CN114106324A - 一种聚酰胺酸溶液及其制备方法和应用 - Google Patents
一种聚酰胺酸溶液及其制备方法和应用 Download PDFInfo
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- CN114106324A CN114106324A CN202111240166.7A CN202111240166A CN114106324A CN 114106324 A CN114106324 A CN 114106324A CN 202111240166 A CN202111240166 A CN 202111240166A CN 114106324 A CN114106324 A CN 114106324A
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- China
- Prior art keywords
- polyamic acid
- acid solution
- methylimidazolium
- ethyl
- ionic liquid
- 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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- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002253 acid Substances 0.000 title description 3
- 239000004952 Polyamide Substances 0.000 title description 2
- 229920002647 polyamide Polymers 0.000 title description 2
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 104
- 229920001721 polyimide Polymers 0.000 claims abstract description 59
- 239000002608 ionic liquid Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 239000002798 polar solvent Substances 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 125000004427 diamine group Chemical group 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 32
- 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 28
- -1 1-ethyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 claims description 26
- 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 claims description 25
- 239000000178 monomer Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 12
- BRNLFPKVZIYUAK-UHFFFAOYSA-N cyanocyanamide;1-ethyl-3-methylimidazol-3-ium Chemical compound N#CNC#N.CCN1C=C[N+](C)=C1 BRNLFPKVZIYUAK-UHFFFAOYSA-N 0.000 claims description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 claims description 2
- XIYUIMLQTKODPS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;acetate Chemical compound CC([O-])=O.CC[N+]=1C=CN(C)C=1 XIYUIMLQTKODPS-UHFFFAOYSA-M 0.000 claims description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 claims description 2
- JOLFMOZUQSZTML-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;chloride Chemical compound [Cl-].CCCN1C=C[N+](C)=C1 JOLFMOZUQSZTML-UHFFFAOYSA-M 0.000 claims description 2
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 claims description 2
- PXKPKGHXANCVMC-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound OS(=O)(=O)C(F)(F)F.CCCCN1CN(C)C=C1 PXKPKGHXANCVMC-UHFFFAOYSA-N 0.000 claims description 2
