CN118146713A - Polyimide electrophoretic paint, preparation method and application thereof - Google Patents
Polyimide electrophoretic paint, preparation method and application thereof Download PDFInfo
- Publication number
- CN118146713A CN118146713A CN202211562563.0A CN202211562563A CN118146713A CN 118146713 A CN118146713 A CN 118146713A CN 202211562563 A CN202211562563 A CN 202211562563A CN 118146713 A CN118146713 A CN 118146713A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- bis
- dianhydride
- aminophenoxy
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004642 Polyimide Substances 0.000 title claims abstract description 225
- 229920001721 polyimide Polymers 0.000 title claims abstract description 225
- 239000003973 paint Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 92
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 238000000576 coating method Methods 0.000 claims abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- -1 diamine compound Chemical class 0.000 claims description 108
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 39
- 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 claims description 35
- 238000002156 mixing Methods 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 19
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 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 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical class NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- 150000002576 ketones Chemical class 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 claims description 6
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 6
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 claims description 6
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical class CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003457 sulfones Chemical class 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 6
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 claims description 5
- 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
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 claims description 5
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- MNUHUVIZSPCLFF-UHFFFAOYSA-N 1-methylhept-6-ene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C(C)C(C(O)=O)CC(C(O)=O)C(C=C)C(O)=O MNUHUVIZSPCLFF-UHFFFAOYSA-N 0.000 claims description 3
- UGEHFOSBNBEWMP-UHFFFAOYSA-N 2,3-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1N UGEHFOSBNBEWMP-UHFFFAOYSA-N 0.000 claims description 3
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 3
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- FYDMBFIJIQPURU-UHFFFAOYSA-N 2-[2-(2-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=CC=C(N)C=1C(C)(C)C1=CC=CC=C1N FYDMBFIJIQPURU-UHFFFAOYSA-N 0.000 claims description 3
- GNQHLRFTGRZHLH-UHFFFAOYSA-N 2-[2-[2-[2-(2-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C(=CC=CC=2)N)C=1C(C)(C)C1=CC=CC=C1OC1=CC=CC=C1N GNQHLRFTGRZHLH-UHFFFAOYSA-N 0.000 claims description 3
- XYLOFWKCCUPQRG-UHFFFAOYSA-N 2-[3-[2-[3-(2-aminophenyl)propyl]phenyl]propyl]aniline Chemical compound NC1=CC=CC=C1CCCC1=CC=CC=C1CCCC1=CC=CC=C1N XYLOFWKCCUPQRG-UHFFFAOYSA-N 0.000 claims description 3
- DUCHOMQDJBOBMI-UHFFFAOYSA-N 2-[4-[4-(2-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC=C1OC1=CC=C(C=2C=CC(OC=3C(=CC=CC=3)N)=CC=2)C=C1 DUCHOMQDJBOBMI-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 3
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 claims description 3
- SMDGQEQWSSYZKX-UHFFFAOYSA-N 3-(2,3-dicarboxyphenoxy)phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O SMDGQEQWSSYZKX-UHFFFAOYSA-N 0.000 claims description 3
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- BCJIMAHNJOIWKQ-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-4-yl)oxy]-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2OC1=CC=CC2=C1C(=O)OC2=O BCJIMAHNJOIWKQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 claims description 3
- OAPDPORYXWQVJE-UHFFFAOYSA-N 4-propylaniline Chemical compound CCCC1=CC=C(N)C=C1 OAPDPORYXWQVJE-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 3
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 229940102253 isopropanolamine Drugs 0.000 claims description 3
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- APZFQORRVULRGX-UHFFFAOYSA-N n,n-diphenyl-9h-fluoren-1-amine Chemical class C=12CC3=CC=CC=C3C2=CC=CC=1N(C=1C=CC=CC=1)C1=CC=CC=C1 APZFQORRVULRGX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical class CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 3
- 229960005323 phenoxyethanol Drugs 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003495 polar organic solvent Substances 0.000 claims description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical class NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- QHDSBTKCTUXBEG-UHFFFAOYSA-N 2-[2-(2-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1OC1=CC=CC=C1N QHDSBTKCTUXBEG-UHFFFAOYSA-N 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 230000032683 aging Effects 0.000 abstract description 13
- 238000005452 bending Methods 0.000 abstract description 12
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 30
- 239000007787 solid Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001652 electrophoretic deposition Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 2
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229920005565 cyclic polymer Polymers 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 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
- 239000011521 glass Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a polyimide electrophoretic coating, a preparation method and application thereof. The polyimide electrophoretic coating provided by the invention comprises a soluble polyimide polymer; the soluble polyimide polymer does not contain silicon element. Compared with the prior art, the polyimide electrophoretic paint film prepared by the polyimide electrophoretic paint disclosed by the invention does not contain silicon element, has excellent adhesive property, and simultaneously has excellent ageing resistance, bending resistance, high temperature resistance, impact resistance and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyimide electrophoretic coating, a preparation method and application thereof.
Background
With the rapid development of new energy automobiles, the industry has higher and higher insulation requirements on metal parts in three-electric systems (i.e. batteries, motors and electric control). In various application scenes, the insulating paint film layer is required to have excellent high voltage resistance, high temperature resistance, chemical resistance, aging resistance and other performances, and also required to have good flexibility, bending resistance, impact resistance and other performances so as to ensure that the insulating paint film layer is not cracked, separated, insulated defects and the like under various bending process conditions in the manufacturing process of the metal parts.
Polyimide (PI) is used as an outstanding representative of engineering plastics, and is a pyramid-tip polymer material with outstanding comprehensive properties such as high-low temperature stability, chemical resistance, mechanical property and electrical insulation property, and is widely applied to the field of high-performance insulating materials.
In the existing polyimide insulating film forming technology, the insulating film layer is formed by a mode of repeated dripping and scraping, and has poor electrical aging resistance and thermal aging resistance; the production efficiency of the wire rod multi-time unreeling, reeling, drying and film forming process is low; the insulation slurry of the drop coating and blade coating technology is wasted greatly, and the pollution solvent is used in large quantity; the R-angle part of the wire is difficult to coat uniformly, and local insulation failure can occur with high probability. The polyimide insulating film prepared by adopting the electrophoresis process can be molded at one time, the uniformity of the material is improved, the use of a polluted solvent is greatly reduced, the utilization rate of raw materials is improved, and more importantly, the insulating film with uniform thickness can be formed at the R angle, so that the insulating defect at the R angle is effectively avoided.
In order to increase the flexibility of the polyimide electrophoretic paint film layer, a method of introducing other specific elements into the structure to change the molecular structure of the conventional polyimide is currently used. For example, japanese patent JP6750146B2 and Chinese patent CN101715474B each disclose an electrophoresable polyimide in which a siloxane structure is incorporated in the polymer in order to increase its flexibility. The siloxane is a polymer containing Si-O-Si bonds to form a main chain structure, is conventionally called organic silicon or polysilicone ether, can be linear, cyclic or cross-linked polymer, and has good ageing resistance and electrical insulation performance. However, the introduction of the siloxane structure may result in a decrease in the surface energy of the insulating paint film layer, and although the hydrophobicity resulting from the decrease in the surface energy may make the insulating paint film layer less likely to be wetted by water, it may also result in more difficult adhesion and bonding of other substances on the surface thereof.
