JPS642612B2 - - Google Patents
Info
- Publication number
- JPS642612B2 JPS642612B2 JP15280084A JP15280084A JPS642612B2 JP S642612 B2 JPS642612 B2 JP S642612B2 JP 15280084 A JP15280084 A JP 15280084A JP 15280084 A JP15280084 A JP 15280084A JP S642612 B2 JPS642612 B2 JP S642612B2
- Authority
- JP
- Japan
- Prior art keywords
- divalent
- group
- tetraphenylthiophene
- general formula
- polyamide
- 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.)
- Expired
Links
- 239000004962 Polyamide-imide Substances 0.000 claims description 30
- 229920002312 polyamide-imide Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- MQFBWJOMLIHUDY-UHFFFAOYSA-N 2,3,4,5-tetraphenylthiophene Chemical group C1=CC=CC=C1C1=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)S1 MQFBWJOMLIHUDY-UHFFFAOYSA-N 0.000 claims description 23
- 150000004985 diamines Chemical class 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- -1 trimellitic anhydride halide Chemical class 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RQXOOKSFELPROF-UHFFFAOYSA-N 4-[5-(4-aminophenyl)-3,4-diphenylthiophen-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C(C=2C=CC(N)=CC=2)S1 RQXOOKSFELPROF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- RZFOAVRHEGQZRV-UHFFFAOYSA-N 2,3-diphenylthiophene Chemical compound S1C=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 RZFOAVRHEGQZRV-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
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- 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
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical compound C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OKBVMLGZPNDWJK-UHFFFAOYSA-N naphthalene-1,4-diamine Chemical compound C1=CC=C2C(N)=CC=C(N)C2=C1 OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- HBJPJUGOYJOSLR-UHFFFAOYSA-N naphthalene-2,7-diamine Chemical compound C1=CC(N)=CC2=CC(N)=CC=C21 HBJPJUGOYJOSLR-UHFFFAOYSA-N 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KTQYWNARBMKMCX-UHFFFAOYSA-N tetraphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C2=C1 KTQYWNARBMKMCX-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 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)
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は新規なポリアミドイミド樹脂および
その製造方法、特に有機溶媒に可溶で、かつ高い
ガラス転移点及び優れた耐熱性を有する新規なポ
リアミドイミド樹脂及びその製造方法に関するも
のである。Detailed Description of the Invention (Field of Industrial Application) This invention relates to a novel polyamide-imide resin and a method for producing the same, particularly a novel polyamide resin that is soluble in organic solvents, has a high glass transition point, and has excellent heat resistance. This invention relates to an imide resin and a method for producing the same.
（従来の技術）
従来全芳香族ポリアミドイミド樹脂は優れた機
械的特性を有し、工業材料として使用されてき
た。これらのポリアミドイミド樹脂は有機溶媒に
対して比較的良好な溶解性を示す。このようなポ
リアミドイミド樹脂については、例えばダブルユ
ー・エム・アルビノ（W.M.Alvino）の報告があ
る（Journal of Applied Polymer Science第19
巻第673頁、1975年）
（発明が解決しようとする問題点）
しかしながら、前記の従来の全芳香族ポリアミ
ドイミド樹脂はそのガラス転移点が低く、耐熱性
に問題がある。(Prior Art) Conventionally, wholly aromatic polyamideimide resins have excellent mechanical properties and have been used as industrial materials. These polyamideimide resins exhibit relatively good solubility in organic solvents. Regarding such polyamide-imide resin, for example, there is a report by WM Alvino (Journal of Applied Polymer Science No. 19).
Vol. 673, 1975) (Problems to be Solved by the Invention) However, the conventional wholly aromatic polyamideimide resins described above have a low glass transition point and a problem in heat resistance.
したがつてこの発明の目的は有機溶媒に可溶
で、かつ高いガラス転移点を有して耐熱性の改良
された新規なポリアミドイミド樹脂を提供するこ
とである。 Therefore, an object of the present invention is to provide a novel polyamide-imide resin which is soluble in organic solvents, has a high glass transition point, and has improved heat resistance.
また、この発明の他の目的は前記新規ポリアミ
ドイミド樹脂の製造方法を提供することである。 Another object of the present invention is to provide a method for producing the novel polyamideimide resin.