- LCXJCNGYHOHMPB-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].C(CCC)[N+]1=CN(C=C1)C.C(CCC)[N+]1=CN(C=C1)C.C(CCC)[N+]1=CN(C=C1)C.C(CCC)[N+]1=CN(C=C1)C Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].C(CCC)[N+]1=CN(C=C1)C.C(CCC)[N+]1=CN(C=C1)C.C(CCC)[N+]1=CN(C=C1)C.C(CCC)[N+]1=CN(C=C1)C LCXJCNGYHOHMPB-UHFFFAOYSA-J 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- ROBLTDOHDSGGDT-UHFFFAOYSA-M sodium;pentane-1-sulfonate Chemical compound [Na+].CCCCCS([O-])(=O)=O ROBLTDOHDSGGDT-UHFFFAOYSA-M 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 4
- XEWLRGVGAZDFCS-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].C(C)C1=[N+](C=CN1C)CC.C(C)C1=[N+](C=CN1C)CC Chemical compound S(=O)(=O)([O-])[O-].C(C)C1=[N+](C=CN1C)CC.C(C)C1=[N+](C=CN1C)CC XEWLRGVGAZDFCS-UHFFFAOYSA-L 0.000 claims 2
- 239000011780 sodium chloride Substances 0.000 claims 2
- 159000000000 sodium salts Chemical class 0.000 claims 2
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 claims 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
- QWSZRRAAFHGKCH-UHFFFAOYSA-M sodium;hexane-1-sulfonate Chemical compound [Na+].CCCCCCS([O-])(=O)=O QWSZRRAAFHGKCH-UHFFFAOYSA-M 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 20
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 87
- 238000006243 chemical reaction Methods 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 28
- 230000008569 process Effects 0.000 description 22
- 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 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 13
- VRFOKYHDLYBVAL-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCN1C=C[N+](C)=C1 VRFOKYHDLYBVAL-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- LQVMZVKOVPITOO-UHFFFAOYSA-N 9h-fluoren-1-ylmethyl carbonochloridate Chemical compound C1C2=CC=CC=C2C2=C1C(COC(=O)Cl)=CC=C2 LQVMZVKOVPITOO-UHFFFAOYSA-N 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 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 4
- 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 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 3
- XDZAFZVZTAGZHI-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CC[NH+]1CN(C)C=C1 XDZAFZVZTAGZHI-UHFFFAOYSA-N 0.000 description 3
- RDMFEHLCCOQUMH-UHFFFAOYSA-N 2,4'-Diphenyldiamine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1N RDMFEHLCCOQUMH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- UPGRRPUXXWPEMV-UHFFFAOYSA-N 5-(2-phenylethynyl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C#CC1=CC=CC=C1 UPGRRPUXXWPEMV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- HSDAJNMJOMSNEV-UHFFFAOYSA-N benzyl chloroformate Chemical compound ClC(=O)OCC1=CC=CC=C1 HSDAJNMJOMSNEV-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LPVHVQFTYXQKAP-YFKPBYRVSA-N (4r)-3-formyl-2,2-dimethyl-1,3-thiazolidine-4-carboxylic acid Chemical compound CC1(C)SC[C@@H](C(O)=O)N1C=O LPVHVQFTYXQKAP-YFKPBYRVSA-N 0.000 description 1
- 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