In the three-electric system of the new energy automobile, all metal parts are generally connected together through metal fusion welding, rivet riveting, adhesive bonding and the like so as to form a stable assembly resistant to long-term vibration fatigue. Only the bonding method can connect nonmetallic surfaces without damaging the surfaces of the metallic components. The adhesive bonding method is generally to bond two metal parts coated with an insulating paint film layer using a structural adhesive (for example, a polyurethane structural adhesive, an epoxy resin structural adhesive, or the like). In the three-electric system of the new energy automobile, the insulating paint film layer of the metal part not only emphasizes the traditional comprehensive performances of high pressure resistance, high flexibility and the like, but also is required to have excellent bonding performance. If the insulating paint film layer structure contains silicon element, the adhesive property of the insulating paint film layer structure is greatly limited.
Based on the defects, the bonding strength of the insulating paint film layer and the structural adhesive is improved while the comprehensive performances of high pressure resistance, high flexibility and the like are ensured, and the adhesive is a problem to be solved by the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyimide electrophoretic coating, a preparation method and application thereof, and an electrophoretic paint film prepared from the polyimide electrophoretic coating of the present invention has excellent adhesion performance.
The invention provides a polyimide electrophoretic coating, which comprises a soluble polyimide polymer;
The soluble polyimide polymer does not contain silicon element.
Preferably, the soluble polyimide polymer is prepared from a raw material including a diamine compound and a dianhydride compound;
The diamine compound comprises at least one of aliphatic diamine and aromatic diamine;
the dianhydride compound includes at least one of aliphatic dianhydride and aromatic dianhydride;
The diamine compound and the dianhydride compound do not contain silicon element.
Preferably, the diamine compound includes at least one of cyclohexanediamine, C1 to C6 alkyl-substituted pentanediamine, ethylenediamine, propylenediamine, hexamethylenediamine, diaminoanilide, diaminodiphenylaminesulfonic acid, diaminobenzenesulfonic acid, bis [ (aminophenoxy) phenyl ] propane, diaminobenzoic acid, phenylenediamine, diaminotoluene, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenyl sulfide, bis (aminophenyl) propane, bis (aminophenyl) hexafluoropropylene, bis (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, bis [ (aminophenyl) propyl ] benzene, bis [ (aminophenoxy) phenyl ] hexafluoropropylene, bis [ (aminophenoxy ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, C1 to C6 alkyl-substituted diaminopyridine, (fluorenyl) diphenylamine, and bis (aminophenyl) diisopropylbenzene;
The dianhydride compound includes at least one of oxydiphthalic anhydride, biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, biphenyl sulfone tetracarboxylic dianhydride, bis (dicarboxyphenyl) ether dianhydride, bicyclo [2, 2] octene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, ethylenediamine tetraacetic dianhydride, bis (dicarboxylic) hexafluoropropane dianhydride group, (acetylene diyl) diphthalic anhydride and benzophenone tetracarboxylic dianhydride.
Preferably, the method comprises the steps of, the diamine compound includes 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, 2-methylpentanediamine, 1, 5-pentanediamine, ethylenediamine, propylenediamine, 1, 6-hexamethylenediamine, 4 '-diaminoanilide, 4' -diaminodiphenylamine-2-sulfonic acid, 2, 5-diaminobenzenesulfonic acid, 1, 3-diamino-4-benzenesulfonic acid, 2 '-bis [4- (4-aminophenoxy) phenyl ] propane, 3, 5-diaminobenzoic acid, 2, 3-diaminobenzoic acid, 3, 4-diaminobenzoic acid, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminotoluene, 4' -diamino-3, 3 '-dimethyl-1, 1' -biphenyl 4,4 '-diamino-3, 3' -dihydroxy-1, 1 '-biphenyl, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide, 2' -bis (4-aminophenyl) propane, 2,2 '-bis (4-aminophenyl) hexafluoropropyl, 1, 3-bis (4-aminophenoxy) phenyl, 1, 4-bis (4-aminophenoxy) phenyl, 4' -bis (4-aminophenoxy) biphenyl, 1, 3-bis [2- (4-aminophenyl) -2-propyl ] phenyl, at least one of 1, 4-bis [2- (4-aminophenyl) -2-propyl ] phenyl, 2' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropyl, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (4-aminophenoxy) phenyl ] sulfone, 2, 6-diaminopyridinyl, 2, 6-diamino-4-methylpyridinyl, 4' - (9-fluorenylidene) diphenylamino and α, α ' -bis (4-aminophenyl) -1, 3-diisopropylphenyl;
the dianhydride compound includes 2, 3',4' -biphenyl tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, biphenyl sulfone tetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bicyclo [2, 2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1,2,3, 4-butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, ethylenediamine tetraacetic dianhydride, 4' - (acetylene-1, 2-diyl) diphthalic anhydride, 2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride group and 3,3', at least one of 4,4' -benzophenone tetracarboxylic dianhydrides.
Preferably, the preparation method comprises the following steps:
The sum of the dosages of the components is 100 percent;
the polyimide solution comprises the soluble polyimide polymer according to any one of claims 1 to 4;
The polyimide electrophoretic paint does not contain silicon element.
Preferably, the basic organic matter includes at least one of N, N-dimethylaminoethanol, triethylamine, triethanolamine, N-dimethylbenzylamine, pyrrole, imidazole, oxazole, pyrazole, isoxazole, thiazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, diethanolamine, monoethanolamine, isopropanolamine, dicyclohexylamine, diglycolamine, morpholine, tetramethylguanidine, and 4-vinylpyridine.
Preferably, the alcohol substance comprises at least one of benzyl alcohol, 4-methyl benzyl alcohol, 4-methoxybenzyl alcohol, ethylene glycol monophenyl ether, phenoxy-2-ethanol, cinnamyl alcohol, furfuryl alcohol, naphthyl methanol, 1-propanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, isopropanol, n-butanol, diethylene glycol, glycerol, ethylene glycol and propylene glycol;
the ketone substance includes ketone containing at least one of phenyl, furfuryl and naphthyl.
Preferably, the first solvent is water;
the second solvent is a water-soluble polar organic solvent and comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, gamma-butyrolactone, gamma-valerolactone and sulfolane.
The invention also provides a preparation method of the polyimide electrophoretic paint, which comprises the following steps:
A) Stirring and mixing the polyimide solution, the second solvent and the alkaline organic matters, then dripping alcohol matters or ketone matters, and stirring and mixing to obtain a polyimide electrophoretic coating intermediate;
B) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent to obtain the polyimide electrophoretic coating.
The invention also provides a polyimide electrophoretic paint film which is prepared by the polyimide electrophoretic paint or the polyimide electrophoretic paint prepared by the preparation method through electrophoretic deposition.
The invention provides a polyimide electrophoretic coating, which comprises a soluble polyimide polymer; the soluble polyimide polymer does not contain silicon element. Compared with the prior art, the polyimide electrophoretic paint film prepared by the polyimide electrophoretic paint disclosed by the invention does not contain silicon element, has excellent adhesive property, and simultaneously has excellent ageing resistance, bending resistance, high temperature resistance, impact resistance and the like.
