホン、ビス−（ターアミノフェニル
フィンプロパン、ビス−（ターアミノフェニル）ビス（
トリフルオロメチル）メタン、私り′−ジアミノベンゾ
フェノン、＋、＋’−メチレンビス−（０−／ロロアニ
リン）、４ｔ、＊’−メチレンビスー（３−メチルアニ
リン）、＋、＋’−メチレンビス−（コーメトキシアニ
リン）、ｑ、ｉｌ−メチレンビス−（コーメチルアニリ
ン）、蓼、り′−オキシビスー（コーメトキシアニリン
）、弘、Ｉ−オキシビス−（コークロ目アニリン）、＋
、弘′−チオビス−（，２−メチルアニリン）、弘、り
′−チオビスー（−一メトキシアニリン）、Ｑ、Ｑ’−
チオビス−（コークロロアニリン）、ｅ、４Ｉ’−スル
ホニルビス−（コーメテルアニリン） 、 ４Ｌ、！’
−、Ｘルホニルビス−（コーエトキシアニリン）、＋
。m- and p-phenylenediamine, co,! -diaminotoluene, t, 4/- and ? ,,? '-diaminodiphenyl ether, tei, 4/- and s, s'-diaminodiphenylmethane, p, +'- and J, 3'-thiodianiline, ! , 4L'- and 7. ．． 7'-diaminobiphenyl, 4t, +'- and 7. ,? '-diaminodiphenylsulfone, bis-(teraminophenylfinpropane, bis-(teraminophenyl)bis(
trifluoromethyl)methane, +, +'-methylenebis-(0-/loloaniline), 4t, *'-methylenebis-(3-methylaniline), +,+'-methylenebis-(comethoxy) Aniline), q, il-methylenebis-(comethylaniline), 蓼, ri′-oxybis(comethoxyaniline), Hiroshi, I-oxybis-(comethoxyaniline), +
, Hiro'-thiobis-(,2-methylaniline), Hiro, ri'-thiobis-(-1methoxyaniline), Q, Q'-
Thiobis-(cochloroaniline), e, 4I'-sulfonylbis-(cometeraniline), 4L,! '
-, X sulfonylbis-(coethoxyaniline), +
.
参′−スルホニルビス−（，２−クロロアニリン）、Ｊ
、ｊ−ジメチル−ａ、４１′−ジアミノベンゾフェノン
、Ｊ、Ｊ’−ジメトキシ−船り′−ジアミノベンゾフェ
ノン１．７．、？’−ジクロロー弘、４１′−ジアミノ
ベンゾフェノンｓ ＪＩＪ’−ジメチルベンジジン、３
゜３−ジメトキシベンジジン、３．ｊ′−ジメチルベン
ジジン等があげられる。また、構造１）を与える芳香族
テトラカルボン酸二無水物としては、ピロメリット酸二
無水物、Ｊ、弘、！、ターヘンシフエノンテトラカルボ
ン酸二無水物、３１．ｙ’、ａ、弘′−ジフェニルテト
ラカルボン酸二無水物、コ、２’、Ｊ。3'-sulfonylbis-(,2-chloroaniline), J
, j-dimethyl-a, 41'-diaminobenzophenone, J, J'-dimethoxy-funari'-diaminobenzophenone 1.7. ,? '-Hiroshi dichloro, 41'-diaminobenzophenone s JIJ'-dimethylbenzidine, 3
゜3-dimethoxybenzidine, 3. Examples include j'-dimethylbenzidine. Further, as the aromatic tetracarboxylic dianhydride giving structure 1), pyromellitic dianhydride, J, Hiromu,! , terhensiphenotetracarboxylic dianhydride, 31. y', a, Hiro'-diphenyltetracarboxylic dianhydride, co, 2', J.
