JP6878808B2 - Method for manufacturing polyimide porous body - Google Patents
Method for manufacturing polyimide porous body Download PDFInfo
- Publication number
- JP6878808B2 JP6878808B2 JP2016190534A JP2016190534A JP6878808B2 JP 6878808 B2 JP6878808 B2 JP 6878808B2 JP 2016190534 A JP2016190534 A JP 2016190534A JP 2016190534 A JP2016190534 A JP 2016190534A JP 6878808 B2 JP6878808 B2 JP 6878808B2
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- JP
- Japan
- Prior art keywords
- polyimide
- porous body
- solvent
- gel
- polyimide porous
- 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.)
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- 229920001721 polyimide Polymers 0.000 title claims description 133
- 239000004642 Polyimide Substances 0.000 title claims description 132
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000000034 method Methods 0.000 title description 18
- 239000002904 solvent Substances 0.000 claims description 67
- 239000002243 precursor Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 41
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000012024 dehydrating agents Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- 230000005661 hydrophobic surface Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 23
- -1 (3,4-dicarboxy) Phenyl Chemical group 0.000 description 22
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 238000005191 phase separation Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 235000013849 propane Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 2
- HMQGJZXLJQZTAP-UHFFFAOYSA-N 4-(4-amino-2,3,5-trichlorophenyl)-2,3,6-trichloroaniline Chemical compound ClC1=C(Cl)C(N)=C(Cl)C=C1C1=CC(Cl)=C(N)C(Cl)=C1Cl HMQGJZXLJQZTAP-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 2
- MHDWQCSVXCLPGW-UHFFFAOYSA-N dibenzothiophene-1,2-diamine Chemical class C1=CC=C2C3=C(N)C(N)=CC=C3SC2=C1 MHDWQCSVXCLPGW-UHFFFAOYSA-N 0.000 description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- HYLLZXPMJRMUHH-UHFFFAOYSA-N 1-[2-(2-methoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOC HYLLZXPMJRMUHH-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- RERATEUBWLKDFE-UHFFFAOYSA-N 1-methoxy-2-[2-(2-methoxypropoxy)propoxy]propane Chemical compound COCC(C)OCC(C)OCC(C)OC RERATEUBWLKDFE-UHFFFAOYSA-N 0.000 description 1
- XCCQFUHBIRHLQT-UHFFFAOYSA-N 1-methyl-4-[2-(4-methylphenyl)ethyl]benzene Chemical group C1=CC(C)=CC=C1CCC1=CC=C(C)C=C1 XCCQFUHBIRHLQT-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- LLPBNQVGGIJVGF-UHFFFAOYSA-N 1h-indole-2,3-diamine Chemical class C1=CC=C2C(N)=C(N)NC2=C1 LLPBNQVGGIJVGF-UHFFFAOYSA-N 0.000 description 1
- UXOXUHMFQZEAFR-UHFFFAOYSA-N 2,2',5,5'-Tetrachlorobenzidine Chemical compound C1=C(Cl)C(N)=CC(Cl)=C1C1=CC(Cl)=C(N)C=C1Cl UXOXUHMFQZEAFR-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- HFEPENYPELKAQF-UHFFFAOYSA-N 2,6-dimethyldibenzothiophene-3,7-diamine Chemical compound S1C2=C(C)C(N)=CC=C2C2=C1C=C(N)C(C)=C2 HFEPENYPELKAQF-UHFFFAOYSA-N 0.000 description 1
- KEMGPCYBTHJENU-UHFFFAOYSA-N 2,8-dimethyldibenzothiophene-3,7-diamine Chemical compound S1C2=CC(N)=C(C)C=C2C2=C1C=C(N)C(C)=C2 KEMGPCYBTHJENU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- QHDSBTKCTUXBEG-UHFFFAOYSA-N 2-[2-(2-aminophenoxy)phenoxy]aniline Chemical class NC1=CC=CC=C1OC1=CC=CC=C1OC1=CC=CC=C1N QHDSBTKCTUXBEG-UHFFFAOYSA-N 0.000 description 1
- FLLRAXRMITXCAH-UHFFFAOYSA-N 2-[2-(2-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical class NC1=CC=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=CC=C1N FLLRAXRMITXCAH-UHFFFAOYSA-N 0.000 description 1
- UKHJVMIIFRUHPF-UHFFFAOYSA-N 2-[2-(2-aminophenyl)phenyl]aniline Chemical class NC1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1N UKHJVMIIFRUHPF-UHFFFAOYSA-N 0.000 description 1
- NQOBNHOXRSNQAH-UHFFFAOYSA-N 2-[2-[2-(2-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical class NC1=CC=CC=C1OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1OC1=CC=CC=C1N NQOBNHOXRSNQAH-UHFFFAOYSA-N 0.000 description 1
- KUDNXTFNTBQKJZ-UHFFFAOYSA-N 2-[2-[2-[2-(2-aminophenoxy)-3-[3-(3-aminophenoxy)phenyl]phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical class NC=1C=C(OC=2C=C(C=CC=2)C=2C(=C(C=CC=2)C(C(F)(F)F)(C(F)(F)F)C2=C(C=CC=C2)OC2=C(C=CC=C2)N)OC2=C(C=CC=C2)N)C=CC=1 KUDNXTFNTBQKJZ-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- YNJLAZQWIJQCDP-UHFFFAOYSA-N 3,7-dimethyldibenzothiophene-2,8-diamine Chemical compound S1C2=CC(C)=C(N)C=C2C2=C1C=C(C)C(N)=C2 YNJLAZQWIJQCDP-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-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
- 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
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- UVUCUHVQYAPMEU-UHFFFAOYSA-N 3-[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound NC1=CC=CC(C(C=2C=C(N)C=CC=2)(C(F)(F)F)C(F)(F)F)=C1 UVUCUHVQYAPMEU-UHFFFAOYSA-N 0.000 description 1
- DVXYMCJCMDTSQA-UHFFFAOYSA-N 3-[2-(3-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=CC(N)=CC=1C(C)(C)C1=CC=CC(N)=C1 DVXYMCJCMDTSQA-UHFFFAOYSA-N 0.000 description 1
- POXPSTWTPRGRDO-UHFFFAOYSA-N 3-[4-(3-aminophenyl)phenyl]aniline Chemical compound NC1=CC=CC(C=2C=CC(=CC=2)C=2C=C(N)C=CC=2)=C1 POXPSTWTPRGRDO-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-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
- DLCFMGVXCCJVFU-UHFFFAOYSA-N 4-(4-amino-2,5-dibromophenyl)-2,5-dibromoaniline Chemical compound C1=C(Br)C(N)=CC(Br)=C1C1=CC(Br)=C(N)C=C1Br DLCFMGVXCCJVFU-UHFFFAOYSA-N 0.000 description 1
- CPBGOWIFSRZWIZ-UHFFFAOYSA-N 4-(4-amino-2-bromophenyl)-3-bromoaniline Chemical compound BrC1=CC(N)=CC=C1C1=CC=C(N)C=C1Br CPBGOWIFSRZWIZ-UHFFFAOYSA-N 0.000 description 1
- XKXPBJBODVHDAW-UHFFFAOYSA-N 4-(4-amino-2-chlorophenyl)-3-chloroaniline Chemical compound ClC1=CC(N)=CC=C1C1=CC=C(N)C=C1Cl XKXPBJBODVHDAW-UHFFFAOYSA-N 0.000 description 1
- QCBOCNIRTOWNIW-UHFFFAOYSA-N 4-(4-amino-3,5-dichlorophenyl)-2,6-dichloroaniline Chemical compound C1=C(Cl)C(N)=C(Cl)C=C1C1=CC(Cl)=C(N)C(Cl)=C1 QCBOCNIRTOWNIW-UHFFFAOYSA-N 0.000 description 1
- QWUSZGIKGARVEC-UHFFFAOYSA-N 4-(4-amino-3-bromophenyl)-2-bromoaniline Chemical compound C1=C(Br)C(N)=CC=C1C1=CC=C(N)C(Br)=C1 QWUSZGIKGARVEC-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical group C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- JZIAOTUERDUSJC-UHFFFAOYSA-N 4-[4-[4-(4-aminophenyl)phenyl]phenyl]aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C=2C=CC(N)=CC=2)C=C1 JZIAOTUERDUSJC-UHFFFAOYSA-N 0.000 description 1
- WOYZXEVUWXQVNV-UHFFFAOYSA-N 4-phenoxyaniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1 WOYZXEVUWXQVNV-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
- GPXSXONLCXOVPA-UHFFFAOYSA-N 5-(4-aminophenyl)cyclohexa-3,5-diene-1,1,2-triamine Chemical class NC1(N)C(N)C=CC(C=2C=CC(N)=CC=2)=C1 GPXSXONLCXOVPA-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
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- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- OUKZUIOFTUUCEN-UHFFFAOYSA-N 7$l^{6}-thiabicyclo[4.1.0]hepta-1,3,5-triene 7,7-dioxide Chemical compound C1=CC=C2S(=O)(=O)C2=C1 OUKZUIOFTUUCEN-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- PFJFNQUFMTYCHB-UHFFFAOYSA-N C[SiH2]N[SiH3] Chemical compound C[SiH2]N[SiH3] PFJFNQUFMTYCHB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 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 class C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- OUWSNHWQZPEFEX-UHFFFAOYSA-N diethyl glutarate Chemical compound CCOC(=O)CCCC(=O)OCC OUWSNHWQZPEFEX-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
本発明は、ポリイミド多孔質体の製造方法、及び概ポリイミド多孔質体を用いた断熱材に関する。 The present invention relates to a method for producing a polyimide porous body and a heat insulating material using the generally polyimide porous body.
