CN104086995B - Hollow microsphere reinforced polyimide-based composite foam material and preparation method thereof - Google Patents
Hollow microsphere reinforced polyimide-based composite foam material and preparation method thereof Download PDFInfo
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- CN104086995B CN104086995B CN201410333015.XA CN201410333015A CN104086995B CN 104086995 B CN104086995 B CN 104086995B CN 201410333015 A CN201410333015 A CN 201410333015A CN 104086995 B CN104086995 B CN 104086995B
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- polyimide
- foam material
- based composite
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- composite foam
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 55
- 229920001721 polyimide Polymers 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000006261 foam material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004005 microsphere Substances 0.000 title abstract 2
- 239000011325 microbead Substances 0.000 claims abstract description 40
- 239000006260 foam Substances 0.000 claims abstract description 35
- 238000005187 foaming Methods 0.000 claims abstract description 33
- 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 29
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000004088 foaming agent Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 41
- 239000011324 bead Substances 0.000 claims description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 10
- -1 radical siloxane Chemical class 0.000 claims description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 9
- 235000011572 Pyrus ussuriensis Nutrition 0.000 claims description 8
- 244000173166 Pyrus ussuriensis Species 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000136 polysorbate Polymers 0.000 claims description 6
- 229950008882 polysorbate Drugs 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 5
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims 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 claims description 5
- 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 claims description 5
- 125000005456 glyceride group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005388 borosilicate glass Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- VVWRJUBEIPHGQF-MDZDMXLPSA-N propan-2-yl (ne)-n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)\N=N\C(=O)OC(C)C VVWRJUBEIPHGQF-MDZDMXLPSA-N 0.000 claims description 4
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 4
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 4
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004156 Azodicarbonamide Substances 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 3
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims 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 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims description 3
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 claims 1
- 230000002708 enhancing effect Effects 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 12
- 238000009413 insulation Methods 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000002253 acid Substances 0.000 description 17
- 150000005690 diesters Chemical class 0.000 description 14
- 230000008602 contraction Effects 0.000 description 9
- 238000005452 bending Methods 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 7
- 238000002203 pretreatment Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 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 6
- 239000001384 succinic acid Substances 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- MEJAPGGFIJZHEJ-UHFFFAOYSA-N 5-acetamido-1,3,4-thiadiazole-2-sulfonyl chloride Chemical compound CC(=O)NC1=NN=C(S(Cl)(=O)=O)S1 MEJAPGGFIJZHEJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Abstract
The invention provides a hollow microsphere reinforced polyimide-based composite foam material and a preparation method thereof, wherein the apparent density of the composite foam material is 0.023g/cm3~0.035g/cm3The foam has a shrinkage of-35.0 to-20.0%, a compressive strength of 0.05 to 0.35MPa, and an impact strength of 20 to 60KJ/m2The average sound absorption coefficient in the frequency range of 125-4000Hz is 0.40-0.51. The preparation method comprises the following steps: after esterification of aromatic dianhydride, mixing with aromatic diamine and surfactant to obtain a foaming precursor; adding into the precursor solutionAdding hollow micro-beads and a foaming agent and heating to obtain a foaming block; finally, the foaming block is hot imidized to obtain the composite foaming material. The invention can prepare the composite foamed plastic with good mechanical property, sound absorption and sound insulation.
Description
Technical field
The invention belongs to polyimide material technical field, strengthen particularly to a kind of hollow beads polyimide-based compound
Expanded material and preparation method thereof.
Background technology
Society is strict to the material requirements for sound absorption and sound insulation.Sound absorption and deadener are used for improving stereophone
Really, undesirable noise level is such as reduced.Generally use plastics for this, these materials are owing to having the viscoelasticity, easily of excellence
In processing and commercially available and become suitable material.The type of service of these plastics is usually porous foam form.
The feature of porous material is that it has good sound absorption in altofrequency, but has low absorption energy at a lower frequency
Power.Plastic foam sound absorption at a lower frequency can carry out improving or strengthening by introducing various fillers.Wherein hollow is micro-
Pearl is applied in various composite widely as dead acoustic barrier filler.
