CN108148201A - Method for producing polyimide film and method for producing graphite film using same - Google Patents
Method for producing polyimide film and method for producing graphite film using same Download PDFInfo
- Publication number
- CN108148201A CN108148201A CN201710556495.XA CN201710556495A CN108148201A CN 108148201 A CN108148201 A CN 108148201A CN 201710556495 A CN201710556495 A CN 201710556495A CN 108148201 A CN108148201 A CN 108148201A
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- China
- Prior art keywords
- catalyst
- film
- polyimide film
- manufacturing
- containing catalyst
- Prior art date
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- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 107
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 73
- 239000010439 graphite Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 208
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 72
- 150000004985 diamines Chemical class 0.000 claims abstract description 62
- 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 abstract description 50
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 34
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 54
- 239000004952 Polyamide Substances 0.000 claims description 49
- 229920002647 polyamide Polymers 0.000 claims description 49
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 27
- 238000003763 carbonization Methods 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- -1 hexafluoro isopropyl alkene Chemical class 0.000 claims description 17
- 238000005087 graphitization Methods 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000005255 carburizing Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 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 claims description 7
- 150000003949 imides Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000002220 fluorenes Chemical class 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 3
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- PUFWGUZSDHANBX-UHFFFAOYSA-N 1-phenyl-9h-fluorene Chemical class C=12CC3=CC=CC=C3C2=CC=CC=1C1=CC=CC=C1 PUFWGUZSDHANBX-UHFFFAOYSA-N 0.000 claims description 2
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 claims description 2
- 241000208140 Acer Species 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008522 N-ethylpiperidines Chemical class 0.000 claims description 2
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 1
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- OENLEHTYJXMVBG-UHFFFAOYSA-N pyridine;hydrate Chemical compound [OH-].C1=CC=[NH+]C=C1 OENLEHTYJXMVBG-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 23
- 239000000463 material Substances 0.000 description 18
- 239000004642 Polyimide Substances 0.000 description 16
- 239000012973 diazabicyclooctane Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000002969 artificial stone Substances 0.000 description 5
- 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 5
- 238000001035 drying Methods 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- JDXPGEWRMWBVAI-UHFFFAOYSA-N O=C(Oc1cccc(c1)-c1cccc(OC(=O)c2ccc3C(=O)OC(=O)c3c2)c1)c1ccc2C(=O)OC(=O)c2c1 Chemical compound O=C(Oc1cccc(c1)-c1cccc(OC(=O)c2ccc3C(=O)OC(=O)c3c2)c1)c1ccc2C(=O)OC(=O)c2c1 JDXPGEWRMWBVAI-UHFFFAOYSA-N 0.000 description 3
- 244000137827 Rumex acetosa Species 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 description 2
- NKYXYJFTTIPZDE-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F NKYXYJFTTIPZDE-UHFFFAOYSA-N 0.000 description 2
- FMACFWAQBPYRFO-UHFFFAOYSA-N 5-[9-(1,3-dioxo-2-benzofuran-5-yl)fluoren-9-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 FMACFWAQBPYRFO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CMTKWUZSCQDNBB-UHFFFAOYSA-N CN1C(=NC=C1)C.CN1C(=NC=C1)C Chemical compound CN1C(=NC=C1)C.CN1C(=NC=C1)C CMTKWUZSCQDNBB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 235000005291 Rumex acetosa Nutrition 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- 235000003513 sheep sorrel Nutrition 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical class CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- CEPCPXLLFXPZGW-UHFFFAOYSA-N 2,4-difluoroaniline Chemical compound NC1=CC=C(F)C=C1F CEPCPXLLFXPZGW-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- OPVHOFITDJSMOD-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1OC1=CC=CC2=C1C(=O)OC2=O OPVHOFITDJSMOD-UHFFFAOYSA-N 0.000 description 1
- HNHQPIBXQALMMN-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 HNHQPIBXQALMMN-UHFFFAOYSA-N 0.000 description 1
- WZGOPUQKVKRIRM-UHFFFAOYSA-N 4-[4-[9-[4-(3,4-dicarboxyphenoxy)phenyl]fluoren-9-yl]phenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(OC=3C=C(C(C(O)=O)=CC=3)C(O)=O)=CC=2)C=C1 WZGOPUQKVKRIRM-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
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- 101000729827 Homo sapiens Barrier-to-autointegration factor-like protein Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 235000015807 Rumex acetosa ssp. acetosa Nutrition 0.000 description 1
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- 235000015441 Rumex acetosa ssp. pseudoxyria Nutrition 0.000 description 1
- 235000015439 Rumex acetosa ssp. thyrsiflorus Nutrition 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for manufacturing a graphite film by using a polyimide film manufacturing method. Then, mixing tetracarboxylic dianhydride with the diamine solution containing the catalyst to form a polyamic acid solution containing the catalyst. Then, the polyamic acid solution containing the catalyst is heated to form a polyamic acid film containing the catalyst. Then, the polyamic acid film containing the catalyst is imidized to form a polyimide film. Finally, the polyimide film is heated to form a graphite film. The step of imidizing the polyamic acid film containing a catalyst to form a polyimide film is catalyzed by a catalyst, which is a tertiary amine.
Description
Technical field
A kind of manufacturing method the present invention relates to manufacturing method of polyimide film and using its graphite film, particularly
It is a kind of that there is the manufacturing method of polyimide film used in the graphite film of superior thermal conductivity energy for manufacture and use this
The manufacturing method of graphite film of the polyimide film manufacture with superior thermal conductivity energy.
Background technology
With the efficiency fast lifting of electronic product, how to meet the radiating requirements of electronic product becomes an important view
Topic.The heat sink material or Heat Conduction Material used in general electronic products is copper, and the coefficient of heat conduction of copper is about 400W/m-K.Have
The heat sink material or Heat Conduction Material often used in the electronic product of lightweight demand is aluminium, and the coefficient of heat conduction of aluminium is about 200W/
m-K.Due to being a kind of low-density with graphite film prepared by native graphite and there is high thermal conductivity, pliability and electromagnetic shielding
The material of property, the coefficient of heat conduction is about 300W/m-K.Therefore, graphite film is also extensive as heat sink material or Heat Conduction Material
It is used in various electronic product.Graphite film prepared by native graphite is mainly by natural graphite flake (graphite flake)
Or other natural graphite materials, through screening, being acidified, after high-temperature expansion and rolling the manufacturing processes such as prolongs, graphite prepared by native graphite
Film is pressed by native graphite one by one, therefore graphite linings structural arrangement is loose discontinuously, lattice defect is more, hole
It is mostly hygroscopic so that its coefficient of heat conduction only between 200 between 400W/m-k, and its structural strength is bad and is easy to brokenly
The situation split or lost powder increases the risk that short circuit occurs for electronic product.
