CN116444394A - 制备聚酰亚胺薄膜用二胺单体及制备方法和聚酰亚胺薄膜 - Google Patents
制备聚酰亚胺薄膜用二胺单体及制备方法和聚酰亚胺薄膜 Download PDFInfo
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- CN116444394A CN116444394A CN202310449381.0A CN202310449381A CN116444394A CN 116444394 A CN116444394 A CN 116444394A CN 202310449381 A CN202310449381 A CN 202310449381A CN 116444394 A CN116444394 A CN 116444394A
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- China
- Prior art keywords
- dianhydride
- polyimide film
- bis
- diamine monomer
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 67
- 239000000178 monomer Substances 0.000 title claims abstract description 64
- 150000004985 diamines Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 58
- 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 53
- 239000002002 slurry Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000004952 Polyamide Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 229920002647 polyamide Polymers 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229920005575 poly(amic acid) Polymers 0.000 claims description 11
- -1 (4- (3, 4-dicarboxybenzoyloxy) phenyl) hexafluoropropane Chemical compound 0.000 claims description 10
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- RGVHBPPWCQVMDR-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 RGVHBPPWCQVMDR-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000630 rising effect Effects 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000007790 scraping Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007821 HATU Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N anhydrous dimethyl-acetamide Natural products CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 2
- KLDLRDSRCMJKGM-UHFFFAOYSA-N 3-[chloro-(2-oxo-1,3-oxazolidin-3-yl)phosphoryl]-1,3-oxazolidin-2-one Chemical compound C1COC(=O)N1P(=O)(Cl)N1CCOC1=O KLDLRDSRCMJKGM-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101100248451 Arabidopsis thaliana RICE2 gene Proteins 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 239000007859 condensation product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BIUPYBKDMWIWJO-UHFFFAOYSA-N 1,1,1,3,3,3-hexachloropropan-2-one;triphenylphosphane Chemical compound ClC(Cl)(Cl)C(=O)C(Cl)(Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BIUPYBKDMWIWJO-UHFFFAOYSA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- AORHLVDUGUXRKN-UHFFFAOYSA-N 1-bromopyrrolidine-2,5-dione;triphenylphosphane Chemical compound BrN1C(=O)CCC1=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 AORHLVDUGUXRKN-UHFFFAOYSA-N 0.000 description 1
- FPIRBHDGWMWJEP-UHFFFAOYSA-N 1-hydroxy-7-azabenzotriazole Chemical compound C1=CN=C2N(O)N=NC2=C1 FPIRBHDGWMWJEP-UHFFFAOYSA-N 0.000 description 1
- PSQZJKGXDGNDFP-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)(F)F PSQZJKGXDGNDFP-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000012317 TBTU Substances 0.000 description 1
- 241000289690 Xenarthra Species 0.000 description 1
- RRWOBMRVLZQKEY-UHFFFAOYSA-N [2-(benzotriazol-1-yloxy)pyrrolidin-1-yl]-dipyrrolidin-1-ylphosphane Chemical compound C1CCCN1P(N1C(CCC1)ON1C2=CC=CC=C2N=N1)N1CCCC1 RRWOBMRVLZQKEY-UHFFFAOYSA-N 0.000 description 1
- RKTBAMPZUATMIO-MXZHIVQLSA-N [[(e)-(1-cyano-2-ethoxy-2-oxoethylidene)amino]oxy-(dimethylamino)methylidene]-dimethylazanium;hexafluorophosphate Chemical compound F[P-](F)(F)(F)(F)F.CCOC(=O)C(\C#N)=N\OC(N(C)C)=[N+](C)C RKTBAMPZUATMIO-MXZHIVQLSA-N 0.000 description 1