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- AYBDPJPUUUNBOG-UHFFFAOYSA-L 1-butyl-3-methylimidazol-3-ium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCCN1C=C[N+](C)=C1.CCCCN1C=C[N+](C)=C1 AYBDPJPUUUNBOG-UHFFFAOYSA-L 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IFFLKGMDBKQMAH-UHFFFAOYSA-N 2,4-diaminopyridine Chemical compound NC1=CC=NC(N)=C1 IFFLKGMDBKQMAH-UHFFFAOYSA-N 0.000 description 1
- XQRUEDXXCQDNOT-UHFFFAOYSA-N 2,5-diaminophenol Chemical compound NC1=CC=C(N)C(O)=C1 XQRUEDXXCQDNOT-UHFFFAOYSA-N 0.000 description 1
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 2-(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C(F)(F)F)=C1 ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 1
- FMZFBOHWVULQIY-UHFFFAOYSA-N 2-ethylcyclohexane-1,4-diamine Chemical compound CCC1CC(N)CCC1N FMZFBOHWVULQIY-UHFFFAOYSA-N 0.000 description 1
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- SFHLLWPKGUSQIK-UHFFFAOYSA-N 2-methylcyclohexane-1,4-diamine Chemical compound CC1CC(N)CCC1N SFHLLWPKGUSQIK-UHFFFAOYSA-N 0.000 description 1
- WNLWBCIUNCAMPH-UHFFFAOYSA-N 2-n,2-n-dimethylpropane-1,2-diamine Chemical compound NCC(C)N(C)C WNLWBCIUNCAMPH-UHFFFAOYSA-N 0.000 description 1
- OVOZYARDXPHRDL-UHFFFAOYSA-N 3,4-diaminophenol Chemical compound NC1=CC=C(O)C=C1N OVOZYARDXPHRDL-UHFFFAOYSA-N 0.000 description 1
- CDVZKYLSVNAIHH-UHFFFAOYSA-N 3,6-bis(trifluoromethyl)benzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(F)(F)F)=C(C(O)=O)C(C(O)=O)=C1C(F)(F)F CDVZKYLSVNAIHH-UHFFFAOYSA-N 0.000 description 1
- NFSQGQXKVFGKSO-UHFFFAOYSA-N 3-(2-phenylphenoxy)aniline Chemical group NC1=CC=CC(OC=2C(=CC=CC=2)C=2C=CC=CC=2)=C1 NFSQGQXKVFGKSO-UHFFFAOYSA-N 0.000 description 1
- JWZGDVIPCFHWPH-UHFFFAOYSA-N 3-(3-aminocyclohexyl)oxycyclohexan-1-amine Chemical compound C1C(N)CCCC1OC1CC(N)CCC1 JWZGDVIPCFHWPH-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- 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
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种聚酰胺酸溶液及其制备方法和应用,属于高分子材料技术领域,聚酰胺酸溶液包括聚酰胺酸、非质子极性溶剂和离子液体,其中,所述离子液体的沸点大于350℃;所述聚酰胺酸包含如下结构式的化合物:
Description
技术领域
本发明涉及高分子材料技术领域,具体是一种聚酰胺酸溶液及其制备方法和应用。
背景技术
近些年来,随着电子信息技术的飞速发展,人们对电子设备、显示装置的要求越来越高,柔性显示器因为拥有轻薄化、可卷曲、外形多样的特点,得到了广泛的关注。聚酰亚胺由于分子链中含有芳香环和酰亚胺环,拥有优异的耐热性、尺寸稳定性和力学性能,可以作为基板应用于电子图像显示装置中。
但是显示器在制作过程中,低温多晶硅等材料的沉积和加工需要极高的温度,这要求显示器的基板拥有良好的耐热性,耐热性越高,越有利于器件的加工;而且,一个显示器件的完成,需要经过多道工艺,这要求基板拥有良好的尺寸稳定性,尺寸变化率小,才能避免与其他功能层由于尺寸变化的差异而产生应力,导致翘曲、断裂等现象发生。
一般情况下,为了提高聚酰亚胺的耐热性和尺寸稳定性,最好的办法是提高聚酰亚胺的分子量,目前,传统聚酰亚胺的制备方法主要是通过二胺和二酐单体在非质子极性溶剂中进行聚合反应,生成聚酰亚胺的前驱体—聚酰胺酸溶液,再对聚酰胺酸溶液进行亚胺化处理,制得聚酰亚胺。随着分子量的增加,聚酰胺酸溶液的粘度也在逐步提高,这使得涂布操作变得困难。对于现有技术,例如:
专利201880084005.3采用了合成具有规定末端结构的聚酰胺酸,引入水在高温条件下解聚的方法,制得的聚酰亚胺膜热膨胀系数达到10ppm/℃以下,但在合成过程中引入水,会导致聚合物工艺难以控制,批次之间存在差异。
