JPH02289621A - Aromatic heterocyclic polyimide - Google Patents
Aromatic heterocyclic polyimideInfo
- Publication number
- JPH02289621A JPH02289621A JP4181990A JP4181990A JPH02289621A JP H02289621 A JPH02289621 A JP H02289621A JP 4181990 A JP4181990 A JP 4181990A JP 4181990 A JP4181990 A JP 4181990A JP H02289621 A JPH02289621 A JP H02289621A
- Authority
- JP
- Japan
- Prior art keywords
- polyamic acid
- polyimide
- formulas
- tables
- aromatic heterocyclic
- 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
- 239000004642 Polyimide Substances 0.000 title claims description 23
- 229920001721 polyimide Polymers 0.000 title claims description 23
- 125000006615 aromatic heterocyclic group Chemical group 0.000 title claims description 10
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 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 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 150000001408 amides Chemical class 0.000 abstract description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 abstract description 3
- PMJNNCUVWHTTMV-UHFFFAOYSA-N [1,3]oxazolo[5,4-f][1,3]benzoxazole Chemical compound C1=C2OC=NC2=CC2=C1N=CO2 PMJNNCUVWHTTMV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 125000005462 imide group Chemical group 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 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 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- -1 3,4-dicarboxyphenyl Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000843 powder 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
- 238000009987 spinning Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-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
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-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
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高弾性率であり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
主鎖中にペンゾビスオキサ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 penzobisoxazole 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
公知のポリマーの中では、ポリｐ−フェニレンベンゾビ
スチアゾール（以下ＰＰＢＴと略記入する。Ｍａｃｒｏ
ｎ＋ｏｌｅｃｕｌｅｓ 上土．９１５ （１９８１）
）が非常に高弾性率な繊維を与えるものとして知られて
いる。(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 the currently known polymers, poly p-phenylenebenzobisthiazole (hereinafter abbreviated as PPBT), Macro
n+olecules upper soil. 915 (1981)
) is known to provide fibers with extremely high modulus of elasticity.
しかし、ＰＰＢＴは不融であり、かつ一般的な有機溶媒
には不溶であるため、成形の困難なボリマーである。However, PPBT is a polymer that is difficult to mold because it is infusible and insoluble in common organic solvents.
本発明者は、ポリアミド酸を経てペンゾビスチアゾール
構造を、ポリイミドに導入する発明を行ない先に特許出
願した（特開昭６２−０８９７５８号公報）。The present inventor has developed an invention for introducing a penzobisthiazole structure into a polyimide via a polyamic acid, and previously filed a patent application (Japanese Patent Laid-Open No. 62-089758).
このポリイミド、代表的にはポリイミドベンゾビスチア
ゾール（ＰＩＢＴ）は不溶、不融である。This polyimide, typically polyimide benzobistiazole (PIBT), is insoluble and infusible.
しかし、該ポリイミドの前駆体のポリアミド酸は、Ｎ−
メチル−２−ピロリドン等の溶媒に溶解することができ
るので、ポリアミド酸の溶液状態で成形し、成形後に閉
環することにより、高弾性率、高耐熱性材料を容易に成
形することができる。However, the polyamic acid that is the precursor of the polyimide is N-
Since it can be dissolved in a solvent such as methyl-2-pyrrolidone, it can be easily molded into a material with high elastic modulus and high heat resistance by molding it in a polyamic acid solution state and ring-closing it after molding.
しかし、チアゾール環より優れた直線性及び耐熱性が予
想される、オキサゾール環を含んだポリイミドは未だ知
られていない。However, a polyimide containing an oxazole ring, which is expected to have better linearity and heat resistance than a thiazole ring, is not yet known.
本発明は、ＰＩＢＴと同等の成形性を有し、かつ、より
剛直性及び耐熱性に優れたボリマーを得ることを目的と
する。The object of the present invention is to obtain a polymer having moldability equivalent to that of PIBT and having better rigidity and heat resistance.