In view of the shortcomings that using aforementioned natural stone ink film, industry starts to replace natural stone ink film as electricity using artificial stone ink film
The thermal component of sub- product.Artificial stone ink sheet is with natural graphite flakes in the raw material of manufacture, whole crystallinity, engineering properties and heat
Conductive performance has notable difference.Artificial stone ink sheet as production of raw material for use, leads to usually with polyimides (polyimide, PI)
Crossing carbonization and graphitization manufacturing process makes polyimides thermal cracking and leaves carbon atom.Then, carbon atom is arranged again at high temperature
Row and formed continuous orderly and close to perfect lamellar graphite crystal structure.Thus, artificial stone ink sheet has compared with natural stone
The excellent engineering properties of ink sheet and heat-conductive characteristic.
However, as electronic product efficiency fast lifting and the volume of electronic product substantially reduce, copper, aluminium, general day
The capacity of heat transmission of graphite film prepared by right graphite and at present the artificial stone ink film prepared by existing polyimide film are led
Thermal energy power can not meet the radiating requirements of miniaturized electronic product.Therefore, the heat-conductive characteristic of graphite film how is promoted, is mesh
One of the problem of preceding urgent need to resolve.
Invention content
The present invention provides a kind of manufacturing method of polyimide film and uses the manufacturing method of its graphite film, and particularly one
The manufacturing method of kind polyimide film and the system using graphite film of this polyimide film manufacture with superior thermal conductivity energy
Method is made, to solve the problems, such as that the heat sink material capacity of heat transmission is insufficient in current electronic product.
One embodiment of the invention discloses a kind of manufacturing method of polyimide film, including one diamines of mixing, a solvent and one
Catalyst is to form a diamine solution containing catalyst；A tetracarboxylic dianhydride is mixed with the diamine solution containing catalyst with shape
Into a polyamic acid solution containing catalyst；The polyamic acid solution containing catalyst is heated to form one containing catalyst
Polyamide acid film；And the imidization polyamide acid film that contains catalyst is to form a polyimide film.Imidization contains catalysis
In the step of polyamide acid film of agent is to form polyimide film, by thermal dehydration and catalyst co-catalysis it is solid containing
The polyamide acid film of catalyst carries out imidization to form solid polyimide film, and catalyst is tertiary amine.
Another embodiment of the present invention discloses a kind of manufacturing method of polyimide film, including one diamines of mixing, a tetrabasic carboxylic acid
Dianhydride, a solvent and a catalyst are to form a polyamic acid solution containing catalyst；Heat the polyamide containing catalyst
Acid solution is to form a polyamide acid film containing catalyst；And the imidization polyamide acid film that contains catalyst is to form one
Polyimide film.Imidization contained in the step of polyamide acid film of catalyst is to form polyimide film, passed through thermal dehydration
Imidization is carried out to form solid polyimide film with the solid polyamide acid film containing catalyst of catalyst co-catalysis,
And catalyst is tertiary amine.
Yet another embodiment of the invention discloses a kind of manufacturing method of graphite film, includes the use of the polyamides of aforementioned any embodiment
The manufacturing method of imines film prepares a polyimide film；And polyimide film is heated to form a graphite film.
The manufacturing method of polyimide film according to the invention described above and the manufacturing method using its graphite film,
Imidization is carried out to obtain preferable imidization effect by thermal dehydration and the solid polyamide acid film of tertiary amine co-catalysis,
Obtain the polyimide film that continuous orderly polyimide molecule arrangement forms.Thus, the present invention is gathered by continuous orderly
In the graphite film that the polyimide film that acid imide molecules align forms is graphitized, graphitic molecules are in continuous orderly stratiform knot
Structure, therefore graphite film has excellent heat-conductive characteristic, solves the problems, such as that the heat sink material capacity of heat transmission is insufficient in electronic product.
Furthermore catalyst has been dispersed in before being contacted with polyamic acid in the diamine solution containing catalyst, improve
Effective contact area and collision frequency between polyamic acid and catalyst so that complete imidization institute in the given time
The catalytic amount needed reduces.Thus, which the present invention is using less catalyst, can to complete imidization in the given time anti-
It should so that manufacture cost reduction of the invention.
The explanation of explanation and implementation below above with respect to the content of present invention to demonstrate and explain the present invention original
Reason, and the claims for providing the present invention are further explained.
Description of the drawings
Fig. 1 is the graphite film manufacturing method flow chart of one embodiment of the invention.
Fig. 2 is the graphite film manufacturing method flow chart of another embodiment of the present invention.
Specific embodiment
The detailed features and advantage of the narration present invention, content are enough to make any ability in detail in embodiments below
The technical staff in domain understands the technology contents of the present invention and implements according to this, and is wanted according to content disclosed in this specification, right
Protection domain and attached drawing are asked, any those skilled in the art can be readily understood upon the relevant purpose of the present invention and advantage.Below
Embodiment the viewpoint of the present invention is further described, but non-anyways to limit scope of the invention.
The manufacturing method of the graphite film of one embodiment of the invention is introduced first, is please referred to Fig.1.Fig. 1 is implemented for the present invention one
The flow chart of the graphite film manufacturing method of example.The manufacturing method of the graphite film of the present embodiment includes the poly- of one embodiment of the invention
Acid imide film manufacturing method.Specifically, step S101 to step S104 is the polyimide film system of one embodiment of the invention
Make method.
First, hybrid diamine, solvent and catalyst are to form the diamine solution (S101) containing catalyst.
Specifically, diamines is added in into polar solvent with catalyst and be stirred, make diamines and catalyst uniform dissolution
To form the diamine solution containing catalyst in polar solvent.Catalyst is tertiary amine, such as triethylene diamine (DABCO,
Triethylenediamine, CAS.No.：280-57-9), N, N- dimethyl cyclohexyl amine (N, N-
Dimethylcyclohexylamine, CAS.No.：98-94-2), DMIZ 1,2 dimethylimidazole (1,2-
Dimethylimidazole), trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, triethanolamine, N, N- dimethylethanolamines, N, N-
Diethyl ethylene diamine, triethylenediamine, the pyridine of N- methylpyrroles, the pyridine of N- N-ethyl pyrrole Ns, N- methyl piperidines, N- ethyl hexahydro pyrroles
Pyridine, imidazoles, pyridine, quinoline or isoquinolin.In order to make diamines, catalyst uniform dissolution in solvent, and reduce required mix
The time is closed, can come quickly to stir solvent with the frequency of 20 hertz (Hertz, Hz) to 100 hertz, diamines is accelerated to disperse with catalyst
In solvent.