Experimental results show that the thickness of the electrophoretic paint film prepared by the invention is 30-45 mu m, the surface energy is 38-54 mN/m, the initial bonding strength is not lower than 14MPa, the double 85 test (200 hrs) is not lower than 16MPa, the double 85 test (600 hrs) is not lower than 11MPa, and the double 85 test (1000 hrs) is not lower than 7MPa; the 90-degree bending and the 180-degree bending are not damaged; through high temperature resistance test, the appearance of the sample is good; the aging resistance can reach 100/100 level according to JIS K5600 standard test; after impact resistance test, the paint film has no phenomena of crack, wrinkle, peeling and the like.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a polyimide electrophoretic coating, which comprises a soluble polyimide polymer;
The soluble polyimide polymer does not contain silicon element.
In certain embodiments of the invention, the soluble polyimide polymer is prepared from a feedstock comprising a diamine compound and a dianhydride compound;
The diamine compound comprises at least one of aliphatic diamine and aromatic diamine;
the dianhydride compound includes at least one of aliphatic dianhydride and aromatic dianhydride;
The diamine compound and the dianhydride compound do not contain silicon element.
In certain embodiments of the present invention, the diamine compound comprises at least one of cyclohexanediamine, C1-C6 alkyl substituted pentanediamine, ethylenediamine, propylenediamine, hexamethylenediamine, diaminoanilide, diaminodiphenylaminesulfonic acid, diaminobenzenesulfonic acid, bis [ (aminophenoxy) phenyl ] propane, diaminobenzoic acid, phenylenediamine, diaminotoluene, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenyl sulfide, bis (aminophenyl) propane, bis (aminophenyl) hexafluoropropylene, bis (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, bis [ (aminophenyl) propyl ] benzene, bis [ (aminophenoxy) phenyl ] hexafluoropropylene, bis [ (aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, C1-C6 alkyl substituted diaminopyridine, (fluorenyl) diphenylamine, and bis (aminophenyl) diisopropylbenzene.
Preferably, the method comprises the steps of, the diamine compound includes 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, 2-methylpentanediamine, 1, 5-pentanediamine, ethylenediamine, propylenediamine, 1, 6-hexamethylenediamine, 4 '-diaminoanilide, 4' -diaminodiphenylamine-2-sulfonic acid, 2, 5-diaminobenzenesulfonic acid, 1, 3-diamino-4-benzenesulfonic acid, 2 '-bis [4- (4-aminophenoxy) phenyl ] propane, 3, 5-diaminobenzoic acid, 2, 3-diaminobenzoic acid, 3, 4-diaminobenzoic acid, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminotoluene, 4' -diamino-3, 3 '-dimethyl-1, 1' -biphenyl 4,4 '-diamino-3, 3' -dihydroxy-1, 1 '-biphenyl, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide, 2' -bis (4-aminophenyl) propane, 2,2 '-bis (4-aminophenyl) hexafluoropropyl, 1, 3-bis (4-aminophenoxy) phenyl, 1, 4-bis (4-aminophenoxy) phenyl, 4' -bis (4-aminophenoxy) biphenyl, 1, 3-bis [2- (4-aminophenyl) -2-propyl ] phenyl, at least one of 1, 4-bis [2- (4-aminophenyl) -2-propyl ] phenyl, 2' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropyl, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (4-aminophenoxy) phenyl ] sulfone, 2, 6-diaminopyridinyl, 2, 6-diamino-4-methylpyridinyl, 4' - (9-fluorenylidene) diphenylamino and α, α ' -bis (4-aminophenyl) -1, 3-diisopropylphenyl.
In certain embodiments of the present invention, the dianhydride compound includes at least one of oxydiphthalic anhydride, biphenyltetracarboxylic anhydride, pyromellitic dianhydride, biphenylsulfone tetracarboxylic anhydride, bis (dicarboxyphenyl) ether dianhydride, bicyclo [2, 2] octene tetracarboxylic anhydride, butane tetracarboxylic anhydride, cyclobutane tetracarboxylic anhydride, ethylenediamine tetraacetic anhydride, bis (dicarboxylic) hexafluoropropane dianhydride, (ethynediyl) diphthalic anhydride, and benzophenone tetracarboxylic dianhydride.
Preferably, the dianhydride compound includes 2, 3',4' -biphenyltetracarboxylic acid dianhydride, 4' -oxydiphthalic acid dianhydride, biphenyltetracarboxylic acid dianhydride, pyromellitic acid dianhydride, biphenylsulfone tetracarboxylic acid dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bicyclo [2, 2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride, 1,2,3, 4-butanetetracarboxylic acid dianhydride, cyclobutane tetracarboxylic acid dianhydride, ethylenediamine tetraacetic acid dianhydride, 4' - (acetylene-1, 2-diyl) diphthalic acid anhydride, 2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride group and 3,3', at least one of 4,4' -benzophenone tetracarboxylic dianhydrides.
In certain embodiments of the present invention, the method of preparing the soluble polyimide polymer comprises the steps of:
And (3) carrying out polymerization reaction on the diamine compound and the dianhydride compound in a third solvent under the atmosphere of nitrogen to obtain the soluble polyimide polymer.
Specifically, the method comprises the following steps:
And (3) stirring and mixing the dianhydride compound and part of the third solvent uniformly in a nitrogen atmosphere, and then adding the diamine compound and the rest of the third solvent for polymerization reaction to obtain the soluble polyimide polymer.
In the preparation method of the soluble polyimide polymer, the adopted raw material components are the same as the above, and are not described in detail here.
In certain embodiments of the invention, the molar ratio of diamine compound to dianhydride compound is 1:1 to 1.15; specifically, it may be 1:1.04.
In certain embodiments of the present invention, the dianhydride compound comprises 2, 3',4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,3, 4-butane tetracarboxylic dianhydride (BDA) in a molar ratio of 0.42:0.1. in certain embodiments of the present invention, the dianhydride compound comprises pyromellitic dianhydride (PMDA) and 4,4' -oxydiphthalic anhydride (ODPA) in a molar ratio of 0.42:0.1. in certain embodiments of the present invention, the dianhydride compound comprises pyromellitic dianhydride (PMDA) and 1,2,3, 4-Butanetetracarboxylic Dianhydride (BDA) in a molar ratio of 0.42:0.1. in certain embodiments of the present invention, the dianhydride compound comprises pyromellitic dianhydride (PMDA) and cyclobutane tetracarboxylic dianhydride (CBDA) in a molar ratio of 0.42:0.1. in certain embodiments of the invention, the dianhydride compound is 4,4' -oxydiphthalic anhydride (ODPA). In certain embodiments of the invention, the dianhydride compound comprises 3,3',4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 4,4' -oxydiphthalic anhydride (ODPA) in a molar ratio of 0.42:0.1.