（課題を解決するための手段）
即ち、本発明は、原料ポリアミド酸の対数粘度η．，，
ｈ力｛η＝７ｈ ＞０．１ ６ｌ／ｇ （ＮＭＰ？容媒
、０．２ｇ７ｄｌ、３０℃）である、下記構造単位（Ｉ
）から実質的になる含芳香族複素環ポリイミドを要旨と
するものである。(Means for Solving the Problem) That is, the present invention provides a method for reducing the logarithmic viscosity η of raw material polyamic acid. ，，
The following structural unit (I
) The gist is an aromatic heterocyclic polyimide consisting essentially of the following.
・・・ （１）
（発明が解決しようとする課題）
・・・ （ＰＩＢＴ）
を示し、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、を示し、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、０ ， ＣＨｚ． Ｓ
， Ｃ ， ＳＯｚ本発明の含芳香
族複素環ポリイミドの前駆体であるポリアミド酸は、２
．６− （４，４’ジアミノージフエニル）ベンゾ（１
，２−ｄ：４，５−ｄ’）ビスオキサゾール
と、下記構造式（ｎ）で示される芳香族テトラカルボン
酸二無水物とをアミド熔媒中で反応させることにより製
造される。... (1) (Problem to be solved by the invention) ... (PIBT) where x and x' are a hydrogen atom, an alkyl group, an alkoxy group, or a halogen group, and Y is a single bond. , x, x'
is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen group, Y is a single bond, 0, CHz. S
, C, SOz The polyamic acid which is the precursor of the aromatic heterocyclic polyimide of the present invention is 2
．． 6-(4,4'diaminodiphenyl)benzo(1
, 2-d:4,5-d') bisoxazole and an aromatic tetracarboxylic dianhydride represented by the following structural formula (n) in an amide solvent.
ＣＨ， ＣＦｆｆ
上記構造式（ｎ）で示される芳香族テトラカルボン酸二
無水物としては、ピロメリソト酸二無水物、３，４．３
’，４’−ベンゾフェノンテトラカルボン酸二無水物、
３．３’，４．４’−ジフエニルテトラカルポン酸二無
水物、２．２’，３３′−ジフエニルテトラカルボン酸
二無水物、２，２−ビス（３，４−ジカルボキシフェニ
ル）ブロバンニ無水物、ビス（３．４−ジカルボキシフ
エニル）ビス（トリフルオロメチル）メタンニ無水物、
ビス（３，４−ジカルボキシフェニル）スルホンニ無水
物、ビス（３．４−ジカルボキシフエニル）エーテル無
水物、ビス（３，４−ジカルボキシフェニル）メタンニ
無水物等があげられる。CH, CFff The aromatic tetracarboxylic dianhydride represented by the above structural formula (n) includes pyromellisotonic dianhydride, 3,4.3
',4'-benzophenonetetracarboxylic dianhydride,
3.3',4.4'-diphenyltetracarboxylic dianhydride, 2.2',33'-diphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl ) Brovannihydride, bis(3,4-dicarboxyphenyl)bis(trifluoromethyl)methanihydride,
Examples include bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether anhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, and the like.
？ミド溶媒としては、Ｎ−メチル−２−ピロリドン（Ｎ
ＭＰ） 、１．３−ジメチル−２−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（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挙げられる。? As a mido solvent, N-methyl-2-pyrrolidone (N
MP), 1,3-dimethyl-2-imidazolidinone (
DMI), N,N-dimethylformamide (DMF)
, N,N-dimethylacetamide (DMAc), hexamethylphosphortriamide (HMPA), and mixed solvents thereof.
このようにして得られた本発明の含芳香族複素環ポリイ
ミドの前駆体であるポリアミド酸は、ＮＭＰに溶解して
濃度０．２ｇ／ｄｆｆに調製し３０℃で対数粘度η■．
を測定した時に、０． １以上、好ましくは１．０以上
のη．，１ｈを有する。The thus obtained polyamic acid, which is a precursor of the aromatic heterocyclic polyimide of the present invention, was dissolved in NMP to a concentration of 0.2 g/dff, and at 30°C had a logarithmic viscosity of η■.
When measured, 0. 1 or more, preferably 1.0 or more. , 1h.
