CN104629365B - Method for preparing carbon fiber-polyimide composite material - Google Patents
Method for preparing carbon fiber-polyimide composite material Download PDFInfo
- Publication number
- CN104629365B CN104629365B CN201510086537.9A CN201510086537A CN104629365B CN 104629365 B CN104629365 B CN 104629365B CN 201510086537 A CN201510086537 A CN 201510086537A CN 104629365 B CN104629365 B CN 104629365B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- polyimide
- composite
- polyamic acid
- carbon
- 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.)
- Expired - Fee Related
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 42
- 239000004642 Polyimide Substances 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 56
- 239000004917 carbon fiber Substances 0.000 claims abstract description 56
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 26
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000005855 radiation Effects 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- -1 carbon fiber compound Chemical class 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 9
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims 1
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 1
- 238000009736 wetting Methods 0.000 abstract 1
- 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 description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000835 fiber Substances 0.000 description 11
- 150000008064 anhydrides Chemical class 0.000 description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QUMDOMSJJIFTCA-UHFFFAOYSA-N 1,1,2-tribromoethane Chemical compound BrCC(Br)Br QUMDOMSJJIFTCA-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 2
- VQZRLBWPEHFGCD-UHFFFAOYSA-N 3-chloro-4-methylphenol Chemical compound CC1=CC=C(O)C=C1Cl VQZRLBWPEHFGCD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- NDWKKKBYNUUHKJ-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C1=CC=CC=C1)=O.C1(=CC=CC=C1)C#C Chemical compound C(C1=CC=CC=C1)(=O)OC(C1=CC=CC=C1)=O.C1(=CC=CC=C1)C#C NDWKKKBYNUUHKJ-UHFFFAOYSA-N 0.000 description 2
- XANPSSKHINCIHQ-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C(#C)C1=CC=CC=C1 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C(#C)C1=CC=CC=C1 XANPSSKHINCIHQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940090668 parachlorophenol Drugs 0.000 description 2
- 229960003742 phenol Drugs 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical group CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YJOAIOIVLVUPST-UHFFFAOYSA-N 4-(4-amino-2-methoxyphenyl)-3-methoxyaniline Chemical compound COC1=CC(N)=CC=C1C1=CC=C(N)C=C1OC YJOAIOIVLVUPST-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- KTEWMWWMJCFDDI-UHFFFAOYSA-N C#CC1=C(C(=C(C2=C1C(=O)OC2=O)F)F)C3=CC=CC=C3 Chemical compound C#CC1=C(C(=C(C2=C1C(=O)OC2=O)F)F)C3=CC=CC=C3 KTEWMWWMJCFDDI-UHFFFAOYSA-N 0.000 description 1
- DYCUQXMMUPNWMY-UHFFFAOYSA-N C(C=1C(C(=O)O)=CC=CC1)(=O)O.C(C=1C(C(=O)O)=CC=CC1)(=O)O.[O] Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)O.C(C=1C(C(=O)O)=CC=CC1)(=O)O.[O] DYCUQXMMUPNWMY-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 244000178289 Verbascum thapsus Species 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AZHPCFQBBJISDG-UHFFFAOYSA-N ethyl(oxido)phosphanium Chemical compound CC[PH2]=O AZHPCFQBBJISDG-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 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
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
- C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides a method for preparing a carbon fiber-polyimide composite material. The method comprises the following steps: (1) putting tetramine and an organic solvent into a reaction kettle, adding C=C-unsaturated-bond-containing carboxylic acid anhydride solid powder, stirring at room temperature until the solid powder is completely dissolved, continuing stirring to react, adding tetracarboxylic acid anhydride, and stirring to react at 2-5 DEG C; (2) preparing a polyamic acid solution into a solution in which the polyamic acid accounts for 35-60 wt%, wetting carbon fiber, heating to 200 DEG C, and baking to obtain the primary composite carbon fiber; (3) uniformly mixing thermosetting polyimide with the primary composite carbon fiber; and (4) carrying out compression molding, crosslinking and solidification on the polyimide-carbon fiber composite raw material obtained in the step (3), and carrying out further radiation crosslinking to obtain the polyimide-carbon fiber composite material. The carbon fiber is firstly coated with the polyamic acid and then compounded with the common thermosetting polyimide to obtain the material with excellent properties.
Description
Technical field
The present invention relates to a kind of method preparing carbon fiber-composite polyimide material.