Polyimides (PI) high molecular polymer belongs to amorphism engineering plastics, has thermostability and the machinery of excellence
Property, excellent dielectric properties and easily realize molecular structure optimize design to meet different performance requirements etc..Polyamides is sub-
Amine foamed composite not only maintains heat resistance and the mechanical performance of polyimides, also have good high temperature barrier,
Noise reduction, impact resistance, stability and anti-flammability, can be as heat insulation, sound insulation and fire proofing, at aircraft, spacecraft, weapon dress
The field application such as standby, naval vessel, bullet train and automobile.
Although polyimide foam has good sound absorption properties in altofrequency, but remains a need in the range of relatively low frequency
Sound absorption and sound insulation improve.
Summary of the invention
It is an object of the invention to provide a kind of hollow beads and strengthen polyimide-based composite foam material, existing poly-to solve
The defects such as the acid imide foam material sound absorption properties and sound-proofing in lower frequency ranges is poor, relatively costly are not enough.
For achieving the above object, the present invention is by the following technical solutions:
A kind of hollow beads strengthens polyimide-based composite foam material, and its apparent density is 0.023g/cm3 ~
0.035g/cm3, foam contraction rate for-35.0% ~-20.0%, compressive strength be 0.05 ~ 0.35MPa, impact strength be 20
~60KJ/m2, the average sound absorption coefficient in 125-4000Hz frequency range is 0.40 ~ 0.51.
Present invention also offers above-mentioned hollow beads and strengthen the preparation method of polyimide-based composite foam material, its technology
Scheme is:
A kind of hollow beads strengthens the preparation method of polyimide-based composite foam material, comprises the following steps:
A) aromatic dianhydride being added in organic polar solvent and dissolve, add fatty alcohol, be heated to 50 ~ 80 DEG C, backflow 1 ~ 3 is little
Time, obtain esterification products；In described esterification products, add aromatic diamines, and continue under the effect of catalyst and surfactant
Continue and carry out reacting 3 ~ 7 hours, obtain foam precursors solution；
B) in the foam precursors solution that step A obtains, add hollow glass microbead and foaming agent, stir 3 ~ 5 hours, and
Put into after being concentrated and drying in mould and be heated to 150 ~ 200 DEG C of pretreatment, after foaming 60 ~ 120 minutes, obtain foaming block；
C) foaming block that step B obtains is heated to 280 ~ 350 DEG C and carries out hot imidization process, after 2 ~ 4 hours, obtain institute
The hollow glass microbead stated strengthens polyimide-based composite foam material.
In foam precursors solution, in parts by weight, proportioning is as follows for each amounts of components:
Aromatic dianhydride 100 parts, aromatic diamines 50 ~ 200 parts, fatty alcohol 1 ~ 25 part, organic polar solvent 50 ~ 1000 parts, urge
Agent 0.01 ~ 10 part, 0.5 ~ 100 part of surfactant, hollow glass microbead 1 ~ 20 part, foaming agent 5 ~ 30 parts.
Preferably, described aromatic dianhydride be pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic acid dianhydride, 3,3 ',
4,4 '-diphenyl ether tetraformic dianhydride, bisphenol A-type diphenyl ether dianhydride, hexafluorodianhydride (6FDA), 3,3 ', 4,4 '-diphenyl thio-ether tetrformate two
Acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride one or more.
Preferably, described fatty alcohol is methanol, ethanol, normal propyl alcohol, isopropanol, capryl alcohol, furfuryl alcohol, Polyethylene Glycol or butanol
One or more.
Preferably, described aromatic diamines is 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, m-diaminobenzene., right
Phenylenediamine, o-phenylenediamine, benzidine, 4,4 '-DADPS, 2,6-diamino-pyridine, 1,6-ethylenediamine, siliceous two
One or many in amine, phosphorous diamidogen, triamine phenyl benzene, 3,4 '-MDA and 4,4 '-MDA
Kind.
Preferably, polar solvent therein is DMF, N,N-dimethylacetamide, N-crassitude
Ketone, hexamethyl phosphoramide, dimethyl sulfoxide, N-pyridine oxide, N-cyclohexyl pyrrolidone, caprolactam, phenol, a phenol,
One or both in paracresol, benzoic acid, Ketohexamethylene and butanone.
Preferably, described catalyst is triethanolamine, N, N-dimethylethanolamine, N, N-lutidines, dimethylbenzyl
Amine, N, a kind of or the most several mixture of N-dimethyl hexadecyl amine, triethylenediamine and triethylamine.