Then, mixing tetracarboxylic dianhydride is molten to form the polyamic acid containing catalyst with the diamine solution containing catalyst
Liquid (S102).
Specifically, tetracarboxylic dianhydride is slowly added into the diamine solution containing catalyst and stirred at room temperature
It mixes, makes tetracarboxylic dianhydride and diamine reactant generation polyamic acid (PAA, the Polyamic in the diamine solution containing catalyst
Acid) solution.At this point, catalyst is dispersed in the polyamic acid solution containing catalyst.Tetracarboxylic dianhydride's molal quantity with
The ratio of diamines molal quantity is 0.98：1 to 1.05:1.Catalyst is with respect to diamines and the weight percent of tetracarboxylic dianhydride's total weight
It is 1 to 50%.
In section Example of the present invention, catalyst is 1 with respect to diamines and the weight percent of tetracarboxylic dianhydride's total weight
To 50%, but not limited to this.In another part embodiment of the invention, catalyst is with respect to diamines and tetracarboxylic dianhydride's total weight
Weight percent be 1 to 10%.In another part embodiment of the present invention, catalyst is with respect to diamines and tetracarboxylic dianhydride's gross weight
The weight percent of amount is 1 to 5%.
In part embodiment of the present invention, when the viscosity of the polyamic acid solution containing catalyst reaches 10,000cps extremely
Between 50,000cps, i.e., when 100 pools (poise, ps) are between 500 pools, stop adding in tetracarboxylic dianhydride and stop stirring.Such as
This one, the viscosity that can avoid the polyamic acid solution containing catalyst is excessively high, cause to be not easy during following process by containing
The polyamic acid solution of catalyst is laid in adjunct circuit plate surface and carries out heating film forming.
Then, it heats the polyamic acid solution containing catalyst and forms the polyamide acid film (S103) containing catalyst.
Specifically, the polyamic acid solution containing catalyst is coated on a carrying material, then coating is contained and is urged
The carrying material of the polyamic acid solution of agent, which is positioned in 120 DEG C to 200 DEG C of hot environment, to be thermally dried.Such one
Coming, the solvent in the polyamic acid solution containing catalyst is left the polyamic acid solution containing catalyst by thermal evaporation, and
And not vaporized catalyst in the polyamic acid solution containing catalyst is made to form the polyamides containing catalyst with polyamic acid
Amino acid film, and not vaporized catalyst is then uniformly distributed in the polyamide acid film containing catalyst.It treats containing catalyst
Solvent in polyamic acid solution is by the polyamide acid film containing catalyst for after thermal evaporation, obtaining being attached to carrying material.It connects
It, the polyamide acid film containing catalyst is removed to carry out subsequent step from material is carried.The temperature of heat drying can match
In the boiling point of solvent.In section Example of the present invention, dry temperature is 120 DEG C to 200 DEG C, but is not limited thereto.
Then, the polyamide acid film that imidization contains catalyst is to form polyimide film (S104).
Specifically, to be higher than the temperature of heat drying, i.e., with 250 DEG C to 400 DEG C of temperature, to gathering containing catalyst
Amide sorrel is heated, and is carried out at the same time the imidization of following two reaction mechanisms.The first is solid to make to be dispersed in
Catalyst polyamic acid in the polyamide garden sorrel of state carries out imidization (imidization) and reacts, and takes off polyamic acid
Water and endless loop and form polyimides.Second is makes solid polyamide acid film be carried out imidization by high-temperature catalytic
(imidization) it reacts, makes polyamic acid dehydration and endless loop and form polyimides.By both the above reaction mechanism
Imidization, in solid-state and the polyamide acid film containing catalyst obtains preferable imidization effect and obtains continuous orderly
The polyimide film that polyimide molecule arrangement forms.Wherein, heating temperature is higher, and the polyamide acid film containing catalyst carries out
Time needed for imidization (imidization) reaction generation polyimide film is shorter.If however, reaction temperature it is excessively high,
Or heating overlong time, then may destroy the bond between the atom in polyimide molecule so that polyimides because
It degrades (degradation) for high temperature.In part of the embodiment of the present invention, heating makes the polyamide acid film containing catalyst
The temperature for carrying out imidization is 270 DEG C to 450 DEG C, but is not limited thereto.In the present invention again part of the embodiment, add
Heat makes the temperature of the polyamide acid film progress imidization containing catalyst be 270 DEG C to 350 DEG C, but be not limited thereto.
In addition, in section Example of the present invention, the polyamide acid film containing catalyst is fixed and heats to carry out imidization with fixture
Reaction, but be not limited thereto.In another part embodiment of the present invention, the polyamide acid film containing catalyst is uniaxially to draw
It stretches and heats to carry out imidization.
Then, carbonization polyimide film is heated with carburizing temperature to form carbonization polyimide film (S105).
Specifically, polyimide film is placed under environment under low pressure, in nitrogen atmosphere or in inert gas atmosphere, with
800 DEG C to 1500 DEG C of carburizing temperature is heated, and the polyimides of polyimide film surface is made to start carbonization and is obtained
Be carbonized polyimide film.For example, can by polyimide film be placed in internal pressure less than an atmospheric pressure heating chamber in into
Row heating is carbonized or will carry out heating carbonization in heating chamber of the polyimide film merging filled with nitrogen.
Finally, graphite film is formed to be higher than the graphitization temperature of carburizing temperature heating graphitization carbonization polyimide film
(S106)。
Specifically, carbonization polyimide film is placed under environment under low pressure or in inert gas atmosphere, with 2500 DEG C extremely
3000 DEG C of graphitization temperature is heated, make carbonization polyimide film surface carbonization polyimides start graphitization and
Graphite film is obtained, completes the preparation of graphite film.It for example, can be by carbonization polyimide film merging filled with argon gas or helium
Heating graphitization is carried out in the heating chamber of gas to obtain graphite film.
Polyimide film carbonization and carbonization polyimide film graphitization in section Example of the present invention can be in differences
Heating chamber in carry out, but not limited to this.In other embodiments of the invention, polyimide film carbonization and carbonization polyamides
After imines film graphitization first can also be carbonized to polyimide film with carburizing temperature in same heating chamber, then will heating
Temperature is increased to graphitization temperature to be graphitized to carbonization polyimide film.
Next the manufacturing method of the graphite film of another embodiment of the present invention is introduced, please refers to Fig. 2.Fig. 2 is another for the present invention
The flow chart of the graphite film manufacturing method of one embodiment.The manufacturing method of the graphite film of the present embodiment includes another reality of the present invention
Apply the polyimides film manufacturing method of example.Specifically, step S201 to step S203 is the poly- of another embodiment of the present invention
Acid imide film manufacturing method.