In certain embodiments of the present invention, the diamine compound comprises 3,4' -diaminodiphenyl ether and 3, 5-diaminobenzoic acid in a molar ratio of 0.2:0.3. in certain embodiments of the present invention, the diamine compound comprises 1, 4-cyclohexanediamine and 3, 5-diaminobenzoic acid in a molar ratio of 0.2:0.3. in certain embodiments of the present invention, the diamine compound comprises 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane and 3, 5-diaminobenzoic acid in a molar ratio of 0.2:0.3. in certain embodiments of the present invention, the diamine compound comprises 3, 5-diaminobenzoic acid and 4,4' -bis (4-aminophenoxy) biphenyl in a molar ratio of 0.2:0.3. in certain embodiments of the present invention, the diamine compound comprises 3, 5-diaminobenzoic acid and 4,4' -bis (4-aminophenoxy) biphenyl (BAPB) in a molar ratio of 0.2:0.3. in certain embodiments of the invention, the diamine compound is 3, 5-diaminobenzoic acid.
In certain embodiments of the invention, the mass ratio of dianhydride compound to a portion of the third solvent is 1:1 to 4; specifically, it may be 1:2.9, 1:3.4, 1:3.7, 1:3.5, 1:3.2, 1:2.5 or 1:2.4. stirring and mixing the dianhydride compound and part of the third solvent uniformly at a rotation speed of 50-500 rpm, specifically 300rpm; the time is 10-60 min, specifically 30min.
In certain embodiments of the invention, the mass ratio of diamine compound to remaining third solvent is 1:2 to 5; specifically, it may be 1:3.4, 1:4.2, 1:2.3, 1:2. 1:2.1 or 1:3.9.
In certain embodiments of the present invention, the third solvent comprises at least one of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylacetamide, sulfolane, and N-methylpyrrolidone.
In certain embodiments of the invention, the polymerization reaction comprises:
Firstly, stirring and reacting for 5-8 h at 130-190 ℃, and then stirring and reacting for 1-3 h at 70-90 ℃.
In certain embodiments, the polymerization reaction comprises:
the reaction was stirred at 180℃for 7h and then at 80℃for 2h.
In some embodiments of the invention, the rotational speed of the stirring reaction is 250-350 rpm at 130-190 ℃; specifically, it may be 200rpm.
In some embodiments of the invention, the rotational speed of the stirring reaction is 350-450 rpm at 70-90 ℃; specifically, it may be 300rpm.
In certain embodiments of the invention, the water removal is performed during the stirring reaction.
In certain embodiments of the present invention, after the polymerization reaction, further comprising: naturally cooling to normal temperature.
In certain embodiments of the present invention, the soluble polyimide polymer has a structure represented by formula (1);
in the formula (1), m, n, x and y are positive integers, the value range of n+x is 10-150, and the value range of m+y is 10-180;
The weight average molecular weight of the soluble polyimide polymer represented by the formula (1) is 185000.
In certain embodiments of the present invention, the soluble polyimide polymer has a structure represented by formula (2);
in the formula (2), the value range of n+x is: 10 to 150, and the value range of m+y: 10 to 180;
the weight average molecular weight of the soluble polyimide polymer represented by the formula (2) was 180000.
In certain embodiments of the present invention, the soluble polyimide polymer has a structure represented by formula (3);
In the formula (3), the value range of n+x is: 10 to 150, and the value range of m+y: 10 to 180;
The weight average molecular weight of the soluble polyimide polymer represented by the formula (3) is 192000.
In certain embodiments of the present invention, the soluble polyimide polymer has a structure represented by formula (4);
In the formula (4), the value range of n+x is: 10 to 150, and the value range of m+y: 10 to 180;
The weight average molecular weight of the soluble polyimide polymer represented by the formula (4) is 187000.
In certain embodiments of the present invention, the soluble polyimide polymer has a structure represented by formula (5);
in the formula (5), x and y are positive integers, and the value range of x is as follows: 10-180, the value range of y: 10 to 230 percent;
The weight average molecular weight of the soluble polyimide polymer represented by the formula (5) is 188000.
In certain embodiments of the invention, the soluble polyimide polymer has a structure represented by formula (6);
In the formula (6), x and y are positive integers, and the value range of x is: 10-180, the value range of y: 10 to 230 percent;
The weight average molecular weight of the soluble polyimide polymer represented by the formula (6) was 175000.
In certain embodiments of the invention, the polyimide electrocoat is prepared from the following raw materials:
The sum of the dosages of the components is 100 percent;
The polyimide solution comprises the soluble polyimide polymer described above;
The polyimide electrophoretic paint does not contain silicon element.
In certain embodiments of the present invention, the polyimide solution is present in the raw material for preparing the polyimide electrophoretic coating in an amount of 47wt%.
In certain embodiments of the present invention, the polyimide solution is obtained by mixing the soluble polyimide polymer described above with a fourth solvent. The solid content of the polyimide solution is 1-25 wt%; specifically, it may be 14.86wt%. The fourth solvent is N-methyl-2-pyrrolidone (NMP). The method for preparing the polyimide solution is not particularly limited, and a solution preparation method well known to those skilled in the art may be adopted.
In certain embodiments of the present invention, the polyimide electrocoat is prepared from a starting material having a basic organic mass content of 3wt%.
In certain embodiments of the present invention, the basic organic material comprises at least one of N, N-dimethylaminoethanol, triethylamine, triethanolamine, N-dimethylbenzylamine, pyrrole, imidazole, oxazole, pyrazole, isoxazole, thiazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, diethanolamine, monoethanolamine, isopropanolamine, dicyclohexylamine, diglycolamine, morpholine, tetramethylguanidine, and 4-vinylpyridine; preferably, at least one of tetramethylguanidine, 4-vinylpyridine, piperidine, morpholine, N-dimethylaminoethanol and monoethanolamine is included.
In some embodiments of the present invention, the mass content of the alcohol or ketone in the raw material for preparing the polyimide electrophoretic coating is 11wt%.
In certain embodiments of the present invention, the alcohol comprises at least one of benzyl alcohol, 4-methyl benzyl alcohol, 4-methoxybenzyl alcohol, ethylene glycol monophenyl ether, phenoxy-2-ethanol, cinnamyl alcohol, furfuryl alcohol, naphthylmethyl alcohol, 1-propanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, isopropyl alcohol, n-butyl alcohol, diethylene glycol, glycerol, ethylene glycol, and propylene glycol.
In certain embodiments of the present invention, the ketone species includes ketones containing at least one of phenyl, furfuryl, and naphthyl.
In certain embodiments of the present invention, the first solvent is present in the polyimide electrophoretic coating formulation at a mass content of 4.1wt%.
In certain embodiments of the invention, the first solvent is water.
In certain embodiments of the present invention, the mass content of the second solvent in the preparation raw material of the polyimide electrophoretic coating is 34.9wt%.
In certain embodiments of the present invention, the second solvent is a water-soluble polar organic solvent including at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, γ -butyrolactone, γ -valerolactone, and sulfolane.
The polyimide electrophoretic paint provided by the invention does not contain silicon element.
The invention also provides a preparation method of the polyimide electrophoretic paint, which comprises the following steps:
A) Stirring and mixing the polyimide solution, the second solvent and the alkaline organic matters, then dripping alcohol matters or ketone matters, and stirring and mixing to obtain a polyimide electrophoretic coating intermediate;
B) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent to obtain the polyimide electrophoretic coating.