Preferably, described surfactant is that dodecylbenzene sodium sulfonate, fatty glyceride, fatty acid Pyrusussuriensis are smooth, poly-
A kind of or the most several mixture in Pyrusussuriensis ester, polydimethylsiloxane, polydimethylsiloxane.
Preferably, described hollow glass microbead is soda lime borosilicate glass, and airtight the most spherical in hollow, particle diameter exists
Between 15 ~ 135 microns, apparent density is at 0.12 ~ 0.60g/cm3Between.
Preferably, described foaming agent be formic acid, acetic acid, ethanedioic acid, propanoic acid, n-butyric acie, succinic acid, azodicarbonamide,
Azoaminobenzene, unifor, p-toluene sulfonylsemicarbazide, azo-bis-isobutyl cyanide, diisopropyl azodiformate, N, N-
Dinitrosopentamethlyene tetramine, N, N-dimethyl-N, N '-dinitroso to benzene, 4,4 '-OBSH, 3,3 '-two
Sulfohydrazide diphenyl sulphone (DPS), Barium azodicarboxylate, Tetramethylene sulfide, 5-tetrazolium are in benzene, sodium bicarbonate, ammonium carbonate, ammonium nilrite
Kind or the most several mixture.
The invention has the beneficial effects as follows: the technique simple possible of the present invention, it is possible to prepare combination property economical and efficient
The polyimide-based composite foam material that excellent and density is controlled.The hollow beads of the present invention strengthens polyimide-based composite foamed
In material, the quality of hollow beads is the 1% ~ 30% of polyimide foam quality, and its outward appearance is spherical in shape, hollow, light weight, mainly becomes
It is divided into soda lime borosilicate glass, belongs to inorganic rigid filler, it is possible to be effectively improved every mechanical performance of material.Due to
The mobility of hollow beads is splendid, can reduce the abrasion to equipment, and improve the dispersion of hollow beads in the course of processing
Property.Hollow beads is owing to there being splendid sound absorption properties and sound-proofing, it is possible to increase substantially the composite foam obstruct to sound.Use
Hollow beads is as the interpolation material of polyimide foam, and by controlling to add the ratio of material, solves double glazing
Microballon dispersibility in polyimide foam and interfacial adhesion sex chromosome mosaicism so as to get Polyimide foam composite material aperture
Uniformly, without splitting bubble and steeping, subside and the incomplete defect of imidizate, thermostability is preferable, and glass transition temperature is high, machinery
Functional, existing various thermoplastic expanded plastics and composite thereof can be replaced to be widely used in each based packaging material, delay
Rush material, automotive trim product, tableware etc., there is the advantage such as environmental protection and excellent performance.
Preparation technology of the present invention is simple, it is not necessary to special equipment, and foaming process is nontoxic.
Detailed description of the invention
It is further appreciated that the present invention by the following examples, but present invention can not be limited.The technology in this field is ripe
Practice personnel and according to the invention described above content, the present invention can be made some nonessential improvement and adjustment.The present invention is raw materials used to be all
Commercially available.
A kind of hollow beads strengthens polyimide-based composite foam material, and its apparent density is 0.023g/cm3 ~
0.035g/cm3, foam contraction rate for-35.0% ~-20.0%, compressive strength be 0.05 ~ 0.35MPa, impact strength be 20
~60KJ/m2, the average sound absorption coefficient in 125-4000Hz frequency range is 0.40 ~ 0.51.
Above-mentioned hollow beads strengthens the preparation method of polyimide-based composite foam material, comprises the following steps:
A) aromatic dianhydride being added in organic polar solvent and dissolve, add fatty alcohol, be heated to 50 ~ 80 DEG C, backflow 1 ~ 3 is little
Time, obtain esterification products；In described esterification products, add aromatic diamines, and continue under the effect of catalyst and surfactant
Continue and carry out reacting 3 ~ 7 hours, obtain foam precursors solution；
B) in the foam precursors solution that step A obtains, add hollow glass microbead and foaming agent, stir 3 ~ 5 hours, and
Put into after being concentrated and drying in mould and be heated to 150 ~ 200 DEG C of pretreatment, after foaming 60 ~ 120 minutes, obtain foaming block；
C) foaming block that step B obtains is heated to 280 ~ 350 DEG C and carries out hot imidization process, after 2 ~ 4 hours, obtain institute
The hollow glass microbead stated strengthens polyimide-based composite foam material.