专利201180036232.7采用了均苯四甲酸二酐、3,3',4,4'-联苯四甲酸二酐和对苯二胺作为主要单体,使用了与水共沸溶剂,制得的聚酰亚胺膜耐热性良好,但其1%热失重温度低于550℃。
专利202011456977.6采用了引入磺化二胺、纳米二氧化硅、离子液体的方法改善聚酰亚胺材料的透明性、力学性能及耐热性,但其仍存在热膨胀系数高的问题。
专利201811209047.3将二胺单体和二酐单体置于离子液体中进行反应,反应结束后将混合物用去离子水析出,得到聚酰亚胺粉末,再将聚酰亚胺粉末溶于非质子极性溶剂中,在基材上成膜;该聚酰亚胺膜的热膨胀系数虽然得到了改善,但仍没有达到10ppm/℃以下。
发明内容
本发明的目的在于提供一种聚酰胺酸溶液及其制备方法和应用,以解决上述背景技术中提出的问题。
为实现上述目的,本发明提供如下技术方案:
一种聚酰胺酸溶液,包括:
聚酰胺酸、非质子极性溶剂和离子液体,其中,
所述离子液体的沸点大于350℃;
所述聚酰胺酸包含如下结构式的化合物:
式中,
X为碳原子数为4-30的脂肪环族或芳香环族的4价四羧酸二酐残基;
Y为碳原子数为4-30的脂肪环族或芳香环族的2价二胺残基;
n为10-600的整数。
作为本发明的进一步技术方案,所述离子液体的含量0.1-1000ppm,在聚酰胺酸溶液中,如果离子液体的含量占比较多,会导致聚酰胺酸的含量减少,由于离子液体是小分子化合物,分子量低,整体上会导致经热亚胺化后得到的聚酰亚胺膜热性能和尺寸稳定性下降,离子液体存在的作用是通过其与聚酰胺酸分子链之间的强物理作用力,使聚酰胺酸分子之间产生间隔,减少分子之间的缠结,提高取向,同时能够起到催化剂的作用,促进链增长反应的进行;因此,需要控制离子液体的量在一个恰当的范围内;以聚酰胺酸溶液的质量为100%计,聚酰胺酸溶液中包含的聚酰胺酸的含量为5-50%,优选为8-40%,更优选为10~35%,在此范围内,制得的聚酰亚胺薄膜结构紧凑,气泡少。
作为本发明的进一步技术方案,所述聚酰胺酸溶液的粘度为1000-20000cp,优选为1000-15000cp,更优选为2000-12000cp,在此范围内的聚酰胺酸溶液拥有良好的成膜性。
作为本发明的更进一步技术方案,所述离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-戊烷磺酸钠、正己烷磺酸钠、1-乙基-3-甲基咪唑醋酸盐、1-丁基-3-甲基咪唑溴盐、1-乙基-3-甲基咪唑硫酸乙酯盐、1-乙基-3-甲基咪唑二氰铵盐、1-乙基-3-甲基咪唑氯盐、1-丙基-3-甲基咪唑氯盐、1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氯化铁、1-丁基-3-甲基咪唑六氟磷酸盐、乙基三苯溴化膦、1-乙基-3-甲基咪唑溴盐、1-丁基-3-甲基咪唑三氟甲磺酸盐、氯化1,3-二(2-甲氧基-2-氧乙基)咪唑、1,3-二(2-甲氧基-2-氧乙基)咪唑四氟硼酸盐中的至少一种。
作为本发明的再进一步技术方案,所述聚酰胺酸重均分子量为3000-200000g/mol,优选为10000-180000g/ml,更优选为30000-150000g/ml;分散度,即重均分子量/数均分子量为1.2-5,优选为1.5-4,更优选为1.7-3。
作为本发明的再进一步技术方案,所述脂肪环族的4价四羧酸二酐可以为1,2,3,4-环丁烷四羧酸二酐、1,2,3,4-环戊烷四羧酸二酐、1,2,4,5-环己烷四甲酸二酐、双环己基-3,4,3',4'四甲酸二酐、双环己基-2,3,2',3'四甲酸二酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-环丁烷四羧酸二酐、乙二胺四乙酸二酐、三环[6.4.0.0(2,7)]十二烷-1,2,7,8-四甲酸二酐等,这些四羧酸二酐可以单独使用,也可以同时使用两种或两种以上。
作为本发明的再进一步技术方案,所述X为四羧酸二酐残基时,90摩尔%以上来自于均苯四羧酸二酐和/或3,3',4,4'-联苯四甲酸二酐,优选为95摩尔%以上;所述芳香环族的4价四羧酸二酐可以为均苯四甲酸二酐、3,3',4,4'-联苯四甲酸二酐、2,3,3',4'-联苯四甲酸二酐、2,2',3,3'-联苯四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、2,2',3,3'-二苯甲酮四甲酸二酐、2,2'-双(3,4-二羧酸)六氟丙烷二酐、4,4氧双邻苯二甲酸二酐、3,4'-氧双邻苯二甲酸酐、1,4-双(三氟甲基)-2,3,5,6-苯四羧酸二酐、双(3,4-二羧基苯基)砜、双(3,4-二羧基苯基)醚、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,4,9,10-苝四羧酸二酐、双(3,4-二羧基苯基)硫醚二酐、双(3,4-二羧基苯基)甲烷二酐、双(3,4-二羧基苯基)丙烷二酐、双(2,3-二羧基苯基)甲烷二酐、双(2,3-二羧基苯基)丙烷二酐、对-亚苯基-双苯偏三酸酯二酐、对-亚苯基-双苯偏三酸酯二酐、对-亚乙基-双偏苯三酸酯二酐、乙二醇双偏苯三酸酐、4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)、3,3',4,4’-三苯双醚四甲酸二酐等、4-(2,5-二氧代四氢呋喃-3-基)-1,2,3,4-四氢萘-1,2-二甲酸酐、1,6,7,12-四叔丁基苯氧基苝-3,4,9,10-四甲酸二酐等,这些四羧酸二酐成分可以单独使用,也可以同时使用两种或两种以上。
作为本发明的再进一步技术方案,为使经过亚胺化后得到的聚酰亚胺膜拥有良好的耐热性能和尺寸稳定性,所述Y为二胺残基时,90摩尔%以上来自于对苯二胺和/或4,4'-二氨基二苯醚,优选为95摩尔%以上;作为参与反应的二胺单体,可以为芳香族二胺单体或脂肪族二胺单体,其中芳香族二胺单体可以列举出下述物质:间苯二胺、对苯二胺、邻苯二胺、2,3-二氨基氟苯、2,4-二氨基氟苯、2,5-二氨基氟苯2,4-二氨基甲苯、2-甲基-1,4-苯二胺、2,5-二氨基三氟甲苯、3,5-二氨基三氟甲苯、2,3-二氨基吡啶、2,4-二氨基吡啶、2,5-二氨基吡啶、3,4-二氨基苯酚、2,5-二氨基苯酚、3,6-二氨基咔唑、2,6-二氨基吡嗪、1,5-萘二胺、1,8-萘二胺、2,3-萘二胺、1,4-萘二胺、2,7-萘二胺、联苯胺、3,3'-二甲基联苯胺、4,4'-二氨基二苯砜、3,3'-二氨基二苯砜、2,2'-二氨基二苯砜、4,4'-二氨基二苯甲烷、3,3'-二氨基二苯甲烷、3,4'-二氨基二苯甲烷、4,4'-二氨基二苯醚、3,3'-二氨基二苯醚、3,4'-二氨基二苯醚、2,6-二氨基蒽醌、2,2'-二(三氟甲基)二氨基联苯、2,2-双(4-氨基苯基)六氟丙烷、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、4,4'-二氨基二苯胺、3,3'-二氨基二苯胺、2,2'-二氨基二苯甲酮、4,4'-二氨基二苯甲酮、3,3'-二氨基二苯甲酮、4,4'-氨基基联苄、4,4'-二氨基二苯二硫醚、2,2'-二氨基二苯二硫醚、4,4'-二氨基苯酰替苯胺、3,3'-二氨基苯酰替苯胺、2,2'-二氨基苯酰替苯胺、3,3',5,5'-四甲基-4,4'-二氨基二苯甲烷、1,4-双(4-氨基苯氧基)苯、1,3-双(4'-氨基苯氧基)苯、1,3-双(3-氨基苯氧基)苯、4,4'-双(4-氨基苯氧基)二苯砜、4,4'-双(3-氨基苯氧基)二苯基砜、4,4'-二(4-氨基苯氧基)联苯、1,4-二(4-氨基苯氧基)-2-苯基苯、4,4'-双(3-氨基苯氧基)联苯、N,N'-1,4-亚苯基双(4-氨基苯甲酰胺)、对苯二甲酸二对氨基苯酯、双[4-(4-氨基苯甲酰基)苯基]醚、双(4-氨基苯氧基)二甲基硅烷、1,3-双[4-(3-氨基苯氧基)苯甲酰基]苯、1,3-双[4-(4-氨基苯氧基)苯甲酰基]苯、新戊基乙二醇双(4-氨基苯基)醚、2,7-二氨基芴、9,9-二(4-氨基-3-甲苯基)芴、9,9-双(4-氨基苯基)芴、三亚甲基双(4-氨基苯甲酸酯)等,这些二胺可以单独使用,也可以同时使用两种或两种以上;脂肪族二胺单体可以为:乙二胺、丙二胺、1,2-丙二胺、二甲基丙二胺、丁二胺、戊二胺、1,4-戊二胺、己二胺、辛二胺、壬二胺、癸二胺、十一烷二胺、十二烷二胺、异佛尔酮二胺、1,2-环己二胺、1,3-环己二胺、1,4-环己二胺、4,4'-二氨基二环己基甲烷、3,3'-二氨基二环己基甲烷、2,2'-二氨基二环己基甲烷、3,4'-二氨基二环己基甲烷、双(4-氨基环己基)醚、双(3-氨基环己基)醚、双环[2.2.1]庚烷-3,4-二胺、双环[2.2.1]庚烷-2,5-二胺、1,4-二氨基-2-甲基环己烷、1,4-二氨基-2-乙基环己烷、1,3-双(3-氨基丙基)四甲基二硅氧烷等、1,3-二氨基环丁烷等,这些二胺单体可以单独使用,也可以同时使用两种或两种以上。
作为本发明的再进一步技术方案,所述聚酰胺酸还包括如下结构式的化合物:
式中,
X为碳原子数为4-30的脂肪环族或芳香环族的4价四羧酸二酐残基;
Y为碳原子数为4-30的脂肪环族或芳香环族的2价二胺残基;
R为苄氧基、芴甲氧基、碳原子数为1-8的烷氧基、碳原子数为3-8的环烷氧基、碳原子数为2-18的烯烃基或碳原子数为2-18的炔基;
n为10-600的整数。
作为本发明的再进一步技术方案,所述聚酰胺酸分子主要由四羧酸二酐、二胺和封端剂聚合而成,为使经过固化后得到的聚酰亚胺膜拥有较高的玻璃化转变温度,能够作为柔性显示器件的基板使用,这要求聚酰亚胺有足够高的分子量,但高分子量会导致聚酰胺酸粘度过高,因此,本发明使用了能够在高温灼烧的条件下进行链增长反应的封端剂。所述的封端剂选自酰氯化合物、叔丁氧羰基化合物、单酸酐化合物、氨基酸中的一种或一种以上;所述R为封端剂反应后的残基,所述封端剂为能够在加热过程中起到链增长作用的化合物,所述封端剂为酰氯化合物、叔丁氧羰基化合物、单酸酐化合物、氨基酸中的至少一种;优选为芴甲氧羰酰氯、二碳酸二叔丁酯、氯甲酸苄酯、乙酰氯、苯甲酰氯、4-苯基乙炔基苯酐、3-苯基乙炔基苯酐、马来酸酐、衣康酸酐、1,2,3,6-四氢邻苯二甲酸酐、甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、甲硫氨酸、色氨酸、苯胺酸、组氨酸、肌肽、L-甘-白二肽、赖氨酸等,更优选为芴甲氧羰酰氯、二碳酸二叔丁酯、氯甲酸苄酯、4-苯基乙炔基苯酐、马来酸酐、甘氨酸,这些单体可以单独使用,也可以同时使用两种或两种以上;以使用的二胺单体总量为100摩尔%计,使用的封端剂的量为50摩尔%以下,0.1摩尔%以上;优选为20摩尔%以下,0.5摩尔%以上,最优选为10摩尔%以下,0.8摩尔%以上;使用上述封端剂的聚酰胺酸能够在加热过程中进行链增长,同时,离子液体的存在促进了反应的发生,得到了高分子量的聚酰亚胺膜,该聚酰亚胺膜的玻璃化转变温度(Tg)在450℃以上;制备聚酰胺酸溶液时使用的非质子极性溶剂优选沸点为120-250℃的非质子极性溶剂,采用此种溶剂制备的聚酰胺酸溶液有良好的存储稳定性,制备的聚酰亚胺膜厚度均匀。
作为本发明的再进一步技术方案,所述非质子极性溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、γ-丁内酯、γ-戊内酯、δ-戊内酯、γ-己内酯、ε-己内酯、二甲基亚砜、1,3-二甲基-2-咪唑啉酮、丙二醇甲醚醋酸酯、乳酸乙酯、二异丁基酮、环己酮、丙二醇单甲醚、丙二醇单乙基醚、二乙二醇单甲醚、二乙二醇单***、三甘醇二甲醚、二甲苯中的至少一种。
作为本发明的再进一步技术方案,聚酰胺酸溶液中还可以包含其他主链上含有酰胺键的树脂,具体可以为聚酰亚胺、聚酰胺酸酯、聚酰胺酸酰胺、聚异酰亚胺等;还可以根据需求加入添加剂,如无机粒子、抗氧剂、抗静电剂、偶联剂、发泡剂、消泡剂、阻燃材料、表面活性剂、染料、流平剂等。
一种聚酰胺酸溶液的制备方法,其特征在于,包括以下步骤:
在0-80℃条件下,通保护气,将二胺单体、封端剂、离子液体和非质子极性溶剂加入反应器中,反应0.5-12h;
向反应器中加入二酐单体,反应2-24h,得到聚酰胺酸溶液。
一种聚酰胺酸溶液的制备方法,其特征在于,包括以下步骤:
在0-80℃条件下,通保护气,将二胺单体、离子液体和非质子极性溶剂加入反应器中;
待二胺单体全部溶解,加入二酐单体,反应2-24h;
加入封端剂,反应0.5-12h后,得到聚酰胺酸溶液。
一种聚酰亚胺膜,由上述的聚酰胺酸溶液制备而成,制备方法包括以下步骤:
将聚酰胺酸溶液进行过滤、脱气泡后均匀涂布到基板上,得到湿膜,在温度为80-150℃条件下持续加热10-100min,进行干燥处理,再将其移置于加热炉中,在惰性气体保护下,将温度阶段性升温至350-480℃,进行干燥固化,冷却至室温,再置于沸水中煮0.5-3h后,将薄膜取下,最后在70-150℃的条件下干燥0.2-5h,得到的聚酰亚胺薄膜。
作为本发明的进一步技术方案:所述过滤可以采用重力过滤、加压过滤、真空过滤等方式除去杂质颗粒,优选为加压过滤;所述过滤器的孔径或其所用滤布的孔径可以为0.1-10μm,优选为0.1-5μm,更优选为0.5-2μm;上述基板没有限定,可以选择玻璃基板,硅晶板,砷化镓基板,陶瓷基板,不锈钢基板等。
作为本发明的进一步技术方案:所述阶段性升温程序优选为由室温升温至160℃-180℃,持续20min-120min;然后,升温至200℃-300℃,持续20min-120min;最后,升温至350℃-480℃,持续20min-120min,升温速率为2-15℃/min。
作为本发明的进一步技术方案:聚酰亚胺膜的厚度为1-100μm,优选为5-50μm,更优选为10-30μm;该聚酰亚胺膜拥有良好的耐热性和尺寸稳定性,玻璃化转变温度在450℃以上,1%热失重温度在550℃以上,50-450℃之间的线性热膨胀系数低于10ppm/℃。
一种显示器件,以上述聚酰亚胺膜作为基板制备而成,制备方法如下:按照上述聚酰亚胺膜的制备方法,在基板上制备厚度为3-12μm的聚酰亚胺膜,在聚酰亚胺膜上沉积无机膜作为隔断层,再利用溅射、蒸镀等方法在隔断层上面形成如液晶显示器、太阳能电池、触控面板等器件的驱动元件、电路;然后,再将聚酰亚胺膜从基板上剥离,剥离方法不做具体限定,例如可以采用激光照射的方法进行剥离,就可以得到柔性显示器件。
与现有技术相比,本发明的有益效果是:
1、通过在聚酰胺酸溶液中引入了离子液体,在制备聚酰亚胺时,离子液体与聚酰亚胺分子之间存在着强烈的相互作用力,将聚酰亚胺分子链隔开,减少了分子链之间的相互缠结,让链段更趋向于有序排列,使得聚酰亚胺膜的热分解温度升高,热膨胀系数下降;
2、使用在加热过程中能够起到链增长作用的封端剂,离子液体能够促进封端剂受热之后进行的链增长反应,有助于分子量的提高,这使得聚酰亚胺膜的玻璃化转变温度得到提高。
具体实施方式
下述实施例和对比例中用到的化合物简称所代表的具体化合物如下:
PMDA:均苯四甲酸二酐;
BPDA:3,3',4,4'-联苯四甲酸二酐;
ODPA:4,4'-氧双邻苯二甲酸酐;
PDA:对苯二胺;
ODA:4,4'-二氨基二苯醚;
DABA:4,4'-二氨基苯甲酰苯胺
NMP:N-甲基-2-吡咯烷酮。
实施例1
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.0101g 1-乙基-3-甲基咪唑二氰铵盐、0.8730g(0.004mol)二碳酸二叔丁酯和111.3920g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,得到固含量为20%的聚酰胺酸溶液。
(2)取上述制得的聚酰胺酸溶液使用过滤器进行过滤,滤膜尺寸为5μm,将过滤后的溶液进行减压脱气,取20mL处理过的溶液置于8寸硅晶板上面,使用旋转涂布机涂膜,转速为700rpm,持续时间为30s,涂布完成后,将硅晶板移至120℃的加热板上面进行干燥,持续时间为15min,干燥处理结束后,将其移置于马弗炉里面,并以10℃/min的升温速率,将温度由120℃升温至150℃,持续30min;再升温至280℃,持续30min;最后升温至450℃,持续60min。自然降至室温后,将硅晶板取出,置于沸水中煮0.5h之后,将聚酰亚胺薄膜取下,置于烘箱中在150℃的条件下干燥5h,得到聚酰亚胺薄膜。
实施例2
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.0638g 1-乙基-3-甲基咪唑二氰铵盐、0.8730g(0.004mol)二碳酸二叔丁酯和111.3920g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,得到固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例3
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.1210g 1-乙基-3-甲基咪唑二氰铵盐、0.8730g(0.004mol)二碳酸二叔丁酯和111.3920g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,得到固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例4
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.1210g 1-戊烷磺酸钠、0.8730g(0.004mol)二碳酸二叔丁酯和111.3920g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例5
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.1210g 1-乙基-3-甲基咪唑硫酸乙酯盐、0.8730g(0.004mol)二碳酸二叔丁酯和111.3920g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例6
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.2017g 1-乙基-3-甲基咪唑硫酸乙酯盐、0.8730g(0.004mol)二碳酸二叔丁酯和245.8853g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,制得固含量为12%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例7