Background technology
Polyimides (pi) are the higher family macromolecule materials of the thermostability growing up the 1950's, resistance to height
Temperature, radiation hardness, and have excellent mechanical performance and tribological property, are described as " kings of plastics ", especially high temperature, high pressure and
There is excellent antifriction lubrication characteristic, in Aeronautics and Astronautics, electrical equipment, machinery, chemical industry and microelectronics etc. under the severe rugged environments such as high speed
High-tech sector is widely applied.Fibre-reinforced polyimides (pi) polymer matrix composites have specific modulus height, ratio
Excellent in mechanical performance under intensity height, radiation hardness, high temperature, using temperature range very wide (- 269 DEG C～+400 DEG C) the features such as, in boat
Empty aerospace craft and Modern weapon system, chemical and medicine industry, textile industry, auto industry, mine and precision optical machinery row
In the case that the metal materials such as industry or Other Engineering plastics cannot meet requirement, all may be selected to use pi composite.But, pure
Pi, because of relatively low tension, comprcssive strength, is not suitable for using separately as friction material, can obtain after needing to add reinforcing fiber
To the pi composite that mechanical property and tribological property are excellent.
Carbon fiber is the inorganic polymer fiber that phosphorus content is higher than 90%.Wherein phosphorus content is higher than 99% title graphite fibre
Dimension.Carbon fiber can use polyacrylonitrile fibre, pitch fibers, viscose or phenolic fibre to be obtained through carbonization respectively；It is divided into by state
Long filament, chopped fiber and chopped strand；It is divided into universal and high-performance type by mechanical property.Common carbon fiber intensity is 1,000,000,000
Handkerchief (mpa), modulus are 100gpa.High-performance carbon fibers be divided into again high-strength (intensity 2000mpa, modulus 250gpa) and
High model (more than modulus 300gpa).Intensity is also called superelevation strong type more than 4000mpa's；Modulus is more than the referred to as super of 450gpa
High model.Carbon fiber has the features such as high temperature resistant, high intensity, high elastic modulus, creep resistant, is to prepare high performance resin base to be combined
The most frequently used reinforcing fiber of material, so conventional carbon fiber carrys out modified polyimide.
But the surface of carbon fiber is inert, the composite fiber of unprocessed preparation and interlaminar resin water ratio limit intensity
Very weak, and then affect the application of material.Therefore, current scientific and technological circle are before with fibre reinforced polyimides, typically first to carbon
Fiber is surface-treated, thus generating more active function groups, and defines gully.It is added in macromolecular material,
Can crystallize around it as nucleus induction macromolecule, such that it is able to improve the order of the macromole of macromolecular material, change
High molecular aggregated structure, and then have influence on the performance of macromolecular material.The carbon fiber modifying method adopting both at home and abroad at present
Complex process and condition harshness, such as air oxidation process (need to be in Muffle furnace, ablation 40 minutes at 450 DEG C) mostly, nitric acid oxidation
Method (by carbon fiber be immersed in nitric acid process a period of time), and low temperature liquid nitrogen process etc. (be immersed in liquid nitrogen (- 196 DEG C)
10 minutes).Said method complicated condition, process time is wayward, and easily causes modulus and the fracture strength of carbon fiber
Decline, thus the performance of its composite is greatly reduced.
Therefore, it is necessary to develop a kind of surface texture that need not change carbon fiber, you can direct combination and performance is more excellent
Different novel carbon fiber and composite polyimide material.
Content of the invention
It is an object of the invention to provide a kind of material that can obtain there is fine mechanical property prepare carbon fiber with
The method of composite polyimide material.
The object of the present invention is achieved like this:
(1) tetramine and organic solvent are put in reactor, under room temperature, after stirring and dissolving is complete, add carbon containing carbon insatiable hunger
With double bond carboxylic acid anhydride pressed powder, stir under room temperature to being completely dissolved, continue stirring reaction, add tetrabasic carboxylic acid anhydride, 2 DEG C -5
Stirring reaction at DEG C, obtains thick polyamic acid solution；
(2) polyamic acid solution is configured to the solution that polyamic acid mass fraction accounts for 35-60%, infiltrates carbon fiber, rise
Temperature, to 200 DEG C, dries the carbon fiber being tentatively combined；
(3) Thermocurable polyimide is mixed homogeneously with described tentatively compound carbon fiber；
(4), after the polyimide carbon fiber compound material compression molding crosslinking curing that step (3) is obtained, radiate further
Crosslinking, obtains polyimide carbon fiber composite.