（問題点を解決するための手段）
本発明者らは前記問題の解決について鋭意研究
を重ねた結果、芳香族ジアミン部の芳香族残基又
はその少なくとも一部として二価のテトラフエニ
ルチオフエン基を用いることにより前記目的に適
合しうることを確かめ、この発明を達成するに至
つた。(Means for Solving the Problems) As a result of extensive research into solving the above-mentioned problems, the present inventors have found that divalent tetraphenylthiophene is used as the aromatic residue or at least a part of the aromatic diamine moiety. It was confirmed that the above object could be achieved by using the group, and the present invention was achieved.
この発明の第一の発明は、一般式
（式中、ArはArが１種の場合は二価のテトラフ
エニルチオフエン基、Arが２種以上の場合はそ
の中の１種として二価のテトラフエニルチオフエ
ン基、他の種として二価の芳香族基、ｎは10〜
200の整数を示す）
で表されるポリアミドイミド樹脂である。 The first invention of this invention is the general formula (In the formula, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and when there are two or more types of Ar, one of them is a divalent tetraphenylthiophene group, and the other type is a divalent tetraphenylthiophene group. as a divalent aromatic group, n is 10~
(representing an integer of 200) is a polyamide-imide resin.
この発明の第二の発明は、一般式
（式中、ArはArが１種の場合は二価のテトラフ
エニルチオフエン基、Arが２種以上の場合はそ
の中の１種として二価のテトラフエニルチオフエ
ン基、他の種として二価の芳香族基、ｎは10〜
200の整数を示す）
で表されるポリアミドイミド樹脂を製造するに当
り、一般式
H2N−Ar−NH2 （）
（式中、ArはArが１種の場合は二価のテトラフ
エニルチオフエン基、Arが２種以上の場合はそ
の中の１種として二価のテトラフエニルチオフエ
ン基、他の種として二価の芳香族基を示す）
で表されるジアミンの１種又は２種以上と、一般
式
（式中、Ｘはハロゲン原子を示す）
で表される無水トリメツト酸ハライドとを有機溶
媒中で反応させるポリアミドイミド樹脂の製造方
法である。 The second invention of this invention is the general formula (In the formula, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and when there are two or more types of Ar, one of them is a divalent tetraphenylthiophene group, and the other type is a divalent tetraphenylthiophene group. as a divalent aromatic group, n is 10~
In manufacturing a polyamideimide resin represented by the general formula H 2 N-Ar-NH 2 () (indicates an integer of 200), Ar is a divalent tetraphenylene resin when one type of Ar is present. (If Ar is two or more types, one of them is a divalent tetraphenylthiophene group, and the other is a divalent aromatic group); or 2 or more types and general formula (In the formula, X represents a halogen atom) This is a method for producing a polyamideimide resin, in which a trimethic anhydride halide represented by the following formula is reacted in an organic solvent.
上記一般式（）で表されるポリアミドイミド
樹脂は上記一般式（）で表されるジアミンと上
記一般式（）で表わされる無水トリメツト酸ハ
ライドから製造されるが、ジアミンとしては上記
（）のArが二価のテトラフエニルチオフエン基
からなるジアミンを単独で使用することもできる
し、あるいは20〜99モル％の上記Arがテトラフ
エニルチオフエン基からなるジアミンに、80〜１
モル％の上記Arが１種又は２種以上の二価の芳
香族基からなるジアミンを混合して使用すること
もできる。ジアミンを混合して使用する場合二価
のテトラフエニルチオフエン基からなるジアミン
が20モル％未満となるとこの発明の特徴であるガ
ラス転移点の上昇をじゆうぶん満足しなくなる。 The polyamide-imide resin represented by the above general formula () is manufactured from the diamine represented by the above general formula () and the trimethic anhydride halide represented by the above general formula (). A diamine consisting of a divalent tetraphenylthiophene group can be used alone, or a diamine consisting of a tetraphenylthiophene group in which 20 to 99 mol% of Ar is divalent, and 80 to 1
It is also possible to use a mixture of diamines in which the mole % of the above Ar is composed of one or more divalent aromatic groups. When using a mixture of diamines, if the diamine consisting of divalent tetraphenylthiophene groups is less than 20 mol %, the increase in glass transition point, which is a feature of the present invention, will not be sufficiently satisfied.
上記一般式（）で表されるジアミンのうち、
Arが二価のテトラフエニルチオフエン基からな
るジアミンとは２，５−ビス（４−アミノフエニ
ル）−３，４−ジフエニルチオフエンを指す。こ
のジアミンは工業的に安価に入手できる塩化ベン
ジルとイオウを原料に製造できることが知られて
いる。例えばベー・デイルテイら（W.Dilthey）
によりジユルナール・プラクテイツシユ・ヘミー
（J.Prakt.Chem.）第２巻第151頁と第257頁
（1938年）に発表されている。 Among the diamines represented by the above general formula (),
The diamine in which Ar is a divalent tetraphenylthiophene group refers to 2,5-bis(4-aminophenyl)-3,4-diphenylthiophene. It is known that this diamine can be produced from benzyl chloride and sulfur, which are industrially available at low cost. For example, W. Dilthey et al.