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.0757g 1-乙基-3-甲基咪唑硫酸乙酯盐、0.873g(0.004mol)二碳酸二叔丁酯和35.7395g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,得到固含量为32%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例8
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.1237g 1-乙基-3-甲基咪唑硫酸乙酯盐和114.8840g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例9
(1)在氮气保护下,将10.814g(0.1mol)PDA、0.1263g 1-乙基-3-甲基咪唑硫酸乙酯盐、1.7460g(0.008mol)二碳酸二叔丁酯和118.3760g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例10
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.1215g 1-乙基-3-甲基咪唑硫酸乙酯盐、1.0348g(0.004mol)芴甲氧羰酰氯和112.0392g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,得到固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例11
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.1196g 1-乙基-3-甲基咪唑硫酸乙酯盐、0.1196g马来酸酐和109.4688g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,得到固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例12
(1)在氮气保护下,将10.814g(0.1mol)PDA、0.1193g 1-乙基-3-甲基咪唑硫酸乙酯盐、0.3003g(0.004mol)甘氨酸和109.1012g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.00g NMP,反应12h后结束实验,得到固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例13
(1)在氮气保护下,将10.2733g(0.095mol)PDA,、1.0012g(0.005mol)ODA、0.1229g1-乙基-3-甲基咪唑硫酸乙酯盐、1.0348g(0.004mol)芴甲氧羰酰氯和113.8812g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例14
(1)在氮气保护下,将10.2733g(0.095mol)PDA、0.4005g(0.002mol)ODA、0.6818g(0.003mol)DABA、0.1245g 1-乙基-3-甲基咪唑硫酸乙酯盐、1.0348g(0.004mol)芴甲氧羰酰氯和116.0476g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入1.0906g(0.005mol)PMDA、1.5511g(0.005mol)ODPA、26.4798g(0.09mol)BPDA和50.00g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例15
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.2017g 1-乙基-3-甲基咪唑二氰铵盐、0.8730g(0.004mol)二碳酸二叔丁酯和111.3920g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,得到固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
实施例16
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.2421g 1-乙基-3-甲基咪唑二氰铵盐、0.8730g(0.004mol)二碳酸二叔丁酯和111.3920g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.0000g NMP,反应12h后结束实验,得到固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
对比例1
(1)在氮气保护下,将10.8140g(0.1mol)PDA、0.8730g(0.004mol)二碳酸二叔丁酯和111.3920g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.00g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
对比例2
(1)在氮气保护下,将10.2733g(0.095mol)PDA,、1.0012g(0.005mol)ODA、1.0348g(0.004mol)芴甲氧羰酰氯和113.8812g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.00g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
对比例3
(1)在氮气保护下,将10.2733g(0.095mol)PDA、0.4005g(0.002mol)ODA、0.6818g(0.003mol)DABA、1.0348g(0.004mol)芴甲氧羰酰氯和116.0476g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入1.0906g(0.005mol)PMDA、1.5511g(0.005mol)ODPA、26.4798g(0.09mol)BPDA和50.00g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