The present invention can also include:
1st, the structure of described polyamic acid is as follows:
Wherein r1It is the group containing carbon carbon unsaturated double-bond；r2For one or more of following structure:Wherein x is selected from one or more of following divalent groups :-
co-、-o-、-s-、-so2-、-ch2-、-c(ch3)2-、-c(cf3)2-.
2nd, described carbon containing carbon unsaturated double-bond carboxylic acid anhydride is one or more of following structure:
3rd, described tetrabasic carboxylic acid anhydride is selected from pyromellitic acid anhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydrides, 3,3 ', 4,4 '-connection
Benzene tertacarbonic acid's dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone
Tetracarboxylic dianhydride, 4,4 '-oxygen connection O-phthalic acid dianhydride, double (3, the 4- dicarboxyphenyi) propane dianhydride of 2,2-, 3,4,9,10-
Tetracarboxylic dianhydride, double (3,4- dicarboxyphenyi) propane dianhydride, double (2,3- dicarboxyphenyi) the ethane dianhydride of 1,1-, 1,1- are double
(3,4- dicarboxyphenyi) ethane dianhydride, double (2,3- dicarboxyphenyi) methane dianhydride, double (3,4- dicarboxyphenyi) ethane two
Acid anhydride, oxygen di- O-phthalic acid dianhydride, two (3,4- dicarboxyphenyi) sulfone dianhydride, to benzene two (trimellitic acid monoester anhydride), sub-
Ethyl double one or more of (trimellitic acid monoester anhydride), bis-phenol a bis- (trimellitic acid monoester anhydride).
Heretofore described Thermocurable polyimide is synthesized by tetracarboxylic dianhydride, diamidogen and end-capping reagent, and described thermosetting gathers
Imido end-capping reagent is fluorine-containing phenylacetylene benzoic anhydride.
Polyamic acid using the present invention first coats to carbon fiber, then carries out again with common Thermocurable polyimide
Close, the material of superior performance can be obtained.
Brief description
Fig. 1 is the infrared spectrogram of section Example.
Specific embodiment
The method preparing carbon fiber-composite polyimide material of the present invention, comprises the following steps:
(1) tetramine and organic solvent are put in reactor, under room temperature, after stirring and dissolving is complete, add carbon containing carbon insatiable hunger
With double bond carboxylic acid anhydride pressed powder, stir under room temperature to being completely dissolved, continue stirring reaction, add tetrabasic carboxylic acid anhydride, 2 DEG C -5
Stirring reaction at DEG C, obtains thick polyamic acid solution；
(2) polyamic acid is prepared into the solution that polyamic acid mass fraction accounts for 35-60%, infiltrates carbon fiber, be warming up to
200 DEG C, dry the carbon fiber being tentatively combined；
(3) Thermocurable polyimide and above-mentioned tentatively compound carbon fiber are provided, and mix homogeneously；
(4) by after polyimide carbon fiber the Molding Forming of Composites crosslinking curing, further crosslinking with radiation, obtain polyamides
Imines carbon fibre composite.
Preferably, described polyamic acid and the mass ratio of carbon fiber are 1/10～1/1；It is highly preferred that described polyamic acid
Mass ratio with carbon fiber is 2/10.
Preferably, the mass fraction that described Thermocurable polyimide accounts for described composite is 10%～100%；More preferably
Ground, the mass fraction that described Thermocurable polyimide accounts for described composite is 40%.
Wherein, the structure of described polyamic acid is as follows:
Described r1It is the group containing carbon carbon unsaturated double-bond, r2Selected from one or more of following structure:
Wherein,
X is selected from one or more of following divalent groups :-co- ,-o- ,-s- ,-so2-、-ch2-、-c(ch3)2-、-c
(cf3)2-.
The equal commercialization of above-mentioned tetrabasic carboxylic acid anhydride can obtain, and can directly be purchased from Reagent Company.
One or more of following structure of described carbon containing carbon unsaturated double-bond carboxylic acid anhydride:
(4- (4- methyl -3- amylene) -4- cyclohexene -1,2- dicarboxylic anhydride),
(polypropylene tetramer base allyl succinic anhydride),
The equal commercialization of above-mentioned carbon containing carbon unsaturated double-bond carboxylic acid anhydride can obtain, and can directly be purchased from Reagent Company.
