CN116444391A - Diamine monomer for preparing polyimide film, preparation method thereof and polyimide film - Google Patents
Diamine monomer for preparing polyimide film, preparation method thereof and polyimide film Download PDFInfo
- Publication number
- CN116444391A CN116444391A CN202310425345.0A CN202310425345A CN116444391A CN 116444391 A CN116444391 A CN 116444391A CN 202310425345 A CN202310425345 A CN 202310425345A CN 116444391 A CN116444391 A CN 116444391A
- Authority
- CN
- China
- Prior art keywords
- dianhydride
- polyimide film
- diamine monomer
- bis
- 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.)
- Pending
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 72
- 229920001721 polyimide Polymers 0.000 title claims abstract description 67
- 150000004985 diamines Chemical class 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000732 arylene group Chemical group 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 6
- 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 57
- 239000002002 slurry Substances 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000004952 Polyamide Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920002647 polyamide Polymers 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000006482 condensation reaction Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- -1 (4- (3, 4-dicarboxybenzoyloxy) phenyl) hexafluoropropane Chemical compound 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920005575 poly(amic acid) Polymers 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
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-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
- 125000004435 hydrogen atom Chemical group [H]* 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
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 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 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 1
- 230000003287 optical effect Effects 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000000630 rising effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 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
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000007821 HATU Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 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
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-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
- 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 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
- 229940125782 compound 2 Drugs 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 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
- 150000007530 organic bases Chemical group 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 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
- 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
- 239000000243 solution Substances 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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- 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
- GUDPJHONHNSJBI-PMMFOGROSA-N C([ClH]([2H])([2H])([2H])([2H])[2H])(Cl)(Cl)[2H] Chemical compound C([ClH]([2H])([2H])([2H])([2H])[2H])(Cl)(Cl)[2H] GUDPJHONHNSJBI-PMMFOGROSA-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
- 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
- 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
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 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
- 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
- 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
- 239000007859 condensation product Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000004427 diamine 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005580 one pot reaction Methods 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
- 239000002798 polar solvent 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
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 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
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
The invention relates to a diamine monomer for preparing a polyimide film, a preparation method thereof and the polyimide film, belonging to the technical field of high polymer materials and synthetic methods thereof. The diamine monomer is represented by formula (M1);
Description
Technical Field
The invention belongs to the technical field of high polymer materials and preparation methods thereof. In particular, the invention relates to a diamine monomer for preparing a polyimide film, a preparation method thereof and the polyimide film.
Background
Aromatic polyimides (CPI) have been widely used in the electronics, automotive and aerospace industries due to their extremely high glass transition temperature (Tg) and excellent thermal stability, good chemical resistance, and good dielectric and mechanical properties. However, intramolecular and intermolecular Charge Transfer (CT) interactions between electron withdrawing dianhydride and electron donating diamine residues produce yellow to dark brown colors, and aromatic polyimide films have lower transparency, higher YI values, and poor optical properties, which prevent their use in the optical and optoelectronic fields. In addition, due to the specificity of aliphatic structures, diamine or dianhydride has specific space configuration, so that the aromatic polyimide molecules obtained after the traditional aliphatic dianhydride or diamine is polymerized are not regular enough, and the polyimide film has higher Coefficient of Thermal Expansion (CTE).
Disclosure of Invention
In order to solve the problems of poor optical performance and high thermal expansion coefficient of the traditional polyimide film, the invention provides a diamine monomer for preparing the polyimide film and a preparation method thereof.
The invention also provides a polyimide film.
The technical scheme of the invention is as follows:
a diamine monomer for preparing a polyimide film is represented by the formula (M1):
wherein X is selected from arylene groups of C6-C18; r is selected from C1-C5 alkyl, C1-C5 haloalkyl, halogen, and hydrogen.
The diamine monomer is shown as a formula (M11);
wherein X is selected from arylene groups of C6-C18; r is selected from C1-C5 alkyl, C1-C5 fluoroalkyl, halogen, and hydrogen.
X is selected from arylene of C6-C12; r is selected from C1-C3 alkyl, C1-C3 fluoroalkyl, halogen, and hydrogen.
X is selected from phenylene; r is selected from hydrogen.
