CN115210286B - 环氧树脂、其原料组合物和制备方法 - Google Patents
环氧树脂、其原料组合物和制备方法 Download PDFInfo
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- CN115210286B CN115210286B CN202080097257.7A CN202080097257A CN115210286B CN 115210286 B CN115210286 B CN 115210286B CN 202080097257 A CN202080097257 A CN 202080097257A CN 115210286 B CN115210286 B CN 115210286B
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- epoxy resin
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- siloxane
- hardener
- diamine
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 115
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 115
- 239000000203 mixture Substances 0.000 title abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002994 raw material Substances 0.000 title abstract description 6
- -1 phosphonium halide Chemical class 0.000 claims description 36
- 150000004985 diamines Chemical class 0.000 claims description 33
- 239000004848 polyfunctional curative Substances 0.000 claims description 31
- 239000004593 Epoxy Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001979 organolithium group Chemical group 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 10
- 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 abstract description 5
- 229930185605 Bisphenol Natural products 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- 239000004721 Polyphenylene oxide Substances 0.000 description 13
- 229920000570 polyether Polymers 0.000 description 13
- 150000002170 ethers Chemical class 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
- 150000004984 aromatic diamines Chemical class 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 7
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 150000008282 halocarbons Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000005462 imide group Chemical group 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 125000000468 ketone group Chemical group 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000004402 polyphenol group Chemical group 0.000 description 4
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 4
- 125000000101 thioether group Chemical group 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical group CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- OZMJXAQDMVDWBK-UHFFFAOYSA-N carbamic acid;ethyl carbamate Chemical group NC(O)=O.CCOC(N)=O OZMJXAQDMVDWBK-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- OSIGJGFTADMDOB-UHFFFAOYSA-N 1-Methoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1 OSIGJGFTADMDOB-UHFFFAOYSA-N 0.000 description 1
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 1
- YBDQLHBVNXARAU-UHFFFAOYSA-N 2-methyloxane Chemical compound CC1CCCCO1 YBDQLHBVNXARAU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- XVEUJTIZHZIHJM-UHFFFAOYSA-N a828782 Chemical group CCOC(N)=O.CCOC(N)=O XVEUJTIZHZIHJM-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HZZUMXSLPJFMCB-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;acetate Chemical compound CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 HZZUMXSLPJFMCB-UHFFFAOYSA-M 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000000854 selenoether group Chemical group 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- YBDQLHBVNXARAU-ZCFIWIBFSA-N tetrahydro-2-methyl-2H-pyran Natural products C[C@@H]1CCCCO1 YBDQLHBVNXARAU-ZCFIWIBFSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
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Abstract
提供一种环氧树脂、其原料组合物和制备方法。该环氧树脂是具有双胺基甲酸酯基团的双酚基缩水甘油醚，由硬化单剂型环氧树脂原料组合物制得。
Description
技术领域
本发明是关于一种环氧树脂、其制造组成和制备方法。特别地，该环氧树脂是双胺基甲酸酯基团的双酚基缩水甘油醚(glycidyl ether of diphenolic bis-carbamate)。该制造组成是单剂型环氧树脂组成。上述的环氧树脂是借由硬化该单剂型环氧树脂组成所制成。
背景技术
环氧树脂广泛应用在各种产业领域，如金属涂布、电子元件、油漆工业和接着工业。一般而言，没有经过硬化的环氧树脂的机械性质、化学惰性和热抵抗性都不佳。现有习知的胺类硬化剂和环氧树脂的硬化反应都是在常温就发生，为了避免环氧树脂和胺类硬化剂在常温就立即反应，环氧树脂和胺类硬化剂必须分开加入，也就是传统的二液型环氧树脂组成。基于优化环氧树脂组成的加工性，避免复杂的包装和使用程序。单剂型环氧树脂组成是亟需研究开发的领域。
综上所述，在现今环氧树脂相关产业，对于开发能提升机械性质的环氧树脂和和热稳定性佳的单剂型环氧树脂组成及其应用实为亟待解决和研发的重要课题。
发明内容
根据以上的发明背景，为了符合产业的需求，本发明的第一目的在于提供一种具有如式(1)所示结构的环氧树脂。具体地，该环氧树脂是具有双胺基甲酸酯基团的双酚基缩水甘油醚(glycidyl ether of diphenolic bis-carbamate)，其具有良好的热稳定性和机械性质。优选地，上述的环氧树脂具有超过250％的拉伸率(strain％)。
式(1)
R是源自于脂肪族二胺、芳香族二胺、硅氧烷基二胺或聚醚二胺；Ep具有如式(2)所示的结构，和(A)n是选自下列群组之一或其组合：结构式(3)、结构式(4)、结构式(5)、结构式(6)、结构式(7)和结构式(8)。
其中R1包含碳数1～5的环状烃基、碳数6～10的多酚基、碳数1～20的直链烃基、碳数1～20的卤代烃基、亚胺基、酰胺基、膦酸酯基、膦基、硅烷基、醚基、硫醚基、磺酰基、硒醚基、酮基、醛基、羧酸基或酯基。
R2包含氢原子、卤素、烷基、烯基、炔基、烃基、氢氧基、胺基、硝基或碳数1～5的烷氧基。
Z和n是分别独立的1～5的整数；m是0～5的整数；和X是1～25的整数。
本发明的第二目的在于提供一种单剂型环氧树脂组成，该单剂型环氧树脂组成是用于制备如第一目的所述的环氧树脂的剂型反应配方；其包含结构如式(9)所示的硬化剂，和环氧化合物；该结构如式(9)所示的硬化剂对该环氧化合物的重量比例是0.5～20；其中R1是源自于脂肪族二胺、芳香族二胺、硅氧烷基二胺或聚醚二胺；和m是选自0～5的整数。
具体地，上述的单剂型环氧树脂组成还包含添加剂，该添加剂包括改质剂、加速剂、活化剂、触媒或其组合。该添加剂功能是催化硬化反应或使硬化后生成的环氧树脂具有交联网状结构。
本发明的单剂型环氧树脂组成的内容物，如硬化剂和环氧化合物，其具有良好的相容性，因此不会有相分离或内容物沉淀的现象发生，所以具有优异的储存安定性。
本发明的第三目的在于提供一种具有胺基甲酸酯(carbamate)基团的环氧树脂的制备方法，其包含如下步骤。
步骤一：提供硬化剂，其结构如式(9)所示，和环氧化合物；该硬化剂对该环氧化合物的重量比例是0.5～20；其中R1是源自于脂肪族二胺、芳香族二胺、硅氧烷基二胺或聚醚二胺；和m是选自1～5的整数。
步骤二：使该硬化剂和该环氧化合物在溶媒中形成环氧树脂预聚物。
步骤三：进行硬化反应，使该环氧树脂预聚物形成所述的具有胺基甲酸酯基团的环氧树脂。
上述的具有胺基甲酸酯(carbamate)基团的环氧树脂的制备方法中的硬化剂可以使用废弃高分子做原料，如废聚碳酸酯，所以该环氧树脂的制备方法还能处理废弃高分子污染环境的问题，达到循环经济的目的，且在制备过程中不会释放二氧化碳，有效的延长的二氧化碳的碳循环。
具体的，上述的硬化反应的反应温度是150～350℃。
综上所述，本发明的技术相较于现有习知技术至少具有如下所述的技术特征和优点：(1)提供具有良好热稳定性和机械性质的环氧树脂；(2)提供具有良好内容物相容性和储存安定性的单剂型环氧树脂组成(配方)；和(3)提供环境友善的具有胺基甲酸酯(carbamate)基团的环氧树脂的制备方法。
附图说明
[图1]单剂型环氧树脂组成E1DP1制成的环氧树脂的氢核磁共振光谱图。
[图2]单剂型环氧树脂组成E1DP1制成的环氧树脂的傅立叶红外光谱图。
[图3]单剂型环氧树脂组成E1DP2制成的环氧树脂的傅立叶红外光谱图。
[图4]单剂型环氧树脂组成E1DP3制成的环氧树脂的傅立叶红外光谱图。
[图5]单剂型环氧树脂组成E1BPA的热示差扫描曲线图。
[图6]单剂型环氧树脂组成E1DP1的热示差扫描曲线图。
[图7]单剂型环氧树脂组成E1DP2的热示差扫描曲线图。
[图8]单剂型环氧树脂组成E1DP3的热示差扫描曲线图。
[图9]单剂型环氧树脂组成E2DP1的热示差扫描曲线图。
[图10]单剂型环氧树脂组成E2DP2的热示差扫描曲线图。
[图11]单剂型环氧树脂组成E2DP3的热示差扫描曲线图。
[图12]单剂型环氧树脂组成E2DP3制成的环氧树脂的热示差扫描曲线图。
[图13]单剂型环氧树脂组成E1DP2制成的环氧树脂的热示差扫描曲线图。
[图14]单剂型环氧树脂组成E2DP2制成的环氧树脂的热示差扫描曲线图。
[图15]单剂型环氧树脂组成E2S430、E1DP3和E2DP3分别制成的环氧树脂的拉伸强度和拉伸率的曲线图。
具体实施方式
本发明的第一实施例在于提供一种具有如式(1)所示结构的环氧树脂。具体地，该环氧树脂是具有双胺基甲酸酯基团的双酚基缩水甘油醚(glycidyl ether of diphenolicbis-carbamate)，其具有良好的热稳定性和机械性质。
式(1)
在一具体实施例，R是源自于脂肪族二胺、芳香族二胺、硅氧烷基二胺或聚醚二胺；m是0～5的整数；和X是1～25的整数。
在一具体实施例，Ep具有如式(2)所示的结构，和(A)n是选自下列群组之一或其组合：结构式(3)、结构式(4)、结构式(5)、结构式(6)、结构式(7)和结构式(8)
在一具体实施例，其中R1包含碳数1～5的环状烃基、碳数6～10的多酚基、碳数1～20的直链烃基、碳数1～20的卤代烃基、亚胺基、酰胺基、膦酸酯基、膦基、硅烷基、醚基、硫醚基、磺酰基、硒醚基、酮基、醛基、羧酸基或酯基。
在一具体实施例，R2包含氢原子、卤素、烷基、烯基、炔基、烃基、氢氧基、胺基、硝基或碳数1～5的烷氧基。
在一具体实施例，Z和n是分别独立的1～5的整数；m是0～5的整数；和X是1～25的整数。
在一具体实施例，该脂肪族二胺包含碳数2～40的直链脂肪族二胺或碳数2～40的支链脂肪族二胺。较佳地，该碳数2～40的直链脂肪族二胺是1,4-丁二胺、1,5-戊二胺或1,6-己二胺。
在一具体实施例，该芳香族二胺包含邻苯二胺、间苯二胺、对苯二胺、4,4'–二氨基二苯醚或其组合。
在一具体实施例，该硅氧烷基二胺的分子量是150～10,000Da。
该硅氧烷基二胺具有的硅氧烷基团的结构如式(10)所式。
在一具体实施例，该聚醚二胺的重量平均分子量是100～5,000Da。较佳的，该聚醚二胺是JEFFAMINE聚醚二胺。
本发明的第二实施例在于提供一种单剂型环氧树脂组成，该单剂型环氧树脂组成是用于制备如第一实施例所述的环氧树脂的剂型反应配方；其包含结构如式(9)所示的硬化剂，和环氧化合物；该结构如式(9)所示的硬化剂对该环氧化合物的重量比例是0.5～20。
在一具体实施例，R1是源自于脂肪族二胺、芳香族二胺、硅氧烷基二胺或聚醚二胺；m是0～5的整数。
上述的单剂型环氧树脂组成还包含添加剂，该添加剂包括改质剂、加速剂、活化剂、触媒或其组合。该添加剂功能是催化硬化反应或使硬化后生成的环氧树脂具有交联网状结构。
该添加剂包含磷系触媒或氮系触媒。
在一具体实施例，该磷系触媒包括季磷卤化物触媒(methyl或ethyltriphenylphosphonium iodide或bromide)、有机磷触媒(triphenylphosphine或tributylphosphine)、羧酸季磷塩(ethyltriphenylphosphonium acetate)、磷酸酯(formylmethylenetriphenylphosphorane)或季磷卤化塩前驱物(formylmethyltriphenylphosphonium chloride)。
在一具体实施例，该氮系触媒包括三级胺，较佳地该三级胺是三甲胺、三乙胺、三乙醇胺、三异丙醇胺、苯甲基二甲胺、二甲基胺基-甲基酚或其衍生物。
在一具体实施例，上述的添加剂包含季磷卤化物触媒、有机磷触媒、羧酸季磷塩、磷酸酯、三级胺、羧酸锡化物、有机锂盐、咪唑或苯咪唑。
在一具体实施例，该脂肪族二胺包含碳数2～40的直链脂肪族二胺或碳数2～40的支链脂肪族二胺。较佳地，该碳数2～40的直链脂肪族二胺是1,4-丁二胺、1,5-戊二胺或1,6-己二胺。
在一具体实施例，该芳香族二胺包含邻苯二胺、间苯二胺、对苯二胺、4,4'–二氨基二苯醚或其组合。
在一具体实施例，该硅氧烷基二胺的分子量是150～10,000Da。
该硅氧烷基二胺具有的硅氧烷基团的结构如式(10)所式。
在一具体实施例，该聚醚二胺的重量平均分子量是100～5,000Da。较佳的，该聚醚二胺是JEFFAMINE聚醚二胺。
在一具体实施例，该环氧化合物具有如式(2)所示的结构，和(A)n是选自下列群组之一或其组合：结构式(3)、结构式(4)、结构式(5)、结构式(6)、结构式(7)和结构式(8)。
在一具体实施例，其中R1包含碳数1～5的环状烃基、碳数6～10的多酚基、碳数1～20的直链烃基、碳数1～20的卤代烃基、亚胺基、酰胺基、膦酸酯基、膦基、硅烷基、醚基、硫醚基、磺酰基、硒醚基、酮基、醛基、羧酸基或酯基。
在一具体实施例，R2包含氢原子、卤素、烷基、烯基、炔基、烃基、氢氧基、胺基、硝基或碳数1～5的烷氧基。
在一具体实施例，Z和n是分别独立的1～5的整数。
较佳的，上述的环氧化合物包含双酚A的聚缩水甘油醚衍生物、聚醚的聚缩水甘油醚衍生物或酚醛树脂的聚缩水甘油醚衍生物。具体的，该双酚A的聚缩水甘油醚衍生物是双酚A二缩水甘油醚(bisphenol A diglycidyl ether(Trade name DER332))；该聚醚的聚缩水甘油醚衍生物是聚丙二醇二缩水甘油醚(diglycidyl ether of poly(propyleneglycol)(Trade name DER736))。
在一具体实施例，该单剂型环氧树脂组成的硬化反应温度是高于150℃,160℃,170℃,180℃,190℃或200℃。
本发明的第三实施例在于提供一种具有胺基甲酸酯(carbamate)基团的环氧树脂的制备方法，其包含如下步骤。
步骤一：提供硬化剂，其结构如式(9)所示，和环氧化合物；该硬化剂对该环氧化合物的重量比例是0.5～20；其中R1是源自于脂肪族二胺、芳香族二胺、硅氧烷基二胺或聚醚二胺；和m是选自1～5的整数。
步骤二：使该硬化剂和该环氧化合物在溶媒中形成环氧树脂预聚物。
步骤三：进行硬化反应，使该环氧树脂预聚物形成所述的具有胺基甲酸酯基团的环氧树脂。
上述的具有胺基甲酸酯(carbamate)基团的环氧树脂的制备方法中的硬化剂可以使用废弃高分子做原料，如废聚碳酸酯，所以该环氧树脂的制备方法还能解决废弃高分子污染环境的问题，达到循环经济的效果，且在制备过程中不会释放二氧化碳，有效的延长的二氧化碳的碳循环。
较佳地，上述的制备方法还会使用改质剂、活化剂、触媒或其组合作为添加剂。该添加剂的功能是催化硬化反应或使硬化后生成的环氧树脂具有交联网状结构。
在一具体实施例，该脂肪族二胺包含碳数2～40的直链脂肪族二胺或碳数2～40的支链脂肪族二胺。较佳地，该碳数2～40的直链脂肪族二胺是1,4-丁二胺、1,5-戊二胺或1,6-己二胺。
在一具体实施例，该芳香族二胺包含邻苯二胺、间苯二胺、对苯二胺、4,4'–二氨基二苯醚或其组合。
在一具体实施例，该硅氧烷基二胺的分子量是150～10,000Da。
该硅氧烷基二胺具有的硅氧烷基团的结构如式(10)所式。
在一具体实施例，该聚醚二胺的重量平均分子量是100～5,000Da。较佳的，该聚醚二胺是JEFFAMINE聚醚二胺。
在一具体实施例，该环氧化合物具有如式(2)所示的结构，和(A)n是选自下列群组之一或其组合：结构式(3)、结构式(4)、结构式(5)、结构式(6)、结构式(7)和结构式(8)。
在一具体实施例，其中R1包含碳数1～5的环状烃基、碳数6～10的多酚基、碳数1～20的直链烃基、碳数1～20的卤代烃基、亚胺基、酰胺基、膦酸酯基、膦基、硅烷基、醚基、硫醚基、磺酰基、硒醚基、酮基、醛基、羧酸基或酯基。
在一具体实施例，R2包含氢原子、卤素、烷基、烯基、炔基、烃基、氢氧基、胺基、硝基或碳数1～5的烷氧基。
在一具体实施例，Z和n是分别独立的1～5的整数。
较佳的，上述的环氧化合物包含双酚A的聚缩水甘油醚衍生物、聚醚的聚缩水甘油醚衍生物或酚醛树脂的聚缩水甘油醚衍生物。具体的，该双酚A的聚缩水甘油醚衍生物是双酚A二缩水甘油醚(bisphenol A diglycidyl ether(Trade name DER332))；该聚醚的聚缩水甘油醚衍生物是聚丙二醇二缩水甘油醚(diglycidyl ether of poly(propyleneglycol)(Trade name DER736))。
具体的，上述的硬化反应的反应温度是150～350℃。
以下是本发明的实验范例。
范例一：本发明硬化剂的通用制备方法
提供一包含溶剂、聚碳酸酯和二胺化合物的混合物；该二胺化合物可以是具有硅氧烷基或聚硅氧烷基的二胺化合物，该混合物还可包含碳酸二苯酯。上述的溶剂包括异丙醚、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。然后在50～200℃混和反应得到粗产物，经过真空蒸馏移除溶剂后，得到所述的硬化剂。通常本制备方法的重量收率大于95％，也就是说1克的聚碳酸酯和1克的二胺化合物反应后可得到1.9～2克的硬化剂。具体的硬化剂反应组成如表一所示。
表一
| 范例 | 聚碳酸酯/克 | 二胺化合物/克 | 硬化剂代号 |
| 1-1 | 3.73 | 1,6-己二胺/0.87 | DP1 |
| 1-2 | 5.16 | 1,6-己二胺/1.20 | DP1 |
| 1-3 | 3.73 | 三乙二醇二胺/1.10 | DP2 |
| 1-4 | 5.16 | 三乙二醇二胺/1.53 | DP2 |
| 1-5 | 3.73 | 含硅氧烷基二胺(Ew＝430)/6.44 | DP3 |
| 1-6 | 5.16 | 含硅氧烷基二胺(Ew＝430)/8.91 | DP3 |
| 1-7 | 3.73 | 含硅氧烷基二胺(Ew＝800)/11.97 | DP4 |
| 1-8 | 5.16 | 含硅氧烷基二胺(Ew＝800)/16.56 | DP4 |
| 1-9 | 3.73 | 含硅氧烷基二胺(Ew＝2000)/32.94 | DP5 |
| 1-10 | 5.16 | 含硅氧烷基二胺(Ew＝2000)/45.56 | DP5 |
上述表一所列的硬化剂DP1、DP2和DP3的结构以氢核磁共振光谱分析，其都在化学位移约7.61ppm具有特征峰，显示其结构具有氨酯(urethane)的基团。
范例二：本发明环氧树脂的通用制备方法
首先将硬化剂加入环氧化合物或环氧树脂、触媒和溶剂中形成混合物，该混合物加热到50～80℃借此形成环氧树脂预聚物。放置隔夜后，将该环氧树脂预聚物放入烘箱进行硬化反应，待硬化反应完成后，得到所述的环氧树脂。具体的，上述硬化反应至少包含四阶段的加热步骤。第一阶段是在60℃维持3小时；第二阶段是在80℃维持3小时；第三阶段是在150℃维持3小时；第四阶段是在180℃维持3小时。
本范例二所使用的硬化剂是范例一所制备的，代表范例的组成如表二所示。其中DER332是双酚A二缩水甘油醚(bisphenol A diglycidyl ether)；DER736是聚丙二醇二缩水甘油醚(diglycidyl ether of poly(propylene glycol))。
表二
本发明的环氧树脂使用氢核磁共振光谱和傅立叶红外光谱进行结构分析。在一代表例，由表二的单剂型环氧树脂组成E1DP1、E1DP2和E1DP3所分别制成的环氧树脂其傅立叶红外光谱分别如图2、图3和图4所示。其特征峰位置和官能基团如表三所示。
表三
| 官能基 | 特征峰位置(cm-1) |
| Oxirane ring | 913 |
| -C＝O(urethane) | 1715 |
| -C＝O(carbonate) | 1775 |
| OH | ～3300 |
本发明的单剂型环氧树脂组成的热示差分析(DSC)
单剂型环氧树脂组成E1BPA、E1DP1、E1DP2、E1DP3、E2DP1、E2DP2和E2DP3的热示差扫描曲线图分别如图5、图6、图7、图8、图9、图10和图11所示。代表的单剂型环氧树脂组成的反应温度如表4所示。根据热示差分析的结果，E1DP1和E2DP1的反应温度是160～280℃；E1DP2、E2DP2和E2DP3是170～290℃；和E1DP3是240～310℃。据此，本发明的单剂型环氧树脂组成的反应温度高于150℃、160℃、170℃、180℃、190℃或200℃。
表四
| 单剂型环氧树脂组成 | 反应温度(℃) |
| E1BPA | 178.2 |
| E2BPA | x |
| E1DP1 | 213.2 |
| E2DP1 | 204.0 |
| E1DP2 | 227.1 |
| E2DP2 | 217.0 |
| E1DP3 | 249.2 |
| E2DP3 | 209.7 |
本发明的环氧树脂的性质分析
本发明的单剂型环氧树脂组成所制成的环氧树脂的性质分析如表五所示。玻璃转移温度(Tg)是由DSC分析测得。所制成的环氧树脂的Tg是在-10～120℃之间。如图12所示由E2DP3所制成的环氧树脂为低玻璃转移温度型的环氧树脂；如图13所示由E1DP2所制成的环氧树脂为低玻璃转移温度型的环氧树脂；如图14所示由E2DP2所制成的环氧树脂为高玻璃转移温度型的环氧树脂。据此，本发明的单剂型环氧树脂组成能够借由组成成份的设计，并在不同的反应温度制造各种玻璃转移温度型的环氧树脂，以应用在不同的产业领域。
表五
| 环氧树脂代号 | 单剂型环氧树脂组成 | 成膜性 | 透明度 | Tg(℃) |
| 1 | E1BPA | 易脆 | 良好 | 80.4 |
| 2 | E2BPA | 易脆 | 良好 | 16.1 |
| 3 | E1DP1 | 易脆 | 良好 | 102.8 |
| 4 | E2DP1 | 易脆 | 良好 | 45.1 |
| 5 | E1DP2 | 易脆 | 良好 | 88.4 |
| 6 | E2DP2 | 易脆 | 良好 | 39.6 |
| 7 | E1DP3 | 具韧性 | 良好 | 39.1 |
| 8 | E2DP3 | 具韧性 | 良好 | -8.8 |
本发明的环氧树脂的拉伸测试
E1DP3、E2DP3和E2S430所制成的环氧树脂使用万能拉力机(厂牌及型号：MTSLandmark 370.02Test System)进行拉伸强度和拉伸率的测试。测试条件是依据ASTM D638标准制备样品大小，测试样品使用的拉伸速度是100mm/min。其结果图15所示，明显地，本发明的单剂型环氧树脂组成E1DP3和E2DP3所制成的环氧树脂具有超过150％的拉伸率，且展现出良好的韧性。但是未使用本发明的硬化剂的环氧树脂组成E2S430所制成的环氧树脂在拉伸测试过程中就断裂。据此，本发明的具有硅烷基团的硬化剂能够制成具有韧性、高拉伸率和高拉伸强度的环氧树脂。
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 (8)
1.一种环氧树脂，其特征在于，其具有如式(1)所示的结构；
其中R是源自于硅氧烷基二胺；Ep具有源自双酚A二缩水甘油醚或聚丙二醇二缩水甘油醚的结构；m是1～5的整数；和X是1～25的整数。
2.根据权利要求1所述的环氧树脂，其特征在于，该硅氧烷基二胺的分子量是150～10,000Da。
3.一种单剂型环氧树脂，其特征在于，其包含结构如式(9)所示的硬化剂，和环氧化合物；该结构如式(9)所示的硬化剂对该环氧化合物的重量比例是0.5～20；其中R1是源自于硅氧烷基二胺，该环氧化合物是双酚A二缩水甘油醚或聚丙二醇二缩水甘油醚；和m是选自1～5的整数。
4.根据权利要求3所述的单剂型环氧树脂，其特征在于，还包含添加剂，该添加剂包含季磷卤化物触媒、有机磷触媒、羧酸季磷塩、磷酸酯、三级胺、羧酸锡化物、有机锂盐、咪唑或苯咪唑。
5.根据权利要求3所述的单剂型环氧树脂，其特征在于，该硅氧烷基二胺的分子量是150～10,000Da。
6.一种具有胺基甲酸酯基团的环氧树脂的制备方法，其特征在于，其包含如下步骤：
(1)提供硬化剂，其结构如式(9)所示，和环氧化合物；该硬化剂对该环氧化合物的重量比例是0.5～20；其中R1是源自于硅氧烷基二胺，该环氧化合物是双酚A二缩水甘油醚或聚丙二醇二缩水甘油醚；和m是选自1～5的整数；
(2)使该硬化剂和该环氧化合物在溶媒中形成环氧树脂预聚物；和
(3)进行硬化反应，使该环氧树脂预聚物形成所述的具有胺基甲酸酯基团的环氧树脂。
7.根据权利要求6所述的具有胺基甲酸酯基团的环氧树脂的制备方法，其特征在于，该硅氧烷基二胺的分子量是150～10,000Da。
8.根据权利要求6所述的具有胺基甲酸酯基团的环氧树脂的制备方法，其特征在于，该硬化反应的反应温度是在150～350℃。
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| TWI798569B (zh) | 2023-04-11 |
| EP4130086A4 (en) | 2024-04-24 |
| CN117229477A (zh) | 2023-12-15 |
| US20210380756A1 (en) | 2021-12-09 |
| EP4130086A1 (en) | 2023-02-08 |
| WO2021243827A1 (zh) | 2021-12-09 |
| US11453743B2 (en) | 2022-09-27 |
| CN115210286A (zh) | 2022-10-18 |
| TW202146509A (zh) | 2021-12-16 |
| JP2023519688A (ja) | 2023-05-12 |
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