The method preparing carbon fiber-composite polyimide material according to first aspect, wherein, described tetrabasic carboxylic acid acid
Acid anhydride be selected from pyromellitic acid anhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 1,2,5,6- naphthalene
Tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen connection is adjacent
Phthalic acid dianhydride, 2,2- double (3,4- dicarboxyphenyi) propane dianhydride, 3,4,9,10- tetracarboxylic dianhydrides, double (3,4- dicarboxyls
Base phenyl) propane dianhydride, double (2,3- dicarboxyphenyi) the ethane dianhydride of 1,1-, double (3, the 4- dicarboxyphenyi) ethane two of 1,1-
Acid anhydride, double (2,3- dicarboxyphenyi) methane dianhydride, double (3,4- dicarboxyphenyi) ethane dianhydride, oxygen di- phthalic acid two
Acid anhydride, two (3,4- dicarboxyphenyi) sulfone dianhydride, to benzene two (trimellitic acid monoester anhydride), ethylenebis (trimellitic acid monoesters acid
Acid anhydride), one or more of bis-phenol a bis- (trimellitic acid monoester anhydride).
The organic solvent using can select n- N-methyl-2-2-pyrrolidone N, n, n- dimethyl acetylamide, n, n- diethyl second
Amide, n, n- dimethylformamide, n, n- diethylformamide, n- methyl caprolactam, hexamethyl phosphoramide, tetramethylene
Sulfone, dimethyl sulfoxide, metacresol, phenol, parachlorophenol, 2- chloro-4-hydroxyl toluene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether.,
Tetraethylene glycol dimethyl ether, dioxane, gamma-butyrolacton, dioxa penta ring, Ketohexamethylene, Ketocyclopentane, dichlorotoleune, chloroform, 1,
2- dichloroethanes, vinyl trichloride, methylene bromide, bromoform, glycol dibromide, 1，1，2-tribromoethane etc.,
Can be applied in combination with two or more.
As carbon fiber, the carbon fiber preferably using in the present invention can use the carbon fiber of all kinds according to purposes,
But from the aspect of resistance to impact, it is however preferred to have the carbon fiber of the tensile modulus of elasticity of highest 400gpa.In addition, from intensity
From the viewpoint of, due to the composite with high rigidity and mechanical strength can be obtained, so being preferably using tensile strength
The carbon fiber of 4.4～6.5gpa.In addition, tensile elongation is also important key element, preferably 1.7～2.3% high intensity is high
Percentage elongation carbon fiber.Therefore, the carbon fiber having following characteristics concurrently is the most preferable, i.e. tensile modulus of elasticity is at least 230gpa, stretching
Intensity is at least 4.4gpa, and tensile elongation is at least 1.7%.
As the commercially available product of carbon fiber, can enumerate " torayca " t800g-24k, " torayca " t800s-24k,
" torayca " t700g-24k, " torayca " t300-3k and " torayca " t700s-12k.
Described Thermocurable polyimide is synthesized by tetracarboxylic dianhydride, diamidogen and end-capping reagent, described Thermocurable polyimide
End-capping reagent is fluorine-containing phenylacetylene benzoic anhydride.The fire resistance of material can be improved by the replacement of fluorine.
The tetracarboxylic dianhydride being used for preparing polyimides in the present invention includes pyromellitic acid anhydride, 2,3,6,7- naphthalene tetracarboxylic acids
Acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid two
Acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen connection O-phthalic acid dianhydride, double (3, the 4- dicarboxyl benzene of 2,2-
Base) propane dianhydride, 3,4,9,10- tetracarboxylic dianhydrides, double (3,4- dicarboxyphenyi) propane dianhydride, double (2, the 3- dicarboxyls of 1,1-
Base phenyl) ethane dianhydride, double (3,4- dicarboxyphenyi) the ethane dianhydride of 1,1-, double (2,3- dicarboxyphenyi) methane dianhydride, double
(3,4- dicarboxyphenyi) ethane dianhydride, oxygen di- O-phthalic acid dianhydride, two (3,4- dicarboxyphenyi) sulfone dianhydride, to benzene two
(trimellitic acid monoester anhydride), ethylenebis (trimellitic acid monoester anhydride), bis-phenol a bis- (trimellitic acid monoester anhydride) and these
Analog, preferably these be used alone or using arbitrary proportion mixture.