In step A):
And (3) stirring and mixing the polyimide solution, the second solvent and the alkaline organic matters, then dripping alcohol matters or ketone matters, and stirring and mixing to obtain the polyimide electrophoretic coating intermediate.
In some embodiments of the invention, the temperature of the stirring and mixing is room temperature for 10-70 min; specifically, it may be 30 minutes.
In some embodiments of the invention, after the alcohol or ketone is added dropwise, stirring and mixing are carried out for 30-90 min; specifically, the time period may be 60 minutes.
In step B):
And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent to obtain the polyimide electrophoretic coating.
The invention also provides an electrophoretic paint film which is prepared from the polyimide electrophoretic paint or the polyimide electrophoretic paint prepared by the preparation method through electrophoretic deposition.
In certain embodiments of the invention, the electrophoretic paint film is prepared according to the following method:
and (3) carrying out electrophoretic deposition on the polyimide electrophoretic coating, and drying to obtain an electrophoretic paint film.
In certain embodiments of the invention, the temperature of the electrophoretic deposition is 15-35 ℃, the voltage is 40-150V, and the time is 30-600 s. In certain embodiments, the electrophoretic deposition is performed at a temperature of 28 ℃, a voltage of 40V, and a time of 200s.
In certain embodiments of the invention, the drying process comprises:
drying at 60-100 deg.c for 10-60 min, heating to 140-180 deg.c for 10-60 min, and heating to 220-260 deg.c for 10-60 min.
In certain embodiments, the drying process comprises:
drying at 80deg.C for 60min, heating to 160deg.C for 60min, and heating to 240 deg.C for 60min.
In certain embodiments of the invention, the thickness of the electrophoretic paint film is 30 to 45 μm.
In certain embodiments of the invention, the surface energy of the electrophoretic paint film is between 38 and 54mN/m.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe in detail a polyimide, a preparation method and an application thereof, but are not to be construed as limiting the scope of the present invention.
The raw materials used in the following examples are all commercially available.
Example 1
Preparation of soluble polyimide polymer:
2, 3',4' -Biphenyltetracarboxylic acid dianhydride (BPDA) (123.570 g,0.42 mol), 1,2,3, 4-butanetetracarboxylic acid dianhydride (BDA) (19.813 g,0.10 mol) and N-methylpyrrolidone (NMP) (398.83 g) were successively charged into a three-port stainless steel reactor equipped with a stirring device having stirring blades, a reflux condenser and a thermometer under a nitrogen atmosphere, and stirred at 300rpm for 30 minutes at room temperature. 3,4' -diaminodiphenyl ether (40.048 g,0.20 mol), 3, 5-diaminobenzoic acid (45.645 g,0.30 mol) and NMP (300 g) were then added, and the reaction was stirred at 200rpm at 180℃for 7 hours and at 300rpm at 80℃for 2 hours. Dewatering in the reaction process, and naturally cooling to normal temperature to obtain a soluble polyimide polymer sample 1; the result is shown in formula (1).
In the formula (1), m, n, x and y are positive integers, the value range of n+x is 10-150, and the value range of m+y is 10-180; nuclear magnetic resonance spectroscopy and infrared spectroscopy were performed on the soluble polyimide polymer sample 1, and the chemical shift ppm of the nuclear magnetic resonance spectrum of the soluble polyimide polymer sample 1 was 2.78, 7.02, 7.71, 8.12, 8.42, and the absorption peak of the infrared spectrum at 1773cm -1、1703cm-1 indicated that the soluble polyimide polymer sample 1 had the structure shown by formula (1).
The weight average molecular weight of the soluble polyimide polymer sample 1 was 185000.
Example 2
Preparation of soluble polyimide polymer:
Into a three-port stainless steel reactor equipped with a stirring apparatus having stirring blades, a reflux condenser and a thermometer, pyromellitic dianhydride (PMDA) (91.610 g,0.42 mol), 4' -oxydiphthalic anhydride (ODPA) (31.021 g,0.10 mol) and N-methylpyrrolidone (NMP) (398.83 g) were successively charged, and the mixture was stirred at 300rpm for 30 minutes by nitrogen substitution at room temperature. 1, 4-cyclohexanediamine (22.838 g,0.20 mol), 3, 5-diaminobenzoic acid (45.645 g,0.30 mol) and NMP (300 g) were then added and reacted at 180℃with stirring at 200rpm for 7 hours and at 80℃with stirring at 300rpm for 2 hours. And (3) removing water in the reaction process, and naturally cooling to normal temperature to obtain a soluble polyimide polymer sample 2 shown in the formula (2).
In the formula (2), m, n, x and y are positive integers, and the value range of n+x is: 10 to 150, and the value range of m+y: 10 to 180; nuclear magnetic resonance spectroscopy and infrared spectroscopy were performed on the soluble polyimide polymer sample 2, and the chemical shift ppm of the nuclear magnetic resonance spectrum of the soluble polyimide polymer sample 2 was 1.51, 1.75, 7.41, 7.63, 8.06, 8.29, and the absorption peak of the infrared spectrum at 1777cm -1、1707cm-1 indicated that the soluble polyimide polymer sample 2 had the structure shown by formula (2).
The weight average molecular weight of the soluble polyimide polymer sample 2 was 180000.
Example 3
Preparation of soluble polyimide polymer:
A three-port stainless steel reactor equipped with a stirring apparatus having stirring blades, a reflux condenser and a thermometer was charged with pyromellitic dianhydride (PMDA) (91.610 g,0.42 mol), 1,2,3, 4-Butanetetracarboxylic Dianhydride (BDA) (19.813 g,0.10 mol) and N-methylpyrrolidone (NMP) (398.83 g) in this order, and the mixture was stirred at 300rpm for 30 minutes by nitrogen substitution at room temperature. 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane (BAPP) (82.102 g,0.20 mol), 3, 5-diaminobenzoic acid (45.645 g,0.30 mol) and NMP (300 g) were then added and reacted at 180℃with stirring at 200rpm for 7 hours and at 80℃with stirring at 300rpm for 2 hours. And (3) removing water in the reaction process, and naturally cooling to normal temperature to obtain a soluble polyimide polymer sample 3 shown in the formula (3).
In the formula (3), m, n, x and y are positive integers, and the value range of n+x is: 10 to 150, and the value range of m+y is 10 to 180; nuclear magnetic resonance spectroscopy and infrared spectroscopy were performed on the soluble polyimide polymer sample 3, and the chemical shift ppm of the nuclear magnetic resonance spectrum of the soluble polyimide polymer sample 3 was 1.82, 2.65, 7.01, 8.11, 8.31, and the absorption peak of the infrared spectrum at 1777cm -1、1711cm-1 indicated that the soluble polyimide polymer sample 3 had the structure shown by formula (3).
The weight average molecular weight of the soluble polyimide polymer sample 3 was 192000.