- CLZISMQKJZCZDN-UHFFFAOYSA-N [benzotriazol-1-yloxy(dimethylamino)methylidene]-dimethylazanium Chemical compound C1=CC=C2N(OC(N(C)C)=[N+](C)C)N=NC2=C1 CLZISMQKJZCZDN-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- COTHYYYVPUZALV-UHFFFAOYSA-N hydroxy(trimethyl)silane;potassium Chemical compound [K].C[Si](C)(C)O COTHYYYVPUZALV-UHFFFAOYSA-N 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于高分子材料及其制备方法技术领域,具体涉及一种制备聚酰亚胺薄膜用二胺单体及制备方法和聚酰亚胺薄膜。本发明提供的二胺单体由式(M5)表示:
Description
技术领域
本发明属于高分子材料及其制备方法技术领域。具体的,本发明涉及制备聚酰亚胺薄膜用二胺单体及制备方法和聚酰亚胺薄膜。
背景技术
芳香族聚酰亚胺(CPI)因其极高的玻璃转移温度(Tg)、优异的热稳定性、良好的耐化学性以及良好的介电和机械性能,已广泛应用于电子、汽车和航空航天等各种工业。然而,吸电子二酐残基和给电子二胺残基之间的分子内和分子间电荷转移(CT)相互作用产生了黄色到深棕色的颜色,导致聚酰亚胺薄膜YI值较高,或YI值较高的同时透光率较低,阻碍了它们在光学和光电子领域的应用。另外,现有芳香族聚酰亚胺分子不够规整,导致了薄膜具有较高的热膨胀系数(CTE),也限制了其应用领域。
发明内容
因此,本发明要解决的技术问题在于克服现有技术中的聚酰亚胺薄膜YI值以及热膨胀系数高的缺陷,从而提供解决上述技术问题的一种制备聚酰亚胺薄膜用二胺单体及制备方法和聚酰亚胺薄膜。
本发明的技术方案:
一种制备聚酰亚胺薄膜用二胺单体,由式(M5)表示:
其中,R选自C1-5的烷基、C1-5的卤代烷基、卤素、H中任一种。
R选自C1-5的烷基、C1-5的氟代烷基、卤素、H中任一种;优选的,R选自H。
所述的二胺单体的制备方法,包括以下步骤:
(1)由式(1)表示的化合物与由式(2)表示的化合物与溶剂混合,在缩合剂和碱的作用下发生缩合反应制备由式(M4)表示的化合物;
(2)由式(M4)表示的化合物发生加氢反应制备由式(M5)表示的化合物;
其中,R选自C1-5的烷基、C1-5的卤代烷基、卤素、H中任一种。
缩合反应温度为-10~100℃,优选的,缩合反应温度为10~60℃,更优选的,缩合反应温度为20~40℃。
缩合反应时间为3~48h;优选的,缩合反应时间为1~36h。
由式(1)表示的化合物与由式(2)表示的化合物的摩尔比为1:(2~3)。
缩合剂选自N,N'-羰基咪唑(CDI)、二环己基碳二亚胺(DCC)、N,N'-二异丙基碳二亚胺(DIC)、1-(3-二甲胺基丙基)-3-乙基碳二亚胺(EDCI)、4-二甲氨基吡啶(DMAP)、4-吡咯烷基吡啶(4-PPY)、1-羟基苯并三唑(HOBt)、N-羟基-7-氮杂苯并三氮唑(HOAt)、N-羟基丁二酰亚胺(HOSu)、N-羟基邻苯二甲酰亚胺(NHPI)、NHNI、五氟苯酚(PFPOH)、O-(7-氮杂苯并三唑-1-基)-N,N,N',N'-四甲基脲六氟磷酸盐(HATU)、牛磺酸(TATU)、O-(苯并三唑-1-基)-N,N,N',N'-四甲基脲六氟磷酸酯(HBTU)、2-(1H-苯并三偶氮L-1-基)-1,1,3,3-四甲基脲四氟硼酸酯(TBTU)、6-氯苯并三氮唑-1,1,3,3-四甲基脲六氟磷酸酯(HCTU)、HAPyU、(苯并三唑-1-基)-N,N,N',N'-二吡咯基脲六氟磷酸酯(HBPyU)、N,N,N,N-四甲基-O-(N-琥珀酰亚胺)脲四氟硼酸盐(TSTU)、2-(内-5-降冰片烯-2,3-二羧酰亚胺)-1,1,3,3-四甲基脲四氟硼酸盐(TNTU)、卡特缩合剂(BOP)、丙烯酸羟丙酯(HOP)、六氟磷酸苯并三唑-1-基-氧基三吡咯烷基磷(PyAOP)、二苯基次膦酰氯(DPPCl)、DECP、叠氮磷酸二苯酯(DPPA)、MPTA、双(2-氧代-3-噁唑烷基)次磷酰氯(BOP-Cl)、三苯基磷-多卤代甲烷、三苯基磷-六氯丙酮、三苯基磷-N-溴代丁二酰亚胺、3-酰基-2-硫噻唑啉中至少一种或几种的组合物。
其中NHNI的结构式为HAPyU的结构式为/>DECP的结构式为/>MPTA的结构式为
缩合反应中使用的碱为有机碱和/或无机碱,所述有机碱选自三乙胺,Hünig碱(N,N-二异丙基乙胺,DIEA),砒碇,叔丁醇钠,叔丁醇钾,二异丙基胺,正丁基锂,异丁基锂,叔丁基锂,二异丙基氨基锂(LDA),双三甲基硅基胺基锂(LiHMDS),双(三甲基硅基)氨基钠(NaHMDS),双(三甲基硅烷基)氨基钾(KHMDS),咪唑,甲醇钠,乙醇钠,氨基钠,三甲基硅烷醇钾,四甲基乙二胺(TMEDA)中至少一种或几种的组合。所述无机碱选自碳酸氢钠,碳酸钠,碳酸钾,碳酸铯,硫代硫酸钠,氢氧化钠,氢氧化锂,氢氧化钾,氨水,氨的甲醇溶液,碳酸氢铵中至少一种或几种的组合。
缩合反应中使用的溶剂选自N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺(DEF)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、环己酮、γ-丁内酯中至少一种或几种的组合。
碱与缩合剂的摩尔比为(1-3):1,优选为(1.2-2.4):1。
还包括对缩合产物进行后处理得到由式(M4)表示的化合物的步骤,所述后处理依次包括对缩合产物进行稀释、萃取、洗涤有机相、干燥、浓缩和纯化。
加氢反应温度为25~80℃。
加氢反应时间为3~36h。
加氢反应中使用的催化剂为钯碳。
一种聚酰亚胺薄膜,制备所述聚酰亚胺薄膜的原料包括所述的二胺单体。
制备所述聚酰亚胺薄膜的原料还包括二酐单体,所述二酐单体为芳香族四羧酸二酐。
所述芳香族四羧酸二酐选自2,2',3,3'-联苯四甲酸二酐、3,3',4,4'-联苯四甲酸二酐、4,4'-氧双邻苯二甲酸酐、9,9-双(3,4-二羧基苯基)芴二酸酐、(4-邻苯二甲酸酐)甲酰氧基-4-邻苯二甲酸酯、双[(3,4-二酸酐)苯基]对苯二甲酸酯、3,3',4,4'-二苯基砜四羧酸二酸酐,对-亚苯基-双苯偏三酸酯二酐、4,4'-对苯二氧双邻苯二甲酸酐、均苯四甲二酐、2,2'-双(3,4-二羧酸)六氟丙烷二酐、2,2-双(4-(3,4-二羧基苯氧基)苯基)六氟丙烷二酐、2,2-双(4-(3,4-二羧基苯甲酰基氧基)苯基)六氟丙烷二酐、2,2'-双(三氟甲基)-4,4'-双(3,4-二羧基苯氧基)联苯二酸酐中的至少一种。
优选的,二酐单体选自3,3',4,4'-联苯四甲酸二酐、2,2'-双(3,4-二羧酸)六氟丙烷二酐、4,4'-对苯二氧双邻苯二甲酸酐中的至少一种。
所述二胺单体与二酐单体的摩尔比为1:(0.9-1.2),优选为1:(0.92-1.1),更优选为1:(0.95-1.05),最优选为1:1。
所述的一种聚酰亚胺薄膜的制备方法,包括如下步骤:将二胺单体与二酐单体、非质子化有机溶剂混合、聚合反应制备聚酰胺酸浆料,所述聚酰胺酸浆料经成膜和加热亚胺化制备所述聚酰亚胺薄膜。
聚合反应温度为-10℃~50℃;优选的,聚合反应温度为-5℃~30℃,更优的,聚合反应温度为-5℃~10℃。
聚合反应时间为3-48h,优选的,聚合反应时间为5-36h,更优选的,聚合反应时间为10-24h。
在氮气或惰性气体氛围下发生聚合反应。
通过梯度升温进行所述加热亚胺化,梯度升温段之间包括保温段,所述加热亚胺化的温度为60℃-300℃,总的保温时间为2-10小时,升温速率为1-10℃/分钟。优选的,加热亚胺化的过程依次包括以下步骤:以1-10℃/分钟的升温速率升温至60-80℃,保温10min-1h;继续以1-10℃/分钟的升温速率升温至90-120℃,保温10min-1h;继续以1-10℃/分钟的升温速率升温至140-160℃,保温10min-1h;继续以1-10℃/分钟的升温速率升温至170-190℃,保温10min-1h;继续以1-10℃/分钟的升温速率升温至190-210℃,保温10min-1h;继续以1-10℃/分钟的升温速率升温至240-260℃,保温10min-1h;继续以1-10℃/分钟的升温速率升温至300℃,保温1-4h。
所述聚酰胺酸浆料经过滤、消泡后再成膜。
本发明技术方案,具有如下优点:
1.本发明的一种制备聚酰亚胺薄膜用二胺单体,同时含有酰胺键、四元环脂肪结构和苯环,且分子构型对称,以其为原料制备的聚酰亚胺薄膜,YI值更低的同时兼具热膨胀系数(CTE)更低,且透明度较高。一方面,该分子结构有利于中断电子共轭,松开链填充,减少甚至消除CT复合物的形成,从而改善聚酰亚胺薄膜的YI值的同时光学透明度较高;另一方面,对称分布的酰胺键的引入,使得聚酰亚胺薄膜分子间引入更多的氢键,且聚酰亚胺薄膜分子更加规整,因而降低了薄膜的热膨胀系数,从而解决了采用传统的二胺单体合成的聚酰亚胺薄膜的YI值和热膨胀系数高的问题。另外,该二胺单体进行聚合时有利于避免在合成聚酰胺酸(PAAs)的过程中形成不溶盐,得不到高分子量PAA浆料的问题。
2、本发明的制备方法,选择含四元脂肪环的二胺与含苯环和硝基的羧酸通过缩合反应合成前体,将前体中的硝基进一步加氢合成该二胺单体。该方法环境友好且简便,无需使用腐蚀性极强的酰氯化试剂;该合成方法可精准控制,通过控制缩合剂的量来精准控制酰胺化的位点和量。
3、本发明提供的聚酰亚胺薄膜以本发明式(M5)表示的二胺单体,与2,2'-双(3,4-二羧酸)六氟丙烷二酐、3,3',4,4'-联苯四甲酸二酐和4,4'-氧双邻苯二甲酸酐等芳香族四羧酸二酐进行聚合制备得到,更利于实现聚酰亚胺薄膜YI值更低的同时光学透明度较高,且热膨胀系数更低,而且避免了采用脂肪二酐反应活性低、无法获得足以形成柔性膜的高分子量的PAA浆料的问题。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明的实施例中固体化合物M4的1HNMR谱图;
图2是本发明的的实施例中二胺单体M5的1HNMR谱图;
图3是本发明的实施例中二胺单体M5的13CNMR谱图。
具体实施方式
实施例和对比例中聚酰胺酸浆料的黏度测试方法为:
使用坎农-芬斯克粘度计测定25℃下聚酰胺酸浆料的对数黏度。对数黏度(μ)通过下式求得。
μ=ln(ts/t0)/C
t0:反应用溶剂流通时间;
ts:浆料流通时间;
C:0.5g/dL。
实施例1
二胺单体M5的制备方法,包括以下步骤:
(1)在冰浴下,向化合物1(12.0g,55.7mmol)和对硝基苯甲酸(23.3g,139mmol)的DMF(200mL)溶液中依次加入HATU(53.0g,139mmol)和DIEA(43.0g,333mmol)。反应在室温下搅拌过夜。得到的反应混合物中加水(400mL)稀释,并用乙酸乙酯萃取,有机相用饱和食盐水洗涤两次,无水硫酸钠干燥后浓缩。残余物通过硅胶柱色谱纯化得到白色固体化合物M4(19.2g)。如图1所示,固体化合物M4的1HNMR谱图(500MHz,DMSO-d6)δ8.45–8.31(m,4H),8.24(d,J=9.2Hz,2H),8.08(d,J=8.8Hz,4H),4.11(d,J=9.2Hz,4H),1.20(s,12H)。
向化合物M4(12.2g)的甲醇(100mL)溶液中加入钯碳(10%,1g),反应混合物在氢气球气氛下加热到45℃并搅拌反应过夜。得到的反应液通过硅藻土过滤,溶液减压浓缩,残余物通过乙醇重结晶得到白色固体粉末产物M5(9.8g)。如图2-3所示,化合物M5的1H NMR(500MHz,DMSO-d6)δ7.67(d,J=8.6Hz,4H),7.34(d,J=9.3Hz,2H),6.62(d,J=8.6Hz,4H),5.66(s,4H),4.07(d,J=9.3Hz,2H),1.18(s,12H);化合物M5的13C NMR(126MHz,DMSO-d6)δ167.19,152.07,129.53,121.88,112.95,58.37,24.90,说明最终合成了以式(M5)表示的二胺单体M5。
实施例2
一种聚酰亚胺薄膜的制备方法,包括以下步骤:
1)聚酰胺酸浆料的制备:氮气保护下,在配有机械搅拌的三口瓶中加入实施例1合成的二胺单体M5(4.4046g,10mmol),无水二甲基乙酰胺(DMAc)(50.2g),搅拌至二胺单体M5完全溶解后,加入2,2'-双(3,4-二羧酸)六氟丙烷二酐(6FDA)(4.4424g,10mmol),搅拌至二酐单体完全溶解得到混合溶液,在混合溶液中二胺单体与二酐单体的总固含量为15.0wt%,在室温下搅拌24h发生聚合反应,过滤、消泡后得到粘稠、均一的聚酰胺酸浆料,黏度为14300cp;
2)聚酰亚胺薄膜的制备:将步骤1)获得的聚胺酸浆料刮涂到玻璃板上,随后以5℃/分钟的升温速率升温至60℃,保温10min,再依次以同样的升温速率升温至100℃,保温10min;升温至150℃,保温10min;升温至180℃,保温10min;升温至200℃,保温10min;升温至250℃,保温10min;升温至300℃,保温1h,冷却至室温后,形成厚度10μm的聚酰亚胺薄膜。
实施例3
一种聚酰亚胺薄膜的制备方法,包括以下步骤:
1)聚酰胺酸浆料的制备:氮气保护下,在配有机械搅拌的三口瓶中加入实施例1合成的二胺单体M5(4.4046g,10mmol),无水二甲基乙酰胺(DMAc)(41.7g),搅拌至二胺单体M5完全溶解后,加入3,3',4,4'-联苯四甲酸二酐(BPDA)(2.9422g,10mmol),搅拌至二酐单体完全溶解得到混合溶液,在混合溶液中二胺单体与二酐单体的总固含量为15.0wt%,在室温下搅拌24h发生聚合反应,过滤、消泡后得到粘稠、均一的聚酰胺酸浆料,黏度为11800cp;
2)聚酰亚胺薄膜的制备:将步骤1)获得的聚酰胺酸浆料刮涂到玻璃板上,随后以5℃/分钟的升温速率升温至60℃,保温10min,依次以同样的升温速率升温至100℃,保温10min;升温至150℃,保温10min;升温至180℃,保温10min;升温至200℃,保温10min;升温至250℃,保温10min;升温至300℃,保温1h,冷却至室温后,形成厚度10μm的聚酰亚胺薄膜。
实施例4
一种聚酰亚胺薄膜的制备方法,包括以下步骤:
1)聚酰胺酸浆料的制备:氮气保护下,在配有机械搅拌的三口瓶中加入实施例1合成的二胺单体M5(4.4046g,10mmol),无水二甲基乙酰胺(DMAc)(42.6g),搅拌至二胺单体M5完全溶解后,加入4,4'-氧双邻苯二甲酸酐(ODPA)(3.1022g,10mmol),搅拌至二酐单体完全溶解得到混合溶液,在混合溶液中二胺单体与二酐单体的总固含量为15.0wt%,在室温下搅拌24h发生聚合反应,过滤、消泡后得到粘稠、均一的聚酰胺酸浆料,黏度为9800cp;
2)聚酰亚胺薄膜的制备:将步骤1)获得的聚酰胺酸浆料刮涂到玻璃板上,随后以5℃/分钟的升温速率升温至60℃,保温10min,依次以同样的升温速率升温至100℃,保温10min;升温至150℃,保温10min;升温至180℃,保温10min;升温至200℃,保温10min;升温至250℃,保温10min;升温至300℃,保温1h,冷却至室温后,形成厚度10μm的聚酰亚胺薄膜。
对比例1
一种聚酰亚胺薄膜的制备方法,包括以下步骤:
1)聚酰胺酸浆料的制备:氮气保护下,在配有机械搅拌的三口瓶中加入对苯二胺(PDA)(1.0814g,10mmol),无水二甲基乙酰胺(DMAc)(31.3g),搅拌至对苯二胺完全溶解后,加入2,2'-双(3,4-二羧酸)六氟丙烷二酐(6FDA)(4.4424g,10mmol),搅拌至二酐单体完全溶解得到混合溶液,在混合溶液中二胺单体与二酐单体的总固含量为15.0wt%,室温反应24h,过滤,消泡后得到粘稠的均一的聚酰胺酸浆料,黏度为16900cp;
2)聚酰亚胺薄膜的制备:将步骤1)获得的聚酰胺酸浆料刮涂到玻璃板上,随后以5℃/分钟的升温速率升温至60℃,保温10min,依次以同样的升温速率升温至100℃,保温10min;升温至150℃,保温10min;升温至180℃,保温10min;升温至200℃,保温10min;升温至250℃,保温10min;升温至300℃,保温1h,冷却至室温后,形成厚度10μm的聚酰亚胺薄膜。
对比例2
一种聚酰亚胺薄膜的制备方法,包括以下步骤:
1)聚酰胺酸浆料的制备:氮气保护下,在配有机械搅拌的三口瓶中加入对苯二胺(PDA)(1.0814g,10mmol),无水二甲基乙酰胺(DMAc)(22.8g),搅拌至对苯二胺完全溶解后,加入3,3',4,4'-联苯四甲酸二酐(BPDA)(2.9422g,10mmol),搅拌至二酐单体完全溶解得到混合溶液,在混合溶液中二胺单体与二酐单体的总固含量为15.1wt%,室温反应24h,过滤,消泡后得到粘稠的均一的聚酰胺酸浆料,黏度24200cp;
2)聚酰亚胺薄膜的制备:将步骤1)获得的聚酰胺酸浆料刮涂到玻璃板上,随后以5℃/分钟的升温速率升温至60℃,保温10min,依次以同样的升温速率升温至100℃,保温10min;升温至150℃,保温10min;升温至180℃,保温10min;升温至200℃,保温10min;升温至250℃,保温10min;升温至300℃,保温1h,冷却至室温后,形成厚度10μm的聚酰亚胺薄膜。
对比例3
一种聚酰亚胺薄膜的制备方法包括以下步骤:
1)聚酰胺酸浆料的制备:氮气保护下,在配有机械搅拌的三口瓶中加入由式N1表示的二胺单体(3.5219g,10mmol)后,45.2g无水二甲基乙酰胺(DMAc),搅拌至二胺单体N1完全溶解后,加入2,2'-双(3,4-二羧酸)六氟丙烷二酐(6FDA)(4.4424g,10mmol),搅拌至二酐单体完全溶解得到混合溶液,在混合溶液中二胺单体与二酐单体的总固含量为15.1wt%,室温搅拌24h发生聚合反应,过滤、消泡后得到粘稠、均一的聚酰胺酸浆料,黏度为18700cp;
2)聚酰亚胺薄膜的制备:将步骤1)获得的聚酰胺酸浆料刮涂到玻璃板上,随后以5℃/分钟的升温速率升温至60℃,保温10min,依次以同样的升温速率升温至100℃,保温10min;升温至150℃,保温10min;升温至180℃,保温10min;升温至200℃,保温10min;升温至250℃,保温10min;升温至300℃,保温1h,冷却至室温后,形成厚度10μm的聚酰亚胺薄膜。
测试例
分别对实施例2-4以及对比例1-3中得到的聚酰亚胺薄膜进行透光率测试、YI测试和CTE性能测试,结果如表1所示。
透光率测试方法的方法为:使用分光光度计(日本电色工业株式会社,COH-400)在400-700nm的整个波长范围内测量聚酰亚胺薄膜的总透光率,单位为百分比(%)。
Y值(YI)测试方法为:使用日本分光(株)制的紫外可见近红外分光光度计“V-670”,测定聚酰亚胺薄膜的黄色度(Yellow Index(黄色指数):YI值)。在没有样品的状态下进行背景测定后,将聚酰亚胺薄膜设置于样品架,对相对于300~800nm的光的透过率进行测定,求出三刺激值(X、Y、Z),基于YI=100×(1.2769X-1.0592Z)/Y的公式计算出YI值。
热膨胀系数测试方法为:利用热机械分析仪TMA(TA公司的Q450),测定热膨胀系数(CTE)。具体而言,将聚酰亚胺薄膜以5×20mm的大小准备后,利用配件装载试料,使测定的膜的长度为16mm。将牵拉膜的力设定为0.02N,在100至200℃的温度范围以4℃/min的升温速度进行1次升温工序后,在200至100℃的温度范围以4℃/min的冷却速度冷却,测定了降温后所得薄膜的热膨胀变化状。
表1.实施例和对比例中聚酰亚胺薄膜的性能比对
实施例2-4表明,采用本发明的含有酰胺键、四元环脂肪结构、苯环且分子构型对称的二胺单体M5与不同芳香族四羧酸二酐单体发生聚合,聚酰亚胺薄膜YI值在1.6以下,CTE在22.5ppm/℃以下,透光率在87.9%以上,且实施例2和3与对应对比例相比,聚酰亚胺薄膜YI值更低的同时热膨胀系数更低,且透光率较高。
对比例1与实施例2,对比例2与实施例3比较,在使用同样的二酐单体时,对比例1采用常规二胺单体所获得的聚酰亚胺薄膜,YI值和CET均高于实施例2,无法兼顾较高的透光率、较低的YI值和CET,对比例2采用常规二胺单体所获得的聚酰亚胺薄膜,透光率远低于实施例3、YI值和CET均高于实施例3。
对比例3与实施例2比较,尽管均含有酰胺键、四元脂肪环和苯环,但对比例3中的酰胺键的位置与实施例2中不同,对比例3所获得的聚酰亚胺薄膜的透光率低于实施例2,YI值和CET值均高于实施例2。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种制备聚酰亚胺薄膜用二胺单体,其特征在于,由式(M5)表示:
其中,R选自C1-5的烷基、C1-5的卤代烷基、卤素、H中任一种。
2.根据权利要求1所述的二胺单体,其特征在于,R选自C1-5的烷基、C1-5的氟代烷基、卤素、H中任一种;
优选的,R选自H。
3.权利要求1或2所述的二胺单体的制备方法,其特征在于,包括以下步骤:
(1)由式(1)表示的化合物与由式(2)表示的化合物与溶剂混合,在缩合剂和碱的作用下发生缩合反应制备由式(M4)表示的化合物;
(2)由式(M4)表示的化合物发生加氢反应制备由式(M5)表示的化合物;
其中,R选自C1-5的烷基、C1-5的卤代烷基、卤素、H中任一种。
4.根据权利要求3所述的制备方法,其特征在于,缩合反应温度为-10~100℃,优选的,缩合反应温度为10~60℃,更优选的,缩合反应温度为20~40℃;
和/或,缩合反应时间为3~48h;优选的,缩合反应时间为1~36h;
和/或,由式(1)表示的化合物与由式(2)表示的化合物的摩尔比为1:(2~3)。
5.根据权利要求3或4所述的制备方法,其特征在于,加氢反应温度为25~80℃;
和/或,加氢反应时间为3~36h。
6.一种聚酰亚胺薄膜,其特征在于,制备所述聚酰亚胺薄膜的原料包括权利要求1或2所述的二胺单体。
7.根据权利要求6所述的一种聚酰亚胺薄膜,其特征在于,制备所述聚酰亚胺薄膜的原料还包括二酐单体,所述二酐单体为芳香族四羧酸二酐;
所述芳香族四羧酸二酐选自2,2',3,3'-联苯四甲酸二酐、3,3',4,4'-联苯四甲酸二酐、4,4'-氧双邻苯二甲酸酐、9,9-双(3,4-二羧基苯基)芴二酸酐、(4-邻苯二甲酸酐)甲酰氧基-4-邻苯二甲酸酯、双[(3,4-二酸酐)苯基]对苯二甲酸酯、3,3',4,4'-二苯基砜四羧酸二酸酐,对-亚苯基-双苯偏三酸酯二酐、4,4'-对苯二氧双邻苯二甲酸酐、均苯四甲二酐、2,2'-双(3,4-二羧酸)六氟丙烷二酐、2,2-双(4-(3,4-二羧基苯氧基)苯基)六氟丙烷二酐、2,2-双(4-(3,4-二羧基苯甲酰基氧基)苯基)六氟丙烷二酐、2,2'-双(三氟甲基)-4,4'-双(3,4-二羧基苯氧基)联苯二酸酐中的至少一种;
优选的,所述二酐单体选自3,3',4,4'-联苯四甲酸二酐、2,2'-双(3,4-二羧酸)六氟丙烷二酐、4,4'-对苯二氧双邻苯二甲酸酐中的至少一种。
8.根据权利要求6或7所述的一种聚酰亚胺薄膜,其特征在于,所述二胺单体与二酐单体的摩尔比为1:(0.9-1.2),优选为1:(0.92-1.1),更优选为1:(0.95-1.05),最优选为1:1。
9.权利要求6-8任一项所述的一种聚酰亚胺薄膜的制备方法,其特征在于,包括如下步骤:将二胺单体与二酐单体、非质子化有机溶剂混合、聚合反应制备聚酰胺酸浆料,所述聚酰胺酸浆料经成膜和加热亚胺化制备所述聚酰亚胺薄膜。
10.根据权利要求9所述的制备方法,其特征在于,聚合反应温度为-10℃~50℃;优选的,聚合反应温度为-5℃~30℃,更优的,聚合反应温度为-5℃~10℃;
和/或,聚合反应时间为3-48h,优选的,聚合反应时间为5-36h,更优选的,聚合反应时间为10-24h;
和/或,在氮气或惰性气体氛围下发生聚合反应;
和/或,通过梯度升温进行所述加热亚胺化,梯度升温段之间包括保温段,所述加热亚胺化的温度为60℃-300℃,总的保温时间为2-10小时,升温速率为1-10℃/分钟;
和/或,所述聚酰胺酸浆料经过滤、消泡后再成膜。
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