The present invention is used for preparing the diamidogen of polyimides, for example, can enumerate 4,4 '-diamino-diphenyl propane, 4,4 '-two
Aminodiphenylmethane, benzidine, 3,3 '-dichloro-benzidine, 3,3 '-dimethylbenzidine, 2,2 '-dimethylbenzidine, 3,
3 '-dimethoxy benzidine, 2,2 '-dimethoxy benzidine, 4,4 '-diamino diphenyl sulfide, 3,3 '-diaminourea hexichol
Sulfone, 4,4 '-DADPS, 4，4′-diaminodipohenyl ether, 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 1,
5- diaminonaphthalene, 4,4 '-diamino-diphenyl diethylsilane, 4,4 '-diamino-diphenyl silane, 4,4 '-diaminourea hexichol
Base ethyl phosphine oxide, 4,4 '-diamino-diphenyl-n- methylamine, 4,4 '-diamino-diphenyl n- aniline, Isosorbide-5-Nitrae-diaminobenzene
(p-phenylenediamine), 1,3- diaminobenzene, 1,2- diaminobenzene, two { 4- (4- amino-benzene oxygen) phenyl } sulfone, two { 4- (4- amino
Phenoxy group) phenyl propane, two { 4- (3- amino-benzene oxygen) phenyl } sulfone, 4,4 '-two (4- amino-benzene oxygen) biphenyl, 4,4 '-two
(3- amino-benzene oxygen) biphenyl, 1,3- bis- (3- amino-benzene oxygen) benzene, 1,3- bis- (4- amino-benzene oxygen) benzene, 1,3- bis- (4- ammonia
Phenoxyl) benzene, 1,3- bis- (3- amino-benzene oxygen) benzene, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone and
These analog etc..
End-capping moiety as polyimides can use dicarboxylic anhydride, monoamine etc..Example can be enumerated as dicarboxylic anhydride
As phthalate anhydride, naphthalic anhydride, biphenyl dicarboxylic acid acid anhydride, 1,2,3,6- tetrahydrochysene phthalate anhydrides, 1,2- cyclohexane dicarboxylic acid
Acid anhydride, 5- norborene -2,3- dicarboxylic anhydride, methyl -5- norborene -2,3- dicarboxylic anhydride, citraconic anhydride, maleic anhydride, 3-
Acetylenylbenzene dioctyl phthalate, 4- acetylenylbenzene dioctyl phthalate, 4- phenylene-ethynylene phthalic acid, 3- fluoro 4- phenylene-ethynylene benzene diformazan
Anhydride etc..Can enumerate for example as monoamine, aniline, amino naphthalenes, aminobphenyl, 3- acetylene aniline, 4- acetylene aniline etc..Preferably
Difluorophenyl acetylenylbenzene dicarboxylic acid anhydride, as end-capping reagent, can suppress candle wick effect.Certainly, it is not limited to as end-capping reagent
This.They can be used alone it is also possible to be used in combination.
The organic solvent using can select n- N-methyl-2-2-pyrrolidone N, n, n- dimethyl acetylamide, n, n- diethyl second
Amide, n, n- dimethylformamide, n, n- diethylformamide, n- methyl caprolactam, hexamethyl phosphoramide, tetramethylene
Sulfone, dimethyl sulfoxide, metacresol, phenol, parachlorophenol, 2- chloro-4-hydroxyl toluene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether.,
Tetraethylene glycol dimethyl ether, dioxane, gamma-butyrolacton, dioxa penta ring, Ketohexamethylene, Ketocyclopentane, dichlorotoleune, chloroform, 1,
2- dichloroethanes, vinyl trichloride, methylene bromide, bromoform, glycol dibromide, 1，1，2-tribromoethane etc.,
Can be applied in combination with two or more.
Catalyst, preferably tertiary amine compound, specifically can enumerate Trimethylamine, triethylamine (tea), tripropylamine, three fourths
Base amine, triethanolamine, n, n- dimethylethanolamine, n, n- diethyl ethylene diamine, triethylenediamine, n- crassitude, n- second
Base pyrrolidine, n- methyl piperidine, n- ethyl piperidine, imidazoles, pyridine, quinoline, isoquinolin etc..Can be selected from these tertiary amine chemical combination
Reacted in the presence of at least one catalyst in thing.When using catalyst, its usage amount, from consumption few and react when
Between as short as possible from the aspect of, 0.1～100 mole of % of preferably tetrabasic carboxylic acid composition (y).
Composite material preparation process:
Add a small amount of coupling agent (resinous total amount 1%) in thermoset polyimide resin, after mix homogeneously with tentatively multiple
The carbon fiber mixing closed, puts into 80 degrees Celsius of baking ovens and carries out pretreatment, and treating solution evaporation after 1 hour, some to be warming up to 160 Celsius
Degree insulation 3 hours, is warming up to 200 degrees Celsius and is incubated 4 hours.Again fiber is put into 250 degrees Celsius of vacuum drying ovens to process 5 hours,
Obtain pre- binder.