A preparation method of diamine monomer for preparing polyimide film comprises the following steps:
a compound represented by formula (M1) is produced by a condensation reaction of a compound represented by formula (2) in reaction formula 1 with a compound represented by formula (3);
reaction 1
Wherein R is selected from C1-C5 alkyl, C1-C5 haloalkyl, halogen, hydrogen; x is selected from arylene groups of C6-C18.
The condensation reaction temperature is-10-100 ℃, preferably, the condensation reaction temperature is 10-60 ℃, more preferably, the condensation reaction temperature is 20-40 ℃;
and/or the condensation reaction time is 3-48h; preferably, the condensation reaction time is 1 to 36 hours, more preferably, the condensation reaction time is 8 to 12 hours.
The molar ratio of the compound represented by formula (2) to the compound represented by formula (3) is 1 (2-3).
The condensing agent is selected from N, N ' -Carbonylimidazole (CDI), dicyclohexylcarbodiimide (DCC), N, N ' -Diisopropylcarbodiimide (DIC), 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDCI), 4-Dimethylaminopyridine (DMAP), 4-pyrrolidinylpyridine (4-PPY), 1-hydroxybenzotriazole (HOBt), N-hydroxy-7-azabenzotriazol (HOAt), N-hydroxysuccinimide (HOSu), N-hydroxyphthalimide (NHPI), NHNI, pentafluorophenol (PFPOH), O- (7-azabenzotriazol-1-yl) -N, N, N ', N ' -tetramethyluronium Hexafluorophosphate (HATU), taurine (TATU), O- (benzotriazol-1-yl) -N, N, N ', N ' -tetramethyluronium Hexafluorophosphate (HBTU), 2- (1H-benzotrisazo L-1-yl) -1, 3-tetramethyluronium tetrafluoro (HOTU), 2- (1H-benzotrisazo-1-yl) -1, 3-tetramethyluronium tetrafluoro (TBTU), 3- (2-azabenzotriazol-1-yl) -N, N, N ' -tetramethyluronium Hexafluorophosphate (HATU), a combination of one or more of N-tetramethyl-O- (N-succinimidyl) urea tetrafluoroborate (TSTU), 2- (endo-5-norbornene-2, 3-dicarboxyimide) -1, 3-tetramethyluronium tetrafluoroborate (TNTU), a cator condensing agent (BOP), hydroxypropyl acrylate (HOP), benzotriazol-1-yl-oxy-tripyrrolidinylphosphine hexafluorophosphate (PyAOP), diphenylphosphinoyl chloride (DPPCl), DECP, diphenyl azide phosphate (DPPA), MPTA, bis (2-oxo-3-oxazolidinyl) phosphinoyl chloride (BOP-Cl), triphenylphosphine-polyhalomethane, triphenylphosphine-hexachloroacetone, triphenylphosphine-N-bromosuccinimide, 3-acyl-2-thiothiazoline.
Wherein the structural formula of NHNI isHAPyU has the structural formula +.>DECP has the formula->MPTA has the structural formula of
The base is organic base or inorganic base, and the organic base is selected from one or more of triethylamine, hunig base (N, N-diisopropylethylamine, DIEA), pyridine, sodium tert-butoxide, potassium tert-butoxide, diisopropylamine, N-butyllithium, isobutyllithium, tert-butyllithium, diisopropyllithium amide (LDA), lithium bis (trimethylsilyl) amide (LiHMDS), sodium bis (trimethylsilyl) amide (NaHMDS), potassium bis (trimethylsilyl) amide (KHMDS), imidazole, sodium methoxide, sodium ethoxide, sodium amide, potassium trimethylsilanol, and tetramethyl ethylenediamine (TMEDA). The inorganic base is selected from one or more of sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium thiosulfate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia water, methanol solution of ammonia and ammonium bicarbonate.
The solvent used in the condensation reaction is selected from one or more of N, N-Dimethylformamide (DMF), N-Diethylformamide (DEF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), cyclohexanone and gamma-butyrolactone.
The molar ratio of the condensing agent to the base is 1 (1-3), preferably 1 (1.2-2.4).