ポリマー多孔質体は、電池用セパレータや電解コンデンサ用隔膜、集塵、精密濾過、膜分離、断熱材など様々な用途に用いられている。特にポリイミド多孔質体はポリイミド由来の耐熱性、力学特性、耐薬品性を有する事からその応用展開が期待されており、非溶媒誘起相分離法（ＮＩＰＳ）、蒸気誘起相分離法（ＶＩＰＳ）、熱誘起相分離法（ＴＩＰＳ）など、種々の方法での製造が検討されている。非溶媒誘起相分離法の例としては、特許文献１にビフェニルテトラカルボン酸成分とジアミン成分とから得られるポリイミド前駆体ワニスキャストフィルムに多孔質フィルムを積層した後、非溶媒に浸漬することを特徴とするポリイミド多孔質膜の製造方法が開示されている。また、蒸気誘起相分離法の例としては、特許文献２にポリイミド前駆体０ ．３〜６０重量％ と溶媒９９ ．７〜４０重量％とからなる溶液をフィルム状に流延し、得られたポリイミド前駆体のフィルム状物に蒸気暴露する処理を行った後、凝固溶媒に浸漬もしくは接触させることを特徴とするポリイミド多孔質膜の製造方法が開示されている。さらに、特許文献３には凝固浴を用いずに多孔質膜を製造する方法として、ポリイミド前駆体と、アミド系溶媒と、アミド系溶媒より５０℃以上高い沸点を有するエーテル系溶媒を含有するポリイミド前駆体溶液を基材上に流延し、加熱乾燥・イミド化させることを特徴とするポリイミド多孔質フィルムの製造方法が開示されている。しかしながら、これらの手法は厚さが概ね１ｍｍ以下のフィルム状の多孔質体は比較的得やすいものの、相分離等に伴い形成された構造を積極的に凍結する事は考慮に入れていない為、１ｍｍ以上の厚膜や、バルクの多孔質体を得ることは、実質上困難であった。 Polymer porous materials are used in various applications such as battery separators, diaphragms for electrolytic capacitors, dust collection, microfiltration, membrane separation, and heat insulating materials. In particular, polyimide porous bodies are expected to be applied because they have heat resistance, mechanical properties, and chemical resistance derived from polyimide. Non-solvent-induced phase separation method (NIPS), steam-induced phase separation method (VIPS), Production by various methods such as a heat-induced phase separation method (TIPS) is being studied. As an example of the non-solvent-induced phase separation method, Patent Document 1 is characterized in that a porous film is laminated on a polyimide precursor varnish cast film obtained from a biphenyltetracarboxylic acid component and a diamine component, and then immersed in a non-solvent. A method for producing a polyimide porous film is disclosed. Further, as an example of the vapor-induced phase separation method, Patent Document 2 describes the polyimide precursor 0. 3-60% by weight and solvent 99. A polyimide characterized by casting a solution consisting of 7 to 40% by weight in the form of a film, subjecting the film-like substance of the obtained polyimide precursor to vapor exposure, and then immersing or contacting the solution in a coagulation solvent. A method for producing a porous film is disclosed. Further, Patent Document 3 describes a polyimide containing a polyimide precursor, an amide solvent, and an ether solvent having a boiling point higher than that of the amide solvent by 50 ° C. or more as a method for producing a porous film without using a coagulation bath. A method for producing a polyimide porous film is disclosed, which comprises casting a precursor solution on a substrate, drying it by heating, and imidizing it. However, although these methods are relatively easy to obtain a film-like porous body having a thickness of about 1 mm or less, they do not take into consideration the positive freezing of the structure formed by phase separation or the like. It was practically difficult to obtain a thick film of 1 mm or more and a bulk porous body.
一方、ポリイミド系樹脂を化学架橋又は物理架橋することによって得られるゲルを、乾燥させることで多孔質体（キセロゲル）を得る方法が、特許文献４、５に開示されている。これらの方法では、架橋によって構造を凍結し、その後乾燥させることで多孔質体を得ているが、得られるゲルの網目構造は非常に小さく、超臨界乾燥等の毛細管力が実質的に生じない乾燥方法以外ではゲルが大幅に収縮し、空孔率の高い多孔質体を得ることは困難であった。 On the other hand, Patent Documents 4 and 5 disclose methods for obtaining a porous body (xerogel) by drying a gel obtained by chemically or physically cross-linking a polyimide resin. In these methods, the structure is frozen by cross-linking and then dried to obtain a porous body, but the network structure of the obtained gel is very small, and capillary force such as supercritical drying does not substantially occur. Other than the drying method, the gel shrank significantly, and it was difficult to obtain a porous material with a high porosity.
本発明の目的は、耐熱性、耐薬品性に優れたポリイミドからなり、高い空孔率を示すポリイミド多孔質体を製造可能な新しい技術を提供することにある。 An object of the present invention is to provide a new technique capable of producing a polyimide porous body which is made of polyimide having excellent heat resistance and chemical resistance and exhibits a high porosity.
本発明者らは、ポリイミドゲルを常圧乾燥させる際に生じる毛細管力を可能な限り低減させる事に着目して鋭意検討を重ねた。その結果、ポリイミドゲル状組成物を、溶媒置換及び表面疎水化処理を経て常圧乾燥させることで、ゲルの収縮を抑制し、高い空孔率を有するポリイミド多孔質体が得られることを見出し、本発明を完成するに至った。
即ち、本発明は、以下の事項に関する。
The present inventors have made extensive studies focusing on reducing the capillary force generated when the polyimide gel is dried under normal pressure as much as possible. As a result, they have found that by drying the polyimide gel-like composition under atmospheric pressure through solvent substitution and surface hydrophobization treatment, shrinkage of the gel is suppressed and a polyimide porous body having a high porosity can be obtained. The present invention has been completed.
That is, the present invention relates to the following matters.
