CN117603250A - 一种从聚碳酸酯制备异氰酸盐的方法 - Google Patents
一种从聚碳酸酯制备异氰酸盐的方法 Download PDFInfo
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- CN117603250A CN117603250A CN202311358730.4A CN202311358730A CN117603250A CN 117603250 A CN117603250 A CN 117603250A CN 202311358730 A CN202311358730 A CN 202311358730A CN 117603250 A CN117603250 A CN 117603250A
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- Prior art keywords
- isocyanate
- ether
- polycarbonate
- oxide
- sulfide
- Prior art date
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 59
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 29
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- -1 amine compound Chemical class 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 12
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 7
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 6
- UNDXPKDBFOOQFC-UHFFFAOYSA-N 4-[2-nitro-4-(trifluoromethyl)phenyl]morpholine Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1N1CCOCC1 UNDXPKDBFOOQFC-UHFFFAOYSA-N 0.000 claims description 6
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 6
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 claims description 6
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 6
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 5
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 claims description 5
- OSIGJGFTADMDOB-UHFFFAOYSA-N 1-Methoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1 OSIGJGFTADMDOB-UHFFFAOYSA-N 0.000 claims description 4
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 4
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 claims description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 4
- JUVLYFQRUBLHEH-UHFFFAOYSA-N tert-butyl 4-(5-formyl-1,3-thiazol-2-yl)piperazine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCN1C1=NC=C(C=O)S1 JUVLYFQRUBLHEH-UHFFFAOYSA-N 0.000 claims description 4
- AGNFWIZBEATIAK-UHFFFAOYSA-N 4-phenylbutylamine Chemical compound NCCCCC1=CC=CC=C1 AGNFWIZBEATIAK-UHFFFAOYSA-N 0.000 claims description 3
- CGNLNKFBSBFJHY-UHFFFAOYSA-N 5-phenylpentan-1-amine Chemical compound NCCCCCC1=CC=CC=C1 CGNLNKFBSBFJHY-UHFFFAOYSA-N 0.000 claims description 3
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 3
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 claims description 2
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 claims description 2
- LYUQWQRTDLVQGA-UHFFFAOYSA-N 3-phenylpropylamine Chemical compound NCCCC1=CC=CC=C1 LYUQWQRTDLVQGA-UHFFFAOYSA-N 0.000 claims description 2
- ZSXRNISZKBBQRN-UHFFFAOYSA-N 6-phenylhexan-1-amine Chemical compound NCCCCCCC1=CC=CC=C1 ZSXRNISZKBBQRN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YBDQLHBVNXARAU-UHFFFAOYSA-N 2-methyloxane Chemical compound CC1CCCCO1 YBDQLHBVNXARAU-UHFFFAOYSA-N 0.000 claims 2
- RSGAUFBYWCDJLA-UHFFFAOYSA-N anisole;2-propan-2-yloxypropane Chemical compound CC(C)OC(C)C.COC1=CC=CC=C1 RSGAUFBYWCDJLA-UHFFFAOYSA-N 0.000 claims 2
- YBDQLHBVNXARAU-ZCFIWIBFSA-N tetrahydro-2-methyl-2H-pyran Natural products C[C@@H]1CCCCO1 YBDQLHBVNXARAU-ZCFIWIBFSA-N 0.000 claims 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001569 carbon dioxide Substances 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 125000005587 carbonate group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 description 64
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 59
- 238000002360 preparation method Methods 0.000 description 22
- 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 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 13
- 239000004005 microsphere Substances 0.000 description 13
- 150000002989 phenols Chemical class 0.000 description 13
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 11
- 239000010954 inorganic particle Substances 0.000 description 11
- 229920002635 polyurethane Polymers 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 11
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 229910010272 inorganic material Inorganic materials 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- 150000003077 polyols Chemical class 0.000 description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 9
- KXADPELPQCWDHL-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1.COC1=CC=CC=C1 KXADPELPQCWDHL-UHFFFAOYSA-N 0.000 description 9
- 150000002484 inorganic compounds Chemical class 0.000 description 9
- 239000003607 modifier Substances 0.000 description 9
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 239000005751 Copper oxide Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 8
- 239000005083 Zinc sulfide Substances 0.000 description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 8
- 229910000431 copper oxide Inorganic materials 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- 238000003980 solgel method Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 8
- 229910001887 tin oxide Inorganic materials 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 229910052984 zinc sulfide Inorganic materials 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 description 6
- RWCDAKQLMGCVLI-UHFFFAOYSA-N 1-isocyanatoicosane Chemical compound CCCCCCCCCCCCCCCCCCCCN=C=O RWCDAKQLMGCVLI-UHFFFAOYSA-N 0.000 description 6
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 6
- CXALGFGVGGHZGI-UHFFFAOYSA-N 1-isocyanatotetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCN=C=O CXALGFGVGGHZGI-UHFFFAOYSA-N 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 150000001924 cycloalkanes Chemical class 0.000 description 6
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 6
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 6
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 6
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 125000004402 polyphenol group Chemical group 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 5
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 229910021523 barium zirconate Inorganic materials 0.000 description 4
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 4
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 229940117975 chromium trioxide Drugs 0.000 description 4
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 4
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- 229910001947 lithium oxide Inorganic materials 0.000 description 4
- 229910000484 niobium oxide Inorganic materials 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
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- UMPNTZKAZZBQGK-UHFFFAOYSA-N CC(C)N=C=O.C1=CC=C(C=C1)CCN=C=O Chemical compound CC(C)N=C=O.C1=CC=C(C=C1)CCN=C=O UMPNTZKAZZBQGK-UHFFFAOYSA-N 0.000 description 3
- HKLZIJGDTNSHBI-UHFFFAOYSA-N C[SiH](C)C.N=C=O Chemical compound C[SiH](C)C.N=C=O HKLZIJGDTNSHBI-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
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- NIZHERJWXFHGGU-UHFFFAOYSA-N isocyanato(trimethyl)silane Chemical compound C[Si](C)(C)N=C=O NIZHERJWXFHGGU-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- VKSCZTWQDPUHIK-UHFFFAOYSA-N isocyanic acid;trimethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OC)(OC)OC VKSCZTWQDPUHIK-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- OOXKPPOCGCKGOG-UHFFFAOYSA-N 2-methylpropan-1-amine Chemical compound CC(C)CN.CC(C)CN OOXKPPOCGCKGOG-UHFFFAOYSA-N 0.000 description 1
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- PFYBXKBLFFEPRJ-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN.CO[Si](OC)(OC)CCCN PFYBXKBLFFEPRJ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- UGBKOURNNQREPE-UHFFFAOYSA-N azepan-1-amine Chemical compound NN1CCCCCC1 UGBKOURNNQREPE-UHFFFAOYSA-N 0.000 description 1
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- ZSCYJHGJGRSPAB-UHFFFAOYSA-N carbamic acid Chemical compound NC(O)=O.NC(O)=O ZSCYJHGJGRSPAB-UHFFFAOYSA-N 0.000 description 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
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- 150000003053 piperidines Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- DSNYFFJTZPIKFZ-UHFFFAOYSA-N propoxybenzene Chemical compound CCCOC1=CC=CC=C1 DSNYFFJTZPIKFZ-UHFFFAOYSA-N 0.000 description 1
- XFTQRUTUGRCSGO-UHFFFAOYSA-N pyrazin-2-amine Chemical compound NC1=CN=CC=N1 XFTQRUTUGRCSGO-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
- C07C265/04—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
- C07C265/06—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
- C07C265/08—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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Abstract
本发明是一种从聚碳酸酯制备异氰酸盐的方法。该包含以下步骤:(1)提供混合物,该混合物是由聚碳酸酯、胺类或含硅基的胺类的化合物和溶剂组成;和(2)进行转化程序,使上述混合物中的该聚碳酸酯和该胺类或含硅基的胺类的化合物转化生成所述的异氰酸盐;该转化程序包含第一加热步骤和第二加热步骤。本发明至少具有以下优点效果:在制备生产异氰酸盐的过程中不会释放碳酸酯类结构中的二氧化碳,大幅度延长了二氧化碳的碳循环,是兼具安全和环保的绿色制造过程。
Description
本申请是国际申请日为2019年9月5日的国际申请PCT/CN2019/104479进入中国国家阶段的申请的申请号为201980098966.4的名称为“一种有机无机混成材料、其制备方法和其起始原料的制备方法”的发明专利申请的分案申请。
技术领域
本发明是关于一有机无机混成材料。该有机无机混成材料包含的无机化合物的重量百分比是5~50wt.%,且在傅立叶红外光谱图约1050±50cm-1的位置有特征峰。其次,本发明也提供该有机无机混成材料的制备方法及其起始原料组成;其中该起始原料组成之一是异氰酸盐和酚类的缩合物。特别地,该异氰酸盐的制备方法是从碳酸酯类转化生成该异氰酸盐,该方法能够解决聚碳酸酯的废弃物问题,且在转化过程中不会释放二氧化碳,是一具经济价值的绿色环保制造过程。
背景技术
复合材料常应用在高科技产业,特别是有机无机混成材料的相关应用,因其特殊的高阻气性、低吸湿性与分散性,相对于传统材料,其材料性质提升明显,目前已成为光学、医材、电子和特殊涂料等高科技应用的必须材料。
复合材料的往往由有机高分子与无机物形成有机-无机混城材料,然而想对于有机高分子的分子链,无机物粒子或粉末具有相对较大的纳米等级尺寸,加上型态变化后为二维平版或片状材料导入高分子过程中,往往出现有机-无机相分离现象,影响复合材料的性质表现与材料的稳定性。
综上所述,如何设计一种添加剂配方与促进有机-无机物间相容性,同时提升复合材料的整体性质如成膜性、吸水性、或阻气性满足应用需求,一直是本技术领域亟需解决克服的问题。
发明内容
鉴于上述的发明背景,为了符合产业上的要求,本发明的第一目的在于提供一种新颖的有机无机混成材料。创新地,本发明的有机无机混成材料是一借由一新颖的改质剂和导入方法所制成。第二,本发明的有机无机混成材料是一可来自碳酸酯或聚碳酸酯回收物重新使用的绿色原料,因此能够达到材料循环使用的目的。
具体地,上述的有机无机混成材料是由结构式(1)所示的化合物或一异氰酸盐和酚类反应的缩合物或碳酸二苯酯或一无机微球,和一高分子的预聚物借由溶凝胶法所制备得到;以该有机无机混成材料的总重量计,其所包含的无机化合物的重量百分比是5~50wt.%,且在傅立叶红外光谱图中约1050±50cm-1的位置有特征峰。
具体地,本发明所述的改质剂就是上述的结构式(1)所示的化合物。
该结构式(1)中所示的BP为苯酚、多苯酚衍生物或含卤素的苯酚类;X可为(-CH2-)m或-O-;m为1到10的正整数;Y为(H)a、(-OH)b、(-OCH3)c、(-OCH2CH3)d或(-OCH2CH2CH3)e且a+b+c+d+e=3的任何组合。
具体地,上述的苯酚包含双酚A(2,2-bis(4-hydroxyphenyl)propane(bisphenolA))、双酚F(2,2-bis(4-hydroxyphenyl)methane(bisphenol F))、结构式(2)所示的化合物、结构式(3)所示的化合物或结构式(4)所示的化合物。
该结构式(2)所示的化合物如下所示
该结构式(3)所示的化合物如下所示
该结构式(4)所示的化合物如下所示
上述结构式(2)、(3)和(4)所示的R1分别可为碳数10以下的长碳链,环烷烃、卤代烷烃、羰基、磺酰基、亚磺酰基、或双取代多酚基;R2分别可为氢或碳数5以下的长碳链,环烷烃、卤代烷烃、羰基、磺酰基、亚磺酰基、或多酚基;Z分别可为各自独立出现的4以下整数、p≦20。
本发明的有机无机混成材料是采用上述的包含改质剂的反应配方,借此增加有机物和无机物之间的相容性,并借由溶凝胶法制成具有一良好物化性质的有机无机混成材料。
具体地,所述的反应配方的主要组成分别是:(1).上述结构式(1)所示的化合物和一高分子的预聚物;(2).上述异氰酸盐和酚类反应的缩合物和一高分子的预聚物;(3).上述碳酸二苯酯(diphenyl carbonate)和一高分子的预聚物;或(4).上述的无机微球和一高分子的预聚物。
具体地,该高分子包含聚氨酯、环氧树脂或聚亚酰胺;其预聚物的分子量是5,000~50,000Da。
本发明的第二目的在于提供第一目的所提供的有机无机混成材料的制备方法。创新地,本发明所提供的方法还能解决聚碳酸酯废弃物的问题,同时也将二氧化碳继续固定于所制备的有机无机混成材料中,延长了二氧化碳在材料中的碳循环,是一兼具环境友善和高经济价值的方法。
具体地,本发明所述的有机无机混成材料的制备方法包含下述步骤:(1).提供一如结构式(1)所示的化合物、一异氰酸盐和酚类反应的缩合物、碳酸二苯酯或一无机微球;(2)加入上述的如结构式(1)所示的化合物、异氰酸盐和酚类反应的缩合物、碳酸二苯酯或无机微球至一分子量是5,000~50,000的高分子的预聚物,借此得到一混合物,该高分子的预聚物的含量占该混合物的10~60质量%(wt.%);和(3)r借由溶凝胶法,使该混合物的组成份进行水解缩合反应,借此形成所述的有机无机混成材料;以该有机无机混成材料的总重量计,其包含的无机化合物的重量百分比是5~50wt.%,且在傅立叶红外光谱图中约1050±50cm-1位置有特征峰。
具体地,上述的混合物还包含一溶剂,借此使该混合物形成一均匀相。该溶剂包含四氢呋喃(Tetrahydrofuran)、二甲基亚砜(Dimethyl Sulfoxide)、二甲基甲酰胺Dimethylformamide、N-甲基吡咯烷酮(N-Methyl-2-Pyrrolidone)或苯甲醚(Anisole)。
较佳地,该水解缩合反应的温度范围是20~60℃。
本发明的第三目的是提供一种从碳酸酯类制备异氰酸盐的方法。根据本方法制备得到的异氰酸盐能够作为本发明第一目的所述的有机无机混成材料的关键原料之一。特别地,该制备方法能够使用废聚碳酸酯作为反应进料之一,在经过两阶段的加热步骤后,就能够使其转化成为异氰酸盐。因此,本发明第三目的所提供的从碳酸酯类制备异氰酸盐的方法还解决了聚碳酸酯废弃物的处理问题。相较于传统的光气法制备异氰酸盐,本方法是一非光气法,在加热步骤中不会释放二氧化碳,因此,本发明第三目的所述的从碳酸酯类制备异氰酸盐的方法兼具了安全和环境友善的优点,是一具有高度原子效益的异氰酸盐制备方法。
具体地,上述的从碳酸酯类制备异氰酸盐的方法包含以下步骤:提供一混合物,该混合物包含一碳酸酯类、一胺类或含硅基的胺类的化合物和一溶剂;该碳酸酯类包含聚碳酸酯、碳酸二苯酯或其组合物;和进行一转化程序,使上述混合物中的该碳酸酯类和该胺类或含硅基的胺类的化合物转化生成所述的异氰酸盐;该转化程序包含第一加热步骤和第二加热步骤,该第一加热步骤的操作温度范围是40~150℃;该第二加热步骤的操作温度范围是100~250℃,且该第二加热步骤的操作压力范围是在0.0001-400mmHg。
具体地,以该混合物的总重量计,该聚碳酸酯、碳酸二苯酯或其组合物的反应浓度是5~50wt.%。
综上所述,本发明提供的一种有机无机混成材料、其制备方法和其起始原料的制备方法至少具备下述的创新性和优点:(1)本发明提供的有机无机混成材料是借由添加特别设计的改质剂,借此增加有机物和无机物的相容性,进一步提升其材料的整体性质,如防水性或成膜性;(2)本发明提供的有机无机混成材料的制备方法使用的反应配方的组成之一是来自废弃的高分子,如聚碳酸酯,因此上述方法还解决了高分子材料的废弃物问题;和(3)本发明的有机无机混成材料的其中一项起始原料是「异氰酸盐」,其是使用碳酸酯类做起始物之一,经过加热步骤就能转化成异氰酸盐,换言之,本发明还提供了一种无使用光气制备异氰酸盐的方法,且该方法在制备生产异氰酸盐的过程中不会释放碳酸酯类结构中的二氧化碳,大幅度延长了二氧化碳的碳循环,是一兼具安全和环保的绿色制造过程。
附图说明
图1是示范例一的傅立叶红外线(FTIR)光谱图。
图2是示范例二的傅立叶红外线(FTIR)光谱图。
图3是示范例三的傅立叶红外线(FTIR)光谱图。
图4是示范例四的傅立叶红外线(FTIR)光谱图。
图5是示范例五的傅立叶红外线(FTIR)光谱图。
图6是示范例十的傅立叶红外线(FTIR)光谱图。
具体实施方式
有关本发明的前述及其他技术内容、特点与功效,在以下配合参考图式之一较佳实施例的详细说明中将可清楚的呈现。为了能彻底地了解本发明,将在下列的描述中提出详尽的步骤及其组成。显然地,本发明的施行并未限定于该领域的技艺者所熟习的特殊细节。另一方面,众所周知的组成或步骤并未描述于细节中,以避免造成本发明不必要的限制。本发明的较佳实施例会详细描述如下,然而除了这些详细描述之外,本发明还可以广泛地施行在其他的实施例中,且本发明的范围不受限定,其以之后的专利范围为准。
根据本发明的第一实施例,本发明提供一种新颖的有机无机混成材料。创新地,本发明的有机无机混成材料是一借由一新颖的改质剂和导入方法所制成。第二,本发明的有机无机混成材料是一可来自碳酸酯或聚碳酸酯回收物重新使用的绿色原料,因此能够达到材料循环使用的目的。
在一具体实施例,上述的有机无机混成材料是由结构式(1)所示的化合物、一异氰酸盐和酚类反应的缩合物、碳酸二苯酯或一无机微球,和一高分子的预聚物借由溶凝胶法所制成;以该有机无机混成材料的总重量计,其包含的无机化合物的重量百分比是5~50wt.%,且在傅立叶红外光谱图中约1050±50cm-1的位置具有特征峰。
具体地,所述的改质剂是结构式(1)所示的化合物。
该结构式(1)中所示的BP为苯酚、多苯酚衍生物或含卤素的苯酚类;X可为(-CH2-)m或-O-;m为1到10的正整数;Y为(H)a、(-OH)b、(-OCH3)c、(-OCH2CH3)d或(-OCH2CH2CH3)e,且a+b+c+d+e=3;即a,b,c,d,e的加总是等于3,较佳地,其中b,c,d或e是1~3的整数。
具体地,上述的苯酚包含双酚A(2,2-bis(4-hydroxyphenyl)propane(bisphenolA))、双酚F(2,2-bis(4-hydroxyphenyl)methane(bisphenol F))、结构式(2)所示的化合物、结构式(3)所示的化合物或结构式(4)所示的化合物。
具体地,该结构式(2)所示的化合物如下所示。
具体地,该结构式(3)所示的化合物如下所示。
具体地,该结构式(4)所示的化合物如下所示。
上述结构式(2)、(3)和(4)所示的R1分别可为碳数10以下的长碳链,环烷烃、卤代烷烃、羰基、磺酰基、亚磺酰基、或双取代多酚基;R2分别可为氢或碳数5以下的长碳链,环烷烃、卤代烷烃、羰基、磺酰基、亚磺酰基、或多酚基;Z分别可为各自独立出现的4以下整数;和p≦20。
在一较佳实施例,具有结构式(1)的化合物是4-(2-(4-苯酚基)丙烷-2-基)苯基(3-(三甲氧基硅烷基)丙基)胺酯(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate;该化合物另一名称是三甲基甲硅烷氧基氨端聚二甲基硅氧烷或3-伯胺丙基三乙氧硅烷;其中硅氧烷上的胺端基团是伯胺基团,其特性使得上述的有机硅聚合物能够在水性体系中较宽的pH范围内形成净正电荷。
在一具体实施例,该异氰酸盐包含脂肪族异氰酸盐、异氰酸己酯(hexylisocyanate)、1-异氰酸辛酯(octyl isocyanate)、十二烷基异氰酸酯(dodecylisocyanate)、十八烷基异氰酸酯(octadecyl isocyanate)、环己基异氰酸酯(cyclohexylisocyanate)、三甲基硅烷异氰酸酯(trimethylsilyl isocyanate)、异氰酸丙基三乙氧基硅烷(3-(triethoxysilyl)propyl isocyanate),异氰酸丙基三甲氧基硅烷(3-(trimethoxysilyl)propyl isocyanate)、异丙基异氰酸酯phenylethyl isocyanate,甲基异氰酸酯(methyl isocyanate)、乙基异氰酸酯(ethyl isocyanate)、丙基异氰酸酯(propyl isocyanate)、二十烷基异氰酸酯(eicosyl isocyanate)或二十四烷基异氰酸酯(tetracosyl isocyanate)。
在一具体实施例,该无机微球是由结构式(1)所示的化合物或该异氰酸盐和酚类反应的缩合物包覆一无机粒子的表面所构成。
在一具体实施例,该无机粒子包含硅氧化物或硫化物、铝氧化物或硫化物、钛氧化物或硫化物、锗氧化物或硫化物、铁氧化物或硫化物、钡氧化物或硫化物、锌氧化物或硫化物、铜氧化物或硫化物、铬氧化物或硫化物、铌氧化物或硫化物、锰氧化物或硫化物、锡氧化物或硫化物、锂氧化物或硫化物、铈氧化物或硫化物、钴氧化物或硫化物、二氧化硅、二氧化钛、氧化锌、氧化锆、氧化铁、钛酸钡、铌酸锂、硒化镉、氧化铜、锆酸钡、三氧化二铬、五氧化二铌、二氧化铈、钛酸铁、硅化铁、氧化铝/氧化钛混合层、氧化铝/氧化锆混合层、氧化锰、氧化锡、或硫化锌。
在一具体实施例,该无机粒子的粒径范围是20~1,000nm。
在一具体实施例,该高分子包含聚氨酯、环氧树脂或聚亚酰胺。
在一具体实施例,该高分子的预聚物的分子量是5,000~50,000Da。
在一具体实施例,该溶凝胶法是一水解缩合反应。
在一具体实施例,该无机化合物包含硅氧化物或硫化物、铝氧化物或硫化物、钛氧化物或硫化物、锗氧化物或硫化物、铁氧化物或硫化物、钡氧化物或硫化物、锌氧化物或硫化物、铜氧化物或硫化物、铬氧化物或硫化物、铌氧化物或硫化物、锰氧化物或硫化物、锡氧化物或硫化物、锂氧化物或硫化物、铈氧化物或硫化物、钴氧化物或硫化物、二氧化硅、二氧化钛、氧化锌、氧化锆、氧化铁、钛酸钡、铌酸锂、硒化镉、氧化铜、锆酸钡、三氧化二铬、五氧化二铌、二氧化铈、钛酸铁、硅化铁、氧化铝/氧化钛混合层、氧化铝/氧化锆混合层、氧化锰、氧化锡、或硫化锌。
根据本发明的第二实施例,本发明提供一种有机无机混成材料的制备方法,其步骤包含:提供一如结构式(1)所示的化合物、一异氰酸盐和酚类反应的缩合物、碳酸二苯酯或一无机微球;加入上述的如结构式(1)所示的化合物、异氰酸盐和酚类反应的缩合物、碳酸二苯酯或无机微球至一分子量是5,000~50,000的高分子的预聚物,借此得到一混合物,该预聚物的含量占该混合物的10~60质量%;和进行溶凝胶法,使该混合物的组成份进行水解缩合反应,借此形成所述的有机无机混成材料,以该有机无机混成材料的总重量计,其包含的无机化合物的重量百分比是5~50wt.%,且其结构能进行共价键重组反应和在傅立叶红外光谱图中约1050±50cm-1位置具有特征峰。
在一具体实施例,该结构式(1)如下所示。
该结构式(1)中所示的BP为苯酚、多苯酚衍生物或含卤素的苯酚类;X可为(-CH2-)m或-O-;m为1到10的正整数;Y为(H)a、(-OH)b、(-OCH3)c、(-OCH2CH3)d或(-OCH2CH2CH3)e且a+b+c+d+e=3的任何组合。
具体地,上述的苯酚包含双酚A(2,2-bis(4-hydroxyphenyl)propane(bisphenolA))、双酚F(2,2-bis(4-hydroxyphenyl)methane(bisphenol F))、结构式(2)所示的化合物、结构式(3)所示的化合物或结构式(4)所示的化合物。
具体地,该结构式(2)所示的化合物如下所示。
具体地,该结构式(3)所示的化合物如下所示。
具体地,该结构式(4)所示的化合物如下所示。
上述结构式(2)、(3)和(4)所示的R1分别可为碳数10以下的长碳链,环烷烃、卤代烷烃、羰基、磺酰基、亚磺酰基、或双取代多酚基;R2分别可为氢或碳数5以下的长碳链,环烷烃、卤代烷烃、羰基、磺酰基、亚磺酰基、或多酚基;Z分别可为各自独立出现的4以下整数;和p≦20。
在一较佳实施例,具有结构式(1)的化合物是4-(2-(4-苯酚基)丙烷-2-基)苯基(3-(三甲氧基硅烷基)丙基)胺酯(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)pro pyl)carbamate;该化合物另一名称是三甲基甲硅烷氧基氨端聚二甲基硅氧烷或3-伯胺丙基三乙氧硅烷;其中硅氧烷上的胺端基团是伯胺基团,其特性使得上述的有机硅聚合物能够在水性体系中较宽的pH范围内形成净正电荷。
在一具体实施例,该异氰酸盐包含脂肪族异氰酸盐、异氰酸己酯(hexylisocyanate)、1-异氰酸辛酯(octyl isocyanate)、十二烷基异氰酸酯(dodecylisocyanate)、十八烷基异氰酸酯(octadecyl isocyanate)、环己基异氰酸酯(cyclohexylisocyanate)、三甲基硅烷异氰酸酯(trimethylsilyl isocyanate)、异氰酸丙基三乙氧基硅烷(3-(triethoxysilyl)propyl isocyanate),异氰酸丙基三甲氧基硅烷(3-(trimethoxysilyl)propyl isocyanate)、异丙基异氰酸酯phenylethyl isocyanate,甲基异氰酸酯(methyl isocyanate)、乙基异氰酸酯(ethyl isocyanate)、丙基异氰酸酯(propyl isocyanate)、二十烷基异氰酸酯(eicosyl isocyanate)或二十四烷基异氰酸酯(tetracosyl isocyanate)。
在一具体实施例,该无机微球是由结构式(1)所示的化合物或该异氰酸盐和酚类反应的缩合物包覆一无机粒子的表面所构成。
在一具体实施例,该无机粒子包含硅氧化物或硫化物、铝氧化物或硫化物、钛氧化物或硫化物、锗氧化物或硫化物、铁氧化物或硫化物、钡氧化物或硫化物、锌氧化物或硫化物、铜氧化物或硫化物、铬氧化物或硫化物、铌氧化物或硫化物、锰氧化物或硫化物、锡氧化物或硫化物、锂氧化物或硫化物、铈氧化物或硫化物、钴氧化物或硫化物、二氧化硅、二氧化钛、氧化锌、氧化锆、氧化铁、钛酸钡、铌酸锂、硒化镉、氧化铜、锆酸钡、三氧化二铬、五氧化二铌、二氧化铈、钛酸铁、硅化铁、氧化铝/氧化钛混合层、氧化铝/氧化锆混合层、氧化锰、氧化锡、或硫化锌
在一具体实施例,该无机粒子的粒径范围是20~1,000nm。
在一具体实施例,该高分子包含聚氨酯、环氧树脂或聚亚酰胺。
在一具体实施例,该高分子的预聚物的分子量是5,000~50,000Da。
在一具体实施例,该混合物还包含一溶剂或一添加剂。
在一具体实施例,该溶剂包含四氢呋喃(Tetrahydrofuran)、二甲基亚砜(Dimethyl Sulfoxide)、二甲基甲酰胺Dimethylformamide、N-甲基吡咯烷酮(N-Methyl-2-Pyrrolidone)或苯甲醚(Anisole)。
在一具体实施例,该添加剂包含硼酸、磷酸、盐酸、硫酸、硝酸、亚硫酸、乙酸、甲酸、丙酸、碱金属氢氧化物、磷酸钠盐、脂肪族胺类、哌啶及其衍生物、咪唑及其衍生物或含氮杂环状化合物。
在一具体实施例,该水解缩合反应的温度范围是20~60℃。
根据本发明的第三实施例,本发明提供一种从碳酸酯类制备异氰酸盐的方法,其步骤包含:提供一混合物,该混合物包含碳酸酯类、胺类或含硅基的胺类化合物和溶剂;该碳酸酯类包含聚碳酸酯、碳酸二苯酯或其组合物;和进行转化程序,使上述混合物中的该碳酸酯类和该胺类或含硅基的胺类化合物转化生成所述的异氰酸盐;该转化程序包含第一加热步骤和第二加热步骤,该第一加热步骤的操作温度是40~150℃,和该第二加热步骤的操作温度是100~250℃,且该第二加热步骤的操作压力在0.0001-400mmHg。
在一具体实施例,该胺类化合物包含苯甲胺(Benzylamine)、正乙胺(Ethylamine)、苯乙胺(Phenethylamine)、正丙胺(Propylamine)、3-苯基丙胺(3-Phenylpropylamine)、正丁胺(Butylamine)、4-苯基丁胺(4-Phenylbutylamine)、正戊胺(Pentylamine)、5-苯基戊胺(5-Phenylpentylamine)、正己胺(Hexylamine)、6-苯基己胺(6-Phenylhexylamine)、异丁胺(Isobutylamine)胺乙基-1,4-二氮己圜(Aminoethylpiperazine)、甲基六氢吡嗪(1-Methylpiperazine)、N-氨丙基吗啉(3-Morpholinopropylamine)或胺乙基-1,4-二氮己圜(Aminoethylpiperazine)。
在一具体实施例,该含硅基的胺类化合物包含3-氨基丙基三乙氧基硅烷((3-Aminopropyl)triethoxysilane)或3-氨基丙基三甲氧基硅烷((3-Aminopropyl)trimethoxysilane)。
在一具体实施例,以该混合物的总重量计,该聚碳酸酯、碳酸二苯酯或其组合物的反应浓度是5~50wt.%。
在一具体实施例,该溶剂包含二乙醚(Diethyl ether)、二丙醚(Di-n-propylether)、异丙醚(Isopropyl ether)苯甲醚(Anisole)、苯乙醚(Ethoxybenzene)、苯丙醚(Propoxybenzene)、苯丁醚(Butoxybenzene)、邻甲基苯甲醚(2-Methoxytoluene)、间甲基苯甲醚(3-Methoxytoluene)、对甲基苯甲醚(4-Methoxytoluene)、苄基乙基醚(Benzylethyl ether)、二苯醚(Diphenyl ether)、二苄醚(Dibenzyl ether)、四氢呋喃(Tetrahydrofuran)、二氢吡喃(2,3-Dihydropyran)、四氢吡喃(Tetrahydropyran)、2-甲基四氢吡喃(2-Methyl Tetrahydropyran)、苯(Benzene)、甲苯(Toluene)、二甲苯(Xylene)、乙苯(Ethylbenzene)、二乙苯(Diethylbenzene)或环己苯(Cyclohexylbenzene)
综上所述,本发明所提供的有机无机混成材料及其制备方法,借由使用新颖的改质剂和导入方式,大幅增加有机物和无机物的相容性,再利用溶凝胶法制成本发明所述的有机无机混成材料。其次,本发明所述的有机无机混成材料可来自碳酸酯或聚碳酸酯回收物重新使用的绿色原料,因此能够达到材料循环使用的目的。第三,本发明提供的从碳酸酯类制备生成异氰酸盐的方法是一非光气法,且在制备异氰酸盐的过程中不会释放二氧化碳,因此延长了二氧化碳的碳循环,是一兼具安全和环保的制备方法。
以下实验例和示范例是依据上述的发明内容和实施例所述的内容所进行的实验,并据此做为本发明的详细说明。
本发明所述的具有结构式(1)的化合物/改质剂的通用制备步骤
取适量的异氰酸酯和苯酚类溶解在非极性溶剂形成一均匀的混合物,在60~100℃之间进行反应,为了加速反应进行可加入微量有机锡、胺、铋或锌等触媒加速反应。经过十二小时观测苯酚类消耗完毕后,再经过纯化并除去溶剂,然后得到如结构式(1)所示的化合物。
改质剂代表实验例:3-伯胺丙基三乙氧硅烷;(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate的制备方式
异氰酸丙基三乙氧基硅烷5g与双酚A(BPA)4.17g溶在甲苯50毫升,在80~100℃之间进行反应,并加入微量有机锡触媒加速反应。经过十二小时使用薄层层析(thin layerchromatography)观测双酚A消耗完毕后,经过纯化并除去溶剂,然后得到3-伯胺丙基三乙氧硅烷7.8g(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate,反应过程以FT-IR监测1716cm-1的胺基甲酸酯(carbamate)的碳氧双键官能基吸收峰生成,最后利用减压蒸馏除去溶剂后得到产物,并进行1H-NMR分析。
FTIR(KBr):1716cm-1,3350cm-1(NH,urethane),950cm-1(Si-O);1H-NMR(400MHz,d-DMSO):δ(ppm)=0.5(t,6H),1.2(t,27H),1.5(t,18H),3.0(m,6H),3.8(m,18H),6.7(m,6H),7.0(m,12H),7.2(m,6H),7.7(t,3H),9.2(s,3H)。
上述的制备具有结构式(1)的化合物的通用步骤所使用的异氰酸酯包含脂肪族的异氰酸酯、单独或混合使用脂肪族异氰酸盐、异氰酸己酯(hexyl isocyanate)、1-异氰酸辛酯(octyl isocyanate)、十二烷基异氰酸酯(dodecyl isocyanate)、十八烷基异氰酸酯(octadecyl isocyanate)、环己基异氰酸酯(cyclohexyl isocyanate)、三甲基硅烷异氰酸酯(trimethylsilyl isocyanate)、异氰酸丙基三乙氧基硅烷(3-(triethoxysilyl)propylisocyanate),异氰酸丙基三甲氧基硅烷(3-(trimethoxysilyl)propyl isocyanate)、异丙基异氰酸酯phenylethyl isocyanate,甲基异氰酸酯(methyl isocyanate)、乙基异氰酸酯(ethyl isocyanate)、丙基异氰酸酯(propyl isocyanate)、二十烷基异氰酸酯(eicosylisocyanate)或二十四烷基异氰酸酯(tetracosyl isocyanate)。
上述的制备具有结构式(1)的化合物的通用步骤所使用的苯酚类可来自双酚或多酚类,该苯酚包含双酚A(2,2-bis(4-hydroxyphenyl)propane(bisphenol A))、双酚F(2,2-bis(4-hydroxyphenyl)methane(bisphenol F))、结构式(2)所示的化合物、结构式(3)所示的化合物或结构式(4)所示的化合物。
本发明所述的无机微球的通用制备步骤
使结构式(1)的含硅氧烷官能基的化合物与无机物颗粒表面的氢氧基(-OH)、胺基(-NH2)或硫醇基(-SH)进行缩合反应,借此将含氨基甲酸酯官能基的结构式(1)的化合物键结固定在无机粒子的表面上,借此形成本发明所述的无机微球,该无机微球是一表面官能基化的无机粒子。其次,该无机粒子的粒径范围20~1,000nm;具体地,该无机粒子包含硅氧化物或硫化物、铝氧化物或硫化物、钛氧化物或硫化物、锗氧化物或硫化物、铁氧化物或硫化物、钡氧化物或硫化物、锌氧化物或硫化物、铜氧化物或硫化物、铬氧化物或硫化物、铌氧化物或硫化物、锰氧化物或硫化物、锡氧化物或硫化物、锂氧化物或硫化物、铈氧化物或硫化物、钴氧化物或硫化物、二氧化硅、二氧化钛、氧化锌、氧化锆、氧化铁、钛酸钡、铌酸锂、硒化镉、氧化铜、锆酸钡、三氧化二铬、五氧化二铌、二氧化铈、钛酸铁、硅化铁、氧化铝/氧化钛混合层、氧化铝/氧化锆混合层、氧化锰、氧化锡、或硫化锌。
本发明所述的有机无机混成材料的通用制备步骤
提供如上述的结构式(1)所示的化合物、该异氰酸盐和酚类反应的缩合物、碳酸二苯酯或上述的无机微球;,特别地,上述的具有胺基甲酸酯官能基(carbamate)的原料与含羰基(carbonyl)的高分子具有良好相容性;提供一高分子预聚物;该高分子预聚物包含聚氨酯(polyurethanes)、环氧树酯(epoxy resins)、聚亚酰胺或聚酰胺酸(Polyamic acid;PAA)等分子量5,000~50,000的高分子的预聚物;将上述结构式(1)的化合物直接加入上述的高分子预聚物当中,并透过红外线光谱仪监控,可在950cm-1观察到Si-O-R的官能基左右的吸收锋出现,将上述包含结构式(1)所示的化合物与上述的高分子预聚物的混合溶液以溶剂进行稀释后,加入0.1~5.0重量比的盐酸、硝酸或醋酸等酸性触媒并搅拌至均匀,成膜烘干并置入60℃的烘箱,24~48小时完成溶胶凝胶反应,然后在真空烘箱中进行干燥去除剩下多余的溶剂。反应完成后950cm-1的Si-O-R官能基消失,重新生成1000-1100cm-1的Si-O-Si官能基,借此完成本发明所述的有机/无机混成材料的制备。
聚氨酯预聚物的通用制备步骤
上述的聚氨酯的预聚物的是利用高分子聚合反应制备而成。具体地,将各种的二异氰酸酯酸酯,如二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)或1,6-己二异氰酸酯(HDI);和聚多元醇如聚醚二醇(PEG)、聚四氢呋喃二醇(PTMEG)、聚己内酯多元醇(PCL)、或聚碳酸酯二醇(PCPO)在60-80℃之间进行缩合聚合反应,反应过程可加入少量溶剂如二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)、四氢呋喃(Tetrahydrofuran)、二甲基亚砜(Dimethyl Sulfoxide)或苯甲醚(Anisole)帮助反应进行,约半小时后完成预聚反应,此时可在FT-IR光谱图上看到胺基甲酸酯官能基的特征峰。
根据上述的聚氨酯的预聚物和有机无机混成材料的通用制备步骤所制备而成的各种含胺基甲酸酯有机无机混成材料如表一所示;其中所列二异氰酸酯和多元醇是聚氨酯预聚物的反应配方;硅(Silica)是代表制备所得到的有机无机混成材料的无机化合物含量。
表一
a)多元醇后方数字表分子量,如聚醚类多元醇2000代表分子量为2000g/mol的聚醚多元醇;b)硅(%)表示整体有机无机混成材料当中无机化合物所占重量百分比例;c)有机无机混成材料平面上水接触角;X表示成膜性质不佳;○表示成膜性质普通;◎表示成膜性质优良。
示范例一为二苯甲烷二异氰酸酯MDI与聚酯类多元醇PCL2000预聚合的聚氨酯,示范例一是未添加结构式(1)的实验对照组,根据图1所示的FT-IR图谱,在1737cm-1左右位置观察到胺基甲酸酯官能基的特征峰。示范例二为MDI与聚酯类多元醇PCL2000聚合的聚氨酯预聚物,然后将结构式(1)所示的化合物或代表实验例所合成的化合物加入上述的MDI与聚酯类多元醇PCL2000聚合的聚氨酯预聚物,借此形成一混合溶液,并以溶剂进行稀释后,加入0.1~5.0重量比的盐酸、硝酸或醋酸等酸性触媒并搅拌至均匀,成膜烘干并置入60℃的烘箱,24~48小时完成溶胶凝胶反应,然后在真空烘箱中进行干燥去除剩下多余的溶剂。反应完成后950cm-1的Si-O-R官能基消失,重新生成Si-O-Si官能基,在FTIR光谱1041cm-1的位置具有特征峰,其光谱图如图2所示,借此完成本发明所述的有机/无机混成材料的制备。示范例三为MDI与聚碳酸酯多元醇PCPO2000预聚合的聚氨酯,示范例三未添加结构式(1),如图3所示,其FTIR图谱在1742cm-1左右观察到胺基甲酸酯和碳酸酯重迭的C=O(carbonyl)官能基。示范例四是MDI与聚碳酸酯多元醇PCPO2000预聚合的聚氨酯,加入结构式(1)所示的化合物或代表实验例所合成的化合物,经由和上述示范例二相同的溶胶凝胶反应步骤和制备程序,可以在FTIR图谱观察到1085cm-1左右观察到新生成的Si-O-Si官能基,所得到的有机/无机混成材料的FTIR图谱如图4所示。
示范例五为MDI与聚醚类多元醇PTMEG2000聚合的聚氨酯,示范例五未添加结构式(1),在FTIR图谱1732cm-1左右看到胺基甲酸酯官能基的特征峰,其FTIR图谱如图5所示。示范例六至十是加入结构式(1)所示的化合物或代表实验例的化合物与上述的高分子预聚物的混合溶液以溶剂进行稀释后,再加入尺寸为20~1,000nm的硅基纳米微球,加入0.1~5.0重量比的等酸性触媒并搅拌至均匀,成膜烘干并置入60℃的烘箱,24~48小时完成溶胶凝胶反应,然后在真空烘箱中进行干燥去除剩下多余的溶剂。反应完成后FTIR图谱位置950cm-1的Si-O-R官能基消失,然后生成(示范例十)1095cm-1的Si-O-Si官能基,借此得到本发明所述的有机无机混成材料,其FTIR图谱如图6所示。
上述示范例一、三、五是没有加入结构式(1)所示的化合物或代表实验例的化合物的实验对照组;上述示范例二、四、六至十四是各种的二异氰酸酯和多元醇所形成的聚氨酯的预聚物和结构式(1)所示化合物或代表实验例的化合物(3-伯胺丙基三乙氧硅烷;(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl(3-(trimethoxysilyl)propyl)carbamate)根据上述的通用步骤所制备得到的有机无机混成材料。
据此,本发明所述的具有胺基甲酸酯官能基(carbamate)的化合物能够有效地协助无机物与高分子预聚物相容,然后借由溶凝胶法制备得到本发明所述的有机无机混成材料,其所包含的无机化合物的重量百分比是5~50wt.%;第二,本发明的有机无机混成材料的平面上水接触角通常在80~90度之间,其具体意义是本发明的有机无机混成材料的抗水性或抗湿润性大幅提升,因此本发明所提供的有机无机混成材料特别利于作为绝缘、密封防水或结构性材料。
本发明所述的由碳酸酯类制备异氰酸酯的代表实验例
3-氨基丙基三甲氧基硅烷((3-Aminopropyl)trimethoxysilane)和聚碳酸酯混合在一溶剂中,该溶剂包含二乙醚(Diethyl ether)、二丙醚(Di-n-propyl ether)、异丙醚(Isopropyl ether)苯甲醚(Anisole)、苯乙醚(Ethoxybenzene)、苯丙醚(Propoxybenzene)、苯丁醚(Butoxybenzene)、邻甲基苯甲醚(2-Methoxytoluene)、间甲基苯甲醚(3-Methoxytoluene)、对甲基苯甲醚(4-Methoxytoluene)、苄基乙基醚(Benzylethyl ether)、二苯醚(Diphenyl ether)、二苄醚(Dibenzyl ether)、四氢呋喃(Tetrahydrofuran)、二氢吡喃(2,3-Dihydropyran)、四氢吡喃(Tetrahydropyran)、2-甲基四氢吡喃(2-Methyl Tetrahydropyran)、苯(Benzene)、甲苯(Toluene)、二甲苯(Xylene)、乙苯(Ethylbenzene)、二乙苯(Diethylbenzene)或环己苯(Cyclohexylbenzene)。先加热至80~90℃反应,然后再升温至200~250℃,同时控制高温的操作压力是在真空下,其压力区间是0.0001-400mmHg,最后得到异氰酸丙基三乙氧基硅烷的异氰酸酯,其FTIR图谱在2260cm-1观察到异氰酸酯的特征吸收峰。
上述的由碳酸酯类制备异氰酸酯的代表实验例所使用的3-氨基丙基三甲氧基硅烷((3-Aminopropyl)trimethoxysilane)可以使用其他的胺类化合物替代,借此制成具有各种烷基或官能基的异氰酸酯,上述的其他的胺类化合物包含脂肪族胺类,如苯甲胺(Benzylamine)、正乙胺(Ethylamine)、苯乙胺(Phenethylamine)、正丙胺(Propylamine)、3-苯基丙胺(3-Phenylpropylamine)、正丁胺(Butylamine)、4-苯基丁胺(4-Phenylbutylamine)、正戊胺(Pentylamine)、5-苯基戊胺(5-Phenylpentylamine)、正己胺(Hexylamine)、6-苯基己胺(6-Phenylhexylamine)、异丁胺(Isobutylamine)胺乙基-1,4-二氮己圜(Aminoethylpiperazine)、甲基六氢吡嗪(1-Methylpiperazine)、N-氨丙基吗啉(3-Morpholinopropylamine)或胺乙基-1,4-二氮己圜(Aminoethylpiperazine)或含硅基胺类化合物,如3-氨基丙基三乙氧基硅烷((3-Aminopropyl)triethoxysilane)。
以上虽以特定实验例说明本发明,但并不因此限定本发明的范围,只要不脱离本发明的要旨,熟悉本技艺者了解在不脱离本发明的意图及范围下可进行各种变形或变更。此外,摘要部分和标题仅是用来辅助专利文件搜寻之用,并非用来限制本发明的权利范围。
Claims (7)
1.一种从聚碳酸酯制备异氰酸盐的方法,其特征在于,其包含以下步骤:
(1)提供混合物,该混合物是由聚碳酸酯、胺类或含硅基的胺类的化合物和溶剂组成;和
(2)进行转化程序,使上述混合物中的该聚碳酸酯和该胺类或含硅基的胺类的化合物转化生成所述的异氰酸盐;该转化程序包含第一加热步骤和第二加热步骤,该第一加热步骤的操作温度是40~150℃,和该第二加热步骤的操作温度是100~250℃,且该第二加热步骤的操作压力是在0.0001-400mmHg。
2.根据权利要求1所述的从聚碳酸酯制备异氰酸盐的方法,其特征在于:该胺类的化合物包含苯甲胺、正乙胺、苯乙胺、正丙胺、3-苯基丙胺、正丁胺、4-苯基丁胺、正戊胺、5-苯基戊胺、正己胺、6-苯基己胺、异丁胺胺乙基-1,4-二氮己圜、甲基六氢吡嗪、N-氨丙基吗啉或胺乙基-1,4-二氮己圜。
3.根据权利要求1所述的制备异氰酸盐的方法,其特征在于:该含硅基的胺类的化合物包含3-氨基丙基三乙氧基硅烷或3-氨基丙基三甲氧基硅烷。
4.根据权利要求1所述的从聚碳酸酯制备异氰酸盐的方法,其特征在于:以该混合物的总重量计,该聚碳酸酯的反应浓度是5~50wt.%。
5.根据权利要求1所述的从聚碳酸酯制备异氰酸盐的方法,其特征在于:该溶剂包含二乙醚、二丙醚、异丙醚苯甲醚、苯乙醚、苯丙醚、苯丁醚、邻甲基苯甲醚、间甲基苯甲醚、对甲基苯甲醚、苄基乙基醚、二苯醚、二苄醚、四氢呋喃、二氢吡喃、四氢吡喃、2-甲基四氢吡喃、苯、甲苯、二甲苯、乙苯、二乙苯或环己苯。
6.一种制备异氰酸丙基三乙氧基硅烷的异氰酸酯的方法,其特征在于,其包含以下步骤:
(1)使3-氨基丙基三甲氧基硅烷和聚碳酸酯混合在溶剂中;
(2)加热至80~90℃反应;和
(3)升温至200~250℃,和在压力区间0.0001-400mmHg下反应,借此得到所述的异氰酸丙基三乙氧基硅烷的异氰酸酯。
7.根据权利要求6所述的制备异氰酸丙基三乙氧基硅烷的异氰酸酯的方法,其特征在于:该溶剂包含二乙醚、二丙醚、异丙醚苯甲醚、苯乙醚、苯丙醚、苯丁醚、邻甲基苯甲醚、间甲基苯甲醚、对甲基苯甲醚、苄基乙基醚、二苯醚、二苄醚、四氢呋喃、二氢吡喃、四氢吡喃、2-甲基四氢吡喃、苯、甲苯、二甲苯、乙苯、二乙苯或环己苯。
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CN104558501B (zh) * | 2014-12-15 | 2017-11-14 | 北京天山新材料技术有限公司 | 一种紫外线和湿气双重固化型改性聚氨酯及其制备方法 |
CN108250406B (zh) * | 2016-12-29 | 2021-06-15 | 大东树脂化学股份有限公司 | 含软链段的多胺基甲酸酯、多元异氰酸酯、胺甲酸酯预聚物及聚胺甲酸酯弹性体及制备方法 |
CN106928659A (zh) * | 2017-03-15 | 2017-07-07 | 中南大学 | 一种高耐磨光固化芳醚基环氧丙烯酸酯/纳米二氧化硅复合材料及其制备方法 |
CN107324333B (zh) * | 2017-06-14 | 2019-09-03 | 万华化学集团股份有限公司 | 一种整体式吸附材料、制备方法及使用其降低二异氰酸酯色数的方法 |
CN107384277B (zh) * | 2017-07-26 | 2020-08-25 | 上海维凯光电新材料有限公司 | 用于太阳能背板多层膜粘结的双组分胶黏剂 |
CN108034352B (zh) * | 2017-12-27 | 2020-02-07 | 科顺防水科技股份有限公司 | 适用于pc建筑的改性硅酮密封胶用底涂剂及其制备方法 |
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