Further comprising the step of subjecting the condensation product to a post-treatment comprising in order dilution, extraction, washing of the organic phase, drying, concentration, purification of the residue, to obtain the compound represented by formula (M1).
The preparation method of the compound represented by the formula (2) comprises the following steps: reacting the compound represented by formula (1) under light conditions to obtain a compound represented by formula (2);
reaction 1'
Wherein R is selected from C1-C5 alkyl, C1-C5 haloalkyl, halogen, hydrogen;
preferably, the illumination condition is 365nm blue light;
preferably, the illumination time is 8-48 hours, more preferably, the illumination time is 12-24 hours.
A polyimide film is prepared from the diamine monomer.
The raw materials for preparing the polyimide film also comprise dianhydride monomers, wherein the dianhydride monomers are aromatic tetracarboxylic dianhydride.
Preferably, the aromatic tetracarboxylic dianhydride is selected from the group consisting of 2,2', 3' -biphenyl tetracarboxylic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride (alias biphenyl dianhydride), 4 '-oxydiphthalic anhydride (alias 4,4' -oxydiphthalic anhydride), 9-bis (3, 4-dicarboxyphenyl) fluorenedianhydride, (4-phthalic anhydride) formyloxy-4-phthalate, bis [ (3, 4-dianhydride) phenyl ] terephthalate, 3', 4' -diphenylsulfone tetracarboxylic dianhydride, at least one of p-phenylene-bis-trimellitate dianhydride, 4 '-terephthaloyl bisphthalic anhydride, pyromellitic dianhydride, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (referred to as "hexafluorodianhydride"), 2-bis (4- (3, 4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2-bis (4- (3, 4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2 '-bis (trifluoromethyl) -4,4' -bis (3, 4-dicarboxyphenoxy) biphenyl dianhydride.
Preferably, the dianhydride monomer is selected from at least one of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 2 '-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 4' -terephthaloxy diphthalic anhydride.
The molar ratio of diamine monomer to dianhydride monomer is 1 (0.9-1.2), preferably 1 (0.92-1.1), more preferably 1: (0.95-1.05), most preferably 1:1.
a preparation method of a polyimide film comprises the following steps: mixing diamine monomer with dianhydride monomer and aprotic organic solvent, and performing polymerization reaction to prepare polyamide acid slurry, wherein the polyamide acid slurry is subjected to film forming and heating imidization to prepare the polyimide film.
The polymerization reaction temperature is-10 ℃ to 50 ℃; preferably, the polymerization temperature is-5 to 30 ℃, more preferably-5 to 10 ℃.
The polymerization time is 3 to 48 hours, preferably 5 to 36 hours, more preferably 10 to 24 hours.
The polymerization reaction takes place under nitrogen or an inert gas atmosphere.
The heating imidization is carried out by gradient heating, a heat preservation section is arranged between gradient heating sections, the temperature of the heating imidization is 60-300 ℃, the total heat preservation time is 2-10 hours, and the heating rate is 1-10 ℃/min. Preferably, the process of thermal imidization comprises the following steps in order: heating to 60-80 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 10min-1h; continuously heating to 90-120 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 10min-1h; continuously heating to 140-160 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 10min-1h; continuously heating to 170-190 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 10min-1h; continuously heating to 190-210 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 10min-1h; continuously heating to 240-260 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 10min-1h; continuously heating to 300 ℃ at the heating rate of 1-10 ℃/min, and preserving heat for 1-4h.
The polyamide acid slurry is defoamed in vacuum and then forms a film.
The thickness of the polyimide film is 10 mu m to 100 mu m.
The solvent used in the polymerization reaction is at least one selected from N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, gamma-butyrolactone, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, ethyl acetate, toluene and methyl ethyl ketone; preferably, the aprotic polar solvent is selected from N, N-dimethylformamide and/or N, N-dimethylacetamide.