In foam precursors solution, in parts by weight, proportioning is as follows for each amounts of components:
Aromatic dianhydride 100 parts, aromatic diamines 50 ~ 200 parts, fatty alcohol 1 ~ 25 part, organic polar solvent 50 ~ 1000 parts, urge
Agent 0.01 ~ 10 part, 0.5 ~ 100 part of surfactant, hollow glass microbead 1 ~ 20 part, foaming agent 5 ~ 30 parts.
Aromatic dianhydride is pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether
Tetracarboxylic acid dianhydride, bisphenol A-type diphenyl ether dianhydride, hexafluorodianhydride (6FDA), 3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride, 3,3 ', 4,4 '-
One or more of benzophenone tetracarboxylic dianhydride.
Fatty alcohol is one or more of methanol, ethanol, normal propyl alcohol, isopropanol, capryl alcohol, furfuryl alcohol, Polyethylene Glycol or butanol.
Aromatic diamines is 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, m-diaminobenzene., p-phenylenediamine, adjacent benzene
Diamidogen, benzidine, 4,4 '-DADPS, 2,6-diamino-pyridine, 1,6-ethylenediamine, siliceous diamidogen, phosphorous diamidogen,
One or more in triamine phenyl benzene, 3,4 '-MDA and 4,4 '-MDA.
Polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, hexamethyl phosphinylidyne
Amine, dimethyl sulfoxide, N-pyridine oxide, N-cyclohexyl pyrrolidone, caprolactam, phenol, a phenol, paracresol, benzoic acid,
One or both in Ketohexamethylene and butanone.
Catalyst is triethanolamine, N, N-dimethylethanolamine, N, N-lutidines, dimethyl benzylamine, N, N-diformazan
A kind of or the most several mixture of base hexadecylamine, triethylenediamine and triethylamine.
Surfactant is that dodecylbenzene sodium sulfonate, fatty glyceride, fatty acid Pyrusussuriensis be smooth, Polysorbate, poly-two
A kind of or the most several mixture in methylsiloxane (PEG-12), polydimethylsiloxane (DC-193).
Hollow glass microbead is soda lime borosilicate glass, and airtight the most spherical in hollow, particle diameter is at 15 ~ 135 microns
Between, apparent density is at 0.12 ~ 0.60g/cm3Between.
Foaming agent be formic acid, acetic acid, ethanedioic acid, propanoic acid, n-butyric acie, succinic acid, azodicarbonamide, azoaminobenzene,
Unifor, p-toluene sulfonylsemicarbazide, azo-bis-isobutyl cyanide, diisopropyl azodiformate, N, N-dinitroso five
Methine tetramine, N, N-dimethyl-N, N '-dinitroso is to benzene, 4,4 '-OBSH, 3,3 '-disulfonyl hydrazide hexichol
Sulfone, Barium azodicarboxylate, Tetramethylene sulfide (THT), 5-tetrazolium are for the one in benzene, sodium bicarbonate, ammonium carbonate, ammonium nilrite or appoint
Anticipate several mixture.
Polyimide matrix is played potentiation by adding hollow glass microbead by the present invention, and catalyst can accelerate to gather
The formation of acid imide matrix, is simultaneously introduced appropriate free radical and causes cross-linking agent, makes resin matrix produce slight cross-linked effect,
Improve precursor intensity, add nano level nucleator and effectively improve the foam structure of material, increase cell density.
