JPH0453830A - New liquid crystalline polymer and production thereof - Google Patents
New liquid crystalline polymer and production thereofInfo
- Publication number
- JPH0453830A JPH0453830A JP16273890A JP16273890A JPH0453830A JP H0453830 A JPH0453830 A JP H0453830A JP 16273890 A JP16273890 A JP 16273890A JP 16273890 A JP16273890 A JP 16273890A JP H0453830 A JPH0453830 A JP H0453830A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- crystalline polymer
- polymer compound
- liquid crystalline
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims description 12
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 23
- 239000004962 Polyamide-imide Substances 0.000 abstract description 20
- 229920002312 polyamide-imide Polymers 0.000 abstract description 20
- 239000000835 fiber Substances 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 230000002535 lyotropic effect Effects 0.000 abstract description 5
- 150000004985 diamines Chemical class 0.000 abstract description 3
- 239000012770 industrial material Substances 0.000 abstract description 2
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- 229920005575 poly(amic acid) Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- -1 poly(p-phenylene terephthalamide) Polymers 0.000 description 6
- 230000001747 exhibiting effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004976 Lyotropic liquid crystal Substances 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 description 1
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 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］
本発明は液晶性を有する新規なポリアミドイミド系高分
子化合物およびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polyamideimide-based polymer compound having liquid crystallinity and a method for producing the same.
［従来の技術］
溶液中で液晶となるリオトロピック液晶の性質を示す高
分子化合物には、芳香族ポリアミド系のポリ（ｐ−フェ
ニレンテレフタルアミド）の他にボ１Ｊ（ｐ−フェニレ
ンベンゾビスチアゾール）、ポリ（テレフタロイルヒド
ラジド）、セルロース誘導体、ポリペプチド系等が知ら
れている。これらの液晶性ポリマーは溶液中で液晶を形
成するので、繊維やフィルムの製造に適している。すな
わち、リオトロピック液晶では、紡糸あるいはキャスト
の際に分子が流動方向に配向するので、機械的強度の優
れた繊維あるいは性質に異方性のあるフィルムなどを製
造することができる。[Prior Art] In addition to aromatic polyamide-based poly(p-phenylene terephthalamide), polymer compounds exhibiting lyotropic liquid crystal properties that become liquid crystals in solution include Bo1J (p-phenylenebenzobisthiazole), Poly(terephthaloyl hydrazide), cellulose derivatives, polypeptides, etc. are known. Since these liquid crystalline polymers form liquid crystals in solution, they are suitable for producing fibers and films. That is, in lyotropic liquid crystals, molecules are oriented in the flow direction during spinning or casting, so it is possible to produce fibers with excellent mechanical strength or films with anisotropic properties.
「発明が解決しようとする課題］
ところで、芳香族ポリアミドイミド系梅脂は耐熱性、機
械的特性、電気的特性のいずれにも優れた樹脂であり、
産業的に非常に有望な材料である。"Problems to be Solved by the Invention" By the way, aromatic polyamideimide-based plum fat is a resin that has excellent heat resistance, mechanical properties, and electrical properties.
It is an extremely promising material industrially.
しかしながら、従来の芳香族ポリアミドイミド系樹脂で
リオトロピック液晶の性質を有するものは知られておら
ず、繊維やフィルムなどに利用しても製品の性能には限
界があった。従って、優れた特性を有する分子の配向し
た繊維やフィルムを製造するために、リオトロピック液
晶性を有する新規な芳香族ポリアミドイミド系樹脂の開
発が切望されている。However, no conventional aromatic polyamide-imide-based resin is known to have lyotropic liquid crystal properties, and even when used for fibers, films, etc., the performance of the product has been limited. Therefore, in order to produce fibers and films with oriented molecules having excellent properties, there is a strong desire to develop a new aromatic polyamide-imide resin having lyotropic liquid crystal properties.