The beneficial technical effects of the invention are as follows:
1. the diamine monomer for preparing the polyimide film contains an amide bond, a four-ring aliphatic structure and a benzene ring, has symmetrical molecular configuration, and the polyimide film prepared from the diamine monomer serving as a raw material has better optical performance and lower thermal expansion coefficient. On one hand, the quaternary alicyclic ring in the molecular structure is favorable for interrupting the electron conjugation, loosening the chain filling, and reducing or even eliminating the formation of CT complex, thereby improving the optical performance of the polyimide film; on the other hand, due to the introduction of the symmetrically distributed amide bonds, more hydrogen bonds are introduced among polyimide film molecules, and the polyimide film molecules are more regular, so that the thermal expansion coefficient of the film is reduced, and the problems of poor optical performance and high thermal expansion coefficient of the polyimide film synthesized by adopting the traditional diamine monomer are solved. In addition, the diamine monomer is beneficial to avoiding the problem that insoluble salts are formed in the process of synthesizing polyamide acid (PAAs) and high molecular weight PAA slurry is not obtained when the diamine monomer is polymerized.
2. The preparation method of the diamine monomer selects carboxylic acid containing quaternary aliphatic ring and benzene ring to be synthesized with diamine with arylene through condensation reaction, is environment-friendly and simple, does not need to use extremely strong corrosive acyl chloride reagent, reduces synthesis steps, and can directly synthesize diamine containing amide bond by a one-pot method. The synthesis method can be accurately controlled, and the amidation site and the amidation amount can be accurately controlled by controlling the amount of the condensing agent.
3. The polyimide film provided by the invention is obtained by polymerizing the diamine monomer represented by the formula (M1) and aromatic tetracarboxylic dianhydrides such as 2,2 '-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 3',4 '-biphenyl tetracarboxylic dianhydride, 4' -oxydiphthalic anhydride and the like, is more beneficial to realizing better optical performance of the polyimide film and has lower thermal expansion coefficient, and simultaneously solves the problems that the reactivity of aliphatic dianhydride is low and PAA slurry with high molecular weight enough to form a flexible film cannot be obtained.
Drawings
FIG. 1 is a diamine monomer M11 1 HNMR spectrogram;
FIG. 2 is a diamine monomer M11 13 CNMR spectra.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, wherein the examples are given for the purpose of illustration only and are not intended to limit the scope of the invention.
The viscosity test method of the polyamic acid slurry in examples and comparative examples is:
the logarithmic viscosity of the polyamic acid slurry at 25℃was measured using a candelan-Finsk viscometer. The logarithmic viscosity (μ) was determined by the following formula.
μ＝ln(t s /t 0 )/C
t 0 : the circulation time of the solvent for reaction;
t s : slurry flow time;
C:0.5g/dL。
example 1
A process for the preparation of diamine monomer M11 comprising the steps of:
(1) Compound 1 (10 g,67.6 mmol) was reacted under 365nm blue LED lamp for 24 hours to give Compound 2 (9.5 g) as pale yellow powder;
reaction 1'
(2) To a solution of compound 2 (9.5 g,32.1 mmol) obtained in step (1) and p-phenylenediamine (7.6 g,70.3 mmol) in N, N-Dimethylformamide (DMF) (200 mL) was added HATU (30.5 g,80.2 mmol) and DIEA (13.0 g,100 mmol) in this order under ice bath, and the mixture was stirred at room temperature for 18h to effect a condensation reaction. The resulting reaction mixture was diluted with 400mL of water and extracted with ethyl acetate, and the organic phase was washed twice with saturated brine, dried over anhydrous sodium sulfate and concentrated to give a residue, which was purified by silica gel column chromatography to give compound M11 (16.0 g) as a white solid.
Reaction 1
As shown in FIG. 1, compound M11 1 HNMR spectra (500 MHz, chloroform-d 6), δ9.40 (s, 1H), 7.32 (d, j=7.2 hz, 2H), 7.25 (t, j=7.6 hz, 2H), 7.14 (s, 1H), 6.83 (d, j=8.6 hz, 2H), 6.35 (d, j=8.7 hz, 2H), 4.75 (s, 2H), 4.36 (dd, j=10.3, 7.1hz, 1H), 3.95 (dd, j=10.4, 7.1hz, 1H); as shown in FIG. 2, compound M11 13 CNMR spectra (126 MHz, methyl sulfoxide-d 6) delta 169.16,145.23,140.59,128.40,128.37,128.11,126.72,122.00,114.04,47.65,41.18. It was revealed that diamine monomer M11 represented by formula (M11) was synthesized by reaction formula 1' and reaction formula 1 in this order.