First, hybrid diamine, tetracarboxylic dianhydride, solvent and catalyst are to form the polyamic acid solution containing catalyst
(S201)。
Specifically, diamines, tetracarboxylic dianhydride and catalyst are added in into polar solvent and are stirred at room temperature, make two
Amine, tetracarboxylic dianhydride and catalyst uniform dissolution make diamines react generation polyamide with tetracarboxylic dianhydride in polar solvent
Sour (PAA, Polyamic acid) solution.At this point, catalyst is dispersed in the polyamic acid solution containing catalyst.Four
The ratio of carboxylic acid dianhydride molal quantity and diamines molal quantity is 0.98：1 to 1.05:1.Catalyst is total with tetracarboxylic dianhydride with respect to diamines
The weight percent of weight is 1 to 50%.In this present embodiment, diamines, tetracarboxylic dianhydride and catalyst are simultaneously added polarity
In solvent, but not limited to this.Catalyst is tertiary amine, such as triethylene diamine (DABCO, Triethylenediamine,
CAS.No.：280-57-9), N, N- dimethyl cyclohexyl amine (N, N-Dimethylcyclohexylamine, CAS.No.：98-94-
2), DMIZ 1,2 dimethylimidazole (1,2-Dimethylimidazole), trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, three ethyl alcohol
Amine, N, N- dimethylethanolamines, N, N- diethyl ethylene diamines, triethylenediamine, the pyridine of N- methylpyrroles, the pyridine of N- N-ethyl pyrrole Ns, N- first
Base hexahydropyridine, N- ethyl piperidines, imidazoles, pyridine, quinoline or isoquinolin.In order to make diamines, tetracarboxylic dianhydride, catalyst
Uniform dissolution simultaneously forms the polyamic acid solution containing catalyst, and reduces required incorporation time, can be with 20 hertz
The frequency of (Hertz, Hz) to 100 hertz quickly is stirred solvent, accelerates diamines, tetracarboxylic dianhydride and catalyst uniform dissolution simultaneously
Form the polyamic acid solution containing catalyst.
In section Example of the present invention, catalyst is 1 with respect to diamines and the weight percent of tetracarboxylic dianhydride's total weight
To 50%, but not limited to this.In another part embodiment of the invention, catalyst is with respect to diamines and tetracarboxylic dianhydride's total weight
Weight percent be 1 to 10%.In another part embodiment of the present invention, catalyst is with respect to diamines and tetracarboxylic dianhydride's gross weight
The weight percent of amount is 1 to 5%.
In part embodiment of the present invention, when the viscosity of the polyamic acid solution containing catalyst reaches 10,000cps extremely
Between 50,000cps, i.e., when 100 pools (poise, ps) are between 500 pools, stop stirring.Thus, it can avoid containing catalysis
The viscosity of the polyamic acid solution of agent is excessively high, causes to be not easy to put down the polyamic acid solution containing catalyst during following process
It is laid on adjunct circuit plate surface and carries out heating film forming.
Then, it is sequentially heated the polyamic acid solution containing catalyst and forms the polyamide acid film containing catalyst
(S202), the polyamide acid film that imidization contains catalyst is heated with carburizing temperature and is carbonized to form polyimide film (S203)
Polyimide film is to form carbonization polyimide film (S204) and to be higher than the graphitization temperature of carburizing temperature heating graphitization
The step of polyimide film that is carbonized forms graphite film (S205).
Since the detailed mode of operation of step S202 to step S205 is identical to step S106 with step S103, herein just not
Repeat the detailed mode of operation for illustrating step S202 to step S205.
Polyamide acid film carry out imidization generation polyimide film can be used alone high temperature imidization method or chemistry it is sub-
Amination method.Need the high temperature using 350 DEG C or more that polyamide acid film is made to carry out imidization in high temperature imidization method.In chemistry
It needs to add pyridine using excessive chemical reagent, such as acetic anhydride in imidization method, polyamide acid film is made to carry out imidization.This
Invention is then that the imidization temperature worked as catalyst using a small amount of tertiary amine and arrange in pairs or groups relatively low obtains preferable imidization effect, into
And obtain the polyimide film that continuous orderly polyimide molecule arrangement forms.Thus, continuous orderly polyimides
The polyimide film that molecules align forms is through being carbonized and being graphitized in the graphite film of formation, by polyimide molecule through carbonization and stone
The graphitic molecules that inkization is formed are in continuous orderly layer structure so that graphite film has excellent heat-conductive characteristic.Furthermore this
During graphite film of the invention manufacture with excellent heat-conductive characteristic, the catalyst total amount used is less than exclusive use chemistry
Imidization method prepares the catalyst total amount needed for polyimide film and heats PA membrane to carry out the temperature of sub- acylation reaction
Also the heating temperature needed for polyimide film is prepared less than exclusive use high temperature imidization method.
In the present invention, before forming the polyamic acid solution containing catalyst, catalyst mixes and shape with diamines and solvent
Into the diamine solution containing catalyst.Therefore, catalyst has been dispersed in before being contacted with polyamic acid containing catalyst
In diamine solution.Due to catalyst chemically react during, the contact area of reactant and catalyst the more or collision
Frequency is higher, then the speed chemically reacted is faster and average and demand of catalyst is lower.Therefore, it is poly- by being promoted
Mixture homogeneity between amic acid and catalyst improves contact area and collision frequency between polyamic acid and catalyst, with compared with
Few catalyst quickly obtains preferable imidization effect, and then obtains the polyimide film of better quality.Thus, this hair
The bright graphite film being graphitized by the polyimide film of better quality has preferable heat conductivity, solves in electronic product
The problem of heat sink material capacity of heat transmission is insufficient.
Furthermore due to the graphite film that the present invention is graphitized by the polyimide film of better quality, the stone in graphite film
Black molecule is in continuous orderly layer structure so that graphite film also has excellent electric conductivity and can be used as conductive material.Cause
This, graphite film of the invention can be applied to as Heat Conduction Material, heat sink material, conductive material, and but not limited to this.
Furthermore catalyst has been dispersed in before being contacted with polyamic acid in the diamine solution containing catalyst so that
Completing the catalytic amount needed for imidization in the given time reduces.Thus, the present invention uses less catalyst
Imidization can be completed in the given time so that manufacture cost reduction of the invention.