Mould pressing process
First contact, is warming up to 280 degrees Celsius, and pressurize mold closing, is continuously heating to 380 degrees Celsius and is incubated 1 hour, blowing is cold
But, 150 degrees Celsius of depannings.After depanning, through processing, the batten obtaining supplies case heat treatment to dry water through 120 degrees Celsius to batten again
Point, after taking-up, standing was tested after 24 hours.
Method of testing
Unnotched impact strength is tested: Chengde testing machine factory, xa-500,50j, gb1043.
Tensile strength is tested: lloyd company of Britain, lloyd-lr-50k, gb1040.
Bending strength is tested: lloyd company of Britain, lloyd-lr-50k, gb9341.
Medium-resistance is tested: gbn547.
Fire-retardant: ul94.
Illustrate below and the present invention is described in more detail.
Embodiment 1
By double [4- (2, the 4- diamino phenoxy) phenyl] propane of 0.2 mole of 2,2- and 1000 milliliters of n, n- dimethylacetamide
Amine is put in reactor, under room temperature, after stirring and dissolving is complete, adds 0.4 mole of 4- (4- methyl -3- amylene) -4- cyclohexene -1,
2- dicarboxylic anhydride, stirs under room temperature to being completely dissolved, and continues stirring reaction after 0.5 hour, adds 0.2 mole of Pyromellitic Acid two
Acid anhydride, stirring reaction 2 hours at 2 DEG C -5 DEG C, the viscosity at controlling 2 DEG C -5 DEG C is 10000 centipoises, stops stirring, obtains thick
Polyamic acid solution.
Polyamic acid is prepared into the solution of polyamic acid mass fraction 50%, infiltrates carbon fiber (" torayca " t800g-
24k), it is warming up to 200 degrees Celsius, (polyamic acid and carbon fiber mass ratio 10:1) is dried and obtained modified carbon fiber a1.
Composite material preparation process:
A small amount of coupling agent kh570 (resinous total amount 1%), mix homogeneously is added in thermoset polyimide resin pmr-15
Mix with modified carbon fiber a1 (the 53% of gross mass) afterwards, put into 80 degrees Celsius of baking ovens and carry out pretreatment, after 1 hour, treat that solution is waved
Send out some and be warming up to 160 degrees Celsius of insulations 3 hours, be warming up to 200 degrees Celsius and be incubated 4 hours.Again fiber is put into 250 degrees Celsius
Vacuum drying oven is processed 5 hours, obtains pre- binder.
Mould pressing process
First contact, is warming up to 280 degrees Celsius, and pressurize mold closing, is continuously heating to 380 degrees Celsius and is incubated 1 hour, blowing is cold
But, 150 degrees Celsius of depannings.After depanning, through processing, the batten obtaining supplies case heat treatment to dry water through 120 degrees Celsius to batten again
Point, after standing 24 hours after taking-up, crosslinking with radiation (cobalt -60 isotopic radiation source, dosage 8000gy), obtain batten b1 test.
Embodiment 2
Carbon containing carbon unsaturated double-bond carboxylic acid anhydride:
Tetrabasic carboxylic acid anhydride: 2,3,6,7- naphthalene tetracarboxylic acid dianhydrides
Control viscosity: 10000
Polyamic acid mass fraction: 60%
Thermoset polyimide resin: 3,4,5, the polyimide resin of-trifluoro-benzene acetylene anhydride end-blocking is (with pmr-15
Single phase is same)
Preparation method is identical with embodiment, obtains batten b2
Embodiment 3
Carbon containing carbon unsaturated double-bond carboxylic acid anhydride:
Tetrabasic carboxylic acid anhydride: 2,3,6,7- naphthalene tetracarboxylic acid dianhydrides
Control viscosity: 9000
Polyamic acid mass fraction: 35%
Preparation method is identical with embodiment, obtains batten b3
Embodiment 4
Carbon containing carbon unsaturated double-bond carboxylic acid anhydride:
Tetrabasic carboxylic acid anhydride: 2,3,6,7- naphthalene tetracarboxylic acid dianhydrides
Control viscosity: 20000
Polyamic acid mass fraction: 35%
Preparation method is identical with embodiment, obtains batten b4
Embodiment 5
Carbon containing carbon unsaturated double-bond carboxylic acid anhydride:
Tetrabasic carboxylic acid anhydride: 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride
Control viscosity: 18000
Polyamic acid mass fraction: 35%
Preparation method is identical with embodiment, obtains batten b5
Embodiment 6
Carbon containing carbon unsaturated double-bond carboxylic acid anhydride: carbic anhydride.Other are same as Example 1, obtain batten b6.