１．下記一般式（１）で示される反復単位からなるポリイミド前駆体と、ポリイミド前駆体の溶媒と、イミド化触媒と、脱水剤を少なくとも混合してなることを特徴とするポリイミドゲル状組成物を、溶媒置換及び表面疎水化処理を経て常圧乾燥させるポリイミド多孔質体の製造方法。 1. 1. A polyimide gel-like composition comprising at least a mixture of a polyimide precursor composed of a repeating unit represented by the following general formula (1), a solvent of the polyimide precursor, an imidization catalyst, and a dehydrating agent. A method for producing a polyimide porous body, which is dried under atmospheric pressure after being subjected to solvent substitution and surface hydrophobization treatment.
２．一般式（１）中、Ｂで示される構造の一部に下記化学式（２）で示される構造を含むことを特徴とする前記項１に記載のポリイミド多孔質体の製造方法。
３．一般式（１）中、Ａで示される構造の一部に下記化学式（３）で示される構造を含むことを特徴とする前記項１又は２に記載のポリイミド多孔質体の製造方法。
４．前記項１〜３のいずれか１項に記載のポリイミド多孔質体の製造方法において、表面疎水化処理が、ヘキサメチルジシラザン、メチルトリクロロシラン、のいずれか又は混合物を用いた処理であることを特徴とするポリイミド多孔質体の製造方法。 4. In the method for producing a polyimide porous body according to any one of Items 1 to 3, the surface hydrophobizing treatment is a treatment using any or a mixture of hexamethyldisilazane and methyltrichlorosilane. A method for producing a polyimide porous body, which is a feature.
５．前記項１〜４のいずれか１項に記載の方法で得られたポリイミド多孔質体を用いた断熱材。 5. A heat insulating material using a polyimide porous body obtained by the method according to any one of Items 1 to 4.
本発明によって、耐熱性、耐薬品性に優れたポリイミドからなり、高い空孔率を有するポリイミド多孔質体を得ることが出来る。本発明で得られるポリイミド多孔質体は、フィルム状の多孔質体のみならず、バルク状の多孔質体を得ることが可能である。 According to the present invention, it is possible to obtain a polyimide porous body made of polyimide having excellent heat resistance and chemical resistance and having a high porosity. As the polyimide porous body obtained in the present invention, not only a film-shaped porous body but also a bulk-shaped porous body can be obtained.
以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のポリイミドゲル状組成物は、ポリイミド前駆体と、ポリイミド前駆体の溶媒と、イミド化触媒と、脱水剤を少なくとも混合してなる事を特徴とするポリイミドゲル状組成物を、溶媒置換及び表面疎水化処理を経て常圧乾燥させることで得られる。 The polyimide gel-like composition of the present invention is prepared by substituting a polyimide precursor, a solvent for the polyimide precursor, an imidization catalyst, and a dehydrating agent at least. It is obtained by subjecting it to surface hydrophobic treatment and then drying it at atmospheric pressure.
＜ポリイミド前駆体モノマー＞
本発明に用いるポリイミド前駆体は、前記一般式（１）で示される反復単位からなり、式中、Ｂはテトラカルボン酸成分に起因する４価のユニットである。また、Ａはジアミン成分に起因する２価のユニットである。ポリイミド前駆体を構成するユニットについて以下に詳述する。
<Polyimide precursor monomer>
The polyimide precursor used in the present invention comprises a repeating unit represented by the general formula (1), in which B is a tetravalent unit derived from a tetracarboxylic acid component. Further, A is a divalent unit due to the diamine component. The units constituting the polyimide precursor will be described in detail below.
ユニットＢは、テトラカルボン酸成分に起因する４価のユニットである。テトラカルボン酸成分はポリイミド前駆体を重合可能な範囲で特に限定されないが例えば、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（ｓ−ＢＰＤＡ）、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物（ａ−ＢＰＤＡ）、２，２’，３，３’−ビフェニルテトラカルボン酸二無水物（ｉ−ＢＰＤＡ）、ピロメリット酸二無水物（ＰＭＤＡ）、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、２，２’，３，３’−ベンゾフェノンテトラカルボン酸二無水物、２、２‐ビス（３，４−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、ビス（２，３−ジカルボキシフェニル）エーテル二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物（ＮＴＤＡ）、１，２，５，６−ナフタレンテトラカルボン酸二無水物、２，２−ビス（３，４−ジカルボキシフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン二無水物（６ＦＤＡ）、２，２−ビス（２，３−ジカルボキシフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン二無水物及びその混合物が挙げられる。その中でも特にｓ−ＢＰＤＡ、ａ−ＢＰＤＡ、ＰＭＤＡがポリイミドゲル状組成物を得る観点、及び得られるポリイミド多孔質体の耐熱性、耐薬品性、力学特性の観点から好ましい。 Unit B is a tetravalent unit due to the tetracarboxylic acid component. The tetracarboxylic acid component is not particularly limited as long as the polyimide precursor can be polymerized, and for example, 3,3', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3', 4'-biphenyltetracarboxylic dianhydride (a-BPDA), 2,2', 3,3'-biphenyltetracarboxylic dianhydride (i-BPDA), pyromellitic dianhydride (PMDA), 3 , 3', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ) Ether dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), 1,2,5,6-naphthalene Tetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedianhydride (6FDA), 2,2-bis ( 2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedianhydride and a mixture thereof can be mentioned. Among them, s-BPDA, a-BPDA, and PMDA are particularly preferable from the viewpoint of obtaining a polyimide gel-like composition, and from the viewpoint of heat resistance, chemical resistance, and mechanical properties of the obtained polyimide porous body.
ユニットＡは、ジアミン成分に起因する２価のユニットである。ジアミン成分はポリイミド前駆体を重合可能な範囲で特に限定されないが例えば、ｐ−フェニレンジアミン（ＰＰＤ）、ｍ−フェニレンジアミン（ＭＰＤ）などのフェニレンジアミン類、３，５−ジアミノ安息香酸などのジアミノ安息香酸類、４，４’−ジアミノジフェニルエーテル（ＯＤＡ）、３，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、３，３’−ジメチル−４，４’−ジアミノジフェニルエーテル、３，３’−ジメトキシ−ジアミノジフェニルエーテルなどのジアミノジフェニルエーテル類、４，４’−ジアミノジフェニルメタン、３，３’−ジアミノビフェニルメタン、３，３’−ジクロロ−４，４’−ジアミノビフェニルメタン、２，２’−ジフルオロ−４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、３，３’−ジメトキシ−４，４’−ジアミノジフェニルメタンなどのジアミノジフェニルメタン類、２，２−ビス（４−アミノフェニル）プロパン、２，２−ビス（３−アミノフェニル）プロパン、２，２−（３，４'−ジアミノジフェニル）プロパンなどのジアミノジフェニルプロパン類、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、２，２−ビス（３−アミノフェニル）ヘキサフルオロプロパンなどのビス（アミノフェニル）ヘキサフルオロプロパン類、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などのジアミノジフェニルスルホン類、３，７−ジアミノ−２，８−ジメチル−ジベンゾチオフェン、２，８−ジアミノ−３，７−ジメチル−ジベンゾチオフェン、３，７−ジアミノ−２，６−ジメチル−ジベンゾチオフェンなどのジアミノジベンゾチオフェン類、３，７−ジアミノ−２，８−ジメチル−ジフェニレンスルフォン、３，７−ジアミノ−２，８−ジエチル−ジフェニレンスルフォン、３，７−ジアミノ−２，８−ジメトキシ−ジフェニレンスルフォン、２，８−ジアミノ−３，７−ジメチル−ジフェニレンスルフォンなどのジアミノジフェニレンスルフォン類（後述のジアミノジベンゾチオフェン＝５，５−ジオキシド類に同じ）、４，４’−ジアミノビベンジル、４，４’−ジアミノ−２，２’−ジメチルビベンジルなどのジアミノビベンジル類、０−ジアニシジン、０−トリジン、ｍ−トリジンなどのジアミノビフェニル類、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノンなどのジアミノベンゾフェノン類、２，２’，５，５’−テトラクロロベンジジン、３，３’，５，５’−テトラクロロベンジジン、３，３’−ジクロロベンジジン、２，２’−ジクロロベンジジン、２，２’，３，３’，５，５’−ヘキサクロロベンジジン、２，２'，５，５’−テトラブロモベンジジン、３，３’，５，５’−テトラブロモベンジジン、３，３’−ジブロモベンジジン、２，２’−ジブロモベンジジン、２，２’，３，３’，５，５’−ヘキサクロロベンジジンなどのジアミノベンジジン類、１，４−ビス（４−アミノフェノキシ）ベンゼン（ＴＰＥ−Ｑ）、１，３−ビス（４−アミノフェノキシ）ベンゼン（ＴＰＥ−Ｒ）などのビス（アミノフェノキシ）ベンゼン類、１，４−ビス（４−アミノフェニル）ベンゼン、１，４−ビス（３−アミノフェニル）ベンゼンなどのジ（アミノフェニル）ベンゼン類、２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン、２，２−ビス〔３−（３−アミノフェノキシ）フェニル〕プロパンなどのビス〔（アミノフェノキシ）フェニル〕プロパン類、２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕ヘキサフルオロプロパン、２，２−ビス〔３−（３−アミノフェノキシ）フェニル〕ヘキサフルオロプロパンなどのビス〔（アミノフェノキシ）フェニル〕ヘキサフルオロプロパン類、ビス〔４−（４−アミノフェノキシ）フェニル〕スルホン、ビス〔４−（３−アミノフェノキシ）フェニル〕スルホンなどのジ〔（アミノフェノキシ）フェニル〕スルホン類、４，４’−ビス（４−アミノフェニル）ビフェニルなどのジ（アミノフェニル）ビフェニル類、５（６）−アミノ−２−（４−アミノフェニル）−ベンゾイミダゾール（ＤＡＰＢＩ）などのジアミノベンゾアゾール類及びその混合物が挙げられる。