Example 2
A preparation method of a polyimide film comprises the following steps:
1) Preparation of polyamic acid slurry: under the protection of nitrogen, adding the diamine monomer M11 (4.7658 g,10 mmol) obtained in the example 1 into a three-port bottle with mechanical stirring, stirring until the diamine monomer M11 is completely dissolved, adding 2,2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6 FDA) (4.4424 g,10 mmol), stirring until the dianhydride monomer is completely dissolved to obtain a mixed solution, stirring at room temperature for 24 hours until the total solid content of the diamine monomer and the dianhydride monomer is 15.0wt%, performing polymerization reaction, filtering, and defoaming to obtain viscous and uniform polyamide acid slurry with the viscosity of 12800cp;
2) Preparation of polyimide film: the polyamide acid slurry obtained in the step 1) is coated on a glass plate in a scraping way, then the temperature is raised to 60 ℃ at the temperature rising rate of 5 ℃/min, the heat is preserved for 10min, and then the temperature is raised to 100 ℃ at the same temperature rising rate in sequence, and the heat is preserved for 10min; heating to 150 ℃, and preserving heat for 10min; heating to 180deg.C, and maintaining for 10min; heating to 200deg.C, and maintaining for 10min; heating to 250 ℃, and preserving heat for 10min; heating to 300 ℃, preserving heat for 1h, and cooling to room temperature to form the polyimide film with the thickness of 10 mu m.
Example 3
A preparation method of a polyimide film comprises the following steps:
1) Preparation of polyamic acid slurry: under the protection of nitrogen, adding the diamine monomer M11 (4.7658 g,10 mmol) obtained in the example 1 into a three-port bottle with mechanical stirring, stirring until the diamine monomer M11 is completely dissolved, adding 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) (2.9422 g,10 mmol), stirring until the dianhydride monomer is completely dissolved to obtain a mixed solution, stirring for 24 hours at room temperature until the total solid content of the diamine monomer and the dianhydride monomer is 14.7wt%, performing polymerization reaction, filtering, and defoaming to obtain thick and uniform polyamic acid slurry with the viscosity of 10100cp;
2) Preparation of polyimide film: the polyamide acid slurry obtained in the step 1) is coated on a glass plate in a scraping way, then the temperature is raised to 60 ℃ at the temperature rising rate of 5 ℃/min, the heat is preserved for 10min, and the temperature is raised to 100 ℃ at the same temperature rising rate in sequence, and the heat is preserved for 10min; heating to 150 ℃, and preserving heat for 10min; heating to 180deg.C, and maintaining for 10min; heating to 200deg.C, and maintaining for 10min; heating to 250 ℃, and preserving heat for 10min; heating to 300 ℃, preserving heat for 1h, and cooling to room temperature to form the polyimide film with the thickness of 10 mu m.
Example 4
A preparation method of a polyimide film comprises the following steps:
1) Preparation of polyamic acid slurry: under the protection of nitrogen, adding the diamine monomer M11 (4.7658 g,10 mmol) obtained in the example 1 into a three-port bottle with mechanical stirring, stirring until the diamine monomer M11 is completely dissolved, adding 4,4' -oxydiphthalic anhydride (ODPA) (3.1022 g,10 mmol), stirring until the mixture is completely dissolved, stirring for obtaining a mixed solution, wherein the total solid content of the diamine monomer and the dianhydride monomer is 15.2wt%, stirring for 24 hours at room temperature for polymerization reaction, filtering, and defoaming to obtain viscous and uniform polyamide acid slurry with the viscosity of 8700cp;
2) Preparation of polyimide film: the polyamide acid slurry obtained in the step 1) is coated on a glass plate in a scraping way, then the temperature is raised to 60 ℃ at the temperature rising rate of 5 ℃/min, the heat is preserved for 10min, and the temperature is raised to 100 ℃ at the same temperature rising rate in sequence, and the heat is preserved for 10min; heating to 150 ℃, and preserving heat for 10min; heating to 180deg.C, and maintaining for 10min; heating to 200deg.C, and maintaining for 10min; heating to 250 ℃, and preserving heat for 10min; heating to 300 ℃, preserving heat for 1h, and cooling to room temperature to form the polyimide film with the thickness of 10 mu m.