Published in J.Prakt.Chem., Volume 2, pages 151 and 257 (1938).
上記一般式（）で表されるジアミンのうち、
二価の芳香族基からなるジアミンとしては、メタ
フエニレンジアミン、パラフエニレンジアミン、
３，3′−ジアミノビフエニル、４，4′−ジアミノ
ビフエニル、３，3′−メチレンジアニリン、４，
4′−メチレンジアニリン、４，4′−エチレンジア
ニリン、４，4′−イソプロピリデンジアニリン、
３，3′−オキシジアニリン、４，4′−オキシジア
ニリン、３，4′−オキシジアニリン、３，3′−チ
オジアニリン、４，4′−チオジアニリン、３，
3′−カルボニルジアニリン、４，4′−カルボニル
ジアニリン、３，3′−スルホニルジアニリン、
４，4′−スルホニルジアニリン、１，４−ナフタ
レンジアミン、１，５−ナフタレンジアミン、
３，６−ナフタレンジアミン等を例示することが
できる。 Among the diamines represented by the above general formula (),
Examples of diamines consisting of divalent aromatic groups include metaphenylenediamine, paraphenylenediamine,
3,3'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-methylene dianiline, 4,
4'-methylene dianiline, 4,4'-ethylene dianiline, 4,4'-isopropylidene dianiline,
3,3'-oxydianiline, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-thiodianiline, 4,4'-thiodianiline, 3,
3'-carbonyl dianiline, 4,4'-carbonyl dianiline, 3,3'-sulfonyl dianiline,
4,4'-sulfonyldianiline, 1,4-naphthalenediamine, 1,5-naphthalenediamine,
Examples include 3,6-naphthalenediamine.
上記一般式（）で表される無水トリメリツト
酸ハライドのハロゲン原子としては、フツ素、塩
素及び臭素を例示することができる。 Examples of the halogen atom of the trimellitic anhydride halide represented by the above general formula () include fluorine, chlorine, and bromine.
上記一般式（）で表されるポリアミドイミド
樹脂の製造方法は、有機溶媒中、上記一般式
（）で表されるジアミン化合物と、上記一般式
（）で表される無水トリメリツト酸ハライドと
を−20〜100℃で数分間から数日間反応させるこ
とにより、一般式
（式中、ArはArが１種の場合は二価のテトラフ
エニルチオフエン基、Arが２種以上の場合はそ
の中の１種として二価のテトラフエニルチオフエ
ン基、他の種として二価の芳香族基、ｎは10〜
200の整数を示す）
で表されるポリアミドアミド酸を中間体として製
造し、次いで該中間体より従来ポリイミド樹脂の
製造に用いられている脱水環化法、例えばシー・
イー・スルーグ（C.E.Sroog）マクロモレキユラ
ー・シンセシス（Macromolecular Synthesis）
コレクテイブボリユーム第１巻、第295頁（1977
年）に記載された方法等により、一般式（）で
表されるポリアミドイミド樹脂を製造するもので
ある。 A method for producing a polyamide-imide resin represented by the above general formula () includes a diamine compound represented by the above general formula () and a trimellitic anhydride halide represented by the above general formula () in an organic solvent. By reacting at 20 to 100℃ for several minutes to several days, the general formula (In the formula, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and when there are two or more types of Ar, one of them is a divalent tetraphenylthiophene group, and the other type is a divalent tetraphenylthiophene group. as a divalent aromatic group, n is 10~
(representing an integer of 200) is produced as an intermediate, and then the intermediate is subjected to dehydration and cyclization methods conventionally used in the production of polyimide resins, such as C.
CESroog Macromolecular Synthesis
Collective Volume Volume 1, Page 295 (1977
A polyamide-imide resin represented by the general formula () is produced by the method described in 2010).