对比例4
(1)在氮气保护下,将9.7326g(0.9mol)PDA、0.1210g四羟甲基氯化磷、0.873g(0.004mol)二碳酸二叔丁酯和100g NMP加入带有搅拌桨、温度计的反应器内,转速为300rpm,在50℃条件下反应2h。加入2.1812g(0.01mol)PMDA、26.4798g(0.09mol)BPDA和50.00g NMP,反应12h后结束实验,制得固含量为20%的聚酰胺酸溶液。
(2)聚酰胺酸溶液后处理与成膜过程同实施例1。
聚酰胺酸溶液和聚酰亚胺薄膜的测试方法如下:(实施例及对比例均采用下述测试方法)
(1)聚酰胺酸溶液中离子液体含量的测定:
使用液相色谱仪(赛默飞,U3000 RSLCnano)测试聚酰胺酸溶液中离子液体的含量,色谱柱型号为Acclaim Trinity P2,测试温度为30℃。
(2)聚酰胺酸溶液粘度测试:
聚酰胺酸溶液的黏度采用Brookfiled旋转黏度计测试,测试温度为25℃。
(3)聚酰胺酸溶液分子量和分子量的多分散性指数测试:
聚酰胺酸的重均分子量和分子量的多分散性指数使用凝胶渗透色谱(Waters-2695,Waters)进行测试,标准品为聚苯乙烯。色谱柱型号为Waters Styrage,流动相使用N-甲基-2-吡咯烷酮,测试温度为40℃。
(4)聚酰亚胺膜玻璃化转变温度(Tg)和线性热膨胀系数(CTE):
将约10μm厚的聚酰亚胺薄膜切成13mm*4mm的长方形,将其用作测试样品片。放置在长度为10mm的夹具中间,使用Perkin Elmer公司的TMA4000热机械膨胀分析仪进行测试,施加约0.15N的载荷,第一阶段以10℃/min的升温速率升温至150℃,保持30min,第二阶段以5℃/min的速率降至30℃,第三阶段以5℃/min升温速率的条件下,将该试验片从30℃加热到600℃进行测定,由得到的TMA曲线得到聚酰亚胺膜在50℃到450℃的CTE,由曲线的拐点得到Tg。
(5)热分解温度Td1%:
准备约10μm厚的聚酰亚胺膜为测试样品片,取10mg左右样品,使用德国耐驰型号为TG209F1的热重分析仪将该样品片在氮气流下,第一阶段以10℃/min的升温速率升温至150℃,保持30min,第二阶段降温至50℃,第三阶段以10℃/min的升温速率从50℃加热至800℃。从所得的重量-温度曲线中确定1%重量损失温度。
上述实施例和对比例的实验数据总结如下表1所示。
表1
根据表1中实施例数据表明,由本发明所述方法制得的聚酰亚胺薄膜热膨胀系数(50-450℃)能够达到10ppm/℃以下,玻璃化转变温度最高可达450℃以上,1%热失重温度能够达到550℃以上,拥有良好的热性能和尺寸稳定性,通过实施例与对比例1-3的对比可知,引入离子液体的聚酰亚胺薄膜能表现出更加优异的热性能和力学性能,通过实施例1-14与实施例15-16的对比可知,引入过多离子液体的聚酰亚胺膜的耐热性和尺寸稳定性有所下降,由此可知,适量的离子液体能够改善聚酰亚胺膜的性能。
本发明在聚酰亚胺中引入了离子液体,离子液体与聚酰亚胺分子之间存在着强烈的相互作用力,将聚酰亚胺分子链隔开,减少了分子链之间的相互缠结,让链段更趋向于有序排列,使得聚酰亚胺膜的热分解温度升高,热膨胀系数下降。
另外,本发明还可以使用在加热过程中能够起到链增长作用的封端剂,离子液体能够促进封端剂受热之后进行的链增长反应,有助于分子量的提高,这使得聚酰亚胺膜的玻璃化转变温度得到提高。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何附图标记视为限制所涉及的权利要求。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (10)
2.根据权利要求1所述的聚酰胺酸溶液,其特征在于,所述离子液体的含量0.1-1000ppm。
3.根据权利要求1所述的聚酰胺酸溶液,其特征在于,所述离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-戊烷磺酸钠、正己烷磺酸钠、1-乙基-3-甲基咪唑醋酸盐、1-丁基-3-甲基咪唑溴盐、1-乙基-3-甲基咪唑硫酸乙酯盐、1-乙基-3-甲基咪唑二氰铵盐、1-乙基-3-甲基咪唑氯盐、1-丙基-3-甲基咪唑氯盐、1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氯化铁、1-丁基-3-甲基咪唑六氟磷酸盐、乙基三苯溴化膦、1-乙基-3-甲基咪唑溴盐、1-丁基-3-甲基咪唑三氟甲磺酸盐、氯化1,3-二(2-甲氧基-2-氧乙基)咪唑、1,3-二(2-甲氧基-2-氧乙基)咪唑四氟硼酸盐中的至少一种。
4.根据权利要求1所述的聚酰胺酸溶液,其特征在于,所述聚酰胺酸重均分子量为3000-200000g/mol;重均分子量/数均分子量为1.2-5。
5.根据权利要求4所述的聚酰胺酸溶液,其特征在于,所述X为四羧酸二酐残基时,90摩尔%以上来自于均苯四羧酸二酐和/或3,3',4,4'-联苯四甲酸二酐;所述Y为二胺残基时,90摩尔%以上来自于对苯二胺和/或4,4'-二氨基二苯醚。
7.根据权利要求6所述的聚酰胺酸溶液,其特征在于,所述R为封端剂反应后的残基,所述封端剂为能够在加热过程中起到链增长作用的化合物,所述封端剂为酰氯化合物、叔丁氧羰基化合物、单酸酐化合物、氨基酸中的至少一种。
8.根据权利要求4所述的聚酰胺酸溶液,其特征在于,所述非质子极性溶剂的沸点为120-250℃。
9.如权利要求1-8任一所述的聚酰胺酸溶液的制备方法,其特征在于,包括以下步骤:
在0-80℃条件下,通保护气,将二胺单体、封端剂、离子液体和非质子极性溶剂加入反应器中,反应0.5-12h;
向反应器中加入二酐单体,反应2-24h,得到聚酰胺酸溶液。
10.如权利要求9所述聚酰胺酸溶液的制备方法制备得到的聚酰胺酸溶液在制备聚酰亚胺膜中的应用。
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金亮;张清华;: "聚酰亚胺在离子液体中的合成与表征", 高分子材料科学与工程, no. 03, pages 25 * |
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