本発明はこのような現状に鑑み、リオトロピック液晶性
を有し、配向させることで機械的特性や熱的特性を向上
できる新規な芳香族ポリアミドイミド系高分子化合物お
よびその製造方法の提供を課題としてなされたものであ
る。In view of the current situation, the present invention aims to provide a novel aromatic polyamideimide-based polymer compound that has lyotropic liquid crystallinity and can improve mechanical properties and thermal properties by orientation, and a method for producing the same. It has been done.
［課題を解決するための手段］
本発明者らは液晶性を示す新規な芳香族ポリアミドイミ
ド系高分子化合物の分子構造およびその合成方法につい
て鋭意検討の結果、下記の（１）で表される高分子化合
物が上記課題を解決できることを確かめ、本発明の目的
を達成するに至った。[Means for Solving the Problems] As a result of intensive studies on the molecular structure and synthesis method of a novel aromatic polyamideimide-based polymer compound exhibiting liquid crystallinity, the present inventors found that it is expressed by the following (1). It has been confirmed that a polymer compound can solve the above problems, and the object of the present invention has been achieved.
すなわち、本発明の第１の発明は 下記一般式（１） ［ｎは２０〜６００の整数を表す１ て表される液晶性高分子化合物を提供する。That is, the first invention of the present invention is General formula (1) below [n represents an integer from 20 to 600 1 A liquid crystalline polymer compound represented by the following is provided.
さらに本発明の第２の発明は 下記一般式（ＩＪ） １ｍは２０〜６００の整数を表す７ て表される液晶性高分子化合物を提供する。Furthermore, the second invention of the present invention is General formula (IJ) below 1m represents an integer from 20 to 6007 A liquid crystalline polymer compound represented by the following is provided.
さらに、本発明は第３、第４の発明として上記（１）１
式（Ｉ］）で表される液晶性高分子化合物の製造方法を
提供するものであり、本発明の第３の発明は下記一般式
（ＩＩＩ）
て表される芳香族ジアミンと、
下記一般式（ＩＶ）
て表される液晶性高分子化合物の製造方法に関する。Furthermore, the present invention provides the above (1) 1 as the third and fourth inventions.
The third invention of the present invention provides a method for producing a liquid crystalline polymer compound represented by the formula (I), and the third aspect of the present invention is an aromatic diamine represented by the following general formula (III) and the following general formula. (IV) The present invention relates to a method for producing a liquid crystalline polymer compound represented by:
また、本発明の第４の発明は上記一般式（１）で表され
るポリアミドアミック酸を２００℃以上の温度で熱処理
するか、または該ポリアミドアミック酸に無水酢酸とピ
リジンとを反応させて、該ポリアミドアミック酸をイミ
ド化することを特徴とする下記一般式（Ｉｔ）
で表される無水塩化トリメット酸とを反応させることを
特徴とする下記一般式（１）
［ｎは２０〜６００の整数を表すａ
［ｒｒｌは２０〜６００の整数を表すでて表される液晶
性高分子化合物の製造方法に関する。Further, the fourth aspect of the present invention is to heat-treat the polyamide amic acid represented by the above general formula (1) at a temperature of 200°C or higher, or to react the polyamide amic acid with acetic anhydride and pyridine, The following general formula (1), characterized by reacting the polyamide amic acid with anhydrous trimethic acid represented by the following general formula (It), which is characterized by imidizing the polyamide amic acid [n is an integer of 20 to 600] It relates to a method for producing a liquid crystalline polymer compound, where a [rrl represents an integer from 20 to 600].
本発明の液晶性高分子化合物は芳香族ポリアミドイミド
系に属する新規な高分子化合物であり、前記のように芳
香族ポリアミドイミド系高分子重合体でリオトロピック
液晶性を示す例は従来報告されておらず、本発明は芳香
族ポリアミドイミド系高分子てもりオトロビノク液晶性
を示す可能性があることを初めて明らかにしたものであ
る。The liquid crystalline polymer compound of the present invention is a novel polymeric compound belonging to the aromatic polyamideimide family, and as mentioned above, no examples of aromatic polyamideimide polymers exhibiting lyotropic liquid crystallinity have been previously reported. First, the present invention reveals for the first time that aromatic polyamideimide-based polymers may exhibit liquid crystallinity.
以下、本発明の芳香族ポリアミドイミド系樹脂について
、その製造方法から詳しく説明してゆく。Hereinafter, the aromatic polyamide-imide resin of the present invention will be explained in detail, starting with its manufacturing method.
本発明の芳香族ポリアミドイミド系高分子化合物は、上
記一般式（ＩＩＩ）の化合物および無水トリメット酸ク
ロライドを原料として合成される。なお、一般式（ＩＩ
Ｉ）で示される芳香族ジアミンは、特願昭６３−２８７
６０９号明細書として既に出願された製法に従い、Ｎ、
Ｎ’−ジフェニル−ｐ−フェニレンジアミンとｐ−二ト
ロ塩化ベンゾイルを出発原料として合成することができ
る。The aromatic polyamideimide-based polymer compound of the present invention is synthesized using the compound of the above general formula (III) and trimethic anhydride chloride as raw materials. In addition, general formula (II
The aromatic diamine represented by I) is disclosed in Japanese Patent Application No. 63-287.
According to the manufacturing method already filed as specification No. 609, N,
It can be synthesized using N'-diphenyl-p-phenylenediamine and p-benzoyl ditrochloride as starting materials.
本発明の高分子化合物の合成方法としては直接重縮合法
、低温溶液重縮合法、高温溶液重縮合法、界面重縮合法
などが挙げられる。簡単には低温溶液重縮合法で合成で
き、このとき使用し得る溶媒は、ジメチルアセトアミド
、Ｎ−メチル−２−ピロリドンなどが挙げられるが、Ｎ
−メチル−２ピロリドンが好ましい。この重合で使用し
得る酸受容剤としては、トリエチルアミン、トリブチル
アミン、トリエチレンジチアミンなどが挙げられる。こ
の重合の初期温度はＯ′Ｃが好ましく、重合が進行して
溶液の粘度が増してからは、３０９Ｃ〜４０°Ｃ程度で
重合を続けるのが好ましい。Examples of methods for synthesizing the polymer compound of the present invention include direct polycondensation, low-temperature solution polycondensation, high-temperature solution polycondensation, and interfacial polycondensation. It can be easily synthesized by a low-temperature solution polycondensation method, and solvents that can be used at this time include dimethylacetamide, N-methyl-2-pyrrolidone, etc.
-Methyl-2-pyrrolidone is preferred. Acid acceptors that can be used in this polymerization include triethylamine, tributylamine, triethylenedithiamine, and the like. The initial temperature of this polymerization is preferably O'C, and after the polymerization progresses and the viscosity of the solution increases, it is preferable to continue the polymerization at about 309C to 40C.
この重合の原料（モノマー）の配合比は、化学量論的に
ジアミン成分と無水トリメット酸クロライド成分とが等
モルとなるのが好ましい。The blending ratio of raw materials (monomers) for this polymerization is preferably such that the diamine component and the trimethic anhydride chloride component are stoichiometrically equimolar.
この重合に適するモノマー濃度は、使用する溶媒により
異なるが、０ 、１ ｍｏｃ／ （！程度が好ましい。The monomer concentration suitable for this polymerization varies depending on the solvent used, but is preferably about 0.1 moc/(!).
この重合の重合時間は、重合温度、使用する溶媒の種類
、モノマー濃度、撹拌の状態などにより大きく左右され
るが、重合溶液の粘度が増加しなくなるまで、数時間か
ら数十時間重合させるのが好ましい。The polymerization time for this polymerization is greatly influenced by the polymerization temperature, type of solvent used, monomer concentration, stirring conditions, etc., but it is recommended to polymerize for several hours to several tens of hours until the viscosity of the polymerization solution no longer increases. preferable.
かくして得られる一般式（１）
［ｎは２０〜６００の整数を表す］
て表される芳香族ポリアミック酸は、トＪ−メチル２−
ピロリドン、ジメチルアセトアミド、ジメチルホルムア
ミド、ジメチルスルホキシドなとの有機溶媒に可溶であ
り、ある濃度以上で液晶性を示す。この液晶性を示す濃
度は、使用する溶媒によって異なるが、約１０重量％程
度で液晶となる。The aromatic polyamic acid represented by the general formula (1) [n represents an integer of 20 to 600] obtained in this way is
It is soluble in organic solvents such as pyrrolidone, dimethylacetamide, dimethylformamide, and dimethyl sulfoxide, and exhibits liquid crystallinity above a certain concentration. The concentration exhibiting liquid crystallinity varies depending on the solvent used, but it becomes liquid crystal at about 10% by weight.
この液晶溶液は、紡糸用原液、フィルムのキャスト液、
ワニスなどに直接利用できる。This liquid crystal solution can be used as spinning stock solution, film casting solution,
Can be used directly for varnish, etc.
次に、上記（１）で示されるポリアミ・ツク酸を加熱す
るか、化学的処理することにより、下記−般式（ＩＩ）
［ｍは２０〜６００の整数を表す］
で表される芳香族ポリアミドイミドに変えることができ
る、これにより、機械的強度、熱的特性、電気的特性が
飛躍的に向上する。この化学構造の変化は、分子内のみ
て起こるのではなく、分子間でも起こり、架橋、分岐し
て分子量は増大する。Next, by heating or chemically treating the polyamic acid represented by (1) above, an aromatic compound represented by the following general formula (II) [m represents an integer of 20 to 600] It can be changed to polyamideimide, which dramatically improves mechanical strength, thermal properties, and electrical properties. This change in chemical structure occurs not only within the molecule, but also between molecules, resulting in an increase in molecular weight through crosslinking and branching.
すなわち、熱処理または化学的処理により大部分は式（
ｎ）で表される閉環したイミド基を有する芳香族ポリア
ミドイミドに変化するが、一部は開環したイミド基によ
り架橋したもの、あるいはアミック酸構造が残っている
部分も含まれる。熱処理によるイミド化の条件は試料の
形状などにより異なるが、最終的には２６０°Ｃ程度の
温度まで段階的に数時間から数十時間かけて行うのか好
ましい。That is, by heat treatment or chemical treatment, the formula (
It changes to an aromatic polyamide-imide having a ring-closed imide group represented by n), but it also includes a part that is crosslinked with a ring-opened imide group, or a part in which an amic acid structure remains. The conditions for imidization by heat treatment vary depending on the shape of the sample, etc., but it is preferable to conduct the imidization stepwise to a final temperature of about 260° C. over several hours to several tens of hours.
なお、化学的処理によるイミド化の方法としては、重合
か終了した反応溶液に無水酢酸とピリジンを加えて加熱
する方法、ポリリン酸、モレキュラーンーブス、シリカ
ケル等の脱水剤を加えてイミド化する方法等かあるが、
工業的には前記の加熱法によるのか有利である。In addition, as a method of imidization by chemical treatment, a method of adding acetic anhydride and pyridine to the polymerized reaction solution and heating it, a method of imidizing by adding a dehydrating agent such as polyphosphoric acid, molecular cubes, silica gel, etc. etc., but
Industrially, the heating method described above is advantageous.
［実施例〕
以下に実施例を示し本発明を具体的に説明するか、本発
明はこれに限定されるものではない。[Example] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.
実施例１ 窒素雰囲気下で、Ｎ、Ｎ’ −ジフェニル−Ｎ。Example 1 N,N'-diphenyl-N under nitrogen atmosphere.
Ｎ’−１，４−フェニレンビス（４−アミノベンズアミ
ド） ４．９９ ｇ （１０ｍｍｏｆｆ）を１００
ｍＱのＮ−メチル−２−ピロリドンに溶解させた。この
溶液を０℃に冷却してからトリエチルアミン１．４ ｍ
ｇ（］ Ｏｎ＋＋ｅｏｆ２）と無水トリメット酸クロラ
イド２．１１ ｇ （１０ｍｓｏｇ） を加えて２時
間撹拌した。さらにこの溶液を室温で６時間撹拌を続け
た。この溶液を３Ｑの撹拌水中に滴下して高分子化合物
を沈澱させた。この高分子化合物を乾燥後、再び１００
ｍｆｆのＮ−メチル−２−ピロリドンに溶解し、この溶
液を３Ｑの撹拌水中に滴下して高分子化合物を沈澱させ
た。再沈後の該高分子化合物の収量は６．１３ｇであっ
た。N'-1,4-phenylenebis(4-aminobenzamide) 4.99 g (10 mmoff) was added to 100
It was dissolved in mQ of N-methyl-2-pyrrolidone. The solution was cooled to 0°C and then 1.4 m of triethylamine was added.
g(]On++eof2) and 2.11 g (10 msog) of trimethic anhydride chloride were added and stirred for 2 hours. This solution was further stirred at room temperature for 6 hours. This solution was dropped into 3Q stirred water to precipitate the polymer compound. After drying this polymer compound, 100%
mff of N-methyl-2-pyrrolidone, and this solution was dropped into 3Q of stirring water to precipitate the polymer compound. The yield of the polymer compound after reprecipitation was 6.13 g.
得られた高分子化合物はゲル浸透クロマトグラフ分析に
より第１図に示すように重量平均分子量（Ｍ）約７万（
ポリスチレン換算）の分子量を有することがわかった。The obtained polymer compound was analyzed by gel permeation chromatography to have a weight average molecular weight (M) of about 70,000 (as shown in Figure 1).
It was found that it has a molecular weight of (polystyrene equivalent).
該高分子化合物はジメチルホルムアミド、ジメチルアセ
トアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピ
ロリドンに可溶であった。この高分子化合物の赤外吸光
分光分析結果は第２図に示したように、アミド結合（１
６５３ｃｍ−’）、カルボキシル基（１７］ ８ ｃｍ
−’）の存在を示した。従って、この高分子化合物は上
記構造式（１）で表される芳香族ポリアミック酸である
と同定できた。The polymer compound was soluble in dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone. As shown in Figure 2, the results of infrared absorption spectrometry analysis of this polymer compound show that the amide bond (1
653 cm-'), carboxyl group (17] 8 cm
-'). Therefore, this polymer compound could be identified as an aromatic polyamic acid represented by the above structural formula (1).
実施例１で得られた芳香族ポリアミック酸２ｇを１２ｍ
Ｃのジメチルアセトアミドに完全に溶解させた。この溶
液を室温で偏光顕微鏡観察したところ、直交差ニコル下
で光学的異方性を示し、この芳香族ポリアミック酸はり
オトロビック液晶となることが確認された。更に、ジメ
チルホルムアミド中の芳香族ポリアミック酸濃度を変え
て、粘度の測定、偏光顕微鏡による光学的異方性の観察
を実施したところ、濃度約１０％までは濃度の増加と共
に粘度が上昇し、溶液は光学的等方性であったが、濃度
約１０％以上で粘度か減少し、溶液か光学的異方性を示
すことが確認された。光学的異方性を示す溶液を希釈し
て濃度を１０％以下にすると、再び光学的等方性を示し
た。2 g of the aromatic polyamic acid obtained in Example 1 was added to 12 m
C was completely dissolved in dimethylacetamide. When this solution was observed under a polarizing microscope at room temperature, it was confirmed that it exhibited optical anisotropy under crossed nicol conditions, and that this aromatic polyamic acid beam became otrobic liquid crystal. Furthermore, we measured the viscosity and observed the optical anisotropy using a polarizing microscope while changing the concentration of the aromatic polyamic acid in dimethylformamide.We found that the viscosity increased as the concentration increased up to about 10%, and the solution was optically isotropic, but the viscosity decreased at concentrations above about 10%, and it was confirmed that the solution exhibited optical anisotropy. When the solution exhibiting optical anisotropy was diluted to a concentration of 10% or less, it again exhibited optical isotropy.
実施例２
実施例１て得られた芳香族ポリアミック酸を窒素雰囲気
下、１００ ’Ｃて１時間、２００℃で１時間、２５０
’Ｃて１時間熱処理した。この熱処理試料の赤外吸光
分光分析結果は第３図に示したように、イミド基（１７
８０ｃｍ−’）の存在を示し、上記構造式（ＩＩ）の芳
香族ポリアミドイミドに変化したことが確認された。Example 2 The aromatic polyamic acid obtained in Example 1 was heated at 100° C. for 1 hour and at 200° C. for 1 hour at 250° C. in a nitrogen atmosphere.
It was heat-treated at 'C for 1 hour. As shown in Figure 3, the results of infrared absorption spectroscopy of this heat-treated sample showed that the imide group (17
80 cm-'), and it was confirmed that the polyamide-imide had changed to the aromatic polyamideimide of the above structural formula (II).
この芳香族ポリアミドイミドの熱重量分析法による熱分
解温度は３６７°Ｃ（昇温速度１０°Ｃ／ ｍ ｉｎ１
空気中）であり、高い耐熱性を有することを確認した。The thermal decomposition temperature of this aromatic polyamide-imide according to thermogravimetric analysis was 367°C (heating rate 10°C/min1
(in air) and was confirmed to have high heat resistance.
［発明の効果〕
本発明はりオトロピノク液晶性を有する一般式（１）で
示される繰り返し単位を有する芳香族ポリアミック酸お
よび一般式（ＩＩ）で示される繰り返し単位を有する芳
香族ポリアミドイミドという新規な構造で且つ液晶性を
有する高分子化合物とこれらの有利な製造方法を提供で
きる。[Effects of the Invention] The present invention provides a novel structure of an aromatic polyamic acid having a repeating unit represented by the general formula (1) and an aromatic polyamideimide having a repeating unit represented by the general formula (II), which have liquid crystallinity. It is possible to provide a polymer compound having a liquid crystal property and an advantageous method for producing the same.
本発明の本発明ポリアミドイミド系樹脂はりオトロビノ
ク液晶性を有するゆえに、繊維、フィルムなとを製造す
る際に分子配向が容易であり、優れた機械的特性を引き
出すことができ、耐熱性も高く、工業材料として価値が
大きい。Since the polyamide-imide resin of the present invention has liquid crystallinity, molecular orientation is easy when manufacturing fibers and films, excellent mechanical properties can be brought out, and heat resistance is high. It has great value as an industrial material.
第１図は一般式（１）で示される本発明の芳香族ポリア
ミック酸の重量平均分子量分布図、第２図は実施例１で
得られた本発明の芳香族ポリアミ７り酸の赤外分光分析
チャート図、第３図は実施例２て得られた本発明の芳香
族ポリアミドイミドの赤外分光分析チャート図を示す。Figure 1 is a weight average molecular weight distribution diagram of the aromatic polyamic acid of the present invention represented by general formula (1), and Figure 2 is an infrared spectrum of the aromatic polyamic acid of the present invention obtained in Example 1. Analysis Chart Figure 3 shows an infrared spectroscopic analysis chart of the aromatic polyamideimide of the present invention obtained in Example 2.
Claims (4)
特徴とする下記一般式（ I ） ▲数式、化学式、表等があります▼ ［ｎは２０〜６００の整数を表す］ で表される液晶性高分子化合物の製造方法。(3) An aromatic diamine represented by the following general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and anhydrous chloride represented by the following general formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A method for producing a liquid crystalline polymer compound represented by the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ [n represents an integer from 20 to 600] characterized by reacting with trimethic acid .
で熱処理するか、または該ポリアミドアミツク酸に無水
酢酸とピリジンとを反応させて、該ポリアミドアミツク
酸をイミド化することを特徴とする下記一般式（II） ▲数式、化学式、表等があります▼ ［ｍは２０〜６００の整数を表す］ で表される液晶性高分子化合物の製造方法。(4) The polyamide amic acid represented by the following general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼ [n represents an integer from 20 to 600] is heat-treated at a temperature of 200℃ or higher, or The following general formula (II) is characterized in that the polyamide amic acid is reacted with acetic anhydride and pyridine to imidize the polyamide amic acid ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [m is 20 represents an integer of ~600] A method for producing a liquid crystalline polymer compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16273890A JPH0453830A (en) | 1990-06-22 | 1990-06-22 | New liquid crystalline polymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16273890A JPH0453830A (en) | 1990-06-22 | 1990-06-22 | New liquid crystalline polymer and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0453830A true JPH0453830A (en) | 1992-02-21 |
Family
ID=15760325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16273890A Pending JPH0453830A (en) | 1990-06-22 | 1990-06-22 | New liquid crystalline polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0453830A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100433809B1 (en) * | 2002-02-25 | 2004-06-04 | 삼성중공업 주식회사 | Method for Excavating and Banking the Ground Using Walls Reinforced By Horizontal Earth Anchor |
| JP2015166844A (en) * | 2014-02-13 | 2015-09-24 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, retardation film, method for producing retardation film, polymer and compound |
-
1990
- 1990-06-22 JP JP16273890A patent/JPH0453830A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100433809B1 (en) * | 2002-02-25 | 2004-06-04 | 삼성중공업 주식회사 | Method for Excavating and Banking the Ground Using Walls Reinforced By Horizontal Earth Anchor |
| JP2015166844A (en) * | 2014-02-13 | 2015-09-24 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, retardation film, method for producing retardation film, polymer and compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chung et al. | Novel organosoluble fluorinated polyimides derived from 1, 6-bis (4-amino-2-trifluoromethylphenoxy) naphthalene and aromatic dianhydrides | |
| US6291635B1 (en) | Fluorine-containing polybenzoxazole | |
| EP3575343A1 (en) | Polyimide-based copolymer and polyimide-based film including same | |
| JP2698774B2 (en) | Poly (imide-amic acid ester) and method for producing the same, and polyimide, polyimide film, polyimide fiber and method for producing the same using the same | |
| Dodda et al. | Preparation, characterization and thermal degradation study of poly (amide imide) s based on tri-component mixture of PMDA/BTDA, diamines and acid chloride | |
| Lei et al. | High temperature shape memory poly (amide-imide) s with strong mechanical robustness | |
| KR102060190B1 (en) | Polyimide-based random copolymers and polyimide-based film comprising the same | |
| Yang et al. | Syntheses and properties of fluorinated polyamides and poly (amide imide) s based on 9, 9-bis [4-(4-amino-2-trifluromethylphenoxy) phenyl] fluroene, aromatic dicarboxylic acids, and various monotrimellitimides and bistrimellitimides | |
| KR19990025576A (en) | Novel soluble polyimide resins having alkoxy substituents and preparation methods thereof | |
| Abouzari-Lotf et al. | Heat-resistant and soluble fluorinated poly (amide imide) s based on non-coplanar ortho-linked diimide-dicarboxylic acid | |
| KR100519652B1 (en) | Polyamic acid random copolymer and Polyimide random copolymer | |
| Koning et al. | Influence of polymerization conditions on melt crystallization of partially aliphatic polyimides | |
| KR100519651B1 (en) | Polyamic acid random copolymer and Polyimide random copolymer | |
| KR102070943B1 (en) | Polyimide-based block copolymer film | |
| Chen et al. | Synthesis and properties of novel meltable fluorinated aromatic oligoimides endcapped with 4-phenylethynylphthalic anhydride | |
| KR20190085778A (en) | Isotropic poly(amide-imide) resin film | |
| KR102078384B1 (en) | Polyimide-based block copolymer film | |
| Sava et al. | Comparison of Properties of Silicon-containing Poly (amide-imide) s | |
| CA2497079A1 (en) | Perdeuterated poliimides, method for the production and use thereof in the form of transparent materials in the range of 2500-3500 cm-1 | |
| JP3621200B2 (en) | Low hygroscopic phenolic hydroxyl group-containing aromatic polyamide resin | |
| KR20200090043A (en) | Preparing method of polyamideimide block copolymer, polyamideimide block copolymer and polymer resin film using the same | |
| Bruma et al. | Fluorinated poly (benzoxazole–imide) s | |
| JPS63241030A (en) | Production of solvent-soluble polyimide | |
| US6384182B2 (en) | Fluorine-containing polybenzoxazole | |
| Yoo et al. | Melt and Solution Processing of the Poly (Hydroxy-Amide) Family of Polymers |