３′−ジフェニルテトラカルボン酸二無水物、コ５−一
ビス（Ｊ、亭−ジカルボキシフェニル］フロパンニ無水
物、ビス（３、ダージカルポキシフェニル）ビス（トリ
フルオロメチル）メタン二無水物、ヒス（、？、４１−
ジカルボキシフェニル）スルホ／二無水物、ビス（，７
，４ｔ−ジカルボキシフェニルフエーテルニ無水物、ビ
ス（Ｊ、弘−ジカルボキシフェニル）メタン二無水物等
があげられる。3'-diphenyltetracarboxylic dianhydride, co-5-bis(J, tei-dicarboxyphenyl)furopannianhydride, bis(3, dicarpoxyphenyl)bis(trifluoromethyl)methane dianhydride, His (,?,41-
dicarboxyphenyl) sulfo/dianhydride, bis(,7
, 4t-dicarboxyphenyl ether dianhydride, bis(J, Hiro-dicarboxyphenyl)methane dianhydride, and the like.
本発明のポリマーは、実質的にジアミン（１）、！１０
モルチとピロメリット酸二無水物ｇｏモルチとから合成
された場合￥Ｃ最も剛直となる。必要に応じて構造式（
１）を与えるジアミン、ピロメリット酸二無水物以外の
構造式（ＩＩＩ）を与えるテトラカルボン酸二無水物を
共重合させることができる。The polymer of the present invention consists essentially of diamine (1),! 10
When synthesized from molti and pyromellitic dianhydride go molti, it becomes the most rigid. If necessary, enter the structural formula (
A diamine giving the formula 1) and a tetracarboxylic dianhydride giving the structural formula (III) other than pyromellitic dianhydride can be copolymerized.
しかしイミド閉環後のポリマーの剛直性を著しく損なわ
ないためには、ポリマー中に実質的にイミド閉環後、下
記構造式で表される構造単位が３０モルＩｓ以上含まれ
ることが好ましい。However, in order not to significantly impair the rigidity of the polymer after imide ring closure, it is preferable that the polymer substantially contains at least 30 moles Is of the structural unit represented by the following structural formula after imide ring closure.
本発明のポリアミド酸は、アミド溶媒中で上記芳香族ジ
アミンと芳香族テトラカルボン酸を反応させることによ
りｇ造することができる。The polyamic acid of the present invention can be produced by reacting the aromatic diamine with the aromatic tetracarboxylic acid in an amide solvent.
ついで化学環化法及び／又は熱環化法によジイミド化す
ることで、本発明のポリイミドを人造することができる
。ポリアミド酸の製造に使用するアミド溶媒としては、
Ｎ−メチルーコーくはリドン（ＩＭＦ ）、／、ｊ−ジ
メチルーコーイミダゾリジノン（ＤＭＺ）、Ｍ、Ｎ−ジ
メチルホルムアミド（ＤＭＦ）、Ｍ、Ｎ−ジメチルアセ
トアミド（ＤＭＡＣ）、ヘキサメチルホスホルトリアミ
ド（ＨＭＰＡ）、及びそれらの混合溶媒等が適している
。The polyimide of the present invention can then be produced by diimidation using a chemical cyclization method and/or a thermal cyclization method. Amide solvents used in the production of polyamic acid include:
N-methyl-co-lydone (IMF), /, j-dimethyl-co-imidazolidinone (DMZ), M, N-dimethylformamide (DMF), M, N-dimethylacetamide (DMAC), hexamethylphosphortriamide ( HMPA), mixed solvents thereof, etc. are suitable.
（実施例）
以下、実施例によシさらに本発明の詳細な説明する。ポ
リアミド酸の重合は窒素気流下、室温で行った。またポ
リアミド酸の対数粘度ηｉｎｈは、ポリマー濃度ｏ、５
ｉ７ａ又はｏ、、ｔ Ｉ ／ ｄｌとなるようにＮＭＰ
で希釈し、３０℃で測定した。(Examples) Hereinafter, the present invention will be further explained in detail using examples. Polymerization of polyamic acid was carried out at room temperature under a nitrogen stream. The logarithmic viscosity ηinh of polyamic acid is the polymer concentration o, 5
NMP to be i7a or o,,t I/dl
It was diluted with water and measured at 30°C.
なお、コ＊ｂ （ダ、ダ′−ジアミノージフェニル）
ベンゾ〔／、コーｄ：ダ、、ｔ −ｄ′］ビスチアゾー
ル１ＤＡＰＢＴ％ダ、弘′−ジアミノジフェニルエーテ
ｙｉＯＤＡ、ピロメリット酸二無水物をＰ Ｍ Ｄ Ａ
。In addition, ko*b (da, da'-diaminodiphenyl)
Benzo[/, code d: da, t-d'] bisthiazole 1DAPBT% da, Hiro'-diaminodiphenyl ether yiODA, pyromellitic dianhydride PMD A
.