Furthermore catalyst has been dispersed in before being contacted with polyamic acid in the diamine solution containing catalyst so that
The polyamic acid solution viscosity containing catalyst formed is controlled to 10,000cps between 50,000cps, i.e., 100 moor
(poise, ps) is between 500 pools.Thus, subsequent heat dry coating is in poly- containing catalyst in additional circuit boards
The film thickness of the obtained polyamide acid film containing catalyst of amide acid solution is more uniform, and film forming is preferable.Relatively, if
Catalyst is added after the polyamic acid solution containing catalyst is formed, stirs the polyamic acid solution containing catalyst with molten
During solving catalyst, the viscosity of the polyamic acid solution containing catalyst rapidly rises and is difficult to control.Thus, plus
The obtained polyamide containing catalyst of the polyamic acid solution containing catalyst that heated drying is coated in additional circuit boards
The film thickness uniformity of sorrel is poor, and the film forming that uneven situation will cause graphite film is shunk when being graphitized caused by film thickness unevenness
It is poor.
In the above-described embodiments, diamines includes but not limited to p-phenylenediamine (PPDA, p-Phenylenediamine), 2,
Bis- (trifluoromethyl) benzidine of 2'- (TFMB, 2,2'-Bis (trifluoromethyl) benzidine, CAS.No.：341-58-
2), bis- [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane (HFBAPP, the 2,2-Bis [4- (4-aminophenoxy) of 2,2-
Phenyl] hexafluoropropane, CAS.No.：69563-88-8), bis- (the trifluoromethyl) -4,4'- diaminobenzenes of 2,2'-
Base ether (BTFDPE, 4,4'-oxybis [3- (trifluoromethyl) benzeneamine], CAS.No.：344-48-9)、4,
4'- [1,4- phenyl is bis- (oxygen)] bis- [3- (trifluoromethyl) aniline] (FAPQ, 4,4'- [1,4-phenylenebis (oxy)] Bis
[3- (trifluoromethyl)] benzenamine, CAS.No.：94525-05-0), 9,9- bis- (the fluoro- 4- aminophenyls of 3-)
Fluorenes (FFDA, 9,9-Bis (4-amino-3-fluorophenyl) fluorine, CAS.No.：127926-65-2), the bis- 4- of 9,9-
(the fluoro- 4- aminophenyls of 3-) phenyl fluorenes (9,9-Bis [4- (4-amino-3-fluorophenyl) benzene] fluorine),
Bis- (4- aminophenyls) fluorenes (BAFL, 9,9-Bis (aminophenyl9fluorene)) of 9,9-, 4,4'- diaminodiphenyl ethers
(ODA, 4,4'-Oxydianiline, CAS.No.：101-80-4).
In the above-described embodiments, tetracarboxylic dianhydride include but not limited to pyromellitic acid anhydride (PMDA, 1,2,4,
5benzenetetracarboxylic dianhydride), biphenyltetracarboxylic dianhydride (BPDA, 3,3', 4,4'-biphenyl
Tetracarboxylic dianhydride), biphenyltetracarboxylic dianhydride (3,4,3', 4'-biphenyl
Tetracarboxylic dianhydride), 2,3,3', 4'- biphenyltetracarboxylic dianhydrides (2,3,3', 4'-biphenyl
Tetracarboxylic dianhydride), diphenyl ether tetracid dianhydride (4,4'-oxydiphthalic anhydride), 3,
4'- diphenyl ether tetracid dianhydrides (3,4'-oxydiphthalic anhydride), benzophenone tetracarboxylic dianhydride
(benzophenonetetracarboxylic dianhydride), 2,2- bis- [(4- (3,4- di carboxyl phenyloxies) phenyl)]
Propane dianhydride (BPADA, 2,2-bis [4- (3,4dicarboxyphenoxy) phenyl] propane dianhydride), 4,
4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids (6FDA, 2,2-bis (3,4-anhydrodicarboxyphenyl)
Hexafluoropropane), diphenyl maple tetracarboxylic dianhydride (3,3', 4,4'-diphenyl
Sulfonetetracarboxylic dianhydride), bis- [(3,4- dicarboxyphenyi)] the fluorenes dianhydrides of 9,9- (BPAF, 9,9-
bis(3,4-dicarboxyphenyl)fluorene dianhydride,CAS.No.：135876-30-1), the bis- [(4- of 9,9-
(3,4- di carboxyl phenyloxies) phenyl)] fluorenes dianhydride (9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl]
fluorene dianhydride,CAS.No.：59507-08-3), naphthalene tetracid dianhydride (1,2,5,6-naphthalene
Tetracarboxylic dianhydride), naphthalene dicarboxylic anhydride (naphthalenetetracaboxylic dianhydride),
Double-(3,4- phthalate anhydride) dimethylsilane (bis (3,4-dicarboxyphenyl) dimethylsilane
Dianhydride), bis- (3,4- the dicarboxyphenyis) -1,1,3,3- tetramethyl disiloxanes dianhydride (1,3-bis (4'- of 1,3-
Phthalic anhydride)-tetramethyldisiloxane), double-(1,3- dioxy -1,3- dihydroisobenzofuran -5-
Carboxylic acid) biphenyl -3,3'- diol ester (BP-TME, bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-
Carboxylic acid) biphenyl-3,3'-diyl ester, [3- [3- (1,3-dioxo-2-benzofuran-5-
carbonyl)oxyphenyl]phenyl]1,3-dioxo-2-benzofuran-5-carboxylate)。
In the above-described embodiments, polar solvent includes but not limited to dimethylformamide (N, N-Dimethyl
Formamide, DMF), dimethylacetylamide (Dimethylacetamide, DMAc), dimethyl sulfoxide (DMSO) (Dimethyl
Sulfoxide, DMSO), N-Methyl pyrrolidone (N-methyl-2-pyrrolidone, NMP), gamma-butyrolacton (gamma-
Butyrolactone, GBL).
Illustrate the graphite film disclosed in this motion below by way of several embodiments and comparative example, and carry out experiment test with
Compare its nature difference.
Embodiment one
First, by 24.06 grams of 4,4'- diaminodiphenyl ethers (ODA) and 1.5 grams of N as catalyst, N- dimethyleyelohexanes
Amine is added in 198.5 grams of dimethylacetylamides (DMAc) and is stirred 0.5 hour, makes ODA and N, N- dimethyl cyclohexyl amines are in DMAc
Middle uniform dissolution and form the diamine solution containing catalyst.
Then, by 25.94 grams of pyromellitic acid anhydrides (PMDA) be slowly added into the diamine solution containing catalyst and
It stirs 6 hours at room temperature, PMDA is made to react to form the polyamic acid solution containing catalyst with ODA.Wherein, catalyst n, N- bis-
Methyl cyclohexylamine is with respect to ODA and the weight percent of PMDA total weights is 3%.