ついで上記ポリアミド酸を、無水酢酸とピリジンとの混
合溶媒と作用させることなどにより、化学的にイミド環
を閉環させる、化学環化法及び／又は高温で熱処理する
ことにより、熱的にイミド環を閉環させる熱環化法によ
り、イミド化することで、本発明の含芳香族複素環ポリ
イミドを製造することができる。Next, the imide ring is thermally closed by chemically closing the imide ring by reacting the polyamic acid with a mixed solvent of acetic anhydride and pyridine, or by a chemical cyclization method and/or heat treatment at high temperature. The aromatic heterocyclic polyimide of the present invention can be produced by imidization using a ring-closing thermal cyclization method.
本発明の含芳香族複素環ポリイミドは、有機熔媒には不
溶である。The aromatic heterocyclic polyimide of the present invention is insoluble in organic solvents.
本発明のポリイミドの前駆体であるポリアミド酸は、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、かかる溶液より極めて
容易に繊維状物を紡出することができる。本発明では、
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容易に製造できる。The polyamic acid, which is the precursor of the polyimide of the present invention, has more flexibility in the final polyimide structure, so it has excellent solubility in polar organic solvents such as amide solvents. A fibrous material can be spun very easily from such a solution. In the present invention,
By imidizing polyamic acid spun fibers and subjecting them to specific treatments, polyimide fibers with high elastic modulus and excellent heat resistance can be easily produced.
即ち、紡出繊維に緊張昇温熱処理を施こすに際し、１０
〜１０００ＭＰａ、好ましくは、５０〜７００ＭＰａの
張力を与えながら最終熱処理温度を４２０〜５５０℃、
好ましくは４８０〜５１０℃に保つ方法である。That is, when subjecting the spun fibers to tension heating heat treatment, 10
The final heat treatment temperature is 420-550°C while applying a tension of ~1000 MPa, preferably 50-700 MPa.
Preferably, the temperature is maintained at 480 to 510°C.
紡出繊維を得る方法としては、公知の湿式紡糸法を挙げ
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−ビ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。As a method for obtaining spun fibers, a known wet spinning method can be mentioned. 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. -By coexisting an imide ring-closing reagent such as pyridine in the coagulation bath or coagulation bath,
Spinning and imide ring closure may be performed simultaneously.
（実施例）
以下、実施例によりさらに本発明を詳細に説明する。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０．２
ｇ／ｄｊ！となるようにＮＭＰで稀釈し、３０℃で測定
した。(Example) Hereinafter, the present invention will be explained in further detail with reference to Examples. Polymerization of polyamic acid was carried out at room temperature under a nitrogen stream. Also,
Logarithmic viscosity ηinh of polyamic acid is polymer concentration 0.2
g/dj! It was diluted with NMP to give the following value and measured at 30°C.
なお、２．６− （４，４’−ジアミノージフェニルベ
ンゾ（１，２−ｄ；４．５−ｄ’）ビスオキサゾールを
ＤＢＯ、ピロメリット酸二無水物をＰＭＤＡ，Ｎ−メチ
ル−２−ピロリドンをＮＭＰ、１．３−ジメチル−２−
イミダゾリジノンをＤＭＩと略する。In addition, 2.6-(4,4'-diaminodiphenylbenzo(1,2-d;4.5-d')bisoxazole was used as DBO, pyromellitic dianhydride was used as PMDA, N-methyl-2- Pyrrolidone with NMP, 1,3-dimethyl-2-
Imidazolidinone is abbreviated as DMI.
実施例Ｉ
ＤＢＯ ３．５ ４ ５ ｇ （１ ０．４ミリモル
）をＮＭＰ３５ｎ＋１に７０℃で溶解させて、室温に戻
した後、ＰＭＤＡの粉末、２．２ ６ ０ ｇ （１
０．４ミリモル）をＮＭＰ２０ｍｌと共に加え重合を開
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１５時間後のこのアミド酸容液のη．，，ｈは
３．７９ｄｌ！／ｇであった。Example I 3.5 45 g (1 0.4 mmol) of DBO were dissolved in NMP35n+1 at 70° C. and after returning to room temperature, 2.2 60 g (1 0.4 mmol) of PMDA powder was dissolved in NMP35n+1 at 70° C.