その中でも特にＯＤＡがポリイミドゲル状組成物を得る観点、及びポリイミド多孔質体の耐熱性、耐薬品性、力学特性の観点から好ましい。その他、脂環族ジアミンとして、イソホロンジアミン、シクロヘキサンジアミンなどを、重合性を妨げない範囲で適宜利用できる。 Unit A is a divalent unit due to the diamine component. The diamine component is not particularly limited as long as the polyimide precursor can be polymerized, but for example, phenylenediamines such as p-phenylenediamine (PPD) and m-phenylenediamine (MPD), and diaminobenzoic acid such as 3,5-diaminobenzoic acid. Acids, 4,4'-diaminodiphenyl ether (ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy Diaminodiphenyl ethers such as −diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminobiphenylmethane, 3,3′-dichloro-4,4′-diaminobiphenylmethane, 2,2′-difluoro-4 , 4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, diaminodiphenylmethanes, 2,2-bis (4- Diaminodiphenyl propanes such as aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) Hexafluoropropane, bis (aminophenyl) hexafluoropropanes such as 2,2-bis (3-aminophenyl) hexafluoropropane, diamino such as 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone Diphenylsulfones, 3,7-diamino-2,8-dimethyl-dibenzothiophene, 2,8-diamino-3,7-dimethyl-dibenzothiophene, 3,7-diamino-2,6-dimethyl-dibenzothiophene, etc. Diaminodibenzothiophenes, 3,7-diamino-2,8-dimethyl-diphenylensulphon, 3,7-diamino-2,8-diethyl-diphenylensulphon, 3,7-diamino-2,8-dimethoxy-di Diaminodiphenylensulphons such as phenylensulphon, 2,8-diamino-3,7-dimethyl-diphenylensulphon (same as diaminodibenzothiophene = 5,5-dioxides described below), 4,4'-diaminobibenzyl , 4,4'-Diamino-2,2'-Diaminobibenzyls such as dimethylbibenzyl, 0-dianicidin, 0-trizine, diaminobiphenyls such as m-trizine, 4,4'- Diaminobenzophenones such as diaminobenzophenone, 3,3'-diaminobenzophenone, 2,2', 5,5'-tetrachlorobenzidine, 3,3', 5,5'-tetrachlorobenzidine, 3,3'-dichloro Benzidine, 2,2'-dichlorobenzidine, 2,2', 3,3', 5,5'-hexachlorobenzidine, 2,2', 5,5'-tetrabromobenzidine, 3,3', 5,5 Diaminobenzidines such as'-tetrabromobenzidine, 3,3'-dibromobenzidine, 2,2'-dibromobenzidine, 2,2', 3,3', 5,5'-hexachlorobenzidine, 1,4-bis Bis (aminophenoxy) benzenes such as (4-aminophenoxy) benzene (TPE-Q), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,4-bis (4-aminophenyl) ) Benzidine, di (aminophenyl) benzenes such as 1,4-bis (3-aminophenyl) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3 -(3-Aminophenoxy) phenyl] bis such as propane [(aminophenoxy) phenyl] propanes, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3 -(3-Aminophenoxy) phenyl] bis [(aminophenoxy) phenyl] hexafluoropropanes such as hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Di [(aminophenoxy) phenyl] sulfones such as phenyl] sulfone, di (aminophenyl) biphenyls such as 4,4'-bis (4-aminophenyl) biphenyl, 5 (6) -amino-2-( Examples thereof include diaminobenzoazoles such as 4-aminophenyl) -benzoimidazole (DAPBI) and mixtures thereof. Among them, ODA is particularly preferable from the viewpoint of obtaining a polyimide gel-like composition, and from the viewpoint of heat resistance, chemical resistance, and mechanical properties of the polyimide porous body. In addition, as the alicyclic diamine, isophorone diamine, cyclohexanediamine and the like can be appropriately used as long as the polymerizable property is not hindered.
＜良溶媒＞
本発明に用いるポリイミド前駆体の溶媒としては、ポリイミド前駆体を溶解するものであれば特に限定されないが、具体的にはアミド系溶媒が挙げられる。アミド系溶媒の例としては、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ−エチル−２−ピロリドン（ＮＥＰ）、ピリジン、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、１，３−ジメチル−２−イミダゾリジノン（ＤＭＩ）等を挙げる事が出来る。これらの良溶媒は、それぞれ単体で用いてもよいし、二種以上の混合物として用いても構わない。
<Good solvent>
The solvent for the polyimide precursor used in the present invention is not particularly limited as long as it dissolves the polyimide precursor, and specific examples thereof include an amide-based solvent. Examples of amide solvents include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), pyridine, N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N. , N-Dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI) and the like. Each of these good solvents may be used alone or as a mixture of two or more kinds.
本発明には、必要に応じてポリイミド前駆体の非溶媒も併用する事が出来る。ポリイミド前駆体の非溶媒は、例えば、ポリイミド前駆体のイミド化の進行に伴う溶媒への溶解性の低下による相分離を制御する為に用いられる。特に、多孔構造のサイズを大きくしたい場合に併用する事で、相分離を促進し、より大きな空孔の多孔質体を得ることが可能となる。 A non-solvent of a polyimide precursor can also be used in combination with the present invention, if necessary. The non-solvent of the polyimide precursor is used, for example, to control phase separation due to a decrease in solubility in a solvent as the imidization of the polyimide precursor progresses. In particular, when it is desired to increase the size of the porous structure, it is possible to promote phase separation and obtain a porous body having larger pores.
非溶媒を用いる場合、特にグリコールジエーテル系溶媒、及び又はカルボン酸ジエステル系溶媒、及び又はグリコールモノエーテルアセテート系溶媒が好ましい。具体的なグリコールジエーテル系溶媒としては、トリエチレングリコールジメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリプロピレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテルなどが好適に利用できる。 When a non-solvent is used, a glycol diether solvent, or a carboxylic acid diester solvent, or a glycol monoether acetate solvent is particularly preferable. As a specific glycol diether solvent, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and the like can be preferably used.