この方法において一般式（）で表されるポリ
アミドイミド樹脂の分子量は一般式（）で表さ
れるジアミン化合物と一般式（）で表される無
水トリメリツト酸ハライドの仕込量によつて制限
され、これらの反応成分を等モル量使用すると高
分子量の上記一般式（）で表されるポリアミド
イミド樹脂を製造することができる。一般式
（）で表されるポリアミドイミド樹脂において
ｎを10〜200の整数に限定した理由は、ｎが10よ
り小ではフイルム等に成形した成形品の機械的特
性や耐熱性等の特性がじゆうぶんでなく、ｎが
200を超えると有機溶媒等への溶解性が悪くなる
からである。 In this method, the molecular weight of the polyamideimide resin represented by the general formula () is limited by the amount of the diamine compound represented by the general formula () and the trimellitic anhydride halide represented by the general formula (). When the reaction components are used in equimolar amounts, a high molecular weight polyamide-imide resin represented by the above general formula () can be produced. The reason why n is limited to an integer between 10 and 200 in the polyamide-imide resin represented by the general formula () is that if n is smaller than 10, the mechanical properties and heat resistance of the molded product, such as a film, will be affected. Not just, but n is
This is because if it exceeds 200, the solubility in organic solvents etc. will deteriorate.
この方法に使用できる有機溶媒としては、Ｎ，
Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルア
セトアミド、Ｎ−メチル−２−ピロリドン等のア
ミド系溶媒、ベンゼン、アニソール、ジフエニル
エーテル、ニトロベンゼン、ベンゾニトリルのよ
うな芳香族系溶媒、クロロホルム、ジクロロメタ
ン、１，２−ジクロロエタン、１，１，２，２−
テトラクロロエタンのようなハロゲン系溶媒等を
例示することができる。このような有機溶媒と共
にピリジン、トリエチルアミンなどの酸受容体を
共存させて反応を行うと効果的である。特にＮ，
Ｎ−ジメチルアセトアミドや、Ｎ−メチル−２−
ピロリドン等のアミド溶媒を使用すると、これら
の溶媒自身が酸受容体となり、高重合体のポリア
ミドイミド樹脂を得ることができる。 Organic solvents that can be used in this method include N,
Amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, chloroform, dichloromethane, 1 ,2-dichloroethane, 1,1,2,2-
Examples include halogenated solvents such as tetrachloroethane. It is effective to carry out the reaction in the presence of an acid acceptor such as pyridine or triethylamine together with such an organic solvent. Especially N,
N-dimethylacetamide, N-methyl-2-
When amide solvents such as pyrrolidone are used, these solvents themselves become acid acceptors, and a high polymer polyamide-imide resin can be obtained.
かくして製造された一般式（）で表されるポ
リアミドイミド樹脂は、使用した一般式（）で
表されるジアミンの種類により、特にその溶解性
が変化するが、Ｎ，Ｎ−ジメチルホルムアミド、
Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホ
キシド、ｍ−クレゾール、ピリジン等の溶媒のす
べてに、または一部に可溶となる。上記一般式
（）で表されるポリアミドイミド樹脂は、300℃
付近までガラス転移点が観測されず、400℃付近
まで加熱しても顕著な重量変化は認められない。 The solubility of the thus produced polyamide-imide resin represented by the general formula () changes depending on the type of diamine represented by the general formula () used, but it can be used in N,N-dimethylformamide, N,N-dimethylformamide,
It becomes soluble in all or part of solvents such as N,N-dimethylacetamide, dimethylsulfoxide, m-cresol, and pyridine. The polyamide-imide resin represented by the above general formula () is heated at 300°C.
No glass transition point was observed up to around 400°C, and no significant weight change was observed even when heated to around 400°C.
（実施例）
以下この発明を実施例により、更に詳細に説明
する。(Examples) The present invention will be explained in more detail below with reference to Examples.
実施例 １
２，５−ジ（４−アミノフエニル）−３，４−
ジフエニルチオフエン2.090ｇ（５ｍmol）とト
リエチルアミン0.505ｇ（５ｍmol）とを18.23ml
のジメチルアセトアミドに溶解した。この溶液を
０℃に冷却し、この温度で無水トリメリツト酸フ
ロリド1.052ｇ（５ｍmol）を一度に加えた。窒
素気流下、室温で３時間撹拌後、溶液を10mlのジ
メチルアセトアミドを希釈し、500mlのメタノー
ルへ投入してポリアミドアミド酸の沈殿を得た。
収量2.89ｇ（98％）ポリアミドアミド酸の固有粘
度は0.44（0.5ｇ／dlの濃度、ジメチルアセトアミ
ド中、30℃で測定）であつた。Example 1 2,5-di(4-aminophenyl)-3,4-
18.23ml of diphenylthiophene 2.090g (5mmol) and triethylamine 0.505g (5mmol)
of dimethylacetamide. The solution was cooled to 0° C. and at this temperature 1.052 g (5 mmol) of trimellitic anhydride was added in one portion. After stirring for 3 hours at room temperature under a nitrogen stream, the solution was diluted with 10 ml of dimethylacetamide and poured into 500 ml of methanol to obtain a precipitate of polyamide amic acid.