0.4 mmol) was added together with 20 ml of NMP to initiate polymerization. The solution gradually became viscous and homogeneous. η of this amic acid solution after 15 hours of polymerization. ,,h is 3.79dl! /g.
続いて、このアミド酸溶液５７ｇに、無水酢酸２．０ｇ
及びピリジン０．５ｇを加えて５時間撹拌することによ
り、下記構造単位（Ｉ′）
・・・ （Ｉ ′）
からなるポリイミドを得た。Subsequently, 2.0 g of acetic anhydride was added to 57 g of this amic acid solution.
By adding 0.5 g of pyridine and stirring for 5 hours, a polyimide consisting of the following structural units (I') ... (I') was obtained.
このポリイミドのＩＲスペクトルを測定したところ１７
７５ｃｍ−’にイミド基由来の特徴ある吸収が強く現わ
れた。When the IR spectrum of this polyimide was measured, 17
A characteristic absorption derived from the imide group appeared strongly at 75 cm-'.
実施例２〜５
ＤＢＯ ４．１ ０ ４ ｇ （１ ２ ｍｍｏｌ）
をＮＭＰ２０ ｍｊ’／ＤＭ１２０ ｍｌからなる混合
溶媒に、スラリー化させた。このスラリーに、ＰＭＤＡ
の粉末を表−１に示される様なモル比率となる様に、Ｎ
ＭＰ １ ０ ｍｌ／ＤＭ １ １ ０ ｍｌｌからな
る混合溶媒とともに加え、更に内湯を５０℃に昇温せし
め、重合を開始させた。Examples 2-5 DBO 4.1 0 4 g (1 2 mmol)
was slurried in a mixed solvent consisting of NMP20 mj'/DM120 ml. Add PMDA to this slurry.
The powder was mixed with N so that the molar ratio was as shown in Table 1.
It was added together with a mixed solvent consisting of 10 ml of MP/110 ml of DM, and the temperature of the inner bath was further raised to 50° C. to initiate polymerization.
溶液は徐々に粘稠となるとともに、均一となった．重合
１０時間後に表−１に示されるポリアミド酸溶液Ａ−Ｄ
が得られた。The solution gradually became viscous and homogeneous. Polyamic acid solutions A-D shown in Table 1 after 10 hours of polymerization
was gotten.
表−１
得られたポリアミド酸溶液Ａ−Ｄを０． ５φのの単孔
ノズルより無水酢酸／ピリジン−７ ０／３ ０（容積
比）からな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。Table-1 The obtained polyamic acid solutions A-D were 0. It was spun into a coagulation bath consisting of acetic anhydride/pyridine-70/30 (volume ratio) through a 5φ 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, thereby obtaining polyimide fibers.
このポリイミドのＩＲスペクトルを測定したところ、１
７７５ｃｍ−’にイミド基由来の特徴ある吸収が強く現
われた。次にこの繊維をトルエン中に移し、３時間浸漬
後、１．５倍に延伸させ、室温下で乾燥させた。この時
点での繊維径は１００μであった。When the IR spectrum of this polyimide was measured, it was found that 1
A characteristic absorption derived from the imide group appeared strongly at 775 cm-'. Next, this fiber was transferred to toluene, immersed for 3 hours, stretched 1.5 times, and dried at room temperature. The fiber diameter at this point was 100μ.
この繊維に表−２に示される一定張力を与えながら下記
に示される熱処理を施こした。The fibers were subjected to the heat treatment shown below while applying a constant tension shown in Table 2.
なお、表−２中の張力は、荷重と最ｖ！：繊維径から算
出したものである。In addition, the tension in Table 2 is the load and the maximum v! : Calculated from fiber diameter.