カルボン酸ジエステル系溶媒としては、こはく酸ジメチル、こはく酸ジエチル、グルタル酸ジメチル、グルタル酸ジエチル、アジピン酸ジメチル、アジピン酸ジエチル等が好ましい。また、こはく酸ジメチル、グルタル酸ジメチル、アジピン酸ジメチルの混合物である二塩基酸エステル（商品名ＤＢＥ：三協化学株式会社）等も好適に用いる事が出来る。 As the carboxylic acid diester solvent, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, diethyl adipate and the like are preferable. Further, a dibasic acid ester (trade name: DBE: Sankyo Chemical Co., Ltd.), which is a mixture of dimethyl succinate, dimethyl glutarate, and dimethyl adipate, can also be preferably used.
グリコールモノエーテルアセテート系溶媒としては、エチルカルビネートアセテート、ブチルカルビネートアセテート等が具体的に挙げられる。これらの非溶媒は、それぞれ単体で用いてもよいし、二種以上の混合物として用いても構わない。 Specific examples of the glycol monoether acetate solvent include ethyl carbinate acetate and butyl carbinate acetate. Each of these non-solvents may be used alone or as a mixture of two or more kinds.
本発明において、非溶媒の混合量は、非溶媒の種類に応じて適宜決定されるが、概ね８０ｗｔ％未満の範囲であり、７０ｗｔ％未満である事がより好ましく、６０ｗｔ％以下であることが特に好ましい。非溶媒の添加量は非溶媒としての強さ、即ちポリイミド前駆体及びポリイミドとの相溶性に応じて適宜調整することが重要である。一般的には、８０ｗｔ％以上加えると、ポリイミド前駆体の段階で混合溶媒に溶解出来なくなってしまい、本技術による多孔質体形成が困難となる。 In the present invention, the mixing amount of the non-solvent is appropriately determined according to the type of the non-solvent, but is generally in the range of less than 80 wt%, more preferably less than 70 wt%, and more preferably 60 wt% or less. Especially preferable. It is important that the amount of the non-solvent added is appropriately adjusted according to the strength as the non-solvent, that is, the compatibility with the polyimide precursor and the polyimide. Generally, if 80 wt% or more is added, it cannot be dissolved in a mixed solvent at the stage of the polyimide precursor, which makes it difficult to form a porous body by the present technology.
＜イミド化触媒・脱水剤＞
本発明では、化学イミド化によりポリイミド前駆体をイミド化する。具体的にはイミド化触媒と脱水剤をポリイミド前駆体に混合する事で、イミド化を促進し、相分離及びゲル化を誘起する事で高次構造が制御されたポリイミドゲルを得ることが出来る。イミド化触媒としては、トリエチルアミン、トリエチレンジアミン等の脂肪族第３級アミン、ジメチルアニリン等の芳香族第３級アミン、イソキノリン、ピリジン、２−メチルピリジン、３−メチルピリジン、４−メチルピリジン、イミダール、ベンズイミダゾール等の複素環第３級アミン等が挙げられるが、臭気や反応性の観点からイソキノリンやメチルピリジン、イミダゾール等がより好ましい。脱水剤としては、無水酢酸、無水プロピオン酸、無水酪酸等の脂肪族酸無水物、無水安息香酸、無水フタル酸等の芳香族酸無水物等が挙げられるが、脂肪族酸無水物が好ましく、無水酢酸がより好ましい。
<Imidation catalyst / dehydrating agent>
In the present invention, the polyimide precursor is imidized by chemical imidization. Specifically, by mixing the imidization catalyst and the dehydrating agent with the polyimide precursor, imidization can be promoted, and phase separation and gelation can be induced to obtain a polyimide gel having a controlled higher-order structure. .. Examples of the imidization catalyst include aliphatic tertiary amines such as triethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, isoquinoline, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine and imidazole. , Heterocyclic tertiary amines such as benzimidazole, etc., but isoquinoline, methylpyridine, imidazole and the like are more preferable from the viewpoint of odor and reactivity. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as benzoic anhydride and phthalic anhydride, but aliphatic acid anhydrides are preferable. Acetic anhydride is more preferred.
＜ポリイミドゲル状組成物＞
本発明のポリイミドゲル状組成物は、ポリイミド前駆体と、ポリイミド前駆体の溶媒と、イミド化触媒、及び脱水剤を少なくとも混合することで得られる。より具体的には、ポリイミド前駆体の溶液を調整し、その中にイミド化触媒、及び脱水剤を加える事でポリイミドゲル状組成物が得られる。
<Polyimide gel-like composition>
The polyimide gel-like composition of the present invention can be obtained by mixing at least a polyimide precursor, a solvent for the polyimide precursor, an imidization catalyst, and a dehydrating agent. More specifically, a polyimide gel-like composition can be obtained by preparing a solution of the polyimide precursor and adding an imidization catalyst and a dehydrating agent therein.
ポリイミド前駆体溶液は、溶媒中において、前記の芳香族テトラカルボン酸二無水物と芳香族ジアミンを用いて、公知の方法で重合することが出来る。非溶媒を加える場合、順序は特に限定されないが、例えば予め良溶媒と非溶媒の混合溶媒中に略等モルの芳香族テトラカルボン酸二無水物と芳香族ジアミンを添加して均一になるまで混合することでポリイミド前駆体溶液を得る事が出来る。また、ポリイミド前駆体の良溶媒中に略等モルの芳香族テトラカルボン酸二無水物と芳香族ジアミンを添加して均一になるまで混合することでポリイミド前駆体の良溶媒溶液を製造し、さらにこれらを撹拌しながら非溶媒を少量ずつ加えて均一になるまで混合する事で、良溶媒と非溶媒を含有したポリイミド前駆体溶液を得る事が出来る。 The polyimide precursor solution can be polymerized in a solvent by a known method using the above-mentioned aromatic tetracarboxylic dianhydride and aromatic diamine. When the non-solvent is added, the order is not particularly limited, but for example, approximately equimolar amounts of aromatic tetracarboxylic acid dianhydride and aromatic diamine are added in advance in a mixed solvent of a good solvent and a non-solvent and mixed until uniform. By doing so, a polyimide precursor solution can be obtained. Further, a good solvent solution of the polyimide precursor is produced by adding approximately equimolar aromatic tetracarboxylic acid dianhydride and aromatic diamine to the good solvent of the polyimide precursor and mixing them until they become uniform. By adding the non-solvent little by little while stirring and mixing until uniform, a polyimide precursor solution containing a good solvent and a non-solvent can be obtained.
芳香族テトラカルボン酸二無水物と芳香族ジアミンを混合する際の反応温度は、−３０〜１２０℃が好ましく、−２０〜８０℃がより好ましい。反応時間は、０．５時間〜１００時間が好ましく、２時間〜４８時間がより好ましい。テトラカルボン酸二無水物と芳香族ジアミンの混合割合は等モルとなるように調整することが好ましいが、これらのモノマーの比率を若干変動させることにより、ポリイミド前駆体の重合度を任意に調節することができる。 The reaction temperature when the aromatic tetracarboxylic dianhydride and the aromatic diamine are mixed is preferably -30 to 120 ° C, more preferably -20 to 80 ° C. The reaction time is preferably 0.5 hours to 100 hours, more preferably 2 hours to 48 hours. The mixing ratio of the tetracarboxylic dianhydride and the aromatic diamine is preferably adjusted to be equimolar, but the degree of polymerization of the polyimide precursor is arbitrarily adjusted by slightly varying the ratio of these monomers. be able to.