Embodiment 7
Carbon containing carbon unsaturated double-bond carboxylic acid anhydride: maleic anhydride.Other are same as Example 1, obtain batten b7.
Comparative example 1
Same as Example 1, but there is no radiation crosslinking step.Obtain batten d1
Comparative example 2
Control viscosity to 30000, other are same as Example 1, obtain batten d2.
Test result is as shown in table 1:
Table 1
The result of table 1 shows, above-mentioned polyimide carbon fiber composite is respectively provided with very excellent mechanical property (stretching
Intensity is all higher than 490mpa), and the mechanical property of this composite can be improved further by crosslinking with radiation.Additionally, experiment
Result also shows that above-mentioned polyimide carbon fiber composite is respectively provided with very excellent fire resistance and (meets ul-0 or ul-1 mark
Accurate).In view of the excellent mechanics of above-mentioned polyimide carbon fiber composite and fire resistance, can be widely applied to Aeronautics and Astronautics,
The high-tech sectors such as electrical equipment, machinery, chemical industry and microelectronics.
Claims (3)
1. a kind of method preparing carbon fiber and composite polyimide material, is characterized in that:
(1) tetramine and organic solvent are put in reactor, under room temperature, after stirring and dissolving is complete, add carbon containing carbon unsaturated double
Key carboxylic acid anhydride pressed powder, stirs under room temperature to being completely dissolved, continues stirring reaction, add tetrabasic carboxylic acid anhydride, at 2 DEG C -5 DEG C
Stirring reaction, obtains thick polyamic acid solution；The structure of described polyamic acid is as follows:
Wherein r1It is the group containing carbon carbon unsaturated double-bond；r2For one or more of following structure:Wherein x is selected from one or more of following divalent groups :-
co-、-o-、-s-、-so2-、-ch2-、-c(ch3)2-、-c(cf3)2-；
(2) polyamic acid solution is configured to the solution that polyamic acid mass fraction accounts for 35-60%, infiltrates carbon fiber, be warming up to
200 DEG C, dry the carbon fiber being tentatively combined；
(3) Thermocurable polyimide is mixed homogeneously with described tentatively compound carbon fiber；
(4), after the polyimide carbon fiber compound material compression molding crosslinking curing obtaining step (3), radiation further is handed over
Connection, obtains polyimide carbon fiber composite.
2. the method preparing carbon fiber and composite polyimide material according to claim 1, is characterized in that described carbon containing
Carbon unsaturated double-bond carboxylic acid anhydride is one or more of following structure:
3. the method preparing carbon fiber and composite polyimide material according to claim 1 and 2, is characterized in that: polyamides
Amino acid is 1/10～1/1 with the mass ratio of carbon fiber；Thermocurable polyimide account for composite mass fraction be 10%～
100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510086537.9A CN104629365B (en) | 2015-02-17 | 2015-02-17 | Method for preparing carbon fiber-polyimide composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510086537.9A CN104629365B (en) | 2015-02-17 | 2015-02-17 | Method for preparing carbon fiber-polyimide composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104629365A CN104629365A (en) | 2015-05-20 |
| CN104629365B true CN104629365B (en) | 2017-02-01 |
Family
ID=53208626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510086537.9A Expired - Fee Related CN104629365B (en) | 2015-02-17 | 2015-02-17 | Method for preparing carbon fiber-polyimide composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104629365B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105015566A (en) * | 2015-07-31 | 2015-11-04 | 株洲时代新材料科技股份有限公司 | Safety bracket used for linear motor railway train and production method thereof |
| CN106067334A (en) * | 2016-05-21 | 2016-11-02 | 国网山东省电力公司高唐县供电公司 | Household electricity aging resistance electric wire |
| CN106978729A (en) * | 2017-03-22 | 2017-07-25 | 安徽键合科技有限公司 | A kind of high temperature resistant aerospace composite |
| CN109545578B (en) * | 2018-11-22 | 2020-08-07 | 中南民族大学 | Amide polymer derived one-dimensional nitrogen-doped nano carbon electrode material and preparation method thereof |
| CN110331462A (en) * | 2019-07-16 | 2019-10-15 | 常州市盛杰合力化纤有限公司 | High-strength anti-flaming polypropylene fibre doughnut and preparation method thereof |
| CN112259977B (en) * | 2020-10-19 | 2021-06-18 | 南京多特蒙电气有限公司 | Binding post that traction force is strong easily dispels heat |