Comparative example 1
A preparation method of a polyimide film comprises the following steps:
1) Preparation of polyamic acid slurry: under the protection of nitrogen, adding p-Phenylenediamine (PDA) (1.0814 g,10 mmol) and 31.3g anhydrous dimethylacetamide (DMAc) into a three-port bottle with mechanical stirring, stirring until the PDA is completely dissolved, adding 2,2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6 FDA) (4.4424 g,10 mmol), stirring until the dianhydride is completely dissolved to obtain a mixed solution, stirring for 24 hours at room temperature until the total solid content of diamine monomer and dianhydride monomer is 15.0wt%, carrying out polymerization reaction, filtering, and defoaming to obtain viscous and uniform polyamide acid slurry with the viscosity of 16900cp;
2) Preparation of polyimide film: the polyamide acid slurry obtained in the step 1) is coated on a glass plate in a scraping way, then the temperature is raised to 60 ℃ at the temperature rising rate of 5 ℃/min, the heat is preserved for 10min, and the temperature is raised to 100 ℃ at the same temperature rising rate in sequence, and the heat is preserved for 10min; heating to 150 ℃, and preserving heat for 10min; heating to 180deg.C, and maintaining for 10min; heating to 200deg.C, and maintaining for 10min; heating to 250 ℃, and preserving heat for 10min; heating to 300 ℃, preserving heat for 1h, and cooling to room temperature to form the polyimide film with the thickness of 10 mu m.
Comparative example 2
A preparation method of a polyimide film comprises the following steps:
1) Preparation of polyamic acid slurry: under the protection of nitrogen, adding p-Phenylenediamine (PDA) (1.0814 g,10 mmol) and 22.8g anhydrous dimethylacetamide (DMAc) into a three-port bottle with mechanical stirring, stirring until the PDA is completely dissolved, adding 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) (2.9422 g,10 mmol), stirring until the mixture is completely dissolved to obtain a mixed solution, stirring for 24 hours at room temperature until the total solid content of diamine monomer and dianhydride monomer in the mixed solution is 15.0wt%, carrying out polymerization reaction, filtering, and defoaming to obtain viscous and uniform polyamide acid slurry with the viscosity of 24200cp;
2) Preparation of polyimide film: the polyamide acid slurry obtained in the step 1) is coated on a glass plate in a scraping way, then the temperature is raised to 60 ℃ at the temperature rising rate of 5 ℃/min, the heat is preserved for 10min, and the temperature is raised to 100 ℃ at the same temperature rising rate in sequence, and the heat is preserved for 10min; heating to 150 ℃, and preserving heat for 10min; heating to 180deg.C, and maintaining for 10min; heating to 200deg.C, and maintaining for 10min; heating to 250 ℃, and preserving heat for 10min; heating to 300 ℃, preserving heat for 1h, and cooling to room temperature to form the polyimide film with the thickness of 10 mu m.
Comparative example 3
A preparation method of a polyimide film comprises the following steps:
1) Preparation of polyamic acid slurry: under the protection of nitrogen, adding diamine monomer (4.7658 g,10 mmol) represented by a formula N1 into a three-port bottle with mechanical stirring, stirring 52.2g of anhydrous dimethylacetamide (DMAc) until the diamine monomer N1 is completely dissolved, adding 2,2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6 FDA) (4.4424 g,10 mmol), stirring until the mixture is completely dissolved to obtain a mixed solution, stirring at room temperature for 24 hours until the total solid content of the diamine monomer and the dianhydride monomer is 15.0wt%, and carrying out polymerization reaction to obtain viscous and uniform polyamide acid slurry with the viscosity of 32300cp after filtering and defoaming;
(N1)；
2) Preparation of polyimide film: the polyamide acid slurry obtained in the step 1) is coated on a glass plate in a scraping way, then the temperature is raised to 60 ℃ at the temperature rising rate of 5 ℃/min, the heat is preserved for 10min, and the temperature is raised to 100 ℃ at the same temperature rising rate in sequence, and the heat is preserved for 10min; heating to 150 ℃, and preserving heat for 10min; heating to 180deg.C, and maintaining for 10min; heating to 200deg.C, and maintaining for 10min; heating to 250 ℃, and preserving heat for 10min; heating to 300 ℃, preserving heat for 1h, and cooling to room temperature to form the polyimide film with the thickness of 10 mu m.