Ｎ−メチル−一−ピロリドンをＮＭＰ、／、３−ジメチ
ルーコーイミダゾリジノンをＤＭ工と略する。N-methyl-1-pyrrolidone is abbreviated as NMP, and /,3-dimethyl-coimidazolidinone is abbreviated as DM.
実施例１
ＤＡＰＢＴダ護９弘９（／コミリモル〕をＩＭＦ卒よプ
にスラリー化させた。このスラリーにＰＭＤＡの粉末コ
、５コ？Ｎ（／／、６ミリモル）をＮＭＰＪＯｄととも
に加え重合を開始させた。Example 1 DAPBT dago9hiro9 (/comimole) was made into a slurry using IMF soup stock. To this slurry, PMDA powder, 5-N (//, 6 mmol) was added together with NMPJOd to start polymerization. I let it happen.
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.
１合１５時間後のこのポリアミド酸溶液の７１ｎｈはｔ
、ｏ ｄｔ／Ｉ （ｏ、：ｔ Ｉ／ｌｉｔ ）であった
。71nh of this polyamic acid solution after 15 hours is t
, o dt/I (o, :t I/lit ).
実施例λ
ＤＡＰＢＴＪ、デ９４．９（ｊミリモルン、ＯＤＡ／、
６０コｔｉｌｔミリモル）をＮＭＰｊＯｍ／にスラリー
化させた。このスラリーにＰＭＤＡＪ、Ｊざ５Ｉｉ（／
ｊ、、！ｔミリモル）をＮＭＰコ！Ｍとともに加え重
合を開始させた。溶液は徐々に粘稠になるとともに均一
となった。重合７５時間後のこのポリアミド酸溶液のη
ｉｎｈはコ、ｔｓ ｒｉｇ／ｌｉ （０−コ１１７ｄｌ
）でありた。Example λ DAPBTJ, de94.9 (j mmoln, ODA/,
60 cotilt mmol) was slurried in NMPjOm/. PMDAJ, Jza5Ii (/
j,,! t mmol) to NMP! It was added together with M to initiate polymerization. The solution gradually became viscous and homogeneous. η of this polyamic acid solution after 75 hours of polymerization
inh is ko, ts rig/li (0-ko 117dl
).
実施例３
実施例／、−のポリアミド酸溶液よシポリイミドフイル
ムを成形した。ポリアミド酸の合成溶液をそのままガラ
ス板上に中ヤストし、水に浸漬し溶媒除去後、無水酢酸
／ピリジン＝７０／ＪＯ溶液にフィルムを／昼夜浸漬さ
せ化学閉環させた。この時フィルムは黄色より赤橙色に
変化した。その後フィルムをｌ−０℃でｉｏ分。Example 3 A polyimide film was molded from the polyamic acid solution of Example/-. The synthetic solution of polyamic acid was directly cast onto a glass plate, and after immersing it in water to remove the solvent, the film was immersed in an acetic anhydride/pyridine = 70/JO solution day and night for chemical ring closure. At this time, the film changed from yellow to reddish-orange. The film was then incubated at l-0°C for io minutes.
λｏｏ℃で／、２分、３４０℃でダ分乾燥φ熱処理して
強靭なフィルムを得た。これらのフィルムの工Ｒスペク
トルでは、／クク！鋼−飄にイオド基由来の吸収が強く
現れた。A tough film was obtained by heat treatment at λoo°C for 2 minutes and by drying at 340°C. In the engineering spectrum of these films, /kuku! Absorption derived from iodo groups appeared strongly in steel.