| CN112375381A (en) * | 2020-12-09 | 2021-02-19 | 安徽威能电源科技有限公司 | Preparation method of high-temperature-resistant polyimide material |
| CN114249911A (en) * | 2021-12-09 | 2022-03-29 | 南京工业大学 | Fiber-reinforced polyimide-based composite material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7572878B2 (en) * | 2005-09-16 | 2009-08-11 | E. I. Du Pont De Nemours And Company | Polycyclic polyimides and compositions and methods relating thereto |
| CN101062985A (en) * | 2006-04-28 | 2007-10-31 | 宋成根 | Processing technique of low-constriction polyimide film |
| CN101062979A (en) * | 2006-04-28 | 2007-10-31 | 宋成根 | Preparation method of nano type polyamic acid resin |
| CN101230196B (en) * | 2008-02-26 | 2010-06-02 | 东南大学 | In-situ polymerization PI modified nylon composite material |
| CN103694487A (en) * | 2013-12-13 | 2014-04-02 | 青岛海洋新材料科技有限公司 | Preparation method of carbon fiber-polyimide composite film |
-
2015
- 2015-02-17 CN CN201510086537.9A patent/CN104629365B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104629365A (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104629365B (en) | Method for preparing carbon fiber-polyimide composite material | |
| CN104403313B (en) | Polyimide composite material and preparation method thereof | |
| Saeed et al. | Effects of monomer structure and imidization degree on mechanical properties and viscoelastic behavior of thermoplastic polyimide films | |
| JP6275648B2 (en) | Epoxy resin composition | |
| Yuan et al. | Preparation and characterization of a polyimide coating on the surface of carbon fibers | |
| JP6604588B2 (en) | Varnishes using 2-phenyl-4,4′-diaminodiphenyl ethers, imide resin compositions excellent in moldability and cured resin molded articles having excellent elongation at break, and prepregs, imide prepregs and heat resistance using them, and Fiber reinforced material with excellent mechanical strength | |
| Gu et al. | Surface modification of HMPBO fibers by silane coupling agent of KH-560 treatment assisted by ultrasonic vibration | |
| EP0307454B1 (en) | Polyamide-imide compositions | |
| Zhang et al. | Influence of matrix modulus on the mechanical and interfacial properties of carbon fiber filament wound composites | |
| Çakir et al. | Characterization of carbon fiber-reinforced thermoplastic and thermosetting polyimide matrix composites manufactured by using various synthesized PI precursor resins | |
| NO339648B1 (en) | Process for the use of citric acid anhydride as an addition curing blanket in reactions to form polyamic acid oligomers and polyimide oligomers; | |
| Jamshidi et al. | Toughening of dicyandiamide-cured DGEBA-based epoxy resins using flexible diamine | |
| Dhanapal et al. | Role of POSS as coupling agent for DGEBA/GF reinforced nanocomposites | |
| Dai et al. | Synthesis of Heterocyclic Aramid Fiber Based on Solid‐Phase Cross‐Linking of Oligomers with Reactive End Group | |
| CN105764989A (en) | Polyimide resin composition comprising terminal-modified imide oligomer prepared using 2-phenyl-4,4'-diaminodiphenyl ether and aromatic thermoplastic polyimide prepared using oxydiphthalic acid, varnish, polyimide resin composition molded article having excellent heat resistance and mechanical properties, prepreg, and fiber-reinforced composite material containing said prepreg | |
| Wang et al. | Improving the interfacial and flexural properties of carbon fiber–epoxy composites via the grafting of a hyperbranched aromatic polyamide onto a carbon fiber surface on the basis of solution polymerization | |
| Wu et al. | Synthesis of a bismaleimide/cyanate ester copolymer containing phenolphthalein functional group with excellent dielectric properties and thermally stable | |
| JPH02284923A (en) | Terminal-modified imide oligomer composition | |
| Ogasawara et al. | Processing and properties of carbon fiber/Triple-A polyimide composites fabricated from imide oligomer dry prepreg | |
| Li et al. | The thermal stability investigation of microencapsulated ammonium polyphosphate/siloxane‐modified epoxy resin composites | |
| Feng et al. | Construction of dendritic polymers on carbon fiber surfaces to improve the interfacial bonding of carbon fiber/silicone rubber composites | |
| JP2014125688A (en) | Sizing agent-coated carbon fiber and method for producing sizing agent-coated carbon fiber | |
| CN108084655A (en) | A kind of low temperature resistant epoxy resin material and preparation method | |
| JP2016199681A (en) | Fiber-reinforced composite material | |
| TWI791718B (en) | Curable epoxy system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170201 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |