CN116041789A - 一种有机硅树脂改性的二氧化硅纳米粒子及其制备方法和应用 - Google Patents
一种有机硅树脂改性的二氧化硅纳米粒子及其制备方法和应用 Download PDFInfo
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- CN116041789A CN116041789A CN202310343265.0A CN202310343265A CN116041789A CN 116041789 A CN116041789 A CN 116041789A CN 202310343265 A CN202310343265 A CN 202310343265A CN 116041789 A CN116041789 A CN 116041789A
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- Prior art keywords
- silane
- resin modified
- silicon dioxide
- acrylate
- organosilicon
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 79
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 35
- 239000010703 silicon Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 239000011347 resin Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 89
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- 238000000016 photochemical curing Methods 0.000 claims abstract description 39
- 238000010146 3D printing Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- -1 (3-methacryloxypropyl-2-hydroxy propoxy) propyl bis (trimethylsiloxy) methyl silane Chemical compound 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000005238 degreasing Methods 0.000 claims description 13
- 229920002050 silicone resin Polymers 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 6
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 5
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 4
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 4
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 claims description 4
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 claims description 4
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 claims description 4
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 4
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 claims description 4
- XAASNKQYFKTYTR-UHFFFAOYSA-N tris(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)O[Si](C)(C)C XAASNKQYFKTYTR-UHFFFAOYSA-N 0.000 claims description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- MFWYAJVOUCTAQI-UHFFFAOYSA-N bis[[ethenyl(dimethyl)silyl]oxy]-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C=C MFWYAJVOUCTAQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 2
- BVTLTBONLZSBJC-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O1 BVTLTBONLZSBJC-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OBBZSGOPJQSCNY-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOCCOC(=O)C(C)=C OBBZSGOPJQSCNY-UHFFFAOYSA-N 0.000 claims description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- HPSGLFKWHYAKSF-UHFFFAOYSA-N 2-phenylethyl prop-2-enoate Chemical compound C=CC(=O)OCCC1=CC=CC=C1 HPSGLFKWHYAKSF-UHFFFAOYSA-N 0.000 claims description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 2
- HBZFBSFGXQBQTB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HBZFBSFGXQBQTB-UHFFFAOYSA-N 0.000 claims description 2
- OKQXCDUCLYWRHA-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)Cl OKQXCDUCLYWRHA-UHFFFAOYSA-N 0.000 claims description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 2
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 claims description 2
- PPBAWVJOPQUAMY-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl prop-2-enoate Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)CCCOC(=O)C=C PPBAWVJOPQUAMY-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- NCAVPEPBIJTYSO-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound C1OC1COCC1CO1.OCCCCOC(=O)C=C NCAVPEPBIJTYSO-UHFFFAOYSA-N 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- RDHSUTIDSFVNJL-UHFFFAOYSA-N OC(=O)C=C.CCCCCCCCCCCC(O)=O Chemical compound OC(=O)C=C.CCCCCCCCCCCC(O)=O RDHSUTIDSFVNJL-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- RKFUZDIZLQCJKA-UHFFFAOYSA-N [dimethyl(phenyl)silyl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC[Si](C)(C)C1=CC=CC=C1 RKFUZDIZLQCJKA-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- GQVVQDJHRQBZNG-UHFFFAOYSA-N benzyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1=CC=CC=C1 GQVVQDJHRQBZNG-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- DHOBOKVTKIYNEK-UHFFFAOYSA-N chloromethyl-dimethyl-prop-1-enylsilane Chemical compound CC=C[Si](C)(C)CCl DHOBOKVTKIYNEK-UHFFFAOYSA-N 0.000 claims description 2
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- FEUIEHHLVZUGPB-UHFFFAOYSA-N oxolan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCO1 FEUIEHHLVZUGPB-UHFFFAOYSA-N 0.000 claims description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 2
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 claims description 2
- FHVAUDREWWXPRW-UHFFFAOYSA-N triethoxy(pentyl)silane Chemical compound CCCCC[Si](OCC)(OCC)OCC FHVAUDREWWXPRW-UHFFFAOYSA-N 0.000 claims description 2
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- OTYBJBJYBGWBHB-UHFFFAOYSA-N trimethylsilyl prop-2-enoate Chemical compound C[Si](C)(C)OC(=O)C=C OTYBJBJYBGWBHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims 2
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Abstract
本发明公开了一种有机硅树脂改性的二氧化硅纳米粒子及其制备方法和应用。本发明的有机硅树脂改性的二氧化硅纳米粒子具有核壳结构,内核为二氧化硅纳米粒子,壳层为含有光敏基团的有机硅低聚物,含有光敏基团的有机硅低聚物由含有光敏基团的有机硅单体和其它有机硅单体进行水解缩聚制成。本发明的有机硅树脂改性的二氧化硅纳米粒子具有较小的尺寸,在多种光活性稀释剂中具有良好的分散性,且其制备工艺简单、成本低,适合用作3D打印材料和光固化涂层原料,具有十分广阔的应用前景。
Description
技术领域
本发明涉及3D打印材料技术领域,具体涉及一种有机硅树脂改性的二氧化硅纳米粒子及其制备方法和应用。
背景技术
二氧化硅以及硅氧碳等陶瓷材料具有优异的机械性能、耐高温性、化学稳定性和声光电磁热等物理特性,近年来被广泛应用在化工、机械、电子、航空航天、生物医学等领域。传统的陶瓷加工技术(例如:浇铸成型、干压成型、注射成型等)存在加工成本高、生产周期长、成品细节部位易存在缺陷等问题,已经无法完全满足日益增长的实际应用要求。3D打印技术,也称为增材制造(AM),被视为新时代制造业的革命,而其中的立体光刻3D打印技术作为一种新型的材料加工成型技术备受关注。光固化3D打印技术具有精密度高、设计灵活性高等优点,如果能够将其应用在陶瓷的加工成型上,则可以为精细结构陶瓷的加工提供更优良的方法,可以克服传统陶瓷加工技术存在的模具复杂、削切困难、工艺周期长等问题。因此,3D打印技术与陶瓷加工工艺的结合是大势所趋。
目前,常见的光固化3D打印二氧化硅陶瓷的方法是将具有低粘度的光活性稀释剂与二氧化硅纳米颗粒混合制成用于3D打印的浆料,再通过立体光刻3D打印成型工艺来制备成型坯体。然而,由于浆料中通常含有大量的有机物,在后续煅烧过程中有机物的分解逸出会带来较大的尺寸收缩,另外,由于二氧化硅纳米粒子的分散性较差以及坯体的层间粘接力较差,因此,在煅烧过程很容易引入缺陷,最终会导致产品的机械强度较差,限制了3D打印二氧化硅材料的实际应用。
因此,开发一种新型的适用于3D打印的高性能二氧化硅粒子具有十分重要的意义。
发明内容
本发明的目的在于提供一种有机硅树脂改性的二氧化硅纳米粒子及其制备方法和应用。
本发明所采取的技术方案是:
一种有机硅树脂改性的二氧化硅纳米粒子,其具有核壳结构,内核为二氧化硅纳米粒子,壳层为含有光敏基团的有机硅低聚物;所述含有光敏基团的有机硅低聚物由含有光敏基团的有机硅单体和其它有机硅单体进行水解缩聚制成。
优选的,所述二氧化硅纳米粒子的粒径为10nm~1μm。
优选的,所述含有光敏基团的有机硅单体为3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、甲基丙烯酰基丙基二甲基氯硅烷、甲基丙烯酰氧基丙基甲基二乙氧基硅烷、甲基丙烯酰氧甲基苯基二甲基硅烷、甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷、甲基丙烯酰氧甲基三甲氧基硅烷、甲基丙烯酰氧基甲基三乙氧基硅烷、(3-丙烯酰氧基丙基)三甲氧基硅烷、(3-丙烯酰氧丙基)三(三甲基硅氧基)硅烷、(3-甲基丙烯酰氧基-2-羟基丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷、3-丙烯酰氧基丙基甲基二甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、丙烯基(氯甲基)二甲基硅烷、(异丙烯氧基)三甲基硅烷、异丙烯氧基三(三甲基硅烷基)硅烷、丙烯酰氧基三甲基硅烷中的至少一种。
进一步优选的,所述含有光敏基团的有机硅单体为3-甲基丙烯酰氧基丙基三甲氧基硅烷、(3-丙烯酰氧基丙基)三甲氧基硅烷、3-丙烯酰氧基丙基甲基二甲氧基硅烷、甲基丙烯酰氧甲基三甲氧基硅烷、甲基丙烯酰氧基丙基甲基二乙氧基硅烷中的至少一种。
优选的,所述其它有机硅单体为甲基三甲氧基硅烷、甲基三乙氧基硅烷、三甲基三乙烯基环三硅氧烷、四甲基四乙烯基环四硅氧烷、六甲基环三硅氧烷、三甲基氯硅烷、氯甲基三乙氧基硅烷、苯基三乙氧基硅烷、二苯基二甲氧基硅烷、烯丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、乙烯基三乙酰氧基硅烷、乙烯基三氯硅烷、甲基乙烯基二氯硅烷、1,3-二乙烯基四甲基二硅氧烷、1,5-二乙烯基六甲基三硅氧烷、2,2-二乙烯基-四甲基环三硅氧烷、氯甲基三乙氧基硅烷、二氯二甲基硅烷、苯胺甲基三甲氧基硅烷、苄基三乙氧基硅烷、三(三甲硅烷氧基)硅烷、二甲基乙氧基硅烷、乙基三乙氧基硅烷、丁基三乙氧基硅烷、丙基三乙氧基硅烷、戊基三乙氧基硅烷、正辛基三乙氧基硅烷、异丁基三乙氧基硅烷、己基三乙氧基硅烷、烯丙基三乙氧基硅烷、二氯(氯甲基)甲基硅烷、甲基乙烯基二氯硅烷、甲基乙烯基二乙氧基硅烷、二异丁基二甲氧基硅烷、二甲基乙烯基氯硅烷、(3-巯基丙基)三甲氧基硅烷、N-丙基三乙氧基硅烷中的至少一种。
进一步优选的,所述其它有机硅单体为甲基三乙氧基硅烷、乙烯基三乙氧基硅烷、异丁基三乙氧基硅烷、苄基三乙氧基硅烷、烯丙基三甲氧基硅烷、苯基三乙氧基硅烷、1,5-二乙烯基六甲基三硅氧烷、丁基三乙氧基硅烷、三(三甲硅烷氧基)硅烷、1,3-二乙烯基四甲基二硅氧烷中的至少一种。
优选的,所述二氧化硅纳米粒子、含有光敏基团的有机硅低聚物的摩尔比为1:9~9:1。
一种如上所述的有机硅树脂改性的二氧化硅纳米粒子的制备方法包括以下步骤:
将含有光敏基团的有机硅单体和其它有机硅单体混合进行预聚,再加入到二氧化硅纳米粒子水分散液中进行水解缩聚,即得有机硅树脂改性的二氧化硅纳米粒子;
或者,将含有光敏基团的有机硅单体和其它有机硅单体加入到二氧化硅纳米粒子水分散液中进行水解缩聚,即得有机硅树脂改性的二氧化硅纳米粒子。
优选的,所述二氧化硅纳米粒子水分散液中的溶剂为水和有机溶剂。
优选的,所述有机溶剂为乙醇、丙醇、丁醇、异丙醇、乙酸乙酯、乙酸丁酯中的至少一种。
优选的,所述预聚在40℃~90℃下进行,反应时间为2h~30h。
优选的,所述水解缩聚在20℃~90℃下进行,反应时间为4h~80h。
一种光固化材料,其包括以下质量百分比的组分:
上述有机硅树脂改性的二氧化硅纳米粒子:1%~90%;
光活性稀释剂:1%~90%;
光引发剂:0.001%~10%。
优选的,所述光活性稀释剂为聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、聚乙二醇甲醚甲基丙烯酸酯、二缩三丙二醇二丙烯酸酯、三羟基甲基丙烷三丙烯酸酯、甲基丙烯酸二甲氨基乙酯、月桂酸丙烯酸酯、丙烯酸十八酯、十三烷基丙烯酸酯、异癸基丙烯酸酯、四氢呋喃丙烯酸酯、丙烯酸丁酯、全氟烷基乙基甲基丙烯酸酯、甲氧基聚乙二醇丙烯酸酯、三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、聚(乙二醇)甲基丙烯酸酯、丙烯酸、乙二醇二甲基丙烯酸酯、2-苯基乙基丙烯酸酯、新戊二醇二丙烯酸酯、奎诺二甲基丙烯酸酯、丙烯酸异冰片酯、四甘醇二丙烯酸酯、4-羟基丁基丙烯酸酯缩水甘油醚、二脲烷二甲基丙烯酸酯、聚丙二醇二丙烯酸酯、季戊四醇三丙烯酸酯、2-(全氟辛基)乙基甲基丙烯酸酯、聚二季戊四醇六丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三乙二醇甲基醚甲基丙烯酸酯、己二醇二丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、二丙二醇二丙烯酸酯、苯氧基聚乙二醇丙烯酸酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、1,6-己二醇二丙烯酸酯中的至少一种。
进一步优选的,所述光活性稀释剂为聚乙二醇二丙烯酸酯、二缩三丙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、三羟基甲基丙烷三丙烯酸酯中的至少一种。
优选的,所述光引发剂为2,2'-双(2-氯苯基)-4,4',5,5'-四苯基-1,2'-联咪唑、二苯基(2,4,6-三甲基苯甲酰基)氧化膦、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、安息香双甲醚、二苯甲酮、α-羟基酮、1-羟环己基苯酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、双2,6-二氟-3-吡咯苯基二茂钛、2-异丙基硫杂蒽酮、2,2-二甲氧基-2-苯基苯乙酮、过氧化苯甲酰中的至少一种。
进一步优选的,所述光引发剂为苯基双(2,4,6-三甲基苯甲酰基)氧化膦、二苯基(2,4,6-三甲基苯甲酰基)氧化膦中的至少一种。
一种有机-无机杂化材料,其由上述光固化材料通过立体光刻3D打印技术制成。
一种如上所述的有机-无机杂化材料的制备方法包括以下步骤:采用光固化材料进行立体光刻3D打印,再进行后固化,即得有机-无机杂化材料。
优选的,所述立体光刻3D打印采用波长为355nm~405nm光源,曝光层厚为0.01mm~1mm,单层曝光时间为0.1s~100s。
优选的,所述后固化的时间为1min~10min。
一种陶瓷材料,其由上述有机-无机杂化材料通过干燥、脱脂和烧结制成。
一种如上所述的陶瓷材料的制备方法包括以下步骤:将有机-无机杂化材料进行干燥、脱脂和烧结,即得陶瓷材料。
优选的,所述干燥在10℃~100℃下进行,干燥时间为1h~48h。
优选的,所述脱脂在300℃~800℃下进行,脱脂时间为1h~12h。
优选的,所述脱脂在空气气氛或氮气气氛中进行。
优选的,所述烧结在800℃~2000℃下进行,烧结时间为10min~24h。
进一步优选的,所述烧结在900℃~1600℃下进行,烧结时间为1h~2h。
优选的,所述烧结在空气气氛、氮气气氛或氩气气氛中进行。
一种薄膜材料,其包括基膜和附着在基膜上的光固化涂层,光固化涂层由上述光固化材料通过光固化制成。
优选的,所述基膜为透明聚酰亚胺薄膜。
优选的,所述光固化涂层的厚度为1μm~20μm、硬度为4H~9H、透明度为80%~95%。
一种如上所述的薄膜材料的制备方法包括以下步骤:将光固化材料涂布在基膜表面,再在光照下进行固化,即得薄膜材料。
优选的,所述涂布的方式为流延、浸渍、喷涂中的一种。
优选的,所述光照采用波长为355nm~405nm的光源,光照时间为1s~24h。
一种如上所述的光固化材料在制备光固化3D打印材料或光固化涂层材料中的应用。
本发明的有益效果是:本发明的有机硅树脂改性的二氧化硅纳米粒子具有较小的尺寸,在多种光活性稀释剂中具有良好的分散性,且其制备工艺简单、成本低,适合用作3D打印材料和光固化涂层原料,具有十分广阔的应用前景。
具体来说:
1)本发明的有机硅树脂改性的二氧化硅纳米粒子具有较小的尺寸,且在多种光活性稀释剂中具有良好的分散性,将其作为主要原料可以制备得到低粘度的3D打印浆料,再通过立体光刻3D打印技术可以制备得到具有较好宏观微观形貌和优异力学强度的有机无机杂化材料,且该杂化材料经过高温煅烧后可以转化为结构完整、机械性能良好、具有复杂精细结构的陶瓷产品;
2)本发明的有机硅树脂改性的二氧化硅纳米粒子由二氧化硅纳米粒子和光敏有机硅低聚物链段共同构成,在光固化过程中,位于有机硅低聚物链段上的光敏基团会与光活性稀释剂在紫外光和自由基引发剂作用下发生交联,很好地结合了无机纳米粒子的刚性和有机硅树脂的柔性,从而形成刚柔兼济的交联网络,因而该二氧化硅纳米粒子除了可以制备3D打印材料,还以制备具有高硬度和柔性的硬化涂层材料,在进一步的高温煅烧过程中,有机硅低聚物链段可以原位转化成陶瓷的一部分,增加陶瓷转化率的同时,还可以作为烧结助剂提高烧结活性,从而增强陶瓷的机械性能;
3)本发明的有机硅树脂改性的二氧化硅纳米粒子的制备工艺简单、成本低廉,可以大规模应用到复杂构型的光固化3D打印材料以及光固化涂层材料等实际应用领域。
附图说明
图1为实施例1中的有机-无机杂化材料的实物图。
图2为实施例1中的有机-无机杂化材料断面的SEM图。
图3为实施例1中的陶瓷材料的实物图。
图4为实施例1中的陶瓷材料断面的SEM图。
图5为实施例2中的陶瓷材料的实物图。
图6为实施例2中的陶瓷材料断面的SEM图。
图7为实施例1~6中的光固化材料制成的有机-无机杂化材料制件的抗压强度测试结果图。
图8为实施例1~6中的光固化材料制成的陶瓷制件的抗压强度测试结果图。
具体实施方式
下面结合具体实施例对本发明作进一步的解释和说明。
实施例1:
一种有机硅树脂改性的二氧化硅纳米粒子,其制备方法包括以下步骤:
1)将100mol的二氧化硅纳米粒子(粒径为10nm)加入500mol的去离子水中,再加入8mol的盐酸和1500mol的异丙醇,搅拌均匀,得到二氧化硅纳米粒子分散液;
2)将20mol的3-甲基丙烯酰氧基丙基三甲氧基硅烷和210mol的甲基三乙氧基硅烷加入2000mol的异丙醇中,搅拌均匀,80℃反应24h,得到预聚物;
3)将预聚物加入二氧化硅纳米粒子分散液中,搅拌均匀,70℃反应48h,再进行旋蒸(除去部分溶剂,浓缩至一半重量),即得有机硅树脂改性的二氧化硅纳米粒子。
一种光固化材料,其制备方法包括以下步骤:
将100质量份的上述有机硅树脂改性的二氧化硅纳米粒子加入15质量份的聚乙二醇二丙烯酸酯中,再加入1质量份的二苯基(2,4,6-三甲基苯甲酰基)氧化膦,搅拌均匀,再进行旋蒸(除去全部溶剂),即得光固化材料。
一种有机-无机杂化材料,其制备方法包括以下步骤:
将本实施例中的光固化材料加入3D打印机的进料槽内,设置打印参数为:光源波长为405nm,单层曝光时间为4s,层厚为0.025mm,进行光固化打印成型,再后固化2min,即得有机-无机杂化材料(网络结构的立方体)。
性能测试:
本实施例的有机-无机杂化材料的实物图如图1所示,断面的扫描电镜(SEM)图如图2所示。
由图1和图2可知:有机-无机杂化材料的表面光滑,内部结构紧密,平整光滑,无明显层状结构,无孔洞等缺陷,具有较好的结构特点。
一种陶瓷材料,其制备方法包括以下步骤:
1)将本实施例中的光固化材料加入3D打印机的进料槽内,设置打印参数为:光源波长为405nm,单层曝光时间为4s,层厚为0.025mm,进行光固化打印成型,再后固化2min,得到有机-无机杂化材料(圆柱形);
2)将有机-无机杂化材料置于烘箱中30℃烘24h,再置于马弗炉中600℃脱脂4h,再升温至900℃烧结2h,即得陶瓷材料(氧化物陶瓷)。
性能测试:
本实施例的陶瓷材料的实物图如图3所示,断面的SEM图如图4所示。
由图3和图4可知:陶瓷材料的表面有少许褶皱,内部结构紧密,没有明显长大的晶粒,没有孔洞等重大缺陷,具有较好的结构特点。
一种薄膜材料,其制备方法包括以下步骤:
将本实施例中的光固化材料通过流延工艺涂布到厚度为50μm的透明聚酰亚胺薄膜上,涂层厚度为4μm,再用波长为365nm的光源照射5s形成光固化涂层,即得薄膜材料。
性能测试:
采用铅笔硬度计对本实施例的薄膜材料(光固化涂层)进行硬度测试以及采用紫外可见光谱仪进行透明度测试。
经测试,光固化涂层的硬度最高可达4H,透明度为92%。
实施例2:
一种有机硅树脂改性的二氧化硅纳米粒子,其制备方法包括以下步骤:
1)将100mol的二氧化硅纳米粒子(粒径为30nm)加入500mol的去离子水中,再加入3mol的盐酸和400mol的异丙醇,搅拌均匀,得到二氧化硅纳米粒子分散液;
2)将3mol的(3-丙烯酰氧基丙基)三甲氧基硅烷、10mol的甲基三乙氧基硅烷和30mol的乙烯基三乙氧基硅烷加入110mol的异丙醇中,搅拌均匀,再加入二氧化硅纳米粒子分散液中,搅拌均匀,75℃反应48h,再进行旋蒸(除去部分溶剂,浓缩至一半重量),即得有机硅树脂改性的二氧化硅纳米粒子。
一种光固化材料,其制备方法包括以下步骤:
将100质量份的上述有机硅树脂改性的二氧化硅纳米粒子加入30质量份的二缩三丙二醇二丙烯酸酯中,再加入1质量份的苯基双(2,4,6-三甲基苯甲酰基)氧化膦,搅拌均匀,再进行旋蒸(除去全部溶剂),即得光固化材料。
一种陶瓷材料,其制备方法包括以下步骤:
1)将本实施例中的光固化材料加入3D打印机的进料槽内,设置打印参数为:光源波长为405nm,单层曝光时间为4s,层厚为0.025mm,进行光固化打印成型,再后固化2min,即得有机-无机杂化材料(网络结构的立方体);
2)将有机-无机杂化材料置于室温干燥24h,再置于充氮气保护的管式炉中800℃脱脂2h,再升温至1550℃烧结2h,即得陶瓷材料(氧化物/碳化物复合陶瓷)。
性能测试:
本实施例的陶瓷材料的实物图如图5所示,断面的SEM图如图6所示。
由图5和图6可知:陶瓷材料的表面光滑,内部结构紧密,虽有少许小孔,但无较大缺陷,总体上具有较好的结构特点。
一种薄膜材料,其制备方法包括以下步骤:
将本实施例中的光固化材料通过流延工艺涂布到厚度为50μm的透明聚酰亚胺薄膜上,涂层厚度为10μm,再用波长为365nm的光源照射5s形成光固化涂层,即得薄膜材料。
经测试(测试方法同实施例1),光固化涂层的硬度最高可达9H,透明度为90%。
实施例3:
一种有机硅树脂改性的二氧化硅纳米粒子,其制备方法包括以下步骤:
1)将100mol的二氧化硅纳米粒子(粒径为50nm)加入500mol的去离子水中,再加入3mol的盐酸和500mol的异丙醇,搅拌均匀,得到二氧化硅纳米粒子分散液;
2)将5mol的3-丙烯酰氧基丙基甲基二甲氧基硅烷、20mol的异丁基三乙氧基硅烷和60mol的苄基三乙氧基硅烷加入650mol的异丙醇中,搅拌均匀,60℃反应24h,得到预聚物;
3)将预聚物加入二氧化硅纳米粒子分散液中,搅拌均匀,室温反应72h,再进行旋蒸(除去部分溶剂,浓缩至一半重量),即得有机硅树脂改性的二氧化硅纳米粒子。
一种光固化材料,其制备方法包括以下步骤:
将100质量份的上述有机硅树脂改性的二氧化硅纳米粒子加入40质量份的1,6-己二醇二丙烯酸酯中,再加入1质量份的二苯基(2,4,6-三甲基苯甲酰基)氧化膦,搅拌均匀,再进行旋蒸(除去全部溶剂),即得光固化材料。
一种薄膜材料,其制备方法包括以下步骤:
将本实施例中的光固化材料通过流延工艺涂布到厚度为50μm的透明聚酰亚胺薄膜上,涂层厚度为15μm,再用波长为365nm的光源照射5s形成光固化涂层,即得薄膜材料。
经测试(测试方法同实施例1),光固化涂层的硬度最高可达6H,透明度为85%。
实施例4:
一种有机硅树脂改性的二氧化硅纳米粒子,其制备方法包括以下步骤:
1)将100mol的二氧化硅纳米粒子(粒径为100nm)加入500mol的去离子水中,再加入3mol的盐酸和500mol的异丙醇,搅拌均匀,得到二氧化硅纳米粒子分散液;
2)将6mol的甲基丙烯酰氧甲基三甲氧基硅烷、15mol的烯丙基三甲氧基硅烷和45mol的苯基三乙氧基硅烷加入500mol的异丙醇中,搅拌均匀,再加入二氧化硅纳米粒子分散液中,搅拌均匀,室温反应72h,再进行旋蒸(除去部分溶剂,浓缩至一半重量),即得有机硅树脂改性的二氧化硅纳米粒子。
一种光固化材料,其制备方法包括以下步骤:
将100质量份的上述有机硅树脂改性的二氧化硅纳米粒子加入35质量份的二缩三丙二醇二丙烯酸酯中,再加入1质量份的二苯基(2,4,6-三甲基苯甲酰基)氧化膦,搅拌均匀,再进行旋蒸(除去全部溶剂),即得光固化材料。
实施例5:
一种有机硅树脂改性的二氧化硅纳米粒子,其制备方法包括以下步骤:
1)将100mol的二氧化硅纳米粒子(粒径为200nm)加入500mol的去离子水中,再加入5mol的盐酸和750mol的异丙醇,搅拌均匀,得到二氧化硅纳米粒子分散液;
2)将10mol的γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、30mol的1,5-二乙烯基六甲基三硅氧烷和90mol的丁基三乙氧基硅烷加入1000mol的异丙醇中,搅拌均匀,再加入二氧化硅纳米粒子分散液中,搅拌均匀,60℃反应48h,再进行旋蒸(除去部分溶剂,浓缩至一半重量),即得有机硅树脂改性的二氧化硅纳米粒子。
一种光固化材料,其制备方法包括以下步骤:
将100质量份的上述有机硅树脂改性的二氧化硅纳米粒子加入40质量份的三羟基甲基丙烷三丙烯酸酯中,再加入1质量份的苯基双(2,4,6-三甲基苯甲酰基)氧化膦,搅拌均匀,再进行旋蒸(除去全部溶剂),即得光固化材料。
实施例6:
一种有机硅树脂改性的二氧化硅纳米粒子,其制备方法包括以下步骤:
1)将100mol的二氧化硅纳米粒子(粒径为500nm)加入500mol的去离子水中,再加入3mol的盐酸和500mol的异丙醇,搅拌均匀,得到二氧化硅纳米粒子分散液;
2)将3mol的甲基丙烯酰氧基丙基甲基二乙氧基硅烷、20mol的三(三甲硅烷氧基)硅烷和40mol的1,3-二乙烯基四甲基二硅氧烷加入500mol的异丙醇中,搅拌均匀,再加入二氧化硅纳米粒子分散液中,搅拌均匀,50℃反应48h,再进行旋蒸(除去部分溶剂,浓缩至一半重量),即得有机硅树脂改性的二氧化硅纳米粒子。
一种光固化材料,其制备方法包括以下步骤:
将100质量份的上述有机硅树脂改性的二氧化硅纳米粒子加入30质量份的聚乙二醇二丙烯酸酯中,再加入1质量份的苯基双(2,4,6-三甲基苯甲酰基)氧化膦,搅拌均匀,再进行旋蒸(除去全部溶剂),即得光固化材料。
抗压强度测试:
1)有机-无机杂化材料的抗压强度:
将实施例1~6中的光固化材料加入3D打印机的进料槽内,设置打印参数为:光源波长为405nm,单层曝光时间为4s,层厚为0.025mm,进行光固化打印成型,再后固化2min,制成长为25mm、直径为10mm的圆柱形有机-无机杂化材料制件。
采用万能力学试验机对有机-无机杂化材料制件进行抗压强度测试,得到的抗压强度测试结果图如图7所示。
由图7可知:实施例1~6中的光固化材料制成的有机-无机杂化材料制件的抗压强度最高可达141.4MPa、300.95MPa、72.2MPa、123.3MPa、136.3MPa和96.4MPa,均具有较好的力学性能。
2)陶瓷材料的抗压强度:
a)将实施例1~6中的光固化材料加入3D打印机的进料槽内,设置打印参数为:光源波长为405nm,单层曝光时间为4s,层厚为0.025mm,进行光固化打印成型,再后固化2min,得到长为25mm、直径为10mm的圆柱形有机-无机杂化材料制件1~6;
b)将有机-无机杂化材料制件1置于烘箱中30℃烘24h,再置于马弗炉中600℃脱脂4h,再升温至900℃烧结2h,得到陶瓷制件1(氧化物陶瓷);
c)将有机-无机杂化材料制件2室温干燥24h,再置于充氮气保护的管式炉中800℃脱脂2h,再升温至1550℃烧结2h,得到陶瓷制件2(氧化物/碳化物复合陶瓷);
d)将有机-无机杂化材料制件3室温干燥24h,再置于充氮气保护的管式炉中800℃脱脂2h,再升温至1500℃烧结2h,得到陶瓷制件3(氧化物/碳化物复合陶瓷);
e)将有机-无机杂化材料制件4室温干燥24h,再置于马弗炉中600℃脱脂4h,再升温至900℃烧结2h,得到陶瓷制件4(氧化物陶瓷);
f)将有机-无机杂化材料制件5室温干燥24h,再置于充氮气保护的管式炉中800℃脱脂2h,再升温至1500℃烧结2h,得到陶瓷制件5(氧化物/碳化物复合陶瓷);
g)将有机-无机杂化材料制件6室温干燥24h,再置于马弗炉中600℃脱脂4h,再升温至900℃烧结2h,得到陶瓷制件6(氧化物陶瓷);
采用万能力学试验机对陶瓷制件1~6进行抗压强度测试,得到的抗压强度测试结果图如图8所示。
由图8可知:实施例1~6中的光固化材料制成的陶瓷制件的抗压强度最高可达10.4MPa、22.08MPa、12.3MPa、9.8MPa、13.5MPa和10.5MPa,均具有一定的力学性能。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种有机硅树脂改性的二氧化硅纳米粒子,其特征在于,具有核壳结构,内核为二氧化硅纳米粒子,壳层为含有光敏基团的有机硅低聚物;所述含有光敏基团的有机硅低聚物由含有光敏基团的有机硅单体和其它有机硅单体进行水解缩聚制成。
2.根据权利要求1所述的有机硅树脂改性的二氧化硅纳米粒子,其特征在于:所述二氧化硅纳米粒子的粒径为10nm~1μm。
3.根据权利要求1或2所述的有机硅树脂改性的二氧化硅纳米粒子,其特征在于:所述含有光敏基团的有机硅单体为3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、甲基丙烯酰基丙基二甲基氯硅烷、甲基丙烯酰氧基丙基甲基二乙氧基硅烷、甲基丙烯酰氧甲基苯基二甲基硅烷、甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷、甲基丙烯酰氧甲基三甲氧基硅烷、甲基丙烯酰氧基甲基三乙氧基硅烷、(3-丙烯酰氧基丙基)三甲氧基硅烷、(3-丙烯酰氧丙基)三(三甲基硅氧基)硅烷、(3-甲基丙烯酰氧基-2-羟基丙氧基)丙基双(三甲基甲硅烷氧基)甲基硅烷、3-丙烯酰氧基丙基甲基二甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、丙烯基(氯甲基)二甲基硅烷、(异丙烯氧基)三甲基硅烷、异丙烯氧基三(三甲基硅烷基)硅烷、丙烯酰氧基三甲基硅烷中的至少一种;所述其它有机硅单体为甲基三甲氧基硅烷、甲基三乙氧基硅烷、三甲基三乙烯基环三硅氧烷、四甲基四乙烯基环四硅氧烷、六甲基环三硅氧烷、三甲基氯硅烷、氯甲基三乙氧基硅烷、苯基三乙氧基硅烷、二苯基二甲氧基硅烷、烯丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、乙烯基三乙酰氧基硅烷、乙烯基三氯硅烷、甲基乙烯基二氯硅烷、1,3-二乙烯基四甲基二硅氧烷、1,5-二乙烯基六甲基三硅氧烷、2,2-二乙烯基-四甲基环三硅氧烷、氯甲基三乙氧基硅烷、二氯二甲基硅烷、苯胺甲基三甲氧基硅烷、苄基三乙氧基硅烷、三(三甲硅烷氧基)硅烷、二甲基乙氧基硅烷、乙基三乙氧基硅烷、丁基三乙氧基硅烷、丙基三乙氧基硅烷、戊基三乙氧基硅烷、正辛基三乙氧基硅烷、异丁基三乙氧基硅烷、己基三乙氧基硅烷、烯丙基三乙氧基硅烷、二氯(氯甲基)甲基硅烷、甲基乙烯基二氯硅烷、甲基乙烯基二乙氧基硅烷、二异丁基二甲氧基硅烷、二甲基乙烯基氯硅烷、(3-巯基丙基)三甲氧基硅烷、N-丙基三乙氧基硅烷中的至少一种。
4.根据权利要求1或2所述的有机硅树脂改性的二氧化硅纳米粒子,其特征在于:所述二氧化硅纳米粒子、含有光敏基团的有机硅低聚物的摩尔比为1:9~9:1。
5.一种如权利要求1~4中任意一项所述的有机硅树脂改性的二氧化硅纳米粒子的制备方法,其特征在于,包括以下步骤:
将含有光敏基团的有机硅单体和其它有机硅单体混合进行预聚,再加入到二氧化硅纳米粒子分散液中进行水解缩聚,即得有机硅树脂改性的二氧化硅纳米粒子;
或者,将含有光敏基团的有机硅单体和其它有机硅单体加入到二氧化硅纳米粒子分散液中进行水解缩聚,即得有机硅树脂改性的二氧化硅纳米粒子。
6.一种光固化材料,其特征在于,包括以下质量百分比的组分:
权利要求1~4中任意一项所述的有机硅树脂改性的二氧化硅纳米粒子:1%~90%;
光活性稀释剂:1%~90%;
光引发剂:0.001%~10%。
7.根据权利要求6所述的光固化材料,其特征在于:所述光活性稀释剂为聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、聚乙二醇甲醚甲基丙烯酸酯、二缩三丙二醇二丙烯酸酯、三羟基甲基丙烷三丙烯酸酯、甲基丙烯酸二甲氨基乙酯、月桂酸丙烯酸酯、丙烯酸十八酯、十三烷基丙烯酸酯、异癸基丙烯酸酯、四氢呋喃丙烯酸酯、丙烯酸丁酯、全氟烷基乙基甲基丙烯酸酯、甲氧基聚乙二醇丙烯酸酯、三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、聚(乙二醇)甲基丙烯酸酯、丙烯酸、乙二醇二甲基丙烯酸酯、2-苯基乙基丙烯酸酯、新戊二醇二丙烯酸酯、奎诺二甲基丙烯酸酯、丙烯酸异冰片酯、四甘醇二丙烯酸酯、4-羟基丁基丙烯酸酯缩水甘油醚、二脲烷二甲基丙烯酸酯、聚丙二醇二丙烯酸酯、季戊四醇三丙烯酸酯、2-(全氟辛基)乙基甲基丙烯酸酯、聚二季戊四醇六丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三乙二醇甲基醚甲基丙烯酸酯、己二醇二丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、二丙二醇二丙烯酸酯、苯氧基聚乙二醇丙烯酸酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、1,6-己二醇二丙烯酸酯中的至少一种;所述光引发剂为2,2'-双(2-氯苯基)-4,4',5,5'-四苯基-1,2'-联咪唑、二苯基(2,4,6-三甲基苯甲酰基)氧化膦、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、安息香双甲醚、二苯甲酮、α-羟基酮、1-羟环己基苯酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、双2,6-二氟-3-吡咯苯基二茂钛、2-异丙基硫杂蒽酮、2,2-二甲氧基-2-苯基苯乙酮、过氧化苯甲酰中的至少一种。
8.一种有机-无机杂化材料,其特征在于,由权利要求6或7所述的光固化材料通过立体光刻3D打印技术制成。
9.一种陶瓷材料,其特征在于,由权利要求8所述的有机-无机杂化材料通过干燥、脱脂和烧结制成。
10.一种薄膜材料,其特征在于,包括基膜和附着在基膜上的光固化涂层;所述光固化涂层由权利要求6或7所述的光固化材料通过光固化制成。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101193988A (zh) * | 2005-05-09 | 2008-06-04 | 莫门蒂夫功能性材料公司 | 可固化组合物和具有由其得到的保护层的物品 |
CN104321376A (zh) * | 2012-05-21 | 2015-01-28 | 昭和电工株式会社 | 可固化组合物及其固化材料 |
CN109400177A (zh) * | 2018-10-30 | 2019-03-01 | 西安点云生物科技有限公司 | 用于3d光固化成型打印的陶瓷材料及陶瓷制件的制备方法 |
CN112920423A (zh) * | 2021-04-01 | 2021-06-08 | 成都思立可科技有限公司 | 一种核壳结构有机硅树脂的制备方法 |
CN113754441A (zh) * | 2021-03-15 | 2021-12-07 | 山东理工大学 | 一种光敏树脂及其制备方法和应用 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101193988A (zh) * | 2005-05-09 | 2008-06-04 | 莫门蒂夫功能性材料公司 | 可固化组合物和具有由其得到的保护层的物品 |
CN104321376A (zh) * | 2012-05-21 | 2015-01-28 | 昭和电工株式会社 | 可固化组合物及其固化材料 |
CN109400177A (zh) * | 2018-10-30 | 2019-03-01 | 西安点云生物科技有限公司 | 用于3d光固化成型打印的陶瓷材料及陶瓷制件的制备方法 |
CN113754441A (zh) * | 2021-03-15 | 2021-12-07 | 山东理工大学 | 一种光敏树脂及其制备方法和应用 |
CN112920423A (zh) * | 2021-04-01 | 2021-06-08 | 成都思立可科技有限公司 | 一种核壳结构有机硅树脂的制备方法 |
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