Then, the polyamic acid solution containing catalyst is coated in additional circuit boards, and is contained with 120 DEG C of heat dryings
There is the polyamic acid solution of catalyst 10 minutes, the polyamide acid film containing catalyst is formed in additional circuit boards, and will
Polyamide acid film containing catalyst is removed from additional circuit boards.
Then, with the 320 DEG C of polyamide acid films 10 minutes of heating containing catalyst, make the polyamide acid film containing catalyst
Imidization is carried out, forms polyimide film.
Then, with 1000 DEG C of carburizing temperature heating carbonization polyimide film in the heating cavity filled with nitrogen atmosphere
60 minutes, form carbonization polyimide film.
Finally, it is poly- with 2800 DEG C of graphitization temperature heating graphitization carbonization in the heating cavity filled with argon gas atmosphere
Acid imide film 30 minutes forms graphite film.
Embodiment two
Embodiment two is similar to embodiment one, and difference is in embodiment two, catalyst n, N- dimethyl cyclohexyl amines
Weight is 2.5 grams, catalyst n, and N- dimethyl cyclohexyl amines are with respect to ODA and the weight percent of PMDA total weights is 5%, solvent
The weight of DMAc is 197.5 grams.
Embodiment three
Embodiment three is similar to embodiment one, and difference is in embodiment three, catalyst triethylene diamine (DABCO)
Weight is 1.5 grams, and catalyst DABCO is 3% with respect to ODA and the weight percent of PMDA total weights, and the weight of solvent DMAc is
200 grams.
Example IV
Example IV is similar to embodiment one, and difference is in example IV, by 15.84 grams of ODA, 5.7 grams to benzene two
Amine (PPDA) and 0.5 gram of N as catalyst, N- dimethyl cyclohexyl amines are added in 200 grams of DMAc and are stirred 0.5 hour, make
ODA, PPDA and N, N- dimethyl cyclohexyl amines in DMAc uniform dissolution and form the diamine solution containing catalyst.Then, will
28.46 grams of pyromellitic acid anhydrides (PMDA) are slowly added into the diamine solution containing catalyst and are stirred at room temperature 6 hours,
PMDA is made to react to form the polyamic acid solution containing catalyst with ODA and PPDA.Wherein, catalyst n, N- dimethyl cyclohexyl amines
Weight percent with respect to ODA, PPDA and PMDA total weight is 1%.
Embodiment five
Embodiment five is similar to example IV, and difference is in embodiment five, catalyst n, N- dimethyl cyclohexyl amines
Weight is 1.5 grams, catalyst n, and N- dimethyl cyclohexyl amines are 3% with respect to the weight percent of ODA, PPDA and PMDA total weight,
The weight of solvent DMAc is 200 grams.
Embodiment six
Embodiment six is similar to example IV, and difference is in embodiment six, and the weight of catalyst DABCO is 1.5 grams,
Catalyst DABCO is 3% with respect to the weight percent of ODA, PPDA and PMDA total weight, and the weight of solvent DMAc is 200 grams.
Embodiment seven
Embodiment seven is similar to embodiment one, and difference is in embodiment seven, by 14.4 grams of ODA, 5.19 grams to benzene two
Amine (PPDA) with as catalyst 2.5 grams of DABCO add in 200 grams of DMAc in and stir 0.5 hour, make ODA, PPDA and
DABCO in DMAc uniform dissolution and form the diamine solution containing catalyst.Then, 12.95 grams PMDA and 17.46 gram is joined
Benzene tertacarbonic acid's dianhydride (BPDA) is slowly added into the diamine solution containing catalyst and is stirred at room temperature 6 hours, make PMDA and
BPDA reacts to form the polyamic acid solution containing catalyst with ODA and PPDA.Wherein, catalyst DABCO with respect to ODA, PPDA,
PMDA and the weight percent of BPDA total weights are 5%.
Embodiment eight
Embodiment eight is similar to embodiment one, and difference is in embodiment eight, by 10.11 grams of ODA, 5.46 grams to benzene two
Amine (PPDA) and 1.5 grams of N as catalyst, N- dimethyl cyclohexyl amines are added in 200 grams of DMAc and are stirred 0.5 hour, make
ODA, PPDA and N, N- dimethyl cyclohexyl amines in DMAc uniform dissolution and form the diamine solution containing catalyst.Then, will
13.08 grams of PMDA and 21.35 gram of BP-TME (Bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-
Carboxylic acid) biphenyl-3,3'-diyl ester) it is slowly added into the diamine solution containing catalyst and in room
The lower stirring of temperature 6 hours, makes PMDA and BP-TME react to form the polyamic acid solution containing catalyst with ODA and PPDA.Wherein,
Catalyst n, N- dimethyl cyclohexyl amines are 3% with respect to the weight percent of ODA, PPDA, PMDA and BP-TME total weight.
Comparative example one
Comparative example one is similar to embodiment one, and difference is to be not added with catalyst in comparative example one.
Comparative example two
Comparative example two is similar to example IV, and difference is to be not added with catalyst in comparative example two.
Comparative example three
Comparative example three is similar to embodiment seven, and difference is to be not added with catalyst in comparative example three.
Comparative example four
Comparative example four is similar to embodiment eight, and difference is to be not added with catalyst in comparative example four.
Embodiment one to embodiment eight and comparative example one to the formula of comparative example four arrangement please refers to table one.
Table one
Embodiment one to embodiment eight and comparative example one to the measurement result of the graphite film of comparative example four arrangement please refers to table
Two.
Table two
Catalyst imidization is not used in comparative example one to comparative example four, and merely with high-temperature catalytic polyamic acid
Polyamic acid in film carries out imidization.Therefore, being heated by each position of polyamide acid film, heating rate is different to be influenced,
Polyamic acid carries out the speed of imidization and degree unevenness so that each position imidization degree of polyimide film of formation is not
Unanimously, the polyimide film that continuous orderly polyimide molecule arrangement forms can not be obtained.Furthermore it subsequently carries out graphited
In the process, the dehydration of each position of the different polyimide film of imidization degree and the speed of carbonization are inconsistent, cause can not to obtain by
The graphite film that continuous orderly lamellar graphite molecule is formed.Therefore the coefficient of heat conduction of comparative example two and the graphite film of comparative example four
Bad with thermal diffusivity, the uneven film thickness of comparative example two is even, comparative example one and comparative example three even occur it is broken and can not
The situation of film forming.
