CN106565877B - A kind of organic-inorganic hybrid molecule composite material and preparation method with high refraction coefficient - Google Patents
A kind of organic-inorganic hybrid molecule composite material and preparation method with high refraction coefficient Download PDFInfo
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- CN106565877B CN106565877B CN201610996024.6A CN201610996024A CN106565877B CN 106565877 B CN106565877 B CN 106565877B CN 201610996024 A CN201610996024 A CN 201610996024A CN 106565877 B CN106565877 B CN 106565877B
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- organic
- refraction coefficient
- composite material
- inorganic hybrid
- high refraction
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 62
- 239000002184 metal Substances 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 30
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 17
- 230000003287 optical effect Effects 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000002671 adjuvant Substances 0.000 claims abstract description 11
- 238000007711 solidification Methods 0.000 claims abstract description 10
- 230000008023 solidification Effects 0.000 claims abstract description 10
- 230000005693 optoelectronics Effects 0.000 claims abstract description 4
- 239000003973 paint Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 28
- -1 aromatic rings alcohols Chemical class 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 239000003607 modifier Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000007524 organic acids Chemical class 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 150000001298 alcohols Chemical class 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012456 homogeneous solution Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 150000003254 radicals Chemical group 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002318 adhesion promoter Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 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 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 239000006254 rheological additive Substances 0.000 claims description 3
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 2
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical compound O=C1OS1(=O)=O OLPZCIDHOZATMA-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 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
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 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
- 239000012965 benzophenone Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Chemical class 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 2
- 239000012954 diazonium Substances 0.000 claims description 2
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Chemical class CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
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- 239000013049 sediment Substances 0.000 claims description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims 2
- NAEHAPZYAHRUTE-UHFFFAOYSA-N 3-phenyl-2-sulfanylprop-2-enoic acid Chemical group OC(=O)C(S)=CC1=CC=CC=C1 NAEHAPZYAHRUTE-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
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- 235000004204 Foeniculum vulgare Nutrition 0.000 claims 1
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- 125000004122 cyclic group Chemical group 0.000 claims 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 1
- 238000001802 infusion Methods 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
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- 239000000470 constituent Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 2
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- 239000000047 product Substances 0.000 description 27
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 7
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- 229910052793 cadmium Inorganic materials 0.000 description 4
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- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002975 chemoattractant Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000012683 free radical ring-opening polymerization Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000001451 organic peroxides Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
-
- 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
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- 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
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a kind of organic-inorganic hybrid molecule composite materials with high refraction coefficient, its main constituents includes: metal oxygen cluster compound and its derivative, the activated monomer containing phenoxy group, the monomer of polymerizable active group or oligomer, solidification adjuvant, additive, main constituents are by mass percentage are as follows: metal oxygen cluster compound and its derivative 2%-52%, activated monomer 2%-88% containing phenoxy group, the monomer or oligomer 0%-90% of active group, solidify adjuvant 0%-10%, additive 0%-10%.The particle size of the metal oxygen cluster compound synthesized in the present invention is all within the scope of sub-nanometer, it is the key component for improving the refraction coefficient of material of the present invention, there is high optical transparency, high refraction coefficient, high stability using hybrid inorganic-organic composite material made from the metal oxygen cluster compound, high-weatherability etc., with good industrial applications prospect, new energy, optical material can be widely applied to, opto-electronic device, a variety of high-tech areas such as functional paint.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of hybrid inorganic-organic with high refraction coefficient point
Sub- composite material and preparation method.
Background technique
Nearly ten years, high refraction coefficient optical material increasingly causes either basic research or high-tech using boundary
Strong interest.This is because wide application prospect of this kind of material in numerous science and technology and industrial circle and huge latent
Power.These applications include advanced opto-electronic device manufacturing industry, optical lens manufacturing industry, hologram recording material, in optics and the sun
Can battery antireflective film, optical cement and encapsulating material in LED and OLED manufacturing industry, 193 nanometers of liquid immersion lithographies
Photoresist used in technology (photoresists for 193-nm immersion lithography), high brightness electronic display
Micro mirror head material in display screen etc..
Many inorganic optical materials have the refraction coefficient for even exceeding 2.0 (for example, TiO2、ZrO2, ZnS and PbS etc.),
There are high intensity, high rigidity, the excellent mechanical properties such as high rigidity simultaneously；But weight is big, extremely low flexibility, it is especially tired
Unmanageable weakness usually to hope and halt using businessman.In comparison, traditional organic material weight is light, impact resistance
Property it is good, especially processability is strong, and the simple advantage of processing technology is extremely tempting, and still, they often only have relatively low refractive power
Coefficient, range is between 1.40-1.60.Especially in the past 10 years, the world's generally concern to environment and human health, does not allow
Organic synthesis is carried out using halogens, and the most important ingredient of halogen exactly organic high refraction coefficient material, this is allowed for
Synthesizing has the pure organic compound of high refraction coefficient more difficult.
Recently, the nano science and nanotechnology of rapid development provide a kind of new effective method, collect inorganic material
With the respective advantage of organic material in one, i.e., so-called organic-inorganic materials technology will be with high refraction coefficient
Inorganic nanoparticles are physically dispersed in the matrix of polymer as filler, form organic-inorganic nano-hybrid material
Material.Regrettably as traditional composite material, this nanocomposite is still a kind of inorganic particle and organic matrix
The physical mixed nonhomogeneous system of multiphase out-phase.Wherein, the mismatch between inorganic phase and organic phase, usually makes material
Expect out-phase separation, causes self cohesion of nano particle or self flocculation, layering, agglomeration, finally lose function and cannot use；Together
When, mismatch is also often the main reason for causing special material rheological behaviour and unfavorable processing technology.More seriously, optics
Using upper, the heterogeneous material of this multiphase out-phase often results in light scattering phenomenon, such as Rayleigh scattering phenomenon, so that material is muddy
It is turbid, optical transparence is lost, and cannot use completely.
Reach the industrialization and industry that hybrid inorganic-organic polymer composite is prepared using sol-gel technique
Change, hinder three questions of substance of this technical industry to become biggest obstacle for a long time, it is necessary to overcome and solve:
1. the uncontrollable problem of hydrolysis and the polycondensation reaction for almost occurring and carrying out simultaneously；The two reactions are almost same
When influenced by following multiple factors, comprising: the stoichiometric ratio of reactant, reaction medium, the type of catalyst, reaction process
The control of temperature, the chemical activity of precursor reagent itself and other reaction conditions etc.；
2. hydrolysis and condensation reaction are difficult to carry out completely.And in final product, unhydrolysed alkoxy and it is not condensed
Hydroxyl can thermal stability to product and hydrolytic stability impact.
3. carrying out industrialized production using traditional sol-gel technique prepares hybrid inorganic-organic macromolecule composite wood
The low yield of material, time-consuming, and consume energy high defect.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of with height in view of the deficiency of the prior art
The hybrid inorganic-organic composite material and preparation method of refraction coefficient, gained hybrid inorganic-organic composite material have bloom
Learn the transparency, high refraction coefficient, high stability, high-weatherability etc..
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
A kind of organic-inorganic hybrid molecule composite material with high refraction coefficient, main constituents include: metal
Oxygen cluster compound and its derivative, the activated monomer containing phenoxy group, the monomer of polymerizable active group or oligomer, solidification are auxiliary
Auxiliary agent, additive.
According to the above scheme, the organic-inorganic hybrid molecule composite material main constituents with high refraction coefficient
By mass percentage are as follows: metal oxygen cluster compound and its derivative 2%-52%, the activated monomer 2%- containing phenoxy group
88%, the monomer or oligomer 0%-90% of active group solidify adjuvant 0%-10%, additive 0%-10%.Preferably,
Its main constituents is by mass percentage are as follows: metal oxygen cluster compound 30-40%, the activated monomer 30- containing phenoxy group
40%, the monomer or oligomer 10-20% of active group solidify adjuvant 0.1-2%, additive 0%-2%.
According to the above scheme, the general formula of the metal oxygen cluster compound and its derivative is MaOb(OR2)c(R3COO)dOr MeOf
(R4COO)g(R3COO)h, M indicates metallic element, OR in formula2Indicate the alcohols ligand containing aromatic rings, R3COO、R4COO
Indicate the organic acid ligand containing aromatic rings, it is nonnegative real number, a and e that a, b, c, d, e, f, g, h, which represent atom number,
Substantially in 2 to 50 ranges, b and f are substantially in the range of 4 to 200, and c and g are substantially in 2 to 100 ranges, and d and h are substantially 2
To 100 ranges.The metallic element M includes but is not limited to zirconium (Zr), titanium (Ti), antimony (Sb), zinc (Zn), iron (Fe), lead
(Pb), cadmium (Cd), tin (Sn) etc., better choice are zirconium (Zr), one of titanium (Ti) and zinc (Zn) etc. or arbitrary proportion
It is several；The OR2、R4COO is respectively derived from the alcohols containing aromatic rings or organic acid R2OH、R4COOH, respectively itself
Refraction coefficient n20 D>=1.52, hydroxy position is preferably primary hydroxyl, and carboxyl site is preferably primary carboxyl.
According to the above scheme, the refraction coefficient of the activated monomer containing phenoxy group itself is not less than 1.51, that is, n20 D≥
1.51.Preferably, the activated monomer containing phenoxy group include but is not limited to 2- phenoxyethyl acrylate (2-PEA,
n20 D=1.518), adjacent phenylphenoxy ethyl propylene acid esters (OPPEA, n20 D=1.575) one or more of etc. any ratio
The mixture of example.
According to the above scheme, the monomer of the polymerizable active group or oligomer are one or more in any proportion mixed
Close object.Wherein, polymerizable active group is double bond, three keys, epoxy group, one of sulfydryl or other polymerizable active groups etc.
Or it is a variety of.Preferably, the monomer of the polymerizable active group or oligomer be include but is not limited to acryloxyalkyl or
Aromatic radical, methacryloxyalkyl or aromatic radical, alkylene, aromatic hydrocarbon alkenyl, alkynes base, cycloalkenyl group, cycloalkynyl group,
Aromatic ring oxyalkyl, chain type aliphatic epoxy alkyl, cyclic aliphatic epoxide alkyl, vinyl ethers, mercapto and cortex cinnamomi
The monomer or oligomer of one or more of acidic group etc. active group.
According to the above scheme, the solidification adjuvant can be divided into free radical photo-initiation, cation light initiator, and heat causes
Agent, curing agent, one or more of catalyst etc..
According to the above scheme, the free radical photo-initiation is 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxy-cyclohexyl
Phenyl ketone, 2,4,6- trimethylbenzoy-dipheny phosphine oxides, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto)
Phenyl] -1- acetone, benzophenone, 4- methyl benzophenone, 4- (dimethylamino)-benzoic acid-(2- ethyl) own ester etc..
According to the above scheme, the cation light initiator is diazonium salt, diaryl iodonium salt, triaryl sulfonium salts, alkyl
Sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silicon oxygen ether etc..
According to the above scheme, the thermal initiator is organic peroxide or azo-initiator, such as potassium peroxydisulfate, persulfuric acid
Ammonium, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile, azobisisoheptonitrile etc..
According to the above scheme, the curing agent is amine, acids, anhydride, phenols, alcohols, thio-alcohol etc..Such as divinyl
Triamine, aromatic polyamine, dicyandiamide, boron trifluoride, ethanedioic acid, phthalic anhydride, hydroquinone, ethylene glycol, 1,4- fourth
Two mercaptan etc..
According to the above scheme, the catalyst is amine, phosphine etc., is such as selected from n-propylamine, triethylamine, N, N- diisopropyl second
Amine, 4-dimethylaminopyridine, triphenylphosphine etc..
According to the above scheme, the additive can be divided into polymerization inhibitor, wetting agent, antioxidant, levelling agent, defoaming agent, rheology
Modifying agent, adhesion promoter etc..The polymerization inhibitor is 4- metoxyphenol, hydroquinone, 1,4-benzoquinone etc..The wetting agent is
Propylene glycol, glycerol etc..The antioxidant is 2,6-di-tert-butyl p-cresol, butylated hydroxy anisole, tert-butyl hydroquinone
Deng.The levelling agent is dimethyl silicone polymer, polyacrylate etc..The defoaming agent is silicone emulsion, high-carbon polyol fatty acid
Ester complexes, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxy
Propylene polyoxyethylene glycerol ether, dimethyl silicone polymer etc..The rheology modifier is fumed silica, castor oil derivative
Deng.The adhesion promoter is silane coupling agent, titanate coupling agent etc..
The preparation method of organic-inorganic hybrid molecule composite material of the present invention with high refraction coefficient, it is main to walk
It is rapid as follows:
A) according to the ratio, metal oxygen cluster compound and its derivative, the activated monomer containing phenoxy group, polymerizable activity are weighed
Monomer or oligomer, the solidification adjuvant, additive of group, it is spare；
B) metal oxygen cluster compound and its derivative are dissolved in the activated monomer containing phenoxy group, obtain clear solution；
C) monomer or oligomer for containing polymerizable active group, solidification auxiliary will be added in clear solution obtained by step b)
After agent, aggregated and/or crosslinking curing obtains the hybrid inorganic-organic composite material with high refraction coefficient.
According to the above scheme, the cured mode is ultraviolet light irradiation, electron beam irradiation, heating etc..Specifically, described solid
Change can be irradiated through ultraviolet light, polymerize by Light lnduced Free Radicals or be crosslinked and reach cured purpose；Alternatively, the solidification can be with
It is irradiated through electron beam, reaches cured purpose by polymerizeing or being crosslinked；Alternatively, the solidification can be heated, pass through free radical
Polymerization and/or ring-opening polymerization reach cured purpose.Wherein, when using electron beam irradiation polymerization or crosslinking, the composition
Photoinitiator can be free of in ingredient.Have high refraction coefficient hybrid inorganic-organic composite material can be with due to of the present invention
Monomer or oligomer comprising one or more different polymerizable active groups, thus the mechanism of curing mode may be it is a kind of or
Person is the combination of several different mechanism.
Heretofore described metal oxygen cluster compound and its derivative the preparation method is as follows: with metal alkyl oxide
For presoma, using water as reactant, control water is reacted with the molar ratio of metallic atom, with the alcohols containing aromatic rings or is had
Machine acids is as surface modifier, to contain the organic acid of aromatic rings as the surface modifier of catalyst and auxiliary, close
It is reacted under conditions of high temperature and pressure in the reaction kettle closed, obtains metal oxygen cluster compound and its derivative.The metal oxygen cluster is multiple
It closes object and its derivative is the modified metal oxygen cluster compound and its derivative in surface.Wherein, the reaction includes hydrolysis contracting
It closes and surface is modified a series of processes.
Further, the preparation method of the metal oxygen cluster compound and its derivative, key step are as follows:
1) organic acid containing aromatic rings is dissolved in the alcohols or organic acid containing aromatic rings, prepares solution A；
Water is dissolved in the alcohols or organic acid containing aromatic rings, solution B is prepared.
2) metal alkoxide is added in solution A, is uniformly mixed, form solution C；
3) solution B is added dropwise under stirring conditions in solution C, forms homogeneous solution D；
4) acquired solution D is transferred to autoclave sealing, is heated to temperature 190-230 degree, the pressure rise in kettle
To 1.4-2.0MPa, heat preservation and 2-6 hour of dwell time, reaction terminate；
5) by the heated rotary evaporation purification of gained crude product in autoclave obtained by step 4) remove solvent and other
The surface modifier for not participating in reaction, obtain white suspended things or white sediment, as metal oxygen cluster compound and
Its derivative.
According to the above scheme, the metal alkyl oxide, with formula M (OR)nIt indicates, wherein M represents metallic element, R generation
Table alkyl, n represent the ligancy for corresponding to metallic element.For example, metallic element M can be selected from zirconium (Zr), and titanium (Ti), antimony
(Sb), zinc (Zn), iron (Fe), lead (Pb), cadmium (Cd), tin (Sn) etc., but preferably zirconium (Zr), titanium (Ti) and zinc (Zn)；N is generally
3,4,5,6, the most common are 4.
According to the above scheme, the molar ratio of metallic atom is excellent 1/1 to 6/1 in the aqueous solvent and metal alkyl oxide
Selection of land is 2/1 to 4/1.Before the reaction, the molar ratio of reactants water and metal alkyl oxide presoma is controlled, to reach control
The molar ratio of water and metallic atom, for example, the mole ratio range of the zirconium in water and zirconium alkoxide compound is 2/1 to 4/1, it is excellent
Select 3/1.
According to the above scheme, the surface modifier is alcohols or organic acid containing aromatic rings, respectively itself
Refraction coefficient n20 D≥1.52.Wherein, the hydroxy position of the alcohol containing aromatic rings is preferably primary hydroxyl；It is described to contain fragrance
The carboxyl site of the organic acid of ring preferably primary carboxyl.Such as: the surface modifier can be benzyl alcohol (n20 D=1.5396),
Cinnamic acid (n20 D=1.616) etc..
According to the above scheme, the surface modifier is with the mole ratio of metallic atom in metal alkyl oxide in 2.0-
Between 5.0.Before the reaction, the molar ratio of surface modifier and metal alkyl oxide presoma is controlled, to reach control surface
The molar ratio of modifying agent and metallic atom.For example, the mole ratio range of benzyl alcohol and four tert-butoxy zirconiums 2.0-5.0 it
Between, preferably between 3.0-4.0.
According to the above scheme, the catalyst and the surface modifier of auxiliary are the organic acids containing aromatic rings.
According to the above scheme, the content of the catalyst and the surface modifier of auxiliary accounts for metal alkyl oxide and surface changes
The 0%-10% of the total weight of property agent.
Optical material, light comprising the organic-inorganic hybrid molecule composite material of the present invention with high refraction coefficient
The products such as electronic device, functional paint are also within protection scope of the present invention.
Compared with prior art, the beneficial effects of the present invention are:
1. the particle size of the metal oxygen cluster compound synthesized in the present invention all within the scope of sub-nanometer, is to improve the present invention
The key component of the refraction coefficient of material, while making using hybrid inorganic-organic composite wood made from the metal oxygen cluster compound
Material has high optical transparency, and high refraction coefficient, high stability, high-weatherability etc. can with good industrial applications prospect
To be widely used in new energy, optical material, opto-electronic device, a variety of high-tech areas such as functional paint.
2. the metal oxygen cluster compound be it is a kind of using metal as core, using oxygen as bridge, the cluster compound of more metal cores,
And in the forming process of this Polyoxometallate, it is completed at the same time organic surface modification；This metal oxygen cluster is compound
Object on a molecular scale, inorganic part and the chemical bond hybridization of organic moiety is got up, not only have high refraction coefficient, together
When to organic matter have fabulous compatibility, effectively prevent traditional nanocomposite kind it is common self cohesion or flocculation
Equal instability problems and therewith caused by Discussion on Light Diffusion Caused.
3, preparing the conventional method of metal oxygen cluster compound in the present invention is sol-gel method, but traditional colloidal sol is solidifying
Glue technology is due to reacting not exclusively, and time-consuming, is easy to produce irreversible precipitating, and industrialization is difficult to realize；And this hair
It is bright that sol-gel method is improved using surface modified chemical, so that there is machine maintenance on the preparation of metal oxygen cluster compound and surface
Decorations are synchronous to carry out, on a molecular scale, by inorganic part together with the chemical bond hybridization of organic moiety, formed it is a kind of it is organic-
Inorganic hybridization compound molecule；In preparation process, while improving reaction temperature, it is hydrolyzed and contracts in closed reaction kettle
Reaction is closed, while intermediate product metal oxygen cluster composite particles are done surface modified, reaction is controllable, and product is stablized, step
Simply, it is suitble to large-scale industrial production, has widened exploitation novel optical functional material approach.
Detailed description of the invention
Fig. 1 is the zirconium oxygen cluster compound ultraviolet-visible spectrum that surface is modified in embodiment 1, is dissolved in 5.0% weight
The measurement of percentage toluene solution.
Fig. 2 is the refraction coefficient variation diagram of products therefrom because synthesis condition changes in embodiment 2.
Fig. 3 is the product in (a) embodiment 1, i.e. the 2-PEA solution of the modified zirconium oxygen cluster compound in surface, transparent
Homogeneous liquid；The comparison for the high refractive power resin material that self is agglomerated or flocculated inorganic nanoparticles are modified occurs with (b).
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
The theoretical chemistry reaction equation of synthesis metal oxygen cluster compound and its derivative of the invention illustrates as follows:
M indicates metallic element, OR in above-mentioned reaction equation2Indicate the alcohols ligand containing aromatic rings, R3COO、R4COO
Indicate the organic acid ligand containing aromatic rings, it is nonnegative real number, a and e that a, b, c, d, e, f, g, h, which represent atom number,
Substantially in 2 to 50 ranges, b and f are substantially in the range of 4 to 200, and c and g are substantially in 2 to 100 ranges, and d and h are substantially 2
To 100 ranges.The metallic element M includes but is not limited to zirconium (Zr), titanium (Ti), antimony (Sb), zinc (Zn), iron (Fe), lead
(Pb), cadmium (Cd), tin (Sn) etc., better choice are zirconium (Zr), one of titanium (Ti) and zinc (Zn) etc. or arbitrary proportion
It is several；The OR2、R4COO is respectively derived from the alcohols containing aromatic rings or organic acid R2OH、R4COOH, respectively itself
Refraction coefficient n20 D>=1.52, hydroxy position is preferably primary hydroxyl, and carboxyl site is preferably primary carboxyl.
The metallic element M includes but is not limited to zirconium (Zr), titanium (Ti), antimony (Sb), zinc (Zn), iron (Fe), lead (Pb),
Cadmium (Cd), tin (Sn) etc. is similar with zirconium, and the electronics number of plies of listed metallic element is more, and electron cloud is easy to polarize, and is easy to and oxygen
In conjunction with, formed oxide, or with the oxygen atom or ion complexation in alcohol or acid, formed metal oxygen cluster compound, thus for
Raising refraction coefficient has the effect of similar.
By four tert-butoxy zirconiums or by taking four tert-butoxy titaniums as an example in following embodiments, according to reactant (metal alcoxyl
Compound, water, surface modifier) input amount (i.e. molar ratio) and theoretical stoichiometric calculating, below reaction equation
List 4 kinds of products, wherein first and second kinds of products are considered as primary product；And minimal amount of not hydrolyzed alkoxy
Group and the minimal amount of hydroxyl not being condensed do not show in equation, because their chemical activity can be ignored
(referring to the experimental result of embodiment 8).
Embodiment 1
The preparation method of zirconium oxygen cluster compound, key step are as follows:
1) 6.0 grams of benzyl alcohol and 0.71 gram of diphenylglycollic acid uniformly mix, and form solution A；1.35 gram deionized water
Benzyl alcohol with 6.0 grams uniformly mixes, and forms solution B；
2) butanol solution (commercially available, mass fraction 80%) of 12.0 grams of four tert-butoxy zirconiums is slowly added into solution A
In, 10 minutes formation solution Cs of uniform stirring；
3) solution B is slowly added dropwise to solution C under conditions of uniform stirring by 50 milliliters of constant pressure funnel
It is interior, form homogeneous solution D；
4) resulting solution D one is transferred completely into seal in cleaning and dried autoclave in advance, slowly plus
Solution D in thermal high kettle to 230 DEG C, pressure in kettle because solvent (butanol and part benzyl alcohol) it is vaporized due to increase, meeting
1.7 megapascal (MPa) left and right, heat preservation and pressure maintaining 4 hours, reaction terminates；After temperature in kettle is cooled to room temperature, high pressure is opened
Reaction kettle, the white suspended things shape of product；
5) white suspended things are transferred in the round-bottomed flask after a drying together with solvent, rotary evaporation in connection
It in instrument, with oil bath heating to 110 DEG C, vacuumizes, removes all volatile solvents and other do not participate in the surface modifier of reaction.
Obtain white depositions, as zirconium oxygen cluster compound；
5 grams of white depositions are taken, 5 grams of 2- phenoxyethyl acrylate is added, are heated at 110 DEG C, stirring, white is sunk
Starch slowly dissolves, and product becomes a transparent homogeneous liquid, n20 D=1.6391.According to theoretical calculation, zirconium oxygen cluster compound
Refraction coefficient be n20 D=1.760.
The white depositions in the step 5) of the synthesis of embodiment 1 are taken out, is dissolved in toluene solvant, is made into 5.0%
The solution of weight ratio；Then using toluene as reference, ultraviolet-visible spectrum such as Fig. 2 is obtained.As shown in Figure 2: products therefrom exists
Between 250-400 nanometers of ultraviolet region, there is the absorption peak of an absorption peak and Zr-O key corresponding；400-800 nanometers can
There is high transparency in light-exposed section without any absorption in visible light region.
Embodiment 2
The synthesis program of embodiment 1 is repeated, but is rubbed to as zirconium atom in initial reactant water and four tert-butoxy zirconiums
You (are labeled as H by number ratio2O/Zr), the time of the temperature, reaction reacted adjusts, to compare and optimize, the parameter of experiment
Variation is as listed in table 1.Other experiment conditions keep identical.
What table 1 synthesized under various conditions, the refraction coefficient of the modified zirconium oxygen cluster complex solution in surface
| Serial number | H2O/Zr | Reaction temperature (DEG C) | Reaction time (hour) | Refraction coefficient (n20 D) |
| Embodiment 2-1 | 1 | 190 | 2 | 1.591 |
| Embodiment 2-2 | 1 | 210 | 4 | 1.618 |
| Embodiment 2-3 | 1 | 230 | 6 | 1.590 |
| Embodiment 2-4 | 2 | 190 | 4 | 1.615 |
| Embodiment 2-5 | 2 | 210 | 6 | 1.614 |
| Embodiment 2-6 | 2 | 230 | 2 | 1.619 |
| Embodiment 2-7 | 3 | 190 | 6 | 1.625 |
| Embodiment 2-8 | 3 | 210 | 2 | 1.605 |
| Embodiment 2-9 | 3 | 230 | 4 | 1.639 |
From table 1 and Fig. 1: being 3.0 in the molal quantity ratio of initial reactant water and zirconium, reaction temperature is 230 DEG C, instead
Synthesis condition between seasonable for 4 hours is best, the refraction coefficient highest of reaction mixture: n20 D=1.639.
Embodiment 3
It repeats the synthesis program of embodiment 1, but using in surface modifier, other than benzyl alcohol, is replaced with cinnamic acid
For the diphenylglycollic acid in embodiment 1, the reagent and synthesis program of every other reaction are completely and embodiment 1 is identical, last
Product is similarly a transparent homogeneous liquid, the n of product20 D=1.6310.
It is preferable relative to cinnamic acid with surface modifier that diphenylglycollic acid is auxiliary, the refraction coefficient of reaction mixture compared with
It is high: n20 D=1.639.
Embodiment 4
The synthesis program of embodiment 1 is repeated, but in using surface modifier, other than benzyl alcohol, with dibenzoyl first
Alkane carrys out the diphenylglycollic acid in alternate embodiment 1, and the reagent and synthesis program of every other reaction are completely and embodiment 1 is identical.
The resulting white suspended things of reaction under high pressure cannot be dissolved into 2- phenoxyethyl acrylate (2-PEA), finally
Product is still white suspended things, can not measure its refraction coefficient, thus cannot be used.Therefore having containing aromatic rings need to be used
Machine acid is as catalyst and the surface modifier of auxiliary.
Embodiment 5
The synthesis program for repeating embodiment 1 carries out the dosage of major surfaces modifying agent benzyl alcohol preferred.At other
Under the premise of reaction condition is all identical, using different amounts of benzyl alcohol, series of parallel experiment is carried out, to hydrolysate in 2-
The difficulty or ease dissolved in phenoxyethyl acrylate (2-PEA), and the refraction coefficient of last solution product compare one by one, with
Determine best benzyl alcohol dosage.In these parallel laboratory tests, four tert-butoxy zirconium of presoma (Zr (OBu)4, commercially available, mass fraction
Butanol solution for 80%) amount it is constant be 12.0 grams (25.0 mMs), the constant amount of deionized water is 0.12 gram, hexichol second
The constant amount of alkyd is 0.71 gram.Experimental result is shown in Table 2.
Product under the different mol ratio example of the conduct major surfaces modifying agent of table 2, benzyl alcohol and zirconium compares
Difficulty or ease and step 6) gained that white depositions obtained by step 5) are comprehensively compared in the dissolution of 2-PEA are transparent molten
Liquid refraction coefficient height, according to table 2: the molar ratio of benzyl alcohol and metal zirconium atom or four tert-butoxy zirconiums is in 2.0-5.0
Between, preferably between 3.0-4.0.
Embodiment 6
The synthesis program for repeating embodiment 1, to dissolving step 6) activated monomer containing phenoxy group is adjusted, other realities
It tests that condition is constant, is selected and optimized according to the dissolution situation of white precipitate, the variation of experiment condition as listed in table 3, can by table 3
Know: the more other activated monomer solvents of 2-PEA, OPPEA, it is easier to which ground obtains fully transparent liquid；It is shunk using bisphenol-A two
Glycerin ether epoxy resin (BADGE) and two acryloyl of A- biphenol the third oxa- acid glycerol alkyd are sour (BAGDA), even if white is suspended
Object cannot be still completely dissolved as low as 20% weight percent.But the 2-PEA solution of zirconium oxygen cluster compound can be very
It is mixed in big degree with BADGE or BAGDA, without generating white opacity.
The result of white suspension in the different activated monomer dissolution embodiments 1 containing phenoxy group of table 3
Embodiment 7
By the white suspended things under the high temperature and pressure in the synthesis program of embodiment 1 together with solvent, i.e. surface is modified
Zirconium oxygen bridge atom family shape compound is divided into 10 parts together with solvent, and every part is equivalent to by 1.2 grams of four tert-butoxy zirconium (cities of presoma
Sell, the butanol solution that mass fraction is 80%) obtained product, take 4 parts as product come out, respectively by every part of white
Suspended things are transferred in the round-bottomed flask after a drying together with solvent, then in this 4 round-bottomed flasks, are separately added into
0.3 gram, 0.4 gram, 0.5 gram and 0.6 gram of 2- phenoxyethyl acrylate (2-PEA), is separately connected Rotary Evaporators
In, continue heating, rotatory vacuum evaporation process, removes all volatile solvents.It is heating, during rotary evaporation, is being added
In the flask of 0.5 gram and 0.6 gram of 2-PEA, white suspended things slowly dissolve, and product becomes transparent homogeneous liquid respectively.It should
The refraction coefficient of two transparency liquids is respectively as follows: n20 D=1.6391, n20 D=1.6189.
And be added in 0.3 gram and 0.4 gram of 2-PEA flask, it, cannot still mixture is muddy though through a long time heats
Become clear solution.So zirconium oxygen bridge atom cluster compound and 2- phenoxyethyl acrylate (2-PEA) that surface is modified
Optimum proportioning ratio should be: obtained by 1.2 grams of four tert-butoxy zirconiums of presoma (commercially available, the butanol solution that mass fraction is 80%)
Product, need to be completely dissolved with 0.5 gram of 2- phenoxyethyl acrylate (2-PEA), that is, its match be 12/5.0, can obtain
It is both transparent and refraction coefficient has higher homogeneous liquid to one.
The dissolution result and refraction coefficient for the product that table 4 is obtained using the quality proportioning of difference four tert-butoxy zirconiums/2-PEA
Embodiment 8
Repeat the synthesis of embodiment 1.Take out the obtained product in the synthesis program of example 1, that is, the modified zirconium oxygen bridge in surface
Atom tufted compound is dissolved in 5.0 grams of solution in 2- phenoxyethyl acrylate (2-PEA), and 0.1 gram of persulfuric acid is added
Potassium K2S2O8, slowly stir, potassium peroxydisulfate is completely dissolved, and after mixing, part solution is poured into form one in evaporating dish
Thickness is about 0.5 millimeter of liquid film；Evaporating dish is put into a baking oven, is slowly heated to 120 DEG C, and keep at such a temperature
3 hours, the liquid film are cured as a fully transparent glassy thin slice.
Glassy thin slice obtained by the present embodiment is tested at 632.8nm using ruby laser refraction coefficient tester,
The refraction coefficient of the glassy thin slice is 1.6552；Also, at room temperature, which is soaked into deionized water,
After three days (72 hours), not by the erosion of any water, appearance is not any change sheet glass.
Embodiment 9
A kind of organic-inorganic hybrid molecule composite material with high refraction coefficient, main constituents include:
34.7% zirconium oxygen cluster compound, 34.7% 2- phenoxyethyl acrylate (2-PEA), 14.8% BADGE, 14.8%
BAGDA, 0.9% 2- hydroxy-2-methyl -1- phenyl -1- acetone (1173 photoinitiator), 0.1% 4- metoxyphenol.
The preparation method of organic-inorganic hybrid molecule composite material described in the present embodiment with high refraction coefficient, specifically
Steps are as follows:
1) 6.0 grams of benzyl alcohol and 0.71 gram of diphenylglycollic acid uniformly mix, and form solution A；1.35 gram deionized water
Benzyl alcohol with 6.0 grams uniformly mixes, and forms solution B；
2) butanol solution (commercially available, mass fraction 80%) of 12.0 grams of four tert-butoxy zirconiums is slowly added into solution A
In, 10 minutes formation solution Cs of uniform stirring；
3) solution B is slowly added dropwise to solution C under conditions of uniform stirring by 50 milliliters of constant pressure funnel
It is interior, form homogeneous solution D；
4) resulting solution D one is transferred completely into seal in cleaning and dried autoclave in advance, slowly plus
Solution D in thermal high kettle to 230 DEG C, pressure in kettle because solvent (butanol and part benzyl alcohol) it is vaporized due to increase, meeting
1.7 megapascal (MPa) left and right, heat preservation and pressure maintaining 4 hours, reaction terminates；After temperature in kettle is cooled to room temperature, high pressure is opened
Reaction kettle, the white suspended things shape of product；
5) white suspended things are transferred in the round-bottomed flask after a drying together with solvent, rotary evaporation in connection
It in instrument, with oil bath heating to 110 DEG C, vacuumizes, removes all volatile solvents and other do not participate in the surface modifier of reaction.
Obtain white depositions, as zirconium oxygen cluster compound；
6) 5 grams of white depositions are taken, 5 grams of 2-PEA, heating stirring are then added, white depositions slowly dissolve, and produce
Object becomes a transparent homogeneous liquid, as the 2-PEA solution of zirconium oxygen cluster compound, n20 D=1.6391.
7) 6.94 grams of 2-PEA solution of zirconium oxygen cluster are taken, 1.48 grams of BADGE and 1.48 gram of BAGDA are added, stir evenly, then
0.01 gram of 4- metoxyphenol is sequentially added, 0.09 gram of 2- hydroxy-2-methyl -1- phenyl -1- acetone is sufficiently stirred, obtains one
A transparent homogeneous liquid, n20 D=1.616.
Embodiment 10
According to 9 the method for embodiment, the ratio of each component is changed, other programs are constant, and it is miscellaneous to obtain a variety of organic and inorganics
Chemoattractant molecule composite material compares their refraction coefficient, such as table 5.
The refraction coefficient comparison of the organic-inorganic hybrid molecule composite material of the different composition ratio of table 5
Embodiment 11
A kind of organic-inorganic hybrid molecule composite material with high refraction coefficient, main constituents include:
34.6% zirconium oxygen cluster compound, 34.6% adjacent phenylphenoxy ethyl propylene acid esters (OPPEA), 14.8% BAGDA,
14.8% Ethoxylated bisphenol A dimethylacrylate (EBADMA), 1.0% 1- hydroxycyclohexyl phenyl ketone (184 light
Initiator), 0.1% 4- metoxyphenol (MeHQ), 0.1% 2,6-di-tert-butyl p-cresol (BHT).
The preparation method of organic-inorganic hybrid molecule composite material described in the present embodiment with high refraction coefficient, specifically
Steps are as follows:
1) 6.0 grams of benzyl alcohol and 0.71 gram of diphenylglycollic acid uniformly mix, and form solution A；1.35 gram deionized water
Benzyl alcohol with 6.0 grams uniformly mixes, and forms solution B；
2) butanol solution (commercially available, mass fraction 80%) of 12.0 grams of four tert-butoxy zirconiums is slowly added into solution A
In, 10 minutes formation solution Cs of uniform stirring；
3) solution B is slowly added dropwise to solution C under conditions of uniform stirring by 50 milliliters of constant pressure funnel
It is interior, form homogeneous solution D；
4) resulting solution D one is transferred completely into seal in cleaning and dried autoclave in advance, slowly plus
Solution D in thermal high kettle to 230 DEG C, pressure in kettle because solvent (butanol and part benzyl alcohol) it is vaporized due to increase, meeting
1.7 megapascal (MPa) left and right, heat preservation and pressure maintaining 4 hours, reaction terminates；After temperature in kettle is cooled to room temperature, high pressure is opened
Reaction kettle, the white suspended things shape of product；
5) white suspended things are transferred in the round-bottomed flask after a drying together with solvent, rotary evaporation in connection
It in instrument, with oil bath heating to 110 DEG C, vacuumizes, removes all volatile solvents and other do not participate in the surface modifier of reaction.
Obtain white depositions, as zirconium oxygen cluster compound；
6) 5 grams of white depositions are taken, 5 grams of OPPEA, heating stirring are then added, white depositions slowly dissolve, and produce
Object becomes a transparent homogeneous liquid, as the OPPEA solution of zirconium oxygen cluster compound, n20 D=1.668.
7) 7.0 grams of OPPEA solution of zirconium oxygen cluster are taken, 1.5 grams of BAGDA are added, 1.5 grams of EBADMA are stirred evenly, then successively
0.01 gram of MeHQ, 0.01 gram of BHT is added, 0.1 gram of 184 photoinitiator is sufficiently stirred, and obtains a transparent homogeneous liquid, n20 D
=1.627.
Embodiment 12
According to 11 the method for embodiment, the ratio of each component is changed, other programs are constant, obtain a variety of organic and inorganics
Hybrid molecule composite material compares their refraction coefficient, such as table 6.
The refraction coefficient comparison of the organic-inorganic hybrid molecule composite material of the different composition ratio of table 6
Contrast test
1, the refraction coefficient of the product of embodiment 1 and the high refraction coefficient material of other classifications compares, as listed by table 6.Institute
The high refraction coefficient material for arranging other classifications is belonging respectively to pure organic compound (by taking bisphenol-A glycerol diacrylate as an example), contains
The organic compound (by taking penta-bromophenyl methacrylate as an example) of halogen, organic compound (4,4'- bis- mercaptos containing element sulphur
For base diphenyl sulfide double methyl methacrylate) three classes material.
The product of 6 embodiment of the present invention 1 of table and the refraction coefficient of other high refraction coefficient materials compare
2, the product of the embodiment of the present invention 1 with produce self cohesion or flocculated high refractive power nanocomposite it is saturating
Bright degree comparison, as shown in Figure 3.Last decade comes, and people are keen to improve the refraction coefficient of material, method using nano particle
Be the inorganic nanoparticles of high refraction coefficient are blended in organic resin, but tend to occur nano particle self
Cohesion or flocculation, to generate Discussion on Light Diffusion Caused, influence the light transmission of material.To avoid the problem that cohesion or generation of flocculating,
People attempt to do the modification of nano particle again, but the modification of nano particle substantially encounters great challenge in industry.And this hair
The organic and inorganic molecular hybrid composite material of bright preparation effectively prevents self common cohesion of traditional nanocomposite kind
Or flocculation etc. instability problems and therewith caused by Discussion on Light Diffusion Caused.Organic-nothing made from the metal oxygen cluster compound
Machine hybrid composite material has high optical transparency, high refraction coefficient, high stability, high-weatherability etc., with industry well
Change application prospect.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.
Claims (16)
1. a kind of organic-inorganic hybrid molecule composite material with high refraction coefficient, it is characterised in that its main composition at
It point include: the monomer or neat of metal oxygen cluster compound and its derivative, the activated monomer containing phenoxy group, polymerizable active group
Aggressiveness, solidification adjuvant, additive, by mass percentage are as follows: metal oxygen cluster compound and its derivative 2%-52% contain
The activated monomer 2%-88% of phenoxy group, the monomer or oligomer 0%-90% of polymerizable active group solidify adjuvant 0%-
10%, additive 0%-10%；
The metal oxygen cluster compound and its derivative are zirconium oxygen cluster compound and its derivative, and preparation method key step is such as
Under:
Using the alkyl oxide of metal zirconium as presoma, using water as reactant, the molar ratio of control water and metal zirconium atom is carried out
Reaction, using contain aromatic rings alcohols or organic acid as surface modifier, using the organic acid that contains aromatic rings as urging
The surface modifier of agent and auxiliary reacts under conditions of high temperature and pressure in closed reaction kettle, and it is compound to obtain zirconium oxygen cluster
Object and its derivative；
The activated monomer containing phenoxy group includes but is not limited to 2- phenoxyethyl acrylate, adjacent phenylphenoxy second
The mixture of one or more of base acrylate arbitrary proportion；
The additive is polymerization inhibitor, wetting agent, antioxidant, levelling agent, defoaming agent, rheology modifier, adhesion promoter
One of or it is a variety of；
The mole ratio of metallic atom is between 2.0-5.0 in the surface modifier and the alkyl oxide of metal zirconium.
2. a kind of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 1, feature
The general formula for being the metal oxygen cluster compound and its derivative is MaOb(OR2)c(R3COO)dOr MeOf(R4COO)g(R3COO)h,
M indicates zr element, OR in formula2Indicate the alcohols ligand containing aromatic rings, R3COO、R4COO indicates to contain aromatic rings
Organic acid ligand, a, b, c, d, e, f, g, h represent atom number, are nonnegative real number.
3. a kind of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 2, feature
It is the OR2、R4COO is respectively derived from the alcohols R containing aromatic rings2OH or organic acid R4COOH, respectively itself
Refraction coefficient n20 D≥1.52。
4. a kind of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 1, feature
It is the refraction coefficient of the activated monomer containing phenoxy group itself not less than 1.51, that is, n20 D≥1.51。
5. a kind of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 1, feature
It is monomer or the oligomer of the polymerizable active group to include but is not limited to acryloxyalkyl or aromatic radical, methyl
Acryloxyalkyl or aromatic radical, alkylene, alkynes base, aromatic ring oxyalkyl, chain type aliphatic epoxy alkyl, cyclic annular rouge
The monomer or oligomer of one or more of fat race epoxy alkyl, vinyl ethers, mercapto, cinnamate group active group.
6. a kind of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 1, feature
It is that the solidification adjuvant is selected from free radical photo-initiation, cation light initiator, thermal initiator, curing agent, in catalyst
One or more.
7