実施側修
重合時間をり時間とした以外は実施例１と同様に反応せ
しめて得られたポリアミド酸（η１ｎｈ＝３．コａ７ｇ
）溶液をＯ，ｊダの単孔ノズルよシ水中に押出して繊維
を成形した。無水酢酸／ピリジン／トルエン（Ｊｓ ／
／ ｊ ／ ｊ Ｏンからなる閉環溶液に一夜浸漬後
トルエン洗浄し、１００℃で１時間、５０Ｏ℃で５０秒
熟熱処理九ポリイミド繊維の動的弾性率（東洋ボルドウ
ィン社製１バイプロンＤＯ’７１型′によ）測定ンは。Polyamic acid (η1nh=3.coa7g
) The solution was extruded into water through a single-hole nozzle of O.J to form fibers. Acetic anhydride/pyridine/toluene (Js/
Dynamic elastic modulus of polyimide fiber (Toyo Baldwin Co., Ltd., 1 Bipron DO'71 type ’) measurement is.
３０℃で７９−ＧＰａでアクた（繊維径；５！μ０）。It was heated at 30°C and 79-GPa (fiber diameter: 5!μ0).
（発明の効果）
本発明の含芳香族複素環ポリイミドよシ高弾性率かつ耐
熱性にも優れた成形品を得ることができる。本発明のポ
リマーは、最終的に高弾性率材料となシネ溶、不融であ
りても、ポリアミド酸を経て製造されるため、容易に溶
液成形することができる。(Effects of the Invention) A molded article having a higher elastic modulus and excellent heat resistance can be obtained from the aromatic heterocyclic polyimide of the present invention. Even if the polymer of the present invention is cine-soluble or infusible and ultimately becomes a high-modulus material, it can be easily solution-molded because it is produced through polyamic acid.
出 願 人 工業技術院長Applicant: Director, Institute of Industrial Science and Technology
Claims (1)
（III）からなり、構造単位（ I ）が全体の１５〜５０
モル％、構造単位（II）が全体の３５〜０モル％、構造
単位（III）が全体の５０モル％であることを特徴とす
る含芳香族複素環ポリイミド。 ▲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） ▲数式、化学式、表等があります▼・・・（III） 〔構造単位（II）、（III）において、Ａｒ＿１は、▲
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▼、Ａｒ＿２は、▲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▼を示す（Ｘ、Ｘ′は
、水素原子、 アルキル基、アルコキシ基又はハロゲン基、Ｙ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▼
を示す。）。〕(1) The structure consists essentially of the following structural units (I), (II) and (III), and the structural unit (I) accounts for 15 to 50 of the total
An aromatic heterocyclic polyimide characterized in that the structural unit (II) accounts for 35 to 0 mol% of the total, and the structural unit (III) accounts for 50 mol% of the total. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) [Structure In units (II) and (III), Ar_1 is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, Ar_2 indicates ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X, X' are hydrogen atoms, alkyl groups, alkoxy groups, or halogen groups , Y is a single bond, -O-, -CH_2-, -S-, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
shows. ). ]
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62089758A JPH0610261B2 (en) | 1987-04-14 | 1987-04-14 | Aromatic heterocyclic polyimide |
| US07/164,899 US4886873A (en) | 1987-04-14 | 1988-03-07 | Aromatic hetero ring-containing polyimide and its composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62089758A JPH0610261B2 (en) | 1987-04-14 | 1987-04-14 | Aromatic heterocyclic polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63256624A true JPS63256624A (en) | 1988-10-24 |
| JPH0610261B2 JPH0610261B2 (en) | 1994-02-09 |
Family
ID=13979618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62089758A Expired - Lifetime JPH0610261B2 (en) | 1987-04-14 | 1987-04-14 | Aromatic heterocyclic polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610261B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7094516B2 (en) * | 2000-01-07 | 2006-08-22 | Mitsui Chemicals, Inc. | Benzobisazole compound and optical recording medium containing the compound |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6289761A (en) * | 1985-10-15 | 1987-04-24 | Matsushita Electric Works Ltd | Unsaturated polyester resin composition |
-
1987
- 1987-04-14 JP JP62089758A patent/JPH0610261B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6289761A (en) * | 1985-10-15 | 1987-04-24 | Matsushita Electric Works Ltd | Unsaturated polyester resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7094516B2 (en) * | 2000-01-07 | 2006-08-22 | Mitsui Chemicals, Inc. | Benzobisazole compound and optical recording medium containing the compound |
| 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 |
|---|---|
| JPH0610261B2 (en) | 1994-02-09 |
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