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
In parts by weight:
Pyromellitic acid anhydride 100 parts
4,4 '-diaminodiphenyl ether 100 parts
Dehydrated alcohol 18 parts
DMAC N,N' dimethyl acetamide 600 parts
Triethylamine 0.5 part
Dodecylbenzene sodium sulfonate 20 parts
Hollow glass microbead 10 parts
6 parts of formic acid
Pyromellitic acid anhydride and N,N-dimethylacetamide solvent are joined in reaction bulb and be sufficiently stirred for, treats equal benzene four
After formic acid dianhydride all dissolves, add dehydrated alcohol and be heated to 50 DEG C of backflows, continuing 1 hour acquisition two acid diesters of reaction molten
Liquid；Described two acid diesters solution temperatures are dropped to room temperature, adds 4,4 '-diaminodiphenyl ether, triethylamine and detergent alkylate sulphur
Acid sodium, continues reaction 3 hours, obtains the precursor solution that foams；Hollow glass microbead and formic acid are added in foaming precursor solution, stirs
Mix 5 hours, concentrate and dried, put in mould and carry out heat pre-treatment 60 minutes at 160 DEG C, after foaming, obtain foaming block；
Then it is warmed up to 300 DEG C of imidizations 4 hours, finally obtains hollow beads and strengthen polyimide-based composite foam material.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material test, obtain it apparent
Density is 0.023 g/cm3, foam contraction rate is-20%, 50% compressive strength 0.31Mpa, and impact strength is 60KJ/m2, at 125-
Average sound absorption coefficient in 4000Hz frequency range is 0.47.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material and is curved test, made
Becoming a height of 5 × 1 × 1 batten of length and width, to bending two ends close to right angle, batten does not ruptures.
Embodiment 2
In parts by weight:
3,3 ', 4,4 '-biphenyltetracarboxylic acid dianhydride 100 parts
3,4 '-diaminodiphenyl ether 80 parts
Methanol 11 parts
N,N-dimethylformamide 800 parts
Triethanolamine 2 parts
Fatty glyceride 30 parts
Hollow glass microbead 5 parts
Acetic acid 10 parts
By 3,3 ', 4,4 '-biphenyltetracarboxylic acid dianhydride and N,N-dimethylformamide solvent join in reaction bulb abundant
Stirring, treats 3,3 ', 4, after 4 '-biphenyltetracarboxylic acid dianhydride all dissolves, adds methanol and is heated to 60 DEG C of backflows, continuing reaction
Within 2 hours, obtain two acid diesters solution；Described two acid diesters solution temperatures are dropped to room temperature, adds 3,4 '-diaminodiphenyl ether, three
Ethanolamine and fatty glyceride, continue reaction 7 hours, obtains the precursor solution that foams；Hollow glass microbead and acetic acid are added
In foaming precursor solution, stir 3 hours, concentrate and dried, put in mould and carry out heat pre-treatment 120 minutes at 150 DEG C,
Foaming block is obtained after foaming；Then it is warmed up to 280 DEG C of imidizations 3 hours, finally obtains hollow beads and strengthen polyimide-based
Composite foam material.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material test, obtain it apparent
Density is 0.035 g/cm3, foam contraction rate is-30%, 50% compressive strength 0.35Mpa, and impact strength is 48KJ/m2, at 125-
Average sound absorption coefficient in 4000Hz frequency range is 0.40.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material and is curved test, made
Becoming a height of 5 × 1 × 1 batten of length and width, to bending two ends close to right angle, batten does not ruptures.
Embodiment 3
In parts by weight:
3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride 100 parts
M-diaminobenzene. 50 parts
Normal propyl alcohol 7 parts
N-Methyl pyrrolidone 400 parts
N, N-dimethylethanolamine 1 part
Smooth 5 parts of fatty acid Pyrusussuriensis
Hollow glass microbead 1 part
Ethanedioic acid 15 parts
By 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride and N-Methyl pyrrolidone solvent join in reaction bulb and fully stir
Mix, treat 3,3 ', 4, after 4 '-diphenyl ether tetraformic dianhydride all dissolves, add normal propyl alcohol and be heated to 70 DEG C of backflows, continuing reaction
Within 3 hours, obtain two acid diesters solution；Described two acid diesters solution temperatures are dropped to room temperature, adds m-diaminobenzene., N, N-dimethyl
Ethanolamine and fatty acid Pyrusussuriensis are smooth, continue reaction 4 hours, obtain the precursor solution that foams；Hollow glass microbead and ethanedioic acid are added
Enter and foam in precursor solution, stir 3 hours, concentrate and dried, put in mould and carry out heat pre-treatment 120 points at 150 DEG C
Clock, obtains foaming block after foaming；Then it is warmed up to 280 DEG C of imidizations 3 hours, finally obtains hollow beads and strengthen polyimides
Base composite foam material.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material test, obtain it apparent
Density is 0.035 g/cm3, foam contraction rate is-35%, 50% compressive strength 0.15Mpa, and impact strength is 20KJ/m2, at 125-
Average sound absorption coefficient in 4000Hz frequency range is 0.48.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material and is curved test, made
Becoming a height of 5 × 1 × 1 batten of length and width, to bending two ends close to right angle, batten does not ruptures.
