JPH0218421A - Production of polyamide-imide - Google Patents
Production of polyamide-imideInfo
- Publication number
- JPH0218421A JPH0218421A JP16685988A JP16685988A JPH0218421A JP H0218421 A JPH0218421 A JP H0218421A JP 16685988 A JP16685988 A JP 16685988A JP 16685988 A JP16685988 A JP 16685988A JP H0218421 A JPH0218421 A JP H0218421A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- component
- acid
- polycondensation
- formula
- 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
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 19
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000004985 diamines Chemical class 0.000 claims abstract description 15
- -1 aromatic tricarboxylic acid Chemical class 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000007790 solid phase Substances 0.000 claims description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 abstract description 11
- 150000008064 anhydrides Chemical class 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000004642 Polyimide Substances 0.000 abstract 1
- 229920001721 polyimide Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 64
- 238000000034 method Methods 0.000 description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- VBIWIGSLGRYEDA-UHFFFAOYSA-N 1,3,5-triethyl-1,3,5-triazinane-2,4,6-trione Chemical compound CCN1C(=O)N(CC)C(=O)N(CC)C1=O VBIWIGSLGRYEDA-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
- UPGLMYCVFCOYJV-UHFFFAOYSA-N 1-phenoxy-4-(4-phenoxyphenyl)sulfonylbenzene Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1S(=O)(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 UPGLMYCVFCOYJV-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-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
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- IJTZNPJNLORUJM-UHFFFAOYSA-N 4-[6-(1,3-dioxoisoindol-4-yl)hexyl]isoindole-1,3-dione Chemical compound O=C1NC(=O)C2=C1C=CC=C2CCCCCCC1=CC=CC2=C1C(=O)NC2=O IJTZNPJNLORUJM-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 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
- 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction 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
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はポリアミドイミドの［ｉ方法に関し、更に詳し
くは溶融成形が可能でかつ機械特性、耐熱性に優れた芳
香族ポリアミドイミドを効率よく製造する方法に関する
。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing polyamide-imide, and more specifically, to efficiently produce aromatic polyamide-imide that can be melt-molded and has excellent mechanical properties and heat resistance. Regarding how to.
〈従来技術〉
トリメリット酸無水物またはその官能性誘導体と芳香族
ジアミンまたはその官能性Ｆｆｇ導体との反応により各
種のポリドーリメリットアミドイミドが得られることは
よく知られている。これらのうち芳香族ジアミンとして
３．４′ −ジアミノジフェニルエーテルを用いたもの
は成形性に優れた耐熱性樹脂としてその製造法が検討さ
れている。<Prior Art> It is well known that various polydorimellitamide imides can be obtained by reacting trimellitic anhydride or its functional derivative with an aromatic diamine or its functional Ffg conductor. Among these, those using 3,4'-diaminodiphenyl ether as the aromatic diamine are being considered as heat-resistant resins with excellent moldability, and their production methods are being investigated.
例えば、米国特許第３８６０５５９号には、アミド系あ
るいはフェノール糸溜剤中リン化合物を触媒としてトリ
メリット酸無水物と芳香族ジアミンとを加熱重縮合する
方法が記載されている。また欧州特許公開第０２１０８
５１号及び特開昭６３−１０６３０号には、生成するポ
リマ“−と相溶し得る低分子化合物（例えばジフェニル
スルホン）の存在下においてトリメリット酸無水物と３
．４１−ジアミノジフェニルエーテルを加熱重縮合する
方法が記載されている。For example, US Pat. No. 3,860,559 describes a method of thermally polycondensing trimellitic anhydride and aromatic diamine using a phosphorus compound in an amide or phenolic thread collecting agent as a catalyst. Also, European Patent Publication No. 02108
No. 51 and JP-A No. 63-10630 disclose that trimellitic anhydride and 3
．． A method for thermal polycondensation of 41-diaminodiphenyl ether is described.
上記の各方法は無溶媒では高粘度のため溶融重合困難な
ポリアミドイミドを溶解乃至可塑化して溶融重合するも
のであるが、これらの方法では重合に極めて長時間を要
し、重合反応が終了した組成物から溶剤もしくは低分子
化合物を除去してポリマーを分離する工程が必須である
ため、工程が煩雑となる上、得られたポリマーが分岐状
になりやすいという問題がある。分岐状ポリマーは見か
け上重合度は高くても、その成形品の機械特性は極めて
不十分なものとなり好ましくない。Each of the above methods melts or plasticizes and melt-polymerizes polyamide-imide, which is difficult to melt-polymerize without a solvent due to its high viscosity. Since a step of separating the polymer by removing the solvent or low-molecular compound from the composition is essential, there are problems in that the step is complicated and the obtained polymer is likely to have a branched shape. Although branched polymers have an apparently high degree of polymerization, the mechanical properties of molded products made using branched polymers are extremely unsatisfactory, making them undesirable.
このポリマーの分岐を防ぐ方法として、芳香族ジアミン
の代りにその低級脂肪酸アミドを用いる方法が考えられ
るが、この方法では芳香族ジアミンを用いる場合より更
に重合反応が遅くなるという問題がある。One possible method for preventing this branching of the polymer is to use a lower fatty acid amide instead of the aromatic diamine, but this method has the problem that the polymerization reaction is slower than when aromatic diamine is used.
〈発明の目的〉
本発明の目的は、従来法の問題を解潤し、線状で高重合
瓜のポリアミドイミドを効率よく工業的に有利に製造す
る方法を提供することにある。<Object of the Invention> An object of the present invention is to solve the problems of conventional methods and to provide a method for efficiently and industrially advantageously producing a linear, highly polymerized melon polyamide-imide.
〈発明の構成〉
かかる本発明の目的は、（Ａ）芳香族トリカルボン酸及
び／またはその酸無水物と（Ｂ）下記式（Ｉ）で示され
るジアミン成分とを、
加熱重縮合することを特徴とするポリアミドイミドの製
造方法によって達成することができる。<Structure of the Invention> The object of the present invention is to perform thermal polycondensation of (A) aromatic tricarboxylic acid and/or its acid anhydride and (B) a diamine component represented by the following formula (I). This can be achieved by the method for producing polyamideimide.
以下、本発明の方法について詳述する。The method of the present invention will be explained in detail below.
本発明方法において（Ａ）成分として用いる芳香族トリ
カルボン酸は、下記一般式（ＩＩＩ）で表わされる化合
物である。The aromatic tricarboxylic acid used as component (A) in the method of the present invention is a compound represented by the following general formula (III).
ＯＯＣ
＼
Ａｒ −ＣＯＯＨ・・・（ＩＮ）
／
ＯＯＣ
［但し、式中Ａｒは２つの結合手の位置が隣接する、３
価の芳香族基である］
上記一般式（ＩＩＩ）におけるＡ−ｒ（３価の芳香族具
体的化合物としてはトリメリット酸が特に好ましい。OOC \ Ar -COOH...(IN) / OOC [However, in the formula, Ar indicates that the two bond positions are adjacent, 3
is a trivalent aromatic group] A-r in the above general formula (III) (as a specific trivalent aromatic compound, trimellitic acid is particularly preferred.
更に、本発明方法において（Ａ）成分として用いる芳香
族トリカルボン酸の酸無水物は、上記−般式（ＩＩＩ）
で表わされる化合物の酸無水物であり、特にトリメリッ
ト酸無水物が好ましい。Furthermore, the acid anhydride of aromatic tricarboxylic acid used as component (A) in the method of the present invention has the above general formula (III).
It is an acid anhydride of a compound represented by, and trimellitic anhydride is particularly preferred.
本発明方法においては、上記芳香族トリカルボン酸及び
／又はその酸無水物の一部を、ジカルボン酸、テトラカ
ルボン酸、テトラカルボン酸無水物等で置換しても良い
。かかる化合物の具体例としては、テレフタル酸、イソ
フタル酸、ナフタレンジカルボン酸、ジフェニルジカル
ボン酸、コハク酸、アジピン酸、セパチン酸、デカンジ
カルボン酸、シクロヘキサンジカルボン酸、ビ０メリツ
ト酸、ピロメリット酸無水物、ジフェニルテトラカルボ
ン酸、ジフェニルテトラカルボン酸無水物。In the method of the present invention, a portion of the aromatic tricarboxylic acid and/or its acid anhydride may be replaced with dicarboxylic acid, tetracarboxylic acid, tetracarboxylic acid anhydride, or the like. Specific examples of such compounds include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, succinic acid, adipic acid, cepatic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, bimellitic acid, pyromellitic anhydride, Diphenyltetracarboxylic acid, diphenyltetracarboxylic anhydride.
ベンゾフェノンテトラカルボン酸、ベンゾフェノンテト
ラカルボン酸無水物等があげられる。これらは全酸成分
当り、４０モル％以下、更には３０モル％以下、特に２
０モル％以下の割合で用いることが好ましい。Examples include benzophenonetetracarboxylic acid and benzophenonetetracarboxylic anhydride. These are 40 mol% or less, further 30 mol% or less, especially 2
It is preferable to use it in a proportion of 0 mol% or less.
方、本発明方法において（Ｂ）成分として用いるジアミ
ン成分は、下記式（Ｉ）で示される化合物である。On the other hand, the diamine component used as component (B) in the method of the present invention is a compound represented by the following formula (I).
この式＜Ｉ）において、Ｒ＋ 、Ｒ２はＨ又はＲ３Ｇｏ
を示し、これらは夫々間−又は異っていてもよい。なお
Ｒ３は炭素数１〜３のアルキルを示し、具体的にはメチ
ル、エチル、プロピルを挙げることができる。Ｒ３とし
てはこれらのうちメチルが好ましい。上記式（Ｉ）にお
いてＲ１とＲ２は、その合計りに対して５〜６０モル％
がＨであり、９５〜４０モル％がＲ３Ｃ０であることが
必要である。従って（Ｂ）成分は、実質上、３．４′ジ
アミノジフエニルエーテル、そのモノアミド及びそのジ
アミドより選ばれた化合物からなる混合物である。In this formula <I), R+, R2 are H or R3Go
, and these may be different or different from each other. Note that R3 represents alkyl having 1 to 3 carbon atoms, and specific examples include methyl, ethyl, and propyl. Among these, methyl is preferred as R3. In the above formula (I), R1 and R2 are 5 to 60 mol% relative to their total
is H, and it is necessary that 95 to 40 mol% be R3C0. Therefore, component (B) is essentially a mixture consisting of a compound selected from 3,4' diaminodiphenyl ether, its monoamide, and its diamide.
本発明者らの研究によれば、芳香族カルボン酸と芳香族
アミンとからアミドが生成する反応速度は、芳香族カル
ボン酸と芳香族アミンの低級脂肪酸アミドとからアミド
が生成する反応速度とほぼ同程度であるが、酸無水物と
芳香族アミンとからイミドが生成する反応速度は、酸無
水物と芳香族アミンの低級脂肪酸アミドからイミドが生
成する反応速度及び上記アミド生成反応速度に比べ著し
く速いこと、及び、ジアミンを単独で用いた場合には、
該ジアミンの低級脂肪酸アミドを単独で用いた場合より
反応は速いが、この場合にはフリーのアミンが高温で長
時間さらされるため、得られるポリマーが分岐状となり
やすいことが判明した。According to the research of the present inventors, the reaction rate for producing an amide from an aromatic carboxylic acid and an aromatic amine is approximately the same as the reaction rate for producing an amide from an aromatic carboxylic acid and a lower fatty acid amide of an aromatic amine. However, the reaction rate for producing an imide from an acid anhydride and an aromatic amine is significantly higher than the reaction rate for producing an imide from a lower fatty acid amide between an acid anhydride and an aromatic amine, and the above-mentioned reaction rate for producing an amide. It is fast and when diamine is used alone,
Although the reaction is faster than when the lower fatty acid amide of the diamine is used alone, it has been found that in this case, the free amine is exposed to high temperature for a long time, so the resulting polymer tends to become branched.
本発明方法は、上記の知見に基づいて、上記Ａ成分（芳
香族トリカルボン酸）と反応させる成分（Ｂ成分）にお
いてその４０〜９５モル％を低級脂肪酸アミドとし、残
りをジアミンのままで反応させるものであり、かくして
イミド化反応は反応の速いアミンにより実施して重合速
度を高め、かつ得られるポリマーの分岐を防ぐようにし
たものである。Based on the above findings, the method of the present invention is based on the above-mentioned findings, in which 40 to 95 mol% of the component (B component) to be reacted with the A component (aromatic tricarboxylic acid) is a lower fatty acid amide, and the remainder is reacted with the diamine as it is. Thus, the imidization reaction is carried out using a fast-reacting amine to increase the polymerization rate and to prevent branching of the resulting polymer.
従って、本発明方法においては上記式（Ｉ）におけるＲ
１及びＲ２におけるＨとＲ３Ｇｏとの割合が重要であり
、上記式（Ｉ）においてＲ１とＲ２はその合計量に対し
て１０〜５５モル％がＨであることがより好ましく、１
５〜５０モル％がＨであることが特に好ましい。Therefore, in the method of the present invention, R in the above formula (I)
The ratio of H and R3Go in 1 and R2 is important, and in the above formula (I), it is more preferable that 10 to 55 mol% of R1 and R2 is H based on the total amount, and 1
It is particularly preferred that 5 to 50 mol % is H.
本発明方法において（Ｂ）成分として用いるジアミンと
しては、上記式（Ｉ）で示されるものの一部を下記の如
きジアミン及び／またはその低級脂肪酸アミドで置きか
えてもよい。As the diamine used as component (B) in the method of the present invention, a part of the diamine represented by the above formula (I) may be replaced with the following diamine and/or its lower fatty acid amide.
かかるジアミンとしては、具体的には、ｐ−フェニレン
ジアミン、ｍ−フェニレンジアミン、トリレンジアミン
、４．４′ −ジアミノジフェニルメタン、４．４’
−ジアミノジフェニルエーテル、３．４′−ジアミノジ
フェニルメタン、４，４′ −ジアミノジフェニル、３
，３′ −ジメチル−４，４′ジアミノジフエニル、４
，４′ −ジアミノベンゾフェノン、４，４′ 〒ジア
ミノジフェニルスルホン、３．３′−ジアミノジフェニ
ルスルホン、エチレンジアミン、テトラメチレンジアミ
ン、ヘキサメチレンジアミン、デカメチレンジアミン等
があげられる。またアミドを形成する低級脂肪酸として
は例えば酢酸、プロピオン酸等が挙げられるが、特に酢
酸が好ましい。これらは全ジアミン成分当り４０モル％
以下、更には３０モル％以下、特に２０モル％以下で用
いることが好ましい。ジアミンの使用割合は、通常（Ａ
）成分に対し実質的に当モルである。Specifically, such diamines include p-phenylenediamine, m-phenylenediamine, tolylenediamine, 4.4'-diaminodiphenylmethane, and 4.4'
-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl, 3
, 3'-dimethyl-4,4'diaminodiphenyl, 4
, 4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, ethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine and the like. Examples of lower fatty acids that form amide include acetic acid and propionic acid, with acetic acid being particularly preferred. These are 40 mol% based on the total diamine component
It is preferably used below, more preferably at most 30 mol%, especially at most 20 mol%. The proportion of diamine used is usually (A
) is substantially equimolar to the component.
本発明方法においては、（Ａ）成分及び（Ｂ）成分とと
もに少割合のアミノカルボン酸例えばｐ−アミノ安息香
酸、ｌ１１−アミノ安息香酸等を併用し、共重合させて
も良い。このアミノカルボン酸の割合は全繰返し単位当
り３０％以下、特に２０％以下が好ましい。In the method of the present invention, a small proportion of an aminocarboxylic acid such as p-aminobenzoic acid, 111-aminobenzoic acid, etc. may be used together with the components (A) and (B) for copolymerization. The proportion of this aminocarboxylic acid is preferably 30% or less, particularly 20% or less, based on all repeating units.
上記ジアミン成分（Ｂ）を重縮合に供する場合には上記
式（ｉ）で示される各成分、すなわち、３．４′−ジア
ミノジフェニルエーテル、そのモノアミドまたはジアミ
ド誘導体を上記式（Ｉ＞におけるＲ１とＲ２がその合計
量に対して５〜６０モル％がＨとなる割合で用いてもよ
いが、３．４１−ジアミノジフェニルエーテルと下記式
（Ｉ）で示される低級脂肪酸の酸無水物の所定回を用い
、Ｒ３Ｃｏ ０−ＯＣＲａ ・・・（ＩＩ）［Ｒ
ａは上記と同じ］
両者を重縮合反応容器中で反応させ、該反応系内におい
て実質上（Ｂ）成分を生成せしめるようにしてもよく、
工業的にはこの方法が最も有利である。When the above diamine component (B) is subjected to polycondensation, each component represented by the above formula (i), that is, 3,4'-diaminodiphenyl ether, its monoamide or diamide derivative, is combined with R1 and R2 in the above formula (I>). may be used in such a proportion that H accounts for 5 to 60 mol% of the total amount, but using a predetermined amount of 3,41-diaminodiphenyl ether and an acid anhydride of a lower fatty acid represented by the following formula (I). , R3Co 0-OCRa ... (II) [R
a is the same as above] Both may be reacted in a polycondensation reaction vessel to substantially produce component (B) within the reaction system,
This method is industrially the most advantageous.
本発明方法においては、いずれの場合も上記各成分を加
熱重縮合することにより目的とするポリアミドイミドが
得られる。かかる加熱重縮合反応は溶融状態、あるいは
同相状態で実施される。この際の反応温度は、好ましく
は２００〜３６０℃、より好ましくは２２０〜３５０℃
、特に好ましくは２４０〜３４０℃であり、反応によっ
て生成する水または低級脂肪酸を系外に留去させながら
行う。上述の反応温度は比較的低い温度から反応の進行
に従って徐々に昇温して行くことが好ましい。In the method of the present invention, the desired polyamide-imide can be obtained by heating and polycondensing the above-mentioned components in any case. Such heating polycondensation reaction is carried out in a molten state or in an in-phase state. The reaction temperature at this time is preferably 200 to 360°C, more preferably 220 to 350°C.
The temperature is particularly preferably 240 to 340°C, and the reaction is carried out while water or lower fatty acids produced by the reaction are distilled out of the system. It is preferable that the above-mentioned reaction temperature is gradually raised from a relatively low temperature as the reaction progresses.
その際の反応雰囲気は常圧、加圧、減圧のいずれでも良
いが、反応により生ずるｎ１生成物を系外に除去するた
め、常圧乃至減圧とすることが好ましい。また反応は窒
素ガス、アルゴンガス等の不活性ガス雰囲気下で行うこ
とが好ましい。The reaction atmosphere at this time may be normal pressure, increased pressure, or reduced pressure, but is preferably normal pressure or reduced pressure in order to remove the n1 product produced by the reaction from the system. Further, the reaction is preferably carried out under an inert gas atmosphere such as nitrogen gas or argon gas.
反応時間は特に制限はないが、好ましくは１０分〜５０
時間、より好ましくは１０分〜４０時間、特に好ましく
は３０分〜３０時間程度である。The reaction time is not particularly limited, but is preferably 10 minutes to 50 minutes.
The time is more preferably about 10 minutes to 40 hours, particularly preferably about 30 minutes to 30 hours.
上記重縮合により、Ｎ−メチル−２−ピロリドン中淵度
１９／ｄｉ、温度３５℃で測定した還元粘度が、０．４
以上のポリアミドイミドを得るようにするのが好ましい
。還元粘度が０．４より小さい場合得られる成形品の機
械特性が不十分となり好ましくない、、得られるポリマ
ーの還元粘度は、より好ましくは０．４５以上、特に好
ましくは０．５以上とする。As a result of the above polycondensation, the reduced viscosity of N-methyl-2-pyrrolidone measured at 19/di and a temperature of 35°C was 0.4.
It is preferable to obtain the above polyamideimide. If the reduced viscosity is less than 0.4, the resulting molded product will have insufficient mechanical properties, which is undesirable.The reduced viscosity of the resulting polymer is more preferably 0.45 or more, particularly preferably 0.5 or more.
上記重縮合の際、所望により、生成するポリマーと相溶
性を有し、かつ該ポリマーと実質的に非反応性である低
分子化合物を共存させることもできる。かかる低分子化
合物の使用は本発明方法では必須としないが、その可塑
化作用によりポリマーの溶融粘度を低下させ、高重合度
のポリマーを比較的低い粘度のままで重縮合することが
できるという利点を有する。During the polycondensation, if desired, a low-molecular compound that is compatible with the polymer to be produced and is substantially non-reactive with the polymer may also be present. Although the use of such a low-molecular compound is not essential to the method of the present invention, it has the advantage that its plasticizing action lowers the melt viscosity of the polymer, allowing polymers with a high degree of polymerization to be polycondensed while maintaining a relatively low viscosity. has.
かかる低分子化合物としては、例えばジフェニルスルホ
ン、４．４’ −ジフェノキシジフェニルスルホン、４
．４′ −ビス（４−または３−または２−オクチルフ
ェノキシ）ジフェニルスルホン等のスルホン系化合物、
トリエチルイソシアヌレート、トリブチルイソシアヌレ
ート等のイソアヌレート系化合物、ヘキサメチレンビス
フタルイミド、ドデカメチレン、ビスフタルイミド、４
．４′ −ビスフタルイミドジフェニルエーテル、Ｎ、
Ｎ’ −ビスオクチルビＯメリットイミド等のイミド系
化合物を例示することができる。Examples of such low molecular weight compounds include diphenylsulfone, 4,4'-diphenoxydiphenylsulfone, 4.
．． Sulfonic compounds such as 4'-bis(4- or 3- or 2-octylphenoxy)diphenylsulfone,
Isoanurate compounds such as triethyl isocyanurate and tributyl isocyanurate, hexamethylene bisphthalimide, dodecamethylene, bisphthalimide, 4
．． 4'-bisphthalimide diphenyl ether, N,
Examples include imide compounds such as N'-bisoctyl biO melitimide.
また、この際の低分子化合物の使用割合は生成するポリ
マーに対して好ましくは５〜２００ｆｆｉ ｆｆｉ％、
より好ましくは１０〜１００重量％、特に好ましくは２
０〜７０１聞％程度の量である。上記低分子化合物を使
用した場合９目的とするポリアミドイミドは低分子化合
物との混合物として得られるが、その場合は、混合物の
まま成形に供してもよいし、低分子化合物を分離してか
ら成形に供してもよい。In addition, the proportion of the low-molecular compound used in this case is preferably 5 to 200 ffi ffi%, based on the produced polymer.
More preferably 10 to 100% by weight, particularly preferably 2
The amount is about 0 to 701%. When the above-mentioned low-molecular-weight compounds are used, the desired polyamide-imide can be obtained as a mixture with the low-molecular-weight compounds, but in that case, the mixture may be subjected to molding as is, or the low-molecular-weight compounds may be separated and then molded. You may also serve it.
低分子化合物の分離は該低分子化合物のみを溶解する有
機溶剤による抽出処理等により行うことが１きる。Separation of low molecular weight compounds can be carried out by extraction treatment with an organic solvent that dissolves only the low molecular weight compounds.
本発明の目的とするポリアミドイミドは、溶融粘度が高
く、上記低分子化合物を使用しない場合、溶ｍ１ｔｔ合
可能な範囲内では十分な高重合度のポリマーを得ること
は困難となる。しかし、本発明方法１は、溶ｍ重合した
ポリマーを、更に固相重縮合することにより、より高重
合度のポリマーを得ることができる。溶融重縮合に引続
いて固相重縮合する場合には、溶ｍ重綜合段階において
前述の条件下において測定した還元粘度が０．２以上と
なるまで重縮合することが好ましい。還元粘度が０．２
より小さい場合には固相重縮合工程において長時間を要
するため好ましくない。The polyamide-imide that is the object of the present invention has a high melt viscosity, and if the above-mentioned low-molecular-weight compound is not used, it is difficult to obtain a polymer with a sufficiently high degree of polymerization within the range that allows melt m1tt polymerization. However, in Method 1 of the present invention, a polymer having a higher degree of polymerization can be obtained by further subjecting the solution-polymerized polymer to solid-phase polycondensation. When solid phase polycondensation is carried out subsequent to melt polycondensation, it is preferable to carry out the polycondensation until the reduced viscosity measured under the above-mentioned conditions becomes 0.2 or more in the melt polycondensation step. Reduced viscosity is 0.2
If it is smaller, the solid phase polycondensation step will take a long time, which is not preferable.
上記溶融ポリマーを固相重縮合できるようにするために
は、溶融ポリマーを固化させ、かつその固体状態におい
てポリマーを結晶化させるなどして、例えばポリマーの
ガラス転移温度以上の如き重縮合反応が進行し得る温度
においてポリマーが溶融あるいは融着等を起こさないよ
うにすることが必要である。このような固体状態を得る
方法は特に制限しないが、例えば溶融重合ポリマーを熱
処理して結晶化させる方法（熱処理法）、溶融重合ポリ
マーを溶剤処理して結晶化させる方法（溶剤処理法）等
を採用することができる。In order to enable solid-state polycondensation of the molten polymer, the molten polymer is solidified and the polymer is crystallized in the solid state, so that the polycondensation reaction proceeds at a temperature higher than the glass transition temperature of the polymer. It is necessary to prevent the polymer from melting or fusing at a temperature that can be used. The method of obtaining such a solid state is not particularly limited, but examples include a method of heat-treating a melt-polymerized polymer to crystallize it (heat treatment method), a method of crystallizing a melt-polymerized polymer by treating it with a solvent (solvent treatment method), etc. Can be adopted.
上記熱処理法の場合、溶融ポリマーを一旦冷却固化して
再度熱処理してもよいし、溶融重合から連続的に熱処理
してもよいが、後者の方が好ましい。この際の熱処理温
度は好ましくは２５０〜３３０℃、より好ましくは２６
０〜３２０℃程度である。熱処理時間はポリマーが結晶
化するに足る時間であればよく、これは熱処理温度によ
っても異なるが好ましくは５分〜３時間、より好ましく
は１０分〜２時間程度である。熱処理雰囲気は窒素、ア
ルゴン等の不活性ガス雰囲気下、常圧乃至減圧下が好ま
しい。In the case of the above heat treatment method, the molten polymer may be once cooled and solidified and then heat treated again, or the heat treatment may be carried out continuously from melt polymerization, but the latter is preferred. The heat treatment temperature at this time is preferably 250 to 330°C, more preferably 26°C.
The temperature is about 0 to 320°C. The heat treatment time may be any time sufficient to crystallize the polymer, and although it varies depending on the heat treatment temperature, it is preferably about 5 minutes to 3 hours, more preferably about 10 minutes to 2 hours. The heat treatment atmosphere is preferably an inert gas atmosphere such as nitrogen or argon under normal pressure or reduced pressure.
一方上記溶剤処理法において、は、溶融重縮合ポリマー
のチップを該ポリマーは溶解しないが膨潤させ得る有機
溶剤（例えばアセトン、メチルエチルケトン、ジオキサ
ン等）中に浸漬して結晶化させる方法、また場合によっ
ては溶融重縮合したポリマーを該ポリマーを溶解する有
機溶剤（例えば、Ｎ−メチル−２−ピロリドン、ジメチ
ルアセトアミド等）に溶解し、該ポリマー溶液をポリマ
ーを溶解しない溶剤（例えば水、メタノール、アセトン
等）を用いて再沈殿させて固化させる方法等を採用する
ことができる。溶剤処理した後、熱処理するなど上記の
溶剤処理法と熱処理法を併用することも可能である。On the other hand, in the above-mentioned solvent treatment method, chips of the melt polycondensation polymer are immersed in an organic solvent that does not dissolve the polymer but can swell it (e.g., acetone, methyl ethyl ketone, dioxane, etc.) to crystallize it. The melt-polycondensed polymer is dissolved in an organic solvent that dissolves the polymer (for example, N-methyl-2-pyrrolidone, dimethylacetamide, etc.), and the polymer solution is mixed in a solvent that does not dissolve the polymer (for example, water, methanol, acetone, etc.). A method of re-precipitation and solidification using a method can be adopted. It is also possible to use the above solvent treatment method and heat treatment method in combination, such as performing heat treatment after solvent treatment.
本発明方法により製造されるポリアミドイミドは上記方
法により結晶化させることができ、固相重縮合すること
が可能となる。The polyamide-imide produced by the method of the present invention can be crystallized by the above method and can be subjected to solid phase polycondensation.
固相重縮合温度は、ポリマーの重縮合反応は進行するが
固体状ポリマーの融着が起らない温度範囲であればよく
、好ましくは２５０〜３３０℃、より好ましくは２６０
〜３２０℃程度である。固相重縮合時間は特に制限しな
いが、好ましくは３０分〜４０時間、より好ましくは１
〜３０時間程度である。固相重縮合の雰囲気としては窒
素ガス、アルゴンガス等の不活性ガス雰囲気下が好まし
く、また、常圧乃至減圧下が好ましい。かかる固相重縮
合によって還元粘度０．４以上のポリマー、好ましくは
０．４５以上、さらに好ましくは０．５以上のポリマー
とする。The solid phase polycondensation temperature may be within a temperature range in which the polycondensation reaction of the polymer proceeds but does not cause fusion of the solid polymer, preferably 250 to 330°C, more preferably 260°C.
~320°C. The solid phase polycondensation time is not particularly limited, but is preferably 30 minutes to 40 hours, more preferably 1 hour.
~30 hours. The atmosphere for solid phase polycondensation is preferably an inert gas atmosphere such as nitrogen gas or argon gas, and preferably normal pressure to reduced pressure. Such solid phase polycondensation produces a polymer having a reduced viscosity of 0.4 or more, preferably 0.45 or more, more preferably 0.5 or more.
本発明のポリアミドイミドの製造法における好ましい実
施態様としては、トリメリット酸無水物、３．４′ −
ジミノジフェニルエーテル及び無水酢酸の各反応成体を
、まず加熱溶融重縮合せしめて還元粘度０．２以上のポ
リマーを得、引き続き熱処理して該ポリマーを結晶化さ
せて固化させた後、更に固相重縮合せしめる方法を挙げ
ることができる。A preferred embodiment of the method for producing polyamideimide of the present invention includes trimellitic anhydride, 3.4'-
The reaction products of diminodiphenyl ether and acetic anhydride are first subjected to heat-melt polycondensation to obtain a polymer having a reduced viscosity of 0.2 or more, followed by heat treatment to crystallize and solidify the polymer, followed by solid phase polymerization. A method of condensation can be mentioned.
溶融ポリマーを固化させる際には静置したままでもよい
し、撹拌等によりポリマーに剪断力を加え、固化と同時
にポリマーを粉末状乃至粒状に粉砕してもよい。When solidifying the molten polymer, it may be allowed to stand still, or it may be pulverized into powder or granules at the same time as solidification by applying shearing force to the polymer by stirring or the like.
この好適な実施態様においては、低分子化合物を用いる
ことなく、溶融重縮合−熱処理一因相用縮合という一連
の工程により、きわめて効率的に分岐の少ない高重合度
のポリアミドイミドが得られる。In this preferred embodiment, a polyamide-imide with a high degree of polymerization and little branching can be obtained very efficiently by a series of steps of melt polycondensation and heat treatment and single-phase condensation without using a low-molecular compound.
なお、本発明のポリアミドイミドを製造するに際し、所
望により各種重合触媒、安定剤、核剤。In addition, when producing the polyamideimide of the present invention, various polymerization catalysts, stabilizers, and nucleating agents may be used as desired.
滑剤２着色剤等の添加剤を配合せしめてもよい。Additives such as a lubricant 2 and a coloring agent may be added.
〈発明の効果〉
上述の如き本発明の方法によれば、線状でかつ高重合度
のポリマーを効率的に製造することができる。すなわち
、従来トリメリット酸及び／又はその酸無水物と３．４
′ −ジアミノジフェニルエーテルとから得られるポリ
アミドイミドは、非品性乃至難結晶性と考えられていた
が、本発明のポリマーは線状で規則性が良好なためが上
述の方法により容易に結晶化させることができ、固相法
により重縮合することが可能で高重合度のポリマーを得
ることができる。<Effects of the Invention> According to the method of the present invention as described above, a linear polymer with a high degree of polymerization can be efficiently produced. That is, conventional trimellitic acid and/or its acid anhydride and 3.4
' -diaminodiphenyl ether was thought to be non-quality or difficult to crystallize, but since the polymer of the present invention is linear and has good regularity, it can be easily crystallized by the method described above. It is possible to perform polycondensation using a solid phase method, and a polymer with a high degree of polymerization can be obtained.
従って本発明の方法によるポリアミドイミドは、耐熱性
、ｉ載物性０寸法安定性、耐溶剤性、成形性に優れ、Ｉ
ｌｍ、フィルム、プラスチックス等あるいは各種複合材
料の原料として極めて有用である。Therefore, the polyamide-imide produced by the method of the present invention has excellent heat resistance, dimensional stability, solvent resistance, and moldability.
It is extremely useful as a raw material for lm, films, plastics, etc., and various composite materials.
〈実施例〉
以下、実施例及び比較例を挙げて本発明を詳述するが、
実施例中「部」は「重Ｇ部」を意味する。<Example> The present invention will be described in detail below with reference to Examples and Comparative Examples.
In the examples, "part" means "heavy G part".
還元粘度は本文中記載の条件にて測定し、ガラス転移温
度（Ｔｇ）、融点（Ｔａ＋ ）はＤＳＧを用い１０℃／
分の昇温速度で測定した。The reduced viscosity was measured under the conditions described in the text, and the glass transition temperature (Tg) and melting point (Ta+) were measured using DSG at 10°C/
The temperature was measured at a heating rate of 1 minute.
実施例１
トリメリッ、ト酸無水物１９２部、３．４′ −ジアミ
ノジフェニルエーテル２００部及び無水酢酸１４３部を
撹拌装置、留出系を備えた反応容器に入れ、窒素気流中
常圧で２００℃より３００℃まで約９０分かけて撹拌し
つつ昇温し生成する酢酸を留出させた。Example 1 Trimelli, 192 parts of toric anhydride, 200 parts of 3.4'-diaminodiphenyl ether, and 143 parts of acetic anhydride were placed in a reaction vessel equipped with a stirring device and a distillation system, and heated from 200°C to 300°C at normal pressure in a nitrogen stream. The temperature was raised to °C over about 90 minutes with stirring, and the acetic acid produced was distilled off.
次いで１５分かけて約１０１１１１８９の弱真空減圧し
、更に１ｓ＋Ｈｓ以下の高真空とした。この溶融反応時
、ポリマーの粘度は徐々に上昇した。高真空反応を１０
分間実施した後、（ポリマーの還元粘度は０．２９に達
した）、撹拌を止め同条件で３０分間熱処理したところ
、褐色透明な溶融ポリマーは徐々に固化して淡茶色不透
明となった。引き続ぎ同条件で１２０分固相重縮合反応
したところ、還元粘度０．５８ 。Next, the pressure was reduced to a weak vacuum of about 10111189 over 15 minutes, and then the pressure was reduced to a high vacuum of 1 s+Hs or less. During this melt reaction, the viscosity of the polymer gradually increased. High vacuum reaction 10
After stirring for 30 minutes (reduced viscosity of the polymer reached 0.29), stirring was stopped and heat treatment was carried out under the same conditions for 30 minutes, and the brown transparent molten polymer gradually solidified and became pale brown and opaque. Subsequently, solid phase polycondensation reaction was carried out under the same conditions for 120 minutes, and the reduced viscosity was 0.58.
Ｔ（１２４１℃のポリマーが得られた。同ポリマーには
３２５℃にＴＩが観測された。A polymer with a temperature of T (1241°C) was obtained. TI was observed in the same polymer at 325°C.
上述の如くして得られたポリマーを、高化式フローテス
ターを用い温度３５０℃で０．５＃φ×１．０ＩＮ！Ｒ
Ｌのノズルより溶融押出した。得られたモノフィラメン
トは褐色透明で極めて強靭であった。また該モノフィラ
メントをＤＳＣ測定したところ、Ｔ（Ｉ＋は２４２℃で
あったが、ＴＩはもはや観測できなかった。The polymer obtained as described above was tested at a temperature of 0.5 #φ x 1.0 IN! at a temperature of 350°C using a Koka type flow tester. R
It was melt extruded from the L nozzle. The obtained monofilament was brown and transparent and extremely tough. Further, when the monofilament was subjected to DSC measurement, T(I+) was 242° C., but TI could no longer be observed.
実施例２
トリメリット酸無水物１９２部、３．４′ −ジアセト
アミドジフェニルエーテル１７０部、及び３．４′−ジ
アミノジフェニルエーテル８０部を実施例１と同様な反
応容器に入れ、窒素気流中常圧で２４０℃に加熱溶融し
、これを約８０分で３２０℃まで昇温しで生成する酢酸
を留去させた。Example 2 192 parts of trimellitic anhydride, 170 parts of 3.4'-diacetamido diphenyl ether, and 80 parts of 3.4'-diaminodiphenyl ether were placed in the same reaction vessel as in Example 1, and the mixture was heated to 240 parts at normal pressure in a nitrogen stream. The mixture was melted by heating to 320° C. in about 80 minutes, and the acetic acid produced was distilled off.
次いで、２０分間で約１０＃１１１Ｈ９の弱真空まで徐
々に減圧としたところ、ポリマーは褐色透明な高粘度の
溶融物となった（ポリマーの還元粘度は０．３３であっ
た）。次に撹拌を止め同温度で約１＃ｌｌｌＨｇの高真
空として３０分間熱処理したところ、溶融ポリマーは次
第に固化し、淡茶色不透明となった。更に同条件で固相
重縮合を１００分間続けた。得られたポリマーは還元粘
度０．６７ 、 Ｔｏ ２４３℃であり、また３２５℃
にＴＩが観測された。Then, the pressure was gradually reduced to a weak vacuum of about 10#111H9 over 20 minutes, and the polymer turned into a brown, transparent, highly viscous melt (the reduced viscosity of the polymer was 0.33). Next, stirring was stopped and heat treatment was performed at the same temperature under a high vacuum of about 1 #lllHg for 30 minutes, and the molten polymer gradually solidified and became light brown and opaque. Further, solid phase polycondensation was continued for 100 minutes under the same conditions. The resulting polymer had a reduced viscosity of 0.67, To 243°C, and 325°C
TI was observed.
実施例３
トリメリット酸無水物１９２部、３．４′−ジアミノジ
フェニルエーテル２００部及び無水酢１１２０部を実施
例１と同様な反応容器に入れ窒素気流中常圧下２００℃
で撹拌上加熱溶融させ約６０分で２８０℃まで界温し同
温度で常圧から約１０ｍＨｓまで１５分間で徐々に減圧
とした。Example 3 192 parts of trimellitic anhydride, 200 parts of 3,4'-diaminodiphenyl ether, and 1120 parts of anhydrous vinegar were placed in a reaction vessel similar to Example 1 and heated at 200°C under normal pressure in a nitrogen stream.
The mixture was heated and melted with stirring, and the ambient temperature reached 280° C. in about 60 minutes, and at the same temperature, the pressure was gradually reduced from normal pressure to about 10 mHs over 15 minutes.
更に１ａＨｓ以下の高真空で４０分間熱処理したところ
ポリマーは固化した。この際高真空反応約５分で撹拌は
停止した。得られたポリマーは還元粘度０．３３であっ
た。該ポリマーを反応容器からとり出し１０−２０メツ
シユの粒径に粉砕し、撹拌装置。When the polymer was further heat-treated for 40 minutes under a high vacuum of 1 aHs or less, the polymer solidified. At this time, stirring was stopped after about 5 minutes of high vacuum reaction. The obtained polymer had a reduced viscosity of 0.33. The polymer was taken out from the reaction vessel and pulverized to a particle size of 10-20 mesh, using a stirring device.
真空留出系を備えた反応器に入れ撹拌し゛ながら０．６
７１１１１８９の高真空下２８０℃で２時間、３００℃
で８時間反応させたところ、還元粘度は０．７１となっ
た。この固相重縮合時、固体ポリマーは融解あるいは融
着することなく撹拌可能であった。0.6 while stirring in a reactor equipped with a vacuum distillation system.
7111189 under high vacuum at 280℃ for 2 hours at 300℃
When the reaction was carried out for 8 hours, the reduced viscosity was 0.71. During this solid phase polycondensation, the solid polymer could be stirred without melting or fusing.
実施例４
トリメリット酸無水物１９２部、３．４′ −ジアミノ
ジフェニルエーテル２００部、無水酢酸１１５部及び４
．４１−ジフェニルジフェニルスルホン１５０部を撹拌
ｔＩ霞、真空留出系を備えた反応容器に入れ、窒素気流
中常圧下２４０℃で３０分次いで３３０℃まで約６０分
で昇温し、生成する水及び酢酸を留去させた。次いで同
温度で１５分で約１０ｍｍＨ９の弱真空まで徐々に減圧
どし、更に１１１１１１１８９以下の高真空として２．
５時間重縮合した。得られたポリマーは褐色透明で均一
な溶融物であった。Example 4 192 parts of trimellitic anhydride, 200 parts of 3.4'-diaminodiphenyl ether, 115 parts of acetic anhydride, and 4
．． 150 parts of 41-diphenyldiphenylsulfone was placed in a reaction vessel equipped with a stirring tI haze and a vacuum distillation system, and the temperature was raised to 240°C under normal pressure in a nitrogen stream for 30 minutes, then to 330°C in about 60 minutes, and the resulting water and acetic acid were heated. was distilled off. Next, the pressure was gradually reduced to a weak vacuum of about 10 mmH9 over 15 minutes at the same temperature, and then the pressure was reduced to a high vacuum of 111111189 or less.
Polycondensation was carried out for 5 hours. The obtained polymer was a brown, transparent, and uniform melt.
該ポリマーをチップ化して還流ジオキサン中に浸漬して
４．４′ −ジフェニルジフェニルスルホンを抽出した
ところ、還元粘度０．７１のポリマーが得られた。When the polymer was formed into chips and immersed in refluxing dioxane to extract 4,4'-diphenyldiphenylsulfone, a polymer with a reduced viscosity of 0.71 was obtained.
実施例５
トリメリット酸無水物１９２部、３．４′ −ジアミノ
ジフェニルエーテル２００部、無水酢酸１５０部及びト
リフェニルホスフィン２．６部を撹拌装置、真空留出系
を備えた反応容器に入れ、窒素気流中２５０℃で３０分
間加熱重縮含させ、次いで約６０分かけて３４０℃まで
昇温した。昇温（股、約１５分かけて１０１ＭＨ９まで
徐々に減圧とし、次いで０．５ＩｌｌＩＩＩＨ９の高真
空とし、９０分間溶融重縮合を実施した。Example 5 192 parts of trimellitic anhydride, 200 parts of 3.4'-diaminodiphenyl ether, 150 parts of acetic anhydride, and 2.6 parts of triphenylphosphine were placed in a reaction vessel equipped with a stirring device and a vacuum distillation system, and the mixture was heated with nitrogen. Polycondensation was carried out by heating at 250°C in an air stream for 30 minutes, and then the temperature was raised to 340°C over about 60 minutes. The pressure was gradually reduced to 101MH9 over a period of about 15 minutes, followed by a high vacuum of 0.5IllIIIH9, and melt polycondensation was carried out for 90 minutes.
上記重縮合後、溶融ポリマーは徐々に粘度が上昇し、生
成する水及び酢酸が留出した。得られたポリマーは還元
粘度０，６１ 、 Ｔｏ ２４２℃であった。After the polycondensation, the viscosity of the molten polymer gradually increased, and the produced water and acetic acid were distilled out. The obtained polymer had a reduced viscosity of 0.61 and a temperature of 242°C.
比較例
トリメリット酸無水物１９２部、３．４′ −ジアミノ
ジフェニルエーテル２００部を撹拌装置、真空留出系を
備えた反応容器に入れ、窒素気流中２６０℃で３０分、
次いで３００℃まで約３０分で昇温し、同温度で約１５
ｍｍＨｓの弱真空となるまで約１５分で徐々に減圧とし
、次に１８８９以下の高真空とした。高真空反応直後の
溶融ポリマーは還元粘度０．３６であったが、１０分後
、溶融ポリマーは次第に増粘し、Ｎ−メチル−２−ピロ
リドンに不溶となり、ポリマーが分岐、ゲル化したこと
が確認された。Comparative Example 192 parts of trimellitic anhydride and 200 parts of 3.4'-diaminodiphenyl ether were placed in a reaction vessel equipped with a stirring device and a vacuum distillation system, and the mixture was heated at 260°C for 30 minutes in a nitrogen stream.
Next, the temperature was raised to 300℃ in about 30 minutes, and the temperature was increased for about 15 minutes at the same temperature.
The pressure was gradually reduced over about 15 minutes until a weak vacuum of mmHs was achieved, and then a high vacuum of 1889 mmHs or less was achieved. The molten polymer immediately after the high vacuum reaction had a reduced viscosity of 0.36, but after 10 minutes, the molten polymer gradually thickened and became insoluble in N-methyl-2-pyrrolidone, indicating that the polymer branched and gelled. confirmed.
特許出願人 帝 人 株 式 会 社Patent applicant Teijin Kaisha Ltd.
Claims (3)
水物と、（Ｂ）下記式（ I ）で示されるジアミン成分
とを、加熱重縮合することを特徴とするポリアミドイミ
ドの製造方法。 ▲数式、化学式、表等があります▼・・・（ I ） 式中、Ｒ＿１、Ｒ＿２はＨ又はＲ＿３ＣＯを示し、かつ
Ｒ＿１とＲ＿２の合計量に対するＨの割合５〜６０モル
％である。Ｒ＿３は炭素数１〜３低級アルキルを示す。(1) A method for producing polyamide-imide, which comprises subjecting (A) an aromatic tricarboxylic acid and/or its acid anhydride to thermal polycondensation of (B) a diamine component represented by the following formula (I). ▲There are numerical formulas, chemical formulas, tables, etc.▼...(I) In the formula, R_1 and R_2 represent H or R_3CO, and the proportion of H with respect to the total amount of R_1 and R_2 is 5 to 60 mol%. R_3 represents lower alkyl having 1 to 3 carbon atoms.
水物と、（Ｂ′）３，４′−ジアミノジフェニルエーテ
ルと、（Ｃ）下記式（II）で示される低級脂肪酸無水物
とを、加熱重縮合させ、反応系中で上記式（ I ）で示
されるアミン成分（Ｂ）を生成せしめることを特徴とす
る請求項（１）に記載のポリアミドイミドの製造方法。 Ｒ＿３ＣＯ−Ｏ−ＯＣＲ＿３・・・（II） ［式中Ｒ＿３は上記式（ I ）と同義］(2) (A) aromatic tricarboxylic acid and/or its acid anhydride, (B') 3,4'-diaminodiphenyl ether, and (C) lower fatty acid anhydride represented by the following formula (II), The method for producing polyamide-imide according to claim 1, wherein the amine component (B) represented by the formula (I) is produced in a reaction system by heating polycondensation. R_3CO-O-OCR_3...(II) [In the formula, R_3 has the same meaning as the above formula (I)]
（Ａ）成分と（Ｂ′）成分と（Ｃ）成分とを、還元粘度
（Ｎ−メチル−２−ピロリドン中、濃度１ｇ／ｄｌ、温
度３５℃で測定）が０．２以上となるまで溶融重縮合し
、次いで固相重縮合により還元粘度が０．４以上となる
まで重合度を上昇せしめることを特徴とする請求項（１
）又は（２）に記載のポリアミドイミドの製造方法。(3) The above (A) component and (B) component, or the above (A) component, (B') component, and (C) component, at a reduced viscosity (concentration of 1 g in N-methyl-2-pyrrolidone) /dl, measured at a temperature of 35°C) is 0.2 or more, followed by solid phase polycondensation to increase the degree of polymerization until the reduced viscosity is 0.4 or more. (1
) or the method for producing polyamideimide according to (2).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16685988A JPH0689141B2 (en) | 1988-07-06 | 1988-07-06 | Method for producing polyamide-imide |
| US07/268,479 US4902740A (en) | 1985-07-26 | 1988-11-08 | Polyamideimides containing 3,4'-diamino-diphenylether as diamine component, with plasticizer |
| US07/433,194 US5068307A (en) | 1985-07-26 | 1989-11-08 | Polyamideimides containing 3,4'-diamino-diphenylether as diamine component and process for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16685988A JPH0689141B2 (en) | 1988-07-06 | 1988-07-06 | Method for producing polyamide-imide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0218421A true JPH0218421A (en) | 1990-01-22 |
| JPH0689141B2 JPH0689141B2 (en) | 1994-11-09 |
Family
ID=15838967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16685988A Expired - Fee Related JPH0689141B2 (en) | 1985-07-26 | 1988-07-06 | Method for producing polyamide-imide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689141B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015151421A (en) * | 2014-02-12 | 2015-08-24 | ユニチカ株式会社 | Method for producing polyamide-imide, and polyamide-imide |
-
1988
- 1988-07-06 JP JP16685988A patent/JPH0689141B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015151421A (en) * | 2014-02-12 | 2015-08-24 | ユニチカ株式会社 | Method for producing polyamide-imide, and polyamide-imide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0689141B2 (en) | 1994-11-09 |
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