Test case
The polyimide films obtained in examples 2 to 4 and comparative examples 1 to 3 were subjected to a light transmittance test, a YI value test and a CTE performance test, respectively, and the results are shown in Table 1.
The light transmittance testing method comprises the following steps: the total light transmittance of the polyimide film was measured in percent (%) using a spectrophotometer (COH-400, japan electric color industry co.) over the entire wavelength range of 400 to 700 nm.
The Y value (YI) test method comprises the following steps: the yellowness (Yellow Index): YI value) of the polyimide film was measured using an ultraviolet visible near infrared spectrophotometer "V-670" manufactured by Japan Spectrophotometer (Co., ltd.). After background measurement is performed in a state where no sample is present, a polyimide film is set in a sample holder, the light transmittance at 300 to 800nm is measured, a tristimulus value (X, Y, Z) is obtained, and a YI value is calculated based on a formula of yi=100× (1.2769X-1.0592Z)/Y.
The thermal expansion coefficient testing method comprises the following steps: the Coefficient of Thermal Expansion (CTE) was measured using a thermo-mechanical analyzer TMA (Q450 of TA company). Specifically, after preparing a polyimide film to a size of 5×20mm, a sample was loaded by a fitting so that the length of the film actually measured was 16mm as well. The force of pulling the film was set to 0.02N, the film was cooled at a cooling rate of 4℃per minute at a temperature range of 200 to 100℃after 1 heating step at a heating rate of 4℃per minute at a temperature range of 100 to 200℃and the change in thermal expansion of the film obtained after the cooling was measured.
TABLE 1 polyimide film Properties
Examples 2 to 4 show that the polyimide film prepared by polymerizing the diamine monomer M11 containing an amide bond, a four-membered ring aliphatic structure and a benzene ring and having a symmetrical molecular configuration with different types of aromatic tetracarboxylic dianhydride monomers has a light transmittance of 88.2% or more, a YI value of 1.4 or less, and a CTE of 24.5 ppm/. Degree.C or less, and that examples 2 and 3 are superior to those prepared by using the same dianhydride monomer and conventional diamine monomer in the corresponding comparative examples, and not only have excellent optical properties (higher light transmittance, lower YI value) but also have a lower thermal expansion coefficient.
Comparative example 1 and example 2, comparative example 2 and example 3, when the same dianhydride monomer is used, the polyimide film obtained by using the conventional diamine monomer in comparative example 1 has higher YI value and CET value than in example 2, and lower light transmittance than in example 2, and the polyimide film obtained by using the conventional diamine monomer in comparative example 2 has much lower light transmittance than in example 3, YI value and CET value than in example 3, and the lower YI value and CET value cannot be considered.
Comparative example 3 was compared with example 2, and the polyimide film obtained, although both of them contained an amide bond and a quaternary aliphatic ring, in which the amine group was located on a benzene ring connected to the quaternary ring, had a light transmittance lower than that of example 2, a YI value higher than that of example 2, and a CET value much higher than that of example 2.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (12)
1. A diamine monomer for producing a polyimide film, characterized by being represented by the formula (M1):
wherein X is selected from arylene groups of C6-C18; r is selected from C1-C5 alkyl, C1-C5 haloalkyl, halogen, and hydrogen.
2. Diamine monomer according to claim 1, wherein the diamine monomer is represented by formula (M11);
wherein X is selected from arylene groups of C6-C18; r is selected from C1-C5 alkyl, C1-C5 fluoroalkyl, halogen, and hydrogen.
3. Diamine monomer according to claim 1 or 2, characterized in that X is selected from arylene groups of C6-C12; r is selected from C1-C3 alkyl, C1-C3 fluoroalkyl, halogen, and hydrogen.
4. A diamine monomer as claimed in any of claims 1 to 3, wherein X is selected from phenylene groups; r is selected from hydrogen.