Compared to comparative example one to comparative example four, the embodiment of the present invention one to embodiment eight uses catalyst polyamides
Amino acid film carries out imidization and forms polyimide film.Polyamic acid under the catalysis with its mixed uniformly catalyst,
Imidization is carried out, and then obtain the consistent polyimide film of imidization degree with similar reaction rate.It is thus, sub-
When the consistent polyimide film of amination degree is subsequently graphitized, the speed of each position dehydration of polyimide film and carbonization is more
Graphite film that is consistent and can obtain better quality.Therefore the embodiment of the present invention one is to the coefficient of heat conduction of the graphite film of embodiment eight
Higher than 1100W/m-K, thermal diffusivity is higher than 6.3mm2/sec, and the capacity of heat transmission is enough the heat dissipation being applied in electronic product member
Part.
Furthermore catalyst has been dispersed in before being contacted with polyamic acid in the diamine solution containing catalyst so that
Completing the catalytic amount needed for imidization in the given time reduces.Thus, the present invention uses less catalyst
Imidization can be completed in the given time so that manufacture cost reduction of the invention.
Furthermore the embodiment of the present invention one to embodiment eight will catalysis before the polyamic acid solution containing catalyst is formed
Agent is dissolved and is dispersed in the diamine solution containing catalyst.Thus, easily controllable diamines and tetracarboxylic dianhydride
Polymerization rate so that the polyamic acid solution viscosity containing catalyst be controlled in 10,000cps to 50,000cps it
Between, i.e., 100 pools (poise, ps) are between 500 pools.Therefore the polyamic acid solution containing catalyst is coated in additional circuit boards
And the film thickness of the obtained polyamide acid film containing catalyst of heat drying is more uniform, and then flat graphite can be made
Film.
In conclusion the manufacturing method of the polyimide film of the present invention is with using in the manufacturing method of its graphite film, leading to
It crosses and uses tertiary amine as the imidization of catalyst polyamic acid and by being promoted between polyamic acid and catalyst
Mixture homogeneity, improve the contact area and collision frequency between polyamic acid and catalyst, obtain preferable imidization effect
And obtain the polyimide film of better quality.Thus, what the present invention was graphitized by the polyimide film of better quality
Graphite film has preferable heat conductivity, solves the problems, such as that the heat sink material capacity of heat transmission is insufficient in electronic product.
Furthermore catalyst has been dispersed in before being contacted with polyamic acid in the diamine solution containing catalyst so that
Completing the catalytic amount needed for imidization in the given time reduces.Thus, the present invention uses less catalyst
Imidization can be completed in the given time so that manufacture cost reduction of the invention.
Furthermore catalyst has been dispersed in before being contacted with polyamic acid in the diamine solution containing catalyst so that
Diamines and the polymerization rate of tetracarboxylic dianhydride are easily controllable, so that the polyamic acid solution viscosity quilt containing catalyst
Control is in 10,000cps between 50,000cps, i.e., 100 pools (poise, ps) are between 500 pools.Thus, subsequent heat
Dry coating is in the obtained polyamic acid containing catalyst of the polyamic acid solution containing catalyst in additional circuit boards
The film thickness of film is more uniform, and then flat graphite film can be made.Thus, the graphite obtained by the manufacturing method of the present invention
During heat sink material of the film as electronic product, it can fit closely to transmit effect to obtain preferably heat with the pyrotoxin of electronic product
Fruit, and then promote the heat dissipation effect of electronic product.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
It knows those skilled in the art and makes various corresponding changes and deformation, but these corresponding changes and change in accordance with the present invention
Shape should all belong to the protection domain of appended claims of the invention.
Claims (15)
1. a kind of manufacturing method of polyimide film, which is characterized in that including：
A diamines, a solvent and a catalyst are mixed to form a diamine solution containing catalyst；
A tetracarboxylic dianhydride is mixed with being somebody's turn to do the diamine solution containing catalyst to form a polyamic acid solution containing catalyst；
The polyamic acid solution for containing catalyst is heated to form a polyamide acid film containing catalyst；And
Imidization is somebody's turn to do the polyamide acid film containing catalyst to form a polyimide film；
Wherein, imidization was somebody's turn to do in the step of polyamide acid film containing catalyst is to form the polyimide film, de- by heating
Water carries out imidization with the solid polyamide acid film that should be containing catalyst of the catalyst co-catalysis and is gathered with forming solid this
Acid imide film, and the catalyst is tertiary amine.
2. a kind of manufacturing method of polyimide film, which is characterized in that including：
A diamines, a tetracarboxylic dianhydride, a solvent and a catalyst are mixed to form a polyamic acid solution containing catalyst；
The polyamic acid solution for containing catalyst is heated to form a polyamide acid film containing catalyst；And
Imidization is somebody's turn to do the polyamide acid film containing catalyst to form a polyimide film；
Wherein, imidization was somebody's turn to do in the step of polyamide acid film containing catalyst is to form the polyimide film, de- by heating
Water carries out imidization with the solid polyamide acid film that should be containing catalyst of the catalyst co-catalysis and is gathered with forming solid this
Acid imide film, and the catalyst is tertiary amine.
3. the manufacturing method of polyimide film according to claim 1 or 2, which is characterized in that the catalyst with respect to this two
Amine and the weight percent of tetracarboxylic dianhydride's total weight are 1 to 50%.
4. the manufacturing method of polyimide film according to claim 3, which is characterized in that the catalyst with respect to the diamines with
The weight percent of tetracarboxylic dianhydride's total weight is 1 to 10%.
5. the manufacturing method of polyimide film according to claim 4, which is characterized in that the catalyst with respect to the diamines with
The weight percent of tetracarboxylic dianhydride's total weight is 1 to 5%.
6. the manufacturing method of polyimide film according to claim 1 or 2, which is characterized in that the poly- of catalyst should be contained
The viscosity of amide acid solution is 10000 to 50000cps.
7. the manufacturing method of polyimide film according to claim 1 or 2, which is characterized in that wherein the diamines include pair
Phenylenediamine, 2,2 '-bis- (trifluoromethyl) benzidine, bis- [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane of 2,2-, 2,2'- are bis-
(trifluoromethyl) -4,4'- diamino-phenyls ether, 4,4'- [1,4- phenyl is bis- (oxygen)] bis- [3- (trifluoromethyl) aniline], 9,9- are bis-
(the fluoro- 4- aminophenyls of 3-) fluorenes, the bis- 4- of 9,9- (the fluoro- 4- aminophenyls of 3-) phenyl fluorenes, bis- (4- aminophenyls) fluorenes or 4 of 9,9-,
4'- diaminodiphenyl ethers.