熱処理：
１００℃〜４００゜Ｃ・・・１０℃／分で定速昇温４５
０゜Ｃ ・・・ ５分保持５００℃
・・・ １分保持この様にして得られる熱処理後の
ポリイミド繊維の動的弾性率（東洋ボールドウィン社製
、バイヴロンＤＯＶｎ型により測定）を測定した。得ら
れた結果を表−２に示した。Heat treatment: 100°C to 400°C...constant temperature increase at 10°C/min 45
0°C...Hold for 5 minutes at 500°C
... The dynamic elastic modulus (measured by Vyvron DOVn model manufactured by Toyo Baldwin Co., Ltd.) of the heat-treated polyimide fiber obtained in this manner was measured. The results obtained are shown in Table-2.
表−２
（発明の効果）
本発明の含芳香族複素環ポリイミドより高弾性率かつ耐
熱性にも優れた繊維、フィルム、シート、成型物等の各
種成形品を得ることができる。本発明のポリマーは、不
溶、不融であるが、前駆体のポリアミド酸は有機溶媒に
可溶である。そのため、ポリアミド酸の溶液状態で任意
の形に成形し、成形後の閉環させることにより、高弾性
率、高耐熱性の成形品を容易に得ることができる。Table 2 (Effects of the Invention) Various molded products such as fibers, films, sheets, and molded products having high elastic modulus and excellent heat resistance can be obtained from the aromatic heterocyclic polyimide of the present invention. The polymer of the present invention is insoluble and infusible, but the precursor polyamic acid is soluble in organic solvents. Therefore, a molded product with a 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.
Claims (1)
＿ｉ＿ｎ＿ｈ＞０．１ｄｌ／ｇ（ＮＭＰ溶媒、０．２ｇ
／ｄｌ、３０℃）である、下記構造単位（ I ）から実
質的にな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 ） （式中、Ａｒ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▼ を示し、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 logarithmic viscosity η_i_n_h of the raw material polyamic acid is η
___i_n_h>0.1dl/g (NMP solvent, 0.2g
/dl, 30°C), an aromatic heterocyclic polyimide consisting essentially of the following structural unit (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, Ar indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, X, ' is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen group, Y is a single bond, -O-, -CH_2, -S-, ▲Mathematical formulas, chemical formulas, tables, etc.▼, -SO_2-, ▲Mathematical formulas, chemical formulas , there are tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4181990A JPH02289621A (en) | 1989-02-22 | 1990-02-22 | Aromatic heterocyclic polyimide |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-40258 | 1989-02-22 | ||
| JP4025889 | 1989-02-22 | ||
| JP4181990A JPH02289621A (en) | 1989-02-22 | 1990-02-22 | Aromatic heterocyclic polyimide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02289621A true JPH02289621A (en) | 1990-11-29 |
Family
ID=26379707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4181990A Pending JPH02289621A (en) | 1989-02-22 | 1990-02-22 | Aromatic heterocyclic polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02289621A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919892A (en) * | 1994-10-31 | 1999-07-06 | The Dow Chemical Company | Polyamic acids and methods to convert polyamic acids into polyimidebenzoxazole films |
| JP2002338710A (en) * | 2001-03-16 | 2002-11-27 | Sumitomo Bakelite Co Ltd | Plastic base plate for indication element |
| JP2005112891A (en) * | 2003-10-03 | 2005-04-28 | Toyobo Co Ltd | Film substrate for semiconductor mounting |
| 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 |
-
1990
- 1990-02-22 JP JP4181990A patent/JPH02289621A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919892A (en) * | 1994-10-31 | 1999-07-06 | The Dow Chemical Company | Polyamic acids and methods to convert polyamic acids into polyimidebenzoxazole films |
| US7094516B2 (en) * | 2000-01-07 | 2006-08-22 | Mitsui Chemicals, Inc. | Benzobisazole compound and optical recording medium containing the compound |
| JP2002338710A (en) * | 2001-03-16 | 2002-11-27 | Sumitomo Bakelite Co Ltd | Plastic base plate for indication element |
| JP2005112891A (en) * | 2003-10-03 | 2005-04-28 | Toyobo Co Ltd | Film substrate for semiconductor mounting |
| JP2006249186A (en) * | 2005-03-09 | 2006-09-21 | Teijin Ltd | Rigid heterocyclic polymer and method for producing the same |
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