5. The process for producing a diamine monomer as described in any one of claims 1 to 4, comprising the steps of:
a compound represented by formula (M1) is produced by a condensation reaction of a compound represented by formula (2) in reaction formula 1 with a compound represented by formula (3);
reaction 1
Wherein R is selected from C1-C5 alkyl, C1-C5 haloalkyl, halogen, hydrogen; x is selected from arylene groups of C6-C18.
6. The preparation method according to claim 5, wherein the condensation reaction temperature is-10 to 100 ℃, preferably the condensation reaction temperature is 10 to 60 ℃, more preferably the condensation reaction temperature is 20 to 40 ℃;
and/or the condensation reaction time is 3-48h; preferably, the condensation reaction time is 1 to 36 hours.
7. The production method according to claim 5 or 6, wherein the molar ratio of the compound represented by the formula (2) to the compound represented by the formula (3) is 1 (2-3).
8. A polyimide film, wherein the raw material for preparing the polyimide film comprises the diamine monomer according to any one of claims 1 to 4.
9. The polyimide film according to claim 8, wherein the raw material for preparing the polyimide film further comprises a dianhydride monomer, wherein the dianhydride monomer is aromatic tetracarboxylic dianhydride;
preferably, the aromatic tetracarboxylic dianhydride is selected from the group consisting of 2,2', 3' -biphenyl tetracarboxylic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4' -oxydiphthalic anhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, (4-phthalic anhydride) formyloxy-4-phthalate, bis [ (3, 4-dianhydride) phenyl ] terephthalate, 3', 4' -diphenylsulfone tetracarboxylic dianhydride, at least one of p-phenylene-bis-trimellitate dianhydride, 4' -terephthaloyl bisphthalic anhydride, pyromellitic dianhydride, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 2-bis (4- (3, 4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2-bis (4- (3, 4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2' -bis (trifluoromethyl) -4,4' -bis (3, 4-dicarboxyphenoxy) biphenyl dianhydride;
more preferably, the dianhydride monomer is at least one selected from 3,3', 4' -biphenyl tetracarboxylic dianhydride, 2 '-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, and 4,4' -terephthaloyl diphthalic anhydride.
10. A polyimide film according to claim 9, characterized in that the molar ratio of diamine monomer to dianhydride monomer is 1 (0.9-1.2), preferably 1 (0.92-1.1), more preferably 1: (0.95-1.05), most preferably 1:1.
11. the method for producing a polyimide film according to any one of claims 8 to 10, comprising the steps of: mixing diamine monomer with dianhydride monomer and aprotic organic solvent, and performing polymerization reaction to prepare polyamide acid slurry, wherein the polyamide acid slurry is subjected to film forming and heating imidization to prepare the polyimide film.
12. The method according to claim 11, wherein the polymerization temperature is-10 ℃ to 50 ℃; preferably, the polymerization temperature is-5-30 ℃, more preferably-5-10 ℃;
and/or the polymerization time is 3 to 48 hours, preferably, the polymerization time is 5 to 36 hours, more preferably, the polymerization time is 10 to 24 hours;
and/or, carrying out polymerization reaction under nitrogen or inert gas atmosphere;
and/or carrying out heating imidization through gradient heating, wherein a heat preservation section is arranged between gradient heating sections, the temperature of the heating imidization is 60-300 ℃, the total heat preservation time is 2-10 hours, and the heating rate is 1-10 ℃/min;
and/or, the polyamic acid slurry is defoamed in vacuum and then formed into a film.
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| EP1295866A1 (en) * | 2001-09-17 | 2003-03-26 | Fuji Photo Film Co., Ltd. | 4-membered ring compound and optical phase retardation plate using the same |
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| JP2020033340A (en) * | 2018-08-24 | 2020-03-05 | 国立大学法人北陸先端科学技術大学院大学 | Quaternary ammonium group-containing polyamide |
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| EP1295866A1 (en) * | 2001-09-17 | 2003-03-26 | Fuji Photo Film Co., Ltd. | 4-membered ring compound and optical phase retardation plate using the same |
| US20140323679A1 (en) * | 2011-11-17 | 2014-10-30 | Japan Advanced Institute Of Science And Technology | Polymer raw material and polymer material |
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