8. the manufacturing method of polyimide film according to claim 1 or 2, which is characterized in that the tetracarboxylic dianhydride includes
Pyromellitic acid anhydride, biphenyltetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 2,3,3', 4'- biphenyltetracarboxylic dianhydrides, diphenyl ether
Bis- [(4- (3,4- di carboxyl phenyloxies) benzene of tetracid dianhydride, 3,4'- diphenyl ether tetracid dianhydrides, benzophenone tetracarboxylic dianhydride, 2,2-
Base)] propane dianhydride, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, diphenyl maple tetracarboxylic dianhydride, bis- [(the 3,4- dicarboxyls of 9,9-
Phenyl)] fluorenes dianhydride, bis- [(4- (3,4- di carboxyl phenyloxies) phenyl)] the fluorenes dianhydrides of 9,9-, naphthalene tetracid dianhydride, naphthalene dicarboxylic anhydride,
Double-(3,4- phthalate anhydride) dimethylsilane, -1,1,3,3- tetramethyl disiloxanes two of 1,3- bis- (3,4- dicarboxyphenyis)
Acid anhydride or double-(1,3- dioxy -1,3- dihydroisobenzofuran -5- carboxylic acids) biphenyl -3,3'- diol ester.
9. the manufacturing method of polyimide film according to claim 1 or 2, which is characterized in that the diamines and the tetrabasic carboxylic acid
The combination for being combined as 4,4'- diaminodiphenyl ethers and pyromellitic acid anhydride of dianhydride or 4,4'- diaminodiphenyl ether, to benzene
The combination of diamines and pyromellitic acid anhydride or 4,4'- diaminodiphenyl ether, p-phenylenediamine, pyromellitic acid anhydride and biphenyl
The combination of tetracarboxylic dianhydride or 4,4'- diaminodiphenyl ether, p-phenylenediamine, pyromellitic acid anhydride with it is double-(1,3- dioxy -1,
3- dihydroisobenzofuran -5- carboxylic acids) biphenyl -3,3'- diol esters combination.
10. the manufacturing method of polyimide film according to claim 1 or 2, which is characterized in that the catalyst includes three second
Alkene diamines, N, N- dimethyl cyclohexyl amines, DMIZ 1,2 dimethylimidazole, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, triethanolamine,
N, N- dimethylethanolamine, N, N- diethyl ethylene diamines, triethylenediamine, the pyridine of N- methylpyrroles, the pyridine of N- N-ethyl pyrrole Ns, N- methyl six
Pyridinium hydroxide, N- ethyl piperidines, imidazoles, pyridine, quinoline or isoquinolin.
11. a kind of manufacturing method of graphite film, which is characterized in that including：
The manufacturing method of polyimide film according to claims 1 to 10 any of which item prepares a polyimide film；With
And
The polyimide film is heated to form a graphite film.
12. the manufacturing method of graphite film according to claim 11, which is characterized in that the coefficient of heat conduction of the graphite film is big
In 1100W/m-K.
13. the manufacturing method of graphite film according to claim 11, which is characterized in that the thermal diffusivity of the graphite film is higher than
6.3cm2/sec。
14. the manufacturing method of the graphite film according to claim 11 to 13 any of which item, which is characterized in that it is poly- to heat this
Acid imide film is included with being formed the step of the graphite film：
It is heated with a carburizing temperature and is carbonized the polyimide film to form a carbonization polyimide film；And
It is heated with a graphitization temperature and is graphitized the carbonization polyimide film to form the graphite film, which is higher than should
Carburizing temperature.
15. the manufacturing method of graphite film according to claim 14, which is characterized in that the carburizing temperature is 900~1500
DEG C, which is 2500~3000 DEG C.
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| CN109911893A (en) * | 2018-12-04 | 2019-06-21 | 重庆云天化瀚恩新材料开发有限公司 | The preparation method of thermally conductive electrographite gasket |
| CN111925524A (en) * | 2020-08-20 | 2020-11-13 | 吉林大学 | Flexible high-temperature-resistant polyimide precursor gel, preparation method and application thereof, and polyimide flexible honeycomb structure |
| CN112574410A (en) * | 2020-11-26 | 2021-03-30 | 浙江中科玖源新材料有限公司 | Polyimide film for artificial graphite film, preparation method of polyimide film and artificial graphite film |
| CN114989429A (en) * | 2022-05-20 | 2022-09-02 | 广东鸿翔瑞材料科技有限公司 | Polyimide film, graphite sheet, corresponding preparation method and resin composition |
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| CN108676514A (en) * | 2018-05-07 | 2018-10-19 | 合肥羿振电力设备有限公司 | It is a kind of to prevent the dry electronic device heat radiating material to fall off |
| TWI715260B (en) * | 2019-10-22 | 2021-01-01 | 臺灣塑膠工業股份有限公司 | Method for synthesizing diamine compound having heterocyclic aryl groups, polyamic acid sensing film and polyimide film |
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| CN101636432A (en) * | 2007-02-09 | 2010-01-27 | Lg化学株式会社 | The polyimide for preparing the method for polyimide and use this method to make |
| CN103193221A (en) * | 2007-05-17 | 2013-07-10 | 株式会社钟化 | Graphite film and manufacturing method thereof |
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| JP6476469B2 (en) * | 2015-04-17 | 2019-03-06 | Ｊｆｅケミカル株式会社 | Polyamic acid composition and polyimide composition |
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| CN101636432A (en) * | 2007-02-09 | 2010-01-27 | Lg化学株式会社 | The polyimide for preparing the method for polyimide and use this method to make |
| CN103193221A (en) * | 2007-05-17 | 2013-07-10 | 株式会社钟化 | Graphite film and manufacturing method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109911893A (en) * | 2018-12-04 | 2019-06-21 | 重庆云天化瀚恩新材料开发有限公司 | The preparation method of thermally conductive electrographite gasket |
| CN111925524A (en) * | 2020-08-20 | 2020-11-13 | 吉林大学 | Flexible high-temperature-resistant polyimide precursor gel, preparation method and application thereof, and polyimide flexible honeycomb structure |
| CN111925524B (en) * | 2020-08-20 | 2021-05-28 | 吉林大学 | Flexible high-temperature-resistant polyimide precursor gel, preparation method and application thereof, and polyimide flexible honeycomb structure |
| CN112574410A (en) * | 2020-11-26 | 2021-03-30 | 浙江中科玖源新材料有限公司 | Polyimide film for artificial graphite film, preparation method of polyimide film and artificial graphite film |
| CN112574410B (en) * | 2020-11-26 | 2023-12-19 | 浙江中科玖源新材料有限公司 | Polyimide film for artificial graphite film, preparation method of polyimide film and artificial graphite film |
| CN114989429A (en) * | 2022-05-20 | 2022-09-02 | 广东鸿翔瑞材料科技有限公司 | Polyimide film, graphite sheet, corresponding preparation method and resin composition |
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