本発明のポリイミド前駆体溶液中のポリイミド前駆体の濃度は、通常１〜５０ｗｔ％、好ましくは５〜３０ｗｔ％である。１ｗｔ％未満では、固形分が不足することで良好なポリイミドゲル状組成物が得られない為に好ましくなく、５０ｗｔ％を超えると溶媒中へのポリイミド前駆体の溶解が難しくなる。 The concentration of the polyimide precursor in the polyimide precursor solution of the present invention is usually 1 to 50 wt%, preferably 5 to 30 wt%. If it is less than 1 wt%, a good polyimide gel-like composition cannot be obtained due to insufficient solid content, which is not preferable. If it exceeds 50 wt%, it becomes difficult to dissolve the polyimide precursor in the solvent.
本発明のポリイミド前駆体溶液の溶液粘度は、１Ｐａ・ｓ〜３０００Ｐａ・ｓ、好ましくは５Ｐａ・ｓ〜１０００Ｐａ・ｓ、特に好ましくは１０Ｐａ・ｓ〜５００Ｐａ・ｓである。溶液粘度が３０００Ｐａ・ｓを越えるとイミド化触媒及び脱水剤を添加後、シート状やバルク状に加工するために、基板上に流延したり、型に流し込んだりする事が困難となる。溶液粘度が１Ｐａ・ｓ未満ではゲルとしての形状を保持できなくなり、良好なポリイミドゲル状組成物が得られにくくなるため、適当ではない。 The solution viscosity of the polyimide precursor solution of the present invention is 1 Pa · s to 3000 Pa · s, preferably 5 Pa · s to 1000 Pa · s, and particularly preferably 10 Pa · s to 500 Pa · s. If the viscosity of the solution exceeds 3000 Pa · s, after adding the imidization catalyst and the dehydrating agent, the solution is processed into a sheet or bulk, which makes it difficult to cast it on a substrate or pour it into a mold. If the solution viscosity is less than 1 Pa · s, the shape as a gel cannot be maintained, and it becomes difficult to obtain a good polyimide gel-like composition, which is not suitable.
本発明では、上記のポリイミド前駆体の良溶媒及び非溶媒からなる溶液に、イミド化触媒、及び脱水剤を加える事でイミド化が進行し、ポリイミドゲル状組成物が得られる。イミド化触媒及び脱水剤の添加量は、ポリイミド前駆体中のカルボキシル基に対して０．１〜４モル当量程度が好ましく、０．５〜２モル当量程度がより好ましい。０．１モル当量未満の場合、ポリイミド前駆体のイミド化が進みづらく、良好なポリイミドゲル状組成物が得られない為に好ましくなく、４モル当量を超えるとポリイミド前駆体のイミド化が急速に進行する為、基板上に流延したり、型に流し込んだりする加工が困難となる。 In the present invention, imidization proceeds by adding an imidization catalyst and a dehydrating agent to the above solution of the polyimide precursor consisting of a good solvent and a non-solvent, and a polyimide gel-like composition is obtained. The amount of the imidization catalyst and the dehydrating agent added is preferably about 0.1 to 4 molar equivalents, more preferably about 0.5 to 2 molar equivalents, relative to the carboxyl group in the polyimide precursor. If it is less than 0.1 molar equivalent, imidization of the polyimide precursor is difficult to proceed, and it is not preferable because a good polyimide gel-like composition cannot be obtained. If it exceeds 4 molar equivalent, imidization of the polyimide precursor is rapidly performed. As it progresses, it becomes difficult to cast it on the substrate or pour it into a mold.
イミド化触媒及び脱水剤を加えた後、ゲル化させる際の温度は、概ね０℃〜１３０℃が好ましく、１０℃〜８０℃がより好ましい。０℃未満だとゲル化が進行しづらくゲル化に長い時間を要するために好ましくなく、１３０℃を超えるとゲル化前に溶媒、イミド化触媒、脱水剤等が蒸発してしまう懸念があり、好ましくない。ゲル化時間はポリイミド前駆体の種類、濃度、イミド化触媒及び脱水剤の種類、添加量、ゲル化させる際の温度等によって適宜調整されるが、概ね１分〜４８時間である。 After adding the imidization catalyst and the dehydrating agent, the temperature at the time of gelation is preferably about 0 ° C. to 130 ° C., more preferably 10 ° C. to 80 ° C. If the temperature is lower than 0 ° C, gelation does not proceed easily and it takes a long time to gel, which is not preferable. If the temperature exceeds 130 ° C, there is a concern that the solvent, imidization catalyst, dehydrating agent, etc. may evaporate before gelation. Not preferred. The gelation time is appropriately adjusted depending on the type and concentration of the polyimide precursor, the type of the imidization catalyst and the dehydrating agent, the amount added, the temperature at the time of gelation, and the like, but is approximately 1 minute to 48 hours.
本発明のポリイミドゲル状組成物には、必要に応じて補強材を添加することが出来る。補強材としては、ポリイミドゲル状組成物を補強する効果のあるものであれば特に限定されないが、特に繊維状物質やそれからなる織布又は不織布等が好ましい。より具体的には、高分子繊維、ガラス繊維、セラミック繊維、炭素繊維、又は生重合体繊維等からなる織布又は不織布等が挙げられる。補強材を添加する場合、イミド化触媒及び脱水剤を混合前又は混合後に、ドープが流動性を保っている間に添加することが好ましい。なお、織布や不織布を補強材として用いる場合は、イミド化触媒及び脱水剤を混合後、ドープが流動性を保っている間に織布や不織布に含浸させて複合させる事が好ましい。 A reinforcing material can be added to the polyimide gel-like composition of the present invention, if necessary. The reinforcing material is not particularly limited as long as it has the effect of reinforcing the polyimide gel-like composition, but a fibrous substance, a woven fabric made of the fibrous material, a non-woven fabric, or the like is particularly preferable. More specifically, woven fabrics or non-woven fabrics made of polymer fibers, glass fibers, ceramic fibers, carbon fibers, biopolymer fibers and the like can be mentioned. When the reinforcing material is added, it is preferable to add the imidization catalyst and the dehydrating agent before or after mixing while the dope maintains fluidity. When a woven fabric or a non-woven fabric is used as a reinforcing material, it is preferable to mix the imidization catalyst and the dehydrating agent and then impregnate the woven fabric or the non-woven fabric with the woven fabric or the non-woven fabric while the dope maintains the fluidity.
本発明のポリイミドゲル状組成物には、必要に応じて各種界面活性剤、有機シラン、顔料、導電性のカーボン粒子や微細炭素繊維、金属微粒子等の充填材、摩滅材、誘電体、潤滑材等の他、公知の添加物を本発明の効果を損なわない範囲で添加することができる。また、他の重合体が本発明の効果を損なわない範囲で添加されていてもよい。 The polyimide gel-like composition of the present invention contains various surfactants, organic silanes, pigments, fillers such as conductive carbon particles and fine carbon fibers, metal fine particles, abrasion materials, dielectrics, and lubricants, if necessary. In addition to the above, known additives can be added as long as the effects of the present invention are not impaired. Further, other polymers may be added as long as the effects of the present invention are not impaired.
＜ポリイミド多孔質体の製造方法＞
＜溶媒置換＞
本発明では、上記ポリイミドゲル状組成物を溶媒置換及び表面疎水化処理を経て常圧乾燥させることで、ポリイミド多孔質体を得ることが出来る。溶媒置換の方法としては、公知の手法を用いる事が出来るが、例えば、ポリイミドゲル状組成物の溶媒と相溶するエタノール、メタノール、イソプロピルアルコール等のアルコールで置換し、更に表面張力の低いヘキサン、ヘプタン、イソオクタン、フッ素系溶媒等へ置換させることが好ましい。
<Manufacturing method of polyimide porous body>
<Solvent replacement>
In the present invention, a polyimide porous body can be obtained by subjecting the above-mentioned polyimide gel-like composition to solvent substitution and surface hydrophobization and drying at atmospheric pressure. As a solvent replacement method, a known method can be used. For example, hexane, which is replaced with an alcohol such as ethanol, methanol, or isopropyl alcohol that is compatible with the solvent of the polyimide gel-like composition, and has a lower surface tension. It is preferable to replace it with heptan, isooctane, a fluorine-based solvent or the like.
＜表面疎水化処理＞
本発明では、溶媒置換と共に表面疎水化処理を行う事で、更に乾燥時の毛細管力によるゲルの収縮を抑制し、高い空孔率を示すポリイミド多孔質体を得ることが可能となる。表面疎水化処理としては、ヘキサン、ヘプタン、イソオクタン、フッ素系溶媒等が蒸発する際に表面張力が小さくなり、乾燥時の毛細管力による収縮を抑制出来るものであれば特に限定されないが、例えば、ヘキサメチルジシラザン（ＨＭＤＳ）、トリクロロメチルシラン（ＴＭＣＳ）及びその混合物等の疎水化剤による処理が挙げられる。より具体的には、ヘキサン、ヘプタン、イソオクタン等の中に疎水化剤を加え、その中に溶媒置換後のポリイミドゲル状組成物を浸漬し、必要に応じて加熱することで、ポリマーの一部に疎水化剤を反応させる事が出来る。表面疎水化処理されたポリイミドゲル状組成物は、再び低表面張力の溶媒中に浸漬して未反応の疎水化剤を洗浄後、常圧乾燥させることで高い空孔率を示すポリイミドゲルが得られる。
<Surface hydrophobization treatment>
In the present invention, by performing the surface hydrophobizing treatment together with the solvent substitution, it is possible to further suppress the shrinkage of the gel due to the capillary force during drying and obtain a polyimide porous body showing a high porosity. The surface hydrophobizing treatment is not particularly limited as long as the surface tension becomes small when hexane, heptane, isooctane, a fluorine-based solvent, etc. evaporates, and shrinkage due to capillary force during drying can be suppressed. Treatment with a hydrophobizing agent such as methyldisilazane (HMDS), trichloromethylsilane (TMCS) and a mixture thereof can be mentioned. More specifically, a hydrophobic agent is added to hexane, heptane, isooctane, etc., the polyimide gel-like composition after solvent substitution is immersed therein, and if necessary, it is heated to form a part of the polymer. Can be reacted with a hydrophobic agent. The surface-hydrophobicized polyimide gel-like composition is immersed in a solvent having a low surface tension again to wash the unreacted hydrophobizing agent, and then dried under atmospheric pressure to obtain a polyimide gel showing a high porosity. Be done.
その他、低表面張力の溶媒の蒸発の際の表面張力を低減できる表面疎水化の方法としては、フッ素系界面活性剤の添加や、フッ素系シランカップリング剤による処理等が挙げられ、これらの処理も好適に用いる事が出来る。 Other methods of surface hydrophobization that can reduce the surface tension during evaporation of a low surface tension solvent include addition of a fluorine-based surfactant and treatment with a fluorine-based silane coupling agent. Can also be preferably used.
以下、実施例により本発明をさらに詳細に説明する。なお、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples.
以下の例で用いた酸二無水物、ジアミン、溶媒、イミド化触媒、脱水剤、疎水化剤は以下のとおりである。
３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（ｓ−ＢＰＤＡ）
４，４’−ジアミノジフェニルエーテル（ＯＤＡ）
Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）
イソキノリン
無水酢酸
ヘキサメチルジシラザン（ＨＭＤＳ）
トリクロロメチルシラン（ＴＭＣＳ）
The acid dianhydride, diamine, solvent, imidization catalyst, dehydrating agent, and hydrophobizing agent used in the following examples are as follows.
3,3', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA)
4,4'-Diaminodiphenyl ether (ODA)
N, N-dimethylacetamide (DMAc)
Isoquinoline Acetic anhydride Hexamethyldisilazane acetate (HMDS)
Trichloromethylsilane (TMCS)
以下の例で用いた特性の測定方法を以下に示す。 The method for measuring the characteristics used in the following example is shown below.
〔多孔構造の観察〕
得られたポリイミド多孔質体の多孔構造を、走査型電子顕微鏡（ＳＥＭ）を用いて観察した。試料を液体窒素中で破断した断面にスパッタリングにより金を蒸着して観察を行った。測定にはＪＥＯＬ社製Ｃａｒｒｙ Ｓｃｏｐｅ ＪＣＭ−５７００を用いた。
[Observation of porous structure]
The porous structure of the obtained polyimide porous body was observed using a scanning electron microscope (SEM). Gold was vapor-deposited on the cross section of the sample broken in liquid nitrogen by sputtering and observed. A Carry Scope JCM-5700 manufactured by JEOL Ltd. was used for the measurement.
〔密度及び空孔率の測定〕
所定の大きさに切り取った多孔質体の面積、厚み、及び質量を測定し、目付質量から密度及び空孔率を下記一般式（２）、（３）によって求めた。
密度（ｇ／ｃｍ３）＝ｗ／Ｓ×ｄ （一般式２）
空孔率（％）＝（１−（ｗ／Ｓ×ｄ）／Ｄ）×１００ （一般式３）
（式中、Ｓは多孔質体の面積、ｄは厚み、ｗは測定した質量、Ｄはポリイミド緻密体の推定密度をそれぞれ意味する。ポリイミド緻密体の推定密度はｓ−ＢＰＤＡ／ＯＤＡポリイミド緻密体の密度を１．３７ｇ／ｃｍ３として計算した。）
[Measurement of density and porosity]
The area, thickness, and mass of the porous body cut to a predetermined size were measured, and the density and porosity were determined from the basis weight by the following general formulas (2) and (3).
Density (g / cm 3 ) = w / S × d (general formula 2)
Porosity (%) = (1- (w / S × d) / D) × 100 (general formula 3)
(In the formula, S means the area of the porous body, d means the thickness, w means the measured mass, and D means the estimated density of the polyimide dense body. The estimated density of the polyimide dense body is s-BPDA / ODA polyimide dense body. The density was calculated as 1.37 g / cm 3.)
〔製造例１〕
撹拌羽、窒素導入管、排気管を取り付けた５００ｍｌのガラス製セパラブルフラスコにＯＤＡ１２．１６ｇ及びＤＭＡｃ２７０ｇを投入し、撹拌混合した。さらにｓ−ＢＰＤＡ約１７．８４ｇを徐々に加えながら撹拌し、室温で４８時間混合してｓ−ＢＰＤＡ／ＯＤＡからなるポリイミド前駆体のＤＭＡｃ溶液（ポリイミド前駆体固形分約１０．０ｗｔ％）を調整した。
[Manufacturing Example 1]
12.16 g of ODA and 270 g of DMAc were put into a 500 ml glass separable flask equipped with a stirring blade, a nitrogen introduction pipe, and an exhaust pipe, and stirred and mixed. Further, about 17.84 g of s-BPDA is gradually added and stirred, and mixed at room temperature for 48 hours to prepare a DMAc solution of a polyimide precursor composed of s-BPDA / ODA (polyimide precursor solid content of about 10.0 wt%). did.
〔実施例１〕
製造例１で得られたポリイミド前駆体のＤＭＡｃ溶液１０ｇと、ＤＭＡｃ１０ｇと、イソキノリン０．５２２ｇ（ポリイミド前駆体の−ＣＯＯＨに対して１モル当量）を混合し均一になるまで攪拌した。さらに、無水酢酸０．４１３ｇ（ポリイミド前駆体の−ＣＯＯＨに対して１モル当量）を加え、ＴＨＩＮＫＹ社製あわとり練太郎（ＡＲＥ−２５０）を用いて２０００ｒｐｍで２分間攪拌、２２００ｒｐｍで２分間脱泡を行い、均一になるように攪拌、脱泡操作を行った。得られた混合溶液をテフロン（登録商標）製のシャーレに移し、湿気が入らないように密閉した状態で、室温で１日静置して、ポリイミドゲル状組成物を得た。得られたポリイミドゲル状組成物をシャーレから取り出し、過剰量のエタノール中に浸漬し、８時間毎にエタノールを交換しながら２４時間溶媒置換を行った。さらに、過剰量のヘプタン中に浸漬し、８時間毎にヘプタンを交換しながら２４時間溶媒置換を行った。溶媒置換後のポリイミドゲル状組成物を、１０ｗｔ％のＨＭＤＳ／ヘプタン溶液に６０℃で２時間浸漬し、表面疎水化処理を行った。さらに、過剰量のヘプタン中に浸漬し、８時間毎にヘプタンを交換しながら２４時間溶媒置換を行って未反応のＨＭＤＳを洗浄し、室温、常圧で２４時間乾燥させた後、１１０℃で２時間乾燥させてポリイミド多孔質体を得た。得られたポリイミド多孔質体の特性を表１に示す。また、得られた多孔質体の断面の走査型電子顕微鏡（ＳＥＭ）像を図１に示す。表面疎水化処理を行う事で、高い空孔率の多孔質体が得られることが示された。
[Example 1]
10 g of the DMAc solution of the polyimide precursor obtained in Production Example 1, 10 g of DMAc, and 0.522 g of isoquinoline (1 molar equivalent with respect to −COOH of the polyimide precursor) were mixed and stirred until uniform. Further, 0.413 g of acetic anhydride (1 molar equivalent with respect to -COOH of the polyimide precursor) was added, and the mixture was stirred at 2000 rpm for 2 minutes using THINKY's Awatori Rentaro (ARE-250) and removed at 2200 rpm for 2 minutes. Foaming was performed, and stirring and defoaming operations were performed so as to be uniform. The obtained mixed solution was transferred to a petri dish made of Teflon (registered trademark) and allowed to stand at room temperature for 1 day in a sealed state so as not to allow moisture to enter to obtain a polyimide gel-like composition. The obtained polyimide gel-like composition was taken out from a petri dish, immersed in an excess amount of ethanol, and subjected to solvent replacement for 24 hours while exchanging ethanol every 8 hours. Further, the mixture was immersed in an excess amount of heptane, and the solvent was replaced for 24 hours while exchanging heptane every 8 hours. The polyimide gel-like composition after solvent substitution was immersed in a 10 wt% HMDS / heptane solution at 60 ° C. for 2 hours to perform surface hydrophobization treatment. Further, the mixture was immersed in an excess amount of heptane, and the unreacted HMDS was washed by solvent substitution for 24 hours while exchanging heptane every 8 hours, dried at room temperature and normal pressure for 24 hours, and then at 110 ° C. It was dried for 2 hours to obtain a polyimide porous body. The characteristics of the obtained polyimide porous body are shown in Table 1. Further, a scanning electron microscope (SEM) image of a cross section of the obtained porous body is shown in FIG. It was shown that a porous body with a high porosity can be obtained by performing the surface hydrophobizing treatment.
〔実施例２〕
１０ｗｔ％のＨＭＤＳ／ヘプタン溶液の代わりに１０ｗｔ％のＴＭＣＳ／ヘプタン溶液を用いた他は、実施例１と同様の方法でポリイミド多孔質体を得た。得られたポリイミド多孔質体の特性を表１に示す。表面疎水化処理を行う事で、高い空孔率の多孔質体が得られることが示された。
[Example 2]
A polyimide porous body was obtained in the same manner as in Example 1 except that a 10 wt% TMCS / heptane solution was used instead of the 10 wt% HMDS / heptane solution. The characteristics of the obtained polyimide porous body are shown in Table 1. It was shown that a porous body with a high porosity can be obtained by performing the surface hydrophobizing treatment.
〔実施例３〕
１０ｗｔ％のＨＭＤＳ／ヘプタン溶液の代わりに、ＨＭＤＳ５ｗｔ％、ＴＭＣＳ５ｗｔ％のヘプタン溶液を用いた他は、実施例１と同様の方法でポリイミド多孔質体を得た。得られたポリイミド多孔質体の特性を表１に示す。表面疎水化処理を行う事で、高い空孔率の多孔質体が得られることが示された。
[Example 3]
A polyimide porous body was obtained in the same manner as in Example 1 except that the HMDS 5 wt% and TMCS 5 wt% heptane solutions were used instead of the 10 wt% HMDS / heptane solution. The characteristics of the obtained polyimide porous body are shown in Table 1. It was shown that a porous body with a high porosity can be obtained by performing the surface hydrophobizing treatment.
〔比較例１〕
１０ｗｔ％のＨＭＤＳ／ヘプタン溶液を用いた表面疎水化処理を行わなかった他は、実施例１と同様の方法でポリイミド多孔質体を得た。得られたポリイミド多孔質体の特性を表１に示す。また、得られた多孔質体の断面の走査型電子顕微鏡（ＳＥＭ）像を図２に示す。表面疎水化処理を行わなかった場合、溶媒置換後の常圧乾燥のみではゲルの収縮を抑制出来ず、高い空孔率の多孔質体は得られなかった。
[Comparative Example 1]
A polyimide porous body was obtained in the same manner as in Example 1 except that the surface hydrophobization treatment using a 10 wt% HMDS / heptane solution was not performed. The characteristics of the obtained polyimide porous body are shown in Table 1. Further, a scanning electron microscope (SEM) image of a cross section of the obtained porous body is shown in FIG. When the surface hydrophobization treatment was not performed, the shrinkage of the gel could not be suppressed only by atmospheric drying after solvent replacement, and a porous body having a high porosity could not be obtained.
本発明により、溶媒置換後の常圧乾燥等、比較的コストのかからない手法で、ポリイミド由来の耐熱性、耐薬品性を兼ね備え、高い空孔率を有するポリイミド多孔質体を得ることが可能である。本発明で得られるポリイミド多孔質体は、断熱材、クッション材、吸液材、分離材、セパレータ、気体用フィルタ、液体用フィルタ、通気部品、気体拡散層などの用途に好適に用いることができる。また、本発明の多孔質ポリイミド膜は、耐熱性に優れ、２５０℃以上の使用温度領域でも使用することができる為、音響部品保護膜、耐熱フィルタ、触媒担体、熱交換器等の用途にも好適に用いることができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a polyimide porous body having both heat resistance and chemical resistance derived from polyimide and having a high porosity by a method such as atmospheric drying after solvent replacement at a relatively low cost. .. The polyimide porous body obtained in the present invention can be suitably used for applications such as heat insulating materials, cushioning materials, liquid absorbing materials, separating materials, separators, gas filters, liquid filters, ventilation parts, and gas diffusion layers. .. Further, since the porous polyimide membrane of the present invention has excellent heat resistance and can be used even in an operating temperature range of 250 ° C. or higher, it can also be used for applications such as acoustic component protective membranes, heat resistant filters, catalyst carriers, and heat exchangers. It can be preferably used.
Claims (7)
前記ポリイミドゲル状組成物がヘキサン、ヘプタン、イソオクタン、フッ素系溶媒から選ばれる溶媒及び疎水化剤を含有するポリイミドゲル状組成物。 A polyimide gel-like composition in which the polyimide gel-like composition contains a solvent selected from hexane, heptane, isooctane, a fluorine-based solvent, and a hydrophobic agent.
前記ポリイミド多孔質体の体積が０．１５１４〜０．２５７８ｃｍThe volume of the polyimide porous body is 0.1514 to 0.2578 cm. ３3 の範囲内にあり、Is within the range of
前記ポリイミド多孔質体の密度が０．５０〜０．８３ｇ／ｃｍThe density of the polyimide porous body is 0.50 to 0.83 g / cm. ３3 の範囲内にあり、Is within the range of
前記ポリイミド多孔質体の空孔率が３９．３〜６３．３％の範囲内にある、The porosity of the polyimide porous body is in the range of 39.3 to 63.3%.
ポリイミド多孔質体。Polyimide porous body.
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