Embodiment 4
In parts by weight:
3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride 100 parts
3,4 '-MDA 80 parts
1 part of butanol
Dimethyl sulfoxide 50 parts
N, N-lutidines 0.01 part
Polysorbate 0.5 part
Hollow glass microbead 1 part
Propanoic acid 5 parts
By 3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride and dimethyl sulfoxide solvent join in reaction bulb and are sufficiently stirred for,
Treat 3,3 ', 4, after 4 '-diphenyl thio-ether tetrformate dianhydride all dissolves, add butanol and be heated to 80 DEG C of backflows, continuing reaction 1 little
Time obtain two acid diesters solution；Described two acid diesters solution temperatures are dropped to room temperature, adds 3,4 '-MDA, N,
N-lutidines and Polysorbate, continue reaction 5 hours, obtains the precursor solution that foams；Hollow glass microbead and propanoic acid are added
Enter and foam in precursor solution, stir 5 hours, concentrate and dried, put in mould and carry out heat pre-treatment 60 points at 180 DEG C
Clock, obtains foaming block after foaming；Then it is warmed up to 290 DEG C of imidizations 2 hours, finally obtains hollow beads and strengthen polyimides
Base composite foam material.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material test, obtain it apparent
Density is 0.033 g/cm3, foam contraction rate is-31%, 50% compressive strength 0.05Mpa, and impact strength is 50KJ/m2, at 125-
Average sound absorption coefficient in 4000Hz frequency range is 0.51.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material and is curved test, made
Becoming a height of 5 × 1 × 1 batten of length and width, to bending two ends close to right angle, batten does not ruptures.
Embodiment 5
In parts by weight:
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 80 parts
Hexafluorodianhydride (6FDA) 20 parts
4,4 '-MDA 200 parts
Polyethylene Glycol 25 parts
N-pyridine oxide 1000 parts
Dimethyl benzylamine 10 parts
PEG-12 100 parts
Hollow glass microbead 18 parts
Succinic acid 30 parts
By 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, hexafluorodianhydride (6FDA) and N-pyridine oxide solvent join in reaction bulb
It is sufficiently stirred for, treats 3,3 ', 4, after 4 '-benzophenone tetracarboxylic dianhydride and hexafluorodianhydride (6FDA) all dissolve, add Polyethylene Glycol and add
Heat, to 50 DEG C of backflows, continues reaction and obtains two acid diesters solution in 1 hour；Described two acid diesters solution temperatures are dropped to room temperature, adds
Entering 4,4 '-MDA, dimethyl benzylamine and PEG-12, continuation is reacted 7 hours, obtains the precursor solution that foams；In Jiang
Empty glass microballoon and succinic acid add in foaming precursor solution, stir 5 hours, concentrate and dried, put in mould at 150 DEG C
Carry out heat pre-treatment 120 minutes, after foaming, obtain foaming block；Then it is warmed up to 350 DEG C of imidizations 3 hours, finally obtains
Hollow beads strengthens polyimide-based composite foam material.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material test, obtain it apparent
Density is 0.030 g/cm3, foam contraction rate is-32%, 50% compressive strength 0.23Mpa, and impact strength is 55KJ/m2, at 125-
Average sound absorption coefficient in 4000Hz frequency range is 0.45.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material and is curved test, made
Becoming a height of 5 × 1 × 1 batten of length and width, to bending two ends close to right angle, batten does not ruptures.
Embodiment 6
In parts by weight:
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 100 parts
4,4 '-MDA 150 parts
Ethanol 5 parts
Polyethylene Glycol 15 parts
Phenol 1000 parts
N, N-dimethyl hexadecyl amine 10 parts
DC-193 100 parts
Hollow glass microbead 20 parts
Diisopropyl azodiformate 30 parts
By 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and phenolic solvent join in reaction bulb and are sufficiently stirred for, and treat 3,
3 ', 4, after 4 '-benzophenone tetracarboxylic dianhydride all dissolves, add ethanol and the mixed liquor of Polyethylene Glycol and be heated to 70 DEG C times
Stream, continues reaction and obtains two acid diesters solution in 2 hours；Described two acid diesters solution temperatures are dropped to room temperature, adds 4,4 '-diamino
Base diphenyl-methane, N, N-dimethyl hexadecyl amine and DC-193, continue reaction 6 hours, obtain the precursor solution that foams；By hollow
Glass microballoon and succinic acid add in foaming precursor solution, stir 3 hours, concentrate and dried, put in mould to enter at 200 DEG C
Row heat pre-treatment 120 minutes, obtains foaming block after foaming；Then 320 DEG C of imidizations 4 hours it are warmed up to, in finally obtaining
Empty microballon strengthens polyimide-based composite foam material.
Embodiment 7
In parts by weight:
3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride 100 parts
3,4 '-MDA 80 parts
O-phenylenediamine 20 parts
1 part of butanol
Dimethyl sulfoxide 50 parts
Phenol 100 parts
N, N-lutidines 0.01 part
Dimethyl benzylamine 1 part
Polysorbate 0.5 part
Smooth 1 part of fatty acid Pyrusussuriensis
Hollow glass microbead 1 part
Propanoic acid 5 parts
Succinic acid 5 parts
By 3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride and dimethyl sulfoxide solvent join in reaction bulb and are sufficiently stirred for,
Treat 3,3 ', 4, after 4 '-diphenyl thio-ether tetrformate dianhydride all dissolves, add butanol and be heated to 90 DEG C of backflows, continuing reaction 2 little
Time obtain two acid diesters solution；Described two acid diesters solution temperatures are dropped to room temperature, adds 3,4 '-MDA, neighbour
Phenylenediamine, N, N-lutidines, dimethyl benzylamine, fatty acid Pyrusussuriensis be smooth and Polysorbate, continues reaction 4 hours, is sent out
Bubble precursor solution；Hollow glass microbead, succinic acid and propanoic acid are added in foaming precursor solution, stir 4 hours, concentrate and be dried
After, put in mould and carry out heat pre-treatment 60 minutes at 170 DEG C, after foaming, obtain foaming block；Then 290 DEG C of imines it are warmed up to
Change 2 hours, finally obtain hollow beads and strengthen polyimide-based composite foam material.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material test, obtain it apparent
Density is 0.033 g/cm3, foam contraction rate is-31%, 50% compressive strength 0.05Mpa, and impact strength is 50KJ/m2, at 125-
Average sound absorption coefficient in 4000Hz frequency range is 0.51.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material and is curved test, made
Becoming a height of 5 × 1 × 1 batten of length and width, to bending two ends close to right angle, batten does not ruptures.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material test, obtain it apparent
Density is 0.028 g/cm3, foam contraction rate is-30%, 50% compressive strength 0.25Mpa, and impact strength is 49KJ/m2, at 125-
Average sound absorption coefficient in 4000Hz frequency range is 0.48.
Hollow glass microbead obtained above is strengthened polyimide-based composite foam material and is curved test, made
Becoming a height of 5 × 1 × 1 batten of length and width, to bending two ends close to right angle, batten does not ruptures.
Claims (9)
1. the preparation method of the hollow beads polyimide-based composite foam material of enhancing, it is characterised in that: include following step
Rapid:
A) aromatic dianhydride being added in organic polar solvent and dissolve, add fatty alcohol, be heated to 50～80 DEG C, backflow 1～3 is little
Time, obtain esterification products；In described esterification products, add aromatic diamines, and continue under the effect of catalyst and surfactant
Continue and carry out reacting 3～7 hours, obtain foam precursors solution；
B) in the foam precursors solution that step A obtains, add hollow glass microbead and foaming agent, stir 3～5 hours, and by it
Put into after concentrating and drying in mould and be heated to 150～200 DEG C of pretreatment, after foaming 60～120 minutes, obtain foaming block；
C) foaming block that step B obtains is heated to 280～350 DEG C and carries out hot imidization process, after 2～4 hours, obtain described
Hollow glass microbead strengthen polyimide-based composite foam material；
In foam precursors solution, in parts by weight, proportioning is as follows for each amounts of components: aromatic dianhydride 100 parts, aromatic diamines 50～200
Part, fatty alcohol 1～25 parts, organic polar solvent 50～1000 parts, catalyst 0.01～10 parts, surfactant 0.5～100
Part, hollow glass microbead 1～20 parts, foaming agent 5～30 parts.
2. hollow beads as claimed in claim 1 strengthens the preparation method of polyimide-based composite foam material, and its feature exists
In: described aromatic dianhydride is pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether four
Formic acid dianhydride, bisphenol A-type diphenyl ether dianhydride, hexafluorodianhydride (6FDA), 3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride, 3,3 ', 4,4 '-two
One or more of benzophenone tetracarboxylic acid dianhydride.
3. hollow beads as claimed in claim 1 strengthens the preparation method of polyimide-based composite foam material, and its feature exists
In: described fatty alcohol is one or more of methanol, ethanol, normal propyl alcohol, isopropanol, capryl alcohol, furfuryl alcohol, Polyethylene Glycol or butanol.
4. hollow beads as claimed in claim 1 strengthens the preparation method of polyimide-based composite foam material, and its feature exists
In: described aromatic diamines is 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, m-diaminobenzene., p-phenylenediamine, adjacent benzene two
Amine, benzidine, 4,4 '-DADPS, 2,6-diamino-pyridine, 1,6-ethylenediamine, siliceous diamidogen, phosphorous diamidogen, three
One or more in amine phenyl benzene, 3,4 '-MDA and 4,4 '-MDA.
5. hollow beads as claimed in claim 1 strengthens the preparation method of polyimide-based composite foam material, and its feature exists
In: described polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, hexamethyl phosphinylidyne
Amine, dimethyl sulfoxide, N-pyridine oxide, N-cyclohexyl pyrrolidone, caprolactam, phenol, a phenol, paracresol, benzoic acid,
One or both in Ketohexamethylene and butanone.
6. hollow beads as claimed in claim 1 strengthens the preparation method of polyimide-based composite foam material, and its feature exists
In: described catalyst is triethanolamine, N, N-dimethylethanolamine, N, N-lutidines, dimethyl benzylamine, N, N-dimethyl
A kind of or the most several mixture of hexadecylamine, triethylenediamine and triethylamine.
7. hollow beads as claimed in claim 1 strengthens the preparation method of polyimide-based composite foam material, and its feature exists
It is that dodecylbenzene sodium sulfonate, fatty glyceride, fatty acid Pyrusussuriensis be smooth, Polysorbate, poly-diformazan in: described surfactant
A kind of or the most several mixture in radical siloxane.
8. hollow beads as claimed in claim 1 strengthens the preparation method of polyimide-based composite foam material, its feature in:
Described hollow glass microbead is soda lime borosilicate glass, airtight the most spherical in hollow, particle diameter 15～135 microns it
Between, apparent density is 0.12～0.60g/cm3Between.
9. hollow beads as claimed in claim 1 strengthens the preparation method of polyimide-based composite foam material, and its feature exists
It is formic acid, acetic acid, ethanedioic acid, propanoic acid, n-butyric acie, succinic acid, azodicarbonamide, azoaminobenzene, right in: described foaming agent
Toluene sulfonyl hydrazide, p-toluene sulfonylsemicarbazide, azo-bis-isobutyl cyanide, diisopropyl azodiformate, N, N-dinitroso five times
Tetramine, N, N-dimethyl-N, N '-dinitroso is to benzene, 4,4 '-OBSH, 3,3 '-disulfonyl hydrazide hexichol
A kind of or the most several in benzene, sodium bicarbonate, ammonium carbonate, ammonium nilrite of sulfone, Barium azodicarboxylate, Tetramethylene sulfide, 5-tetrazolium
The mixture planted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410333015.XA CN104086995B (en) | 2014-07-14 | Hollow microsphere reinforced polyimide-based composite foam material and preparation method thereof |
Applications Claiming Priority (1)
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| KR20140026087A (en) * | 2012-08-24 | 2014-03-05 | 현대이피 주식회사 | Method for manufacturing expandable styrene polymer containing aluminium particles, and expandable styrene polymer produced thereby |
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| KR20140026087A (en) * | 2012-08-24 | 2014-03-05 | 현대이피 주식회사 | Method for manufacturing expandable styrene polymer containing aluminium particles, and expandable styrene polymer produced thereby |
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