Example 4
Preparation of soluble polyimide polymer:
A three-port stainless steel reactor equipped with a stirring apparatus having stirring blades, a reflux condenser and a thermometer was charged with pyromellitic dianhydride (PMDA) (91.610 g,0.42 mol), cyclobutane tetracarboxylic dianhydride (CBDA) (19.611 g,0.10 mol) and N-methylpyrrolidone (NMP) (398.83 g) in this order, and the mixture was stirred at 300rpm for 30 minutes by nitrogen substitution at room temperature. 3, 5-diaminobenzoic acid (30.43 g,0.20 mol), 4' -bis (4-aminophenoxy) biphenyl (BAPB) (110.528 g,0.30 mol) and NMP (300 g) were then added, and reacted at 180℃with stirring at 200rpm for 7 hours and at 80℃with stirring at 300rpm for 2 hours. And (3) removing water in the reaction process, and naturally cooling to normal temperature to obtain a soluble polyimide polymer sample 4, wherein the soluble polyimide polymer sample is shown in a formula (4).
In the formula (4), m, n, x and y are positive integers, and the value range of n+x is as follows: 10 to 150, and the value range of m+y is 10 to 180; nuclear magnetic resonance spectroscopy and infrared spectroscopy were performed on the soluble polyimide polymer sample 4, and the chemical shift ppm of the nuclear magnetic resonance spectrum of the soluble polyimide polymer sample 4 was 3.92, 7.0, 7.11, 7.71, 8.11, 8.33, and the absorption peak at 1772cm -1、1711cm-1 of the infrared spectrum indicated that the soluble polyimide polymer sample 4 had the structure shown by formula (4).
The weight average molecular weight of the soluble polyimide polymer sample 4 was 187000.
Example 5
Preparation of soluble polyimide polymer:
Into a three-port stainless steel reactor equipped with a stirring apparatus having stirring blades, a reflux condenser and a thermometer, 4' -oxydiphthalic anhydride (ODPA) (161.309 g,0.52 mol) and N-methylpyrrolidone (NMP) (398.83 g) were successively charged, and the mixture was purged with nitrogen at room temperature, and stirred at 300rpm for 30 minutes. 3, 5-diaminobenzoic acid (30.43 g,0.20 mol), 4' -bis (4-aminophenoxy) biphenyl (BAPB) (110.528 g,0.30 mol) and NMP (300 g) were then added, and reacted at 180℃with stirring at 200rpm for 7 hours and at 80℃with stirring at 300rpm for 2 hours. And (3) removing water in the reaction process, and naturally cooling to normal temperature to obtain a soluble polyimide polymer sample 5, wherein the soluble polyimide polymer sample is shown in a formula (5).
In the formula (5), x and y are positive integers, and the value range of x is as follows: 10-180, the value range of y: 10 to 230 percent; nuclear magnetic resonance spectroscopy and infrared spectroscopy were performed on the soluble polyimide polymer sample 5, and the chemical shift ppm of the nuclear magnetic resonance spectrum of the soluble polyimide polymer sample 5 was 7.0, 7.15, 7.58, 7.80, 8.11, and the absorption peak at 1775cm -1、1720cm-1 of the infrared spectrum indicated that the soluble polyimide polymer sample 5 had the structure represented by formula (5).
The weight average molecular weight of the soluble polyimide polymer sample 5 was 188000.
Example 6
Preparation of soluble polyimide polymer:
3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) (135.335 g,0.42 mol), 4' -oxydiphthalic anhydride (ODPA) (31.021 g,0.10 mol) and N-methylpyrrolidone (NMP) (398.83 g) were successively charged into a three-port stainless steel reactor equipped with a stirring device having stirring blades, a reflux condenser and a thermometer, and the mixture was stirred at 300rpm for 30 minutes by nitrogen substitution at room temperature. 3, 5-diaminobenzoic acid (76.075 g,0.50 mol) and NMP (300 g) were then added, reacted at 180℃with stirring at 200rpm for 7h, and at 80℃with stirring at 300rpm for 2h. And (3) removing water in the reaction process, and naturally cooling to normal temperature to obtain a soluble polyimide polymer sample 6, wherein the soluble polyimide polymer sample is shown in a formula (6).
In the formula (6), x and y are positive integers, and the value range of x is: 10-180, the value range of y: 10 to 230 percent; nuclear magnetic resonance spectroscopy and infrared spectroscopy were performed on the soluble polyimide polymer sample 6, and the chemical shift ppm of the nuclear magnetic resonance spectrum of the soluble polyimide polymer sample 6 was 7.52, 7.91, 8.11, 8.21, and the absorption peak of the infrared spectrum at 1781cm -1、1720cm-1 indicated that the soluble polyimide polymer sample 6 had the structure shown by formula (6).
The weight average molecular weight of the soluble polyimide polymer sample 6 was 175000.
Example 7
The polyimide electrophoretic paint is prepared from the following raw materials:
The soluble polyimide polymer in the polyimide solution was soluble polyimide polymer sample 1 prepared in example 1;
The polyimide solution is prepared by the following steps:
the soluble polyimide polymer was mixed with N-methylpyrrolidone (NMP) to give a polyimide solution having a solids content of 14.86 wt%.
The preparation of the polyimide electrophoretic paint comprises the following steps:
1) Stirring and mixing 1000g of polyimide solution, a second solvent and an alkaline organic matter for 30min at room temperature, then dripping alcohol substances, and stirring and mixing for 1h to obtain a polyimide electrophoretic coating intermediate;
2) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent water to obtain the polyimide electrophoretic coating with the solid content of 6.9 wt%.
Example 8
The polyimide electrophoretic paint is prepared from the following raw materials:
The soluble polyimide polymer in the polyimide solution was soluble polyimide polymer sample 2 prepared in example 2;
The polyimide solution is prepared by the following steps:
the soluble polyimide polymer was mixed with N-methylpyrrolidone (NMP) to give a polyimide solution having a solids content of 14.86 wt%.
The preparation of the polyimide electrophoretic paint comprises the following steps:
1) Stirring and mixing 1000g of polyimide solution, a second solvent and an alkaline organic matter for 30min at room temperature, then dripping alcohol substances, and stirring and mixing for 1h to obtain a polyimide electrophoretic coating intermediate;
2) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent water to obtain the polyimide electrophoretic coating with the solid content of 6.9 wt%.
Example 9
The polyimide electrophoretic paint is prepared from the following raw materials:
the soluble polyimide polymer in the polyimide solution was soluble polyimide polymer sample 3 prepared in example 3;
The polyimide solution is prepared by the following steps:
the soluble polyimide polymer was mixed with N-methylpyrrolidone (NMP) to give a polyimide solution having a solids content of 14.86 wt%.
The preparation of the polyimide electrophoretic paint comprises the following steps:
1) Stirring and mixing 1000g of polyimide solution, a second solvent and an alkaline organic matter for 30min at room temperature, then dripping alcohol substances, and stirring and mixing for 1h to obtain a polyimide electrophoretic coating intermediate;
2) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent water to obtain the polyimide electrophoretic coating with the solid content of 6.9 wt%.
Example 10
The polyimide electrophoretic paint is prepared from the following raw materials:
the soluble polyimide polymer in the polyimide solution was soluble polyimide polymer sample 4 prepared in example 4;
The polyimide solution is prepared by the following steps:
the soluble polyimide polymer was mixed with N-methylpyrrolidone (NMP) to give a polyimide solution having a solids content of 14.86 wt%.
The preparation of the polyimide electrophoretic paint comprises the following steps:
1) Stirring and mixing 1000g of polyimide solution, a second solvent and an alkaline organic matter for 30min at room temperature, then dripping alcohol substances, and stirring and mixing for 1h to obtain a polyimide electrophoretic coating intermediate;
2) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent water to obtain the polyimide electrophoretic coating with the solid content of 6.9 wt%.
Example 11
The polyimide electrophoretic paint is prepared from the following raw materials:
The soluble polyimide polymer in the polyimide solution was soluble polyimide polymer sample 5 prepared in example 5;
The polyimide solution is prepared by the following steps:
the soluble polyimide polymer was mixed with N-methylpyrrolidone (NMP) to give a polyimide solution having a solids content of 14.86 wt%.
The preparation of the polyimide electrophoretic paint comprises the following steps:
1) Stirring and mixing 1000g of polyimide solution, a second solvent and an alkaline organic matter for 30min at room temperature, then dripping alcohol substances, and stirring and mixing for 1h to obtain a polyimide electrophoretic coating intermediate;
2) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent water to obtain the polyimide electrophoretic coating with the solid content of 6.9 wt%.
Example 12
The polyimide electrophoretic paint is prepared from the following raw materials:
The soluble polyimide polymer in the polyimide solution was soluble polyimide polymer sample 6 prepared in example 6;
The polyimide solution is prepared by the following steps:
the soluble polyimide polymer was mixed with N-methylpyrrolidone (NMP) to give a polyimide solution having a solids content of 14.86 wt%.
The preparation of the polyimide electrophoretic paint comprises the following steps:
1) Stirring and mixing 1000g of polyimide solution, a second solvent and an alkaline organic matter for 30min at room temperature, then dripping alcohol substances, and stirring and mixing for 1h to obtain a polyimide electrophoretic coating intermediate;
2) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent water to obtain the polyimide electrophoretic coating with the solid content of 6.9 wt%.
Application example
Preparation of polyimide electrophoretic paint film:
The electrodeposition coating materials of examples 7 to 12 and comparative example 1 (commercially available silicone-containing polyimide electrodeposition coating materials having a solid content of 6.9% by weight) were respectively subjected to electrodeposition using an anodic electrodeposition apparatus;
the conditions of the electrophoretic deposition are as follows: temperature: 28 ℃, 40V, 200s (charge amount 45C);
After the electrophoretic deposition is finished, an electrophoretic paint wet film is obtained on an aluminum sheet, and drying treatment is carried out: drying at 80deg.C for 60min, heating to 160deg.C for 60min, and further heating to 240 deg.C for 60min.
Performance test:
each performance of the prepared paint film is detected, the obtained performance data are shown in tables 1-3, and related tests are as follows:
1. film thickness test: reference is made to QB8015-2000 "film thickness determination of paint film";
2. surface energy test: carrying out paint film surface energy test by adopting surface energy test ink;
3. Adhesive strength test: and bonding the test samples pairwise, and fixing the test samples on a tensile machine to test the shearing strength after the structural adhesive is cured, namely the bonding strength. The structural adhesive for testing can be one or more of epoxy, polyurethane, polyimide and silicone. The sizing process comprises the following steps: sizing amount is 12.5 x 25 x 2.5mm 3, curing condition is 80 ℃ for 4 hours;
4. Bending resistance test: bending the sample by 90 degrees and 180 degrees, and observing whether the appearance of a paint film is damaged or not;
5. high temperature resistance test: selecting a sample to be subjected to high temperature resistance test, placing the sample in a blast oven, heating to 350 ℃, keeping for 60min, taking out, cooling to room temperature, and observing the appearance of the sample;
6. and (3) ageing resistance test: directly performing double-85 aging resistance test on an aluminum sheet sample of the electrophoretic paint film; then, the adhesive force of the paint film is tested by a hundred-grid method, and the paint film is tested according to JIS K5600 standard;
7. Impact resistance test: according to the QB8017-2000 standard test of the paint film impact resistance measurement method; the paint film should be free from cracks, wrinkles, flaking and the like when observed with a four-fold magnifying glass with normal vision (or corrected normal vision).
TABLE 1 film thickness and surface energy test results of polyimide electrophoretic paint films
Electrophoretic paint | Film thickness (mum) | Surface energy (mN/m) |
Example 7 | 30-40 | 54 |
Example 8 | 30-45 | 42 |
Example 9 | 30-40 | 48 |
Example 10 | 35-40 | 38 |
Example 11 | 30-40 | 40 |
Example 12 | 40-45 | 52 |
Comparative example 1 | 35-50 | 30 |
As can be seen from Table 1, the thickness of the electrophoretic paint film prepared by the invention is in the range of 30-45 μm, and can achieve thinner and uniform thickness; the surface energy is basically 38-54 mN/m, which shows that the paint film surface has excellent adhesive property.
TABLE 2 test results of adhesion, aging and bending resistance of polyimide electrophoretic paint films
As can be seen from Table 2, the adhesive strength and bending resistance of the electrophoretic paint film prepared by the invention are obviously superior to those of the polyimide electrophoretic paint film containing silicon; the initial bonding strength is not lower than 14MPa, the double 85 test (200 h) is not lower than 16MPa, the double 85 test (600 h) is not lower than 11MPa, and the double 85 test (1000 h) is not lower than 7MPa; the 90-degree bending and the 180-degree bending are not damaged.
TABLE 3 results of high temperature resistance, aging resistance and impact resistance of the electrophoretic paint film
Sequence number | High temperature resistance | Aging resistance | Impact-resistant |
Example 7 | Good appearance | 100/100 Level | By passing through |
Example 8 | Good appearance | 100/100 Level | By passing through |
Example 9 | Good appearance | 100/100 Level | By passing through |
Example 10 | Good appearance | 100/100 Level | By passing through |
Example 11 | Good appearance | 100/100 Level | By passing through |
Example 12 | Good appearance | 100/100 Level | By passing through |
Comparative example 1 | Good appearance | 100/100 Level | By passing through |
As can be seen from Table 3, the electrophoretic paint film prepared by the invention has better high temperature resistance, aging resistance and impact resistance. Through high temperature resistance test, the appearance of the sample is good; the aging resistance can reach 100/100 level according to JIS K5600 standard test; after impact resistance test, the paint film has no phenomena of crack, wrinkle, peeling and the like.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A polyimide electrophoretic coating comprising a soluble polyimide polymer;
The soluble polyimide polymer does not contain silicon element.
2. The polyimide electrophoretic coating of claim 1, wherein the soluble polyimide polymer is prepared from raw materials including a diamine compound and a dianhydride compound;
The diamine compound comprises at least one of aliphatic diamine and aromatic diamine;
the dianhydride compound includes at least one of aliphatic dianhydride and aromatic dianhydride;
The diamine compound and the dianhydride compound do not contain silicon element.
3. The polyimide electrocoating of claim 1, wherein said diamine compound comprises at least one of cyclohexanediamine, C1-C6 alkyl-substituted pentanediamine, ethylenediamine, propylenediamine, hexamethylenediamine, diaminoanilide, diaminodiphenylaminesulfonic acid, diaminobenzenesulfonic acid, bis [ (aminophenoxy) phenyl ] propane, diaminobenzoic acid, phenylenediamine, diaminotoluene, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenyl sulfide, bis (aminophenyl) propane, bis (aminophenyl) hexafluoropropyl, bis (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, bis [ (aminophenyl) propyl ] benzene, bis [ (aminophenoxy) phenyl ] hexafluoropropyl, bis [ (aminophenoxy ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, C1-C6 alkyl-substituted diaminopyridine, (fluorenyl) diphenylamine, and bis (aminophenyl) diisopropylbenzene;
The dianhydride compound includes at least one of oxydiphthalic anhydride, biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, biphenyl sulfone tetracarboxylic dianhydride, bis (dicarboxyphenyl) ether dianhydride, bicyclo [2, 2] octene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, ethylenediamine tetraacetic dianhydride, bis (dicarboxylic) hexafluoropropane dianhydride group, (acetylene diyl) diphthalic anhydride and benzophenone tetracarboxylic dianhydride.
4. The polyimide electrophoretic coating of claim 1, wherein, the diamine compound includes 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, 2-methylpentanediamine, 1, 5-pentanediamine, ethylenediamine, propylenediamine, 1, 6-hexamethylenediamine, 4 '-diaminoanilide, 4' -diaminodiphenylamine-2-sulfonic acid, 2, 5-diaminobenzenesulfonic acid, 1, 3-diamino-4-benzenesulfonic acid, 2 '-bis [4- (4-aminophenoxy) phenyl ] propane, 3, 5-diaminobenzoic acid, 2, 3-diaminobenzoic acid, 3, 4-diaminobenzoic acid, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminotoluene, 4' -diamino-3, 3 '-dimethyl-1, 1' -biphenyl 4,4 '-diamino-3, 3' -dihydroxy-1, 1 '-biphenyl, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide, 2' -bis (4-aminophenyl) propane, 2,2 '-bis (4-aminophenyl) hexafluoropropyl, 1, 3-bis (4-aminophenoxy) phenyl, 1, 4-bis (4-aminophenoxy) phenyl, 4' -bis (4-aminophenoxy) biphenyl, 1, 3-bis [2- (4-aminophenyl) -2-propyl ] phenyl, at least one of 1, 4-bis [2- (4-aminophenyl) -2-propyl ] phenyl, 2' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropyl, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (4-aminophenoxy) phenyl ] sulfone, 2, 6-diaminopyridinyl, 2, 6-diamino-4-methylpyridinyl, 4' - (9-fluorenylidene) diphenylamino and α, α ' -bis (4-aminophenyl) -1, 3-diisopropylphenyl;
the dianhydride compound includes 2, 3',4' -biphenyl tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, biphenyl sulfone tetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bicyclo [2, 2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1,2,3, 4-butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, ethylenediamine tetraacetic dianhydride, 4' - (acetylene-1, 2-diyl) diphthalic anhydride, 2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride group and 3,3', at least one of 4,4' -benzophenone tetracarboxylic dianhydrides.
5. The polyimide electrophoretic coating according to claim 1, which is prepared from the following raw materials:
The sum of the dosages of the components is 100 percent;
the polyimide solution comprises the soluble polyimide polymer according to any one of claims 1 to 4;
The polyimide electrophoretic paint does not contain silicon element.
6. The polyimide electrocoating of claim 5, wherein said basic organic material comprises at least one of N, N-dimethylaminoethanol, triethylamine, triethanolamine, N-dimethylbenzylamine, pyrrole, imidazole, oxazole, pyrazole, isoxazole, thiazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, diethanolamine, monoethanolamine, isopropanolamine, dicyclohexylamine, diglycolamine, morpholine, tetramethylguanidine, and 4-vinylpyridine.
7. The polyimide electrophoretic coating of claim 5, wherein the alcohol substance comprises at least one of benzyl alcohol, 4-methyl benzyl alcohol, 4-methoxy benzyl alcohol, ethylene glycol monophenyl ether, phenoxy-2-ethanol, cinnamyl alcohol, furfuryl alcohol, naphthyl methanol, 1-propanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, isopropanol, n-butanol, diethylene glycol, glycerol, ethylene glycol, and propylene glycol;
the ketone substance includes ketone containing at least one of phenyl, furfuryl and naphthyl.
8. The polyimide electrocoat of claim 5, wherein the first solvent is water;
the second solvent is a water-soluble polar organic solvent and comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, gamma-butyrolactone, gamma-valerolactone and sulfolane.
9. A method for preparing the polyimide electrophoretic paint according to any one of claims 1 to 8, comprising the steps of:
A) Stirring and mixing the polyimide solution, the second solvent and the alkaline organic matters, then dripping alcohol matters or ketone matters, and stirring and mixing to obtain a polyimide electrophoretic coating intermediate;
B) And uniformly mixing the polyimide electrophoretic coating intermediate with the first solvent to obtain the polyimide electrophoretic coating.
10. A polyimide electrodeposition paint film prepared by electrodeposition of the polyimide electrodeposition paint according to any one of claims 1 to 8 or the polyimide electrodeposition paint prepared by the preparation method of claim 9.
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CN202211562563.0A CN118146713A (en) | 2022-12-07 | 2022-12-07 | Polyimide electrophoretic paint, preparation method and application thereof |
PCT/CN2023/130096 WO2024120097A1 (en) | 2022-12-07 | 2023-11-07 | Polyimide electrophoretic coating, preparation method therefor, and application thereof |
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CN202211562563.0A CN118146713A (en) | 2022-12-07 | 2022-12-07 | Polyimide electrophoretic paint, preparation method and application thereof |
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JP3089195B2 (en) * | 1995-10-12 | 2000-09-18 | 大日本塗料株式会社 | Polyimide composition for electrodeposition |
JPH11152433A (en) * | 1997-11-20 | 1999-06-08 | Nippon Petrochem Co Ltd | Composition for electrodeposition and electrodeposition using the same |
JP4311606B2 (en) * | 2002-05-07 | 2009-08-12 | 株式会社ピーアイ技術研究所 | Polyimide electrodeposition composition and polyimide electrodeposition method |
JP4215452B2 (en) * | 2002-05-07 | 2009-01-28 | 株式会社ピーアイ技術研究所 | Electrodeposition block copolymerized polyimide composition |
JP2008050635A (en) * | 2006-08-23 | 2008-03-06 | National Institute Of Advanced Industrial & Technology | Cu-Ni-ORGANIC ELECTRODEPOSITED THIN FILM STACKED STRUCTURE AND METHOD FOR FORMING THE SAME |
JP4998871B2 (en) * | 2006-08-23 | 2012-08-15 | 独立行政法人産業技術総合研究所 | Electrodeposited polyimide thin film and method for forming the same |
JP5994955B1 (en) * | 2015-05-25 | 2016-09-21 | 三菱マテリアル株式会社 | Electrodeposition solution for water-dispersed insulation film formation |
JP7169784B2 (en) * | 2018-06-15 | 2022-11-11 | 住友精化株式会社 | POLYIMIDE RESIN, COATING COMPOSITION, ELECTRODEPOSITION COATING COMPOSITION, ARTICLE HAVING POLYIMIDE RESIN COATING AND MANUFACTURING METHOD THEREOF |
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