The yield of 2.89 g (98%) polyamide amic acid had an intrinsic viscosity of 0.44 (measured at 30° C. in dimethylacetamide at a concentration of 0.5 g/dl).
赤外線吸収スペクトル
（KBr）cm-1：1720、1650、1590、1480、700
得られたポリアミドアミド酸をジメチルアセト
アミド溶液よりガラス板上に流延し、フイルムを
得た。このフイルムを窒素気流下180〜220℃で加
熱し、ポリアミドイミドのフイルムを得た。Infrared absorption spectrum (KBr) cm -1 : 1720, 1650, 1590, 1480, 700 The obtained polyamide amic acid was cast onto a glass plate from a dimethylacetamide solution to obtain a film. This film was heated at 180 to 220°C under a nitrogen stream to obtain a polyamideimide film.
赤外線吸収スペクトル
（フイルム）cm-1：1780、1720、1675、720
熱重量測定法による10％重量減少温度は、窒素
気流下で600℃、空気中で580℃であつた。熱機械
分析法によるガラス転移点は330℃であつた。ポ
リアミドイミドフイルムは、濃硫酸、ｍ−クレゾ
ール、ｎ−メチル−２−ピロリドンなどに易容で
あつた。Infrared absorption spectrum (film) cm -1 : 1780, 1720, 1675, 720 The 10% weight loss temperature measured by thermogravimetry was 600°C under a nitrogen stream and 580°C in air. The glass transition point determined by thermomechanical analysis was 330°C. The polyamide-imide film was easily treated with concentrated sulfuric acid, m-cresol, n-methyl-2-pyrrolidone, and the like.
実施例 ２
実施例１と同様の操作により、２，５−ジ（４
−アミノフエニル）−３，４−ジフエニルチオフ
エン1.045ｇ（2.5ｍmol）、４，4′−オキシジアニ
リン0.490ｇ（2.5ｍmol）と無水トリメリツト酸
クロリド1.052ｇ（５ｍmol）からポリアミド酸
2.40ｇ（99％）を得た。固有粘度は0.49（0.5ｇ／
dlの濃度、ジメチルアセトアミド中30℃で測定）
であつた。更にこのものの熱処理により、ポリア
ミドイミドのフイルムを得た。熱重量測定法によ
る10％重量減少温度は、窒素中560℃、空気中540
℃であつた。Example 2 By the same operation as in Example 1, 2,5-di(4
-Aminophenyl)-3,4-diphenylthiophene 1.045g (2.5mmol), 4,4'-oxydianiline 0.490g (2.5mmol) and trimellitic anhydride 1.052g (5mmol) to polyamic acid
Obtained 2.40g (99%). Intrinsic viscosity is 0.49 (0.5g/
dl concentration, measured in dimethylacetamide at 30 °C)
It was hot. Further, this product was heat-treated to obtain a polyamideimide film. The 10% weight loss temperature by thermogravimetry is 560°C in nitrogen and 540°C in air.
It was warm at ℃.
機械分析法によるガラス転移点は300℃であつ
た。得られたポリアミドイミドフイルムは、濃硫
酸、ｍ−クレゾール、ジメチルスルホキシド、Ｎ
−メチル−２−ピロリドン及びピリジンに易容で
あつた。 The glass transition point determined by mechanical analysis was 300°C. The obtained polyamide-imide film was prepared using concentrated sulfuric acid, m-cresol, dimethyl sulfoxide, N
-Methyl-2-pyrrolidone and pyridine.
参考例 １
実施例１と同様の操作により、４，4′−オキシ
ジアニリン１ｇ（５ｍmol）と無水トリメリツト
酸クロリド1.052ｇ（５ｍmol）からポリアミド
アミド酸1.85ｇ（99％）を得た。固有粘度は0.51
（0.5ｇ／dlの濃度、ジメチルアセトアミド中30℃
で測定）であつた。Reference Example 1 In the same manner as in Example 1, 1.85 g (99%) of polyamideamic acid was obtained from 1 g (5 mmol) of 4,4'-oxydianiline and 1.052 g (5 mmol) of trimellitic anhydride chloride. Intrinsic viscosity is 0.51
(concentration of 0.5 g/dl, 30°C in dimethylacetamide)
).
さらにこのものの熱処理により、ポリアミドイ
ミドのフイルムを得た。熱重量測定法による10％
重量減少温度は窒素中510℃、空気中495℃あつ
た。 Further, this material was heat-treated to obtain a polyamideimide film. 10% by thermogravimetry
The weight loss temperature was 510°C in nitrogen and 495°C in air.
機械分析法によるガラス転移点は260℃であつ
た。得られたポリアミドイミドフイルムは濃硫
酸、ｍ−クレゾール、Ｎ−メチル−２−ピロリド
ン、ジメチルスルホキシド等に易溶であつた。 The glass transition point determined by mechanical analysis was 260°C. The obtained polyamide-imide film was easily soluble in concentrated sulfuric acid, m-cresol, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like.
（発明の効果）
この発明は一般式（）で表される新規ポリア
ミドイミド樹脂およびその有利な製造方法を提供
する。従来のポリアミドイミド樹脂が有機溶媒に
可溶でありながらガラス転移点が比較的低かつた
のに対して、この発明のポリアミドイミド樹脂は
有機溶媒に可溶で成形が容易であり、しかも高ガ
ラス転移点を有するために優れた耐熱性を有する
ので工業材料としての価値が大きい。(Effects of the Invention) The present invention provides a novel polyamideimide resin represented by the general formula () and an advantageous method for producing the same. While conventional polyamide-imide resins are soluble in organic solvents and have a relatively low glass transition point, the polyamide-imide resin of the present invention is soluble in organic solvents, easy to mold, and has a high glass transition point. Since it has a transition point and has excellent heat resistance, it is of great value as an industrial material.
Claims (1)
エニルチオフエン基、Arが２種以上の場合はそ
の中の１種として二価のテトラフエニルチオフエ
ン基、他の種として二価の芳香族基、ｎは10〜
200の整数を示す） で表されるポリアミドイミド樹脂。 ２ 一般式 （式中、ArはArが１種の場合は二価のテトラフ
エニルチオフエン基、Arが２種以上の場合はそ
の中の１種として二価のテトラフエニルチオフエ
ン基、他の種として二価の芳香族基、ｎは10〜
200の整数を示す） で表されるポリアミドイミド樹脂を製造するに当
り、一般式 H2N−Ar−NH2 （式中、ArはArが１種の場合は二価のテトラフ
エニルチオフエン基、Arが２種以上の場合はそ
の中の１種として二価のテトラフエニルチオフエ
ン基、他の種として二価の芳香族基を示す） で表されるジアミンの１種又は２種以上と、一般
式 （式中、Ｘはハロゲン原子を示す） で表される無水トリメリツト酸ハライドとを有機
溶媒中で反応させることを特徴とするポリアミド
イミド樹脂の製造方法。[Claims] 1. General formula (In the formula, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and when there are two or more types of Ar, one of them is a divalent tetraphenylthiophene group, and the other type is a divalent tetraphenylthiophene group. as a divalent aromatic group, n is 10~
(representing an integer of 200) is a polyamide-imide resin. 2 General formula (In the formula, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and when there are two or more types of Ar, one of them is a divalent tetraphenylthiophene group, and the other type is a divalent tetraphenylthiophene group. as a divalent aromatic group, n is 10~
(representing an integer of 200), the general formula H 2 N-Ar-NH 2 (wherein, Ar is a divalent tetraphenylthiophene when there is only one type of Ar) is used. If there are two or more types of Ar, one type of diamine is a divalent tetraphenylthiophene group, and the other type is a divalent aromatic group). Above, general formula (wherein, X represents a halogen atom) A method for producing a polyamide-imide resin, which comprises reacting trimellitic anhydride halide represented by the formula (wherein, X represents a halogen atom) in an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15280084A JPS6131432A (en) | 1984-07-25 | 1984-07-25 | Polyamide-imide resin and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15280084A JPS6131432A (en) | 1984-07-25 | 1984-07-25 | Polyamide-imide resin and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6131432A JPS6131432A (en) | 1986-02-13 |
| JPS642612B2 true JPS642612B2 (en) | 1989-01-18 |
Family
ID=15548425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15280084A Granted JPS6131432A (en) | 1984-07-25 | 1984-07-25 | Polyamide-imide resin and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6131432A (en) |
-
1984
- 1984-07-25 JP JP15280084A patent/JPS6131432A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6131432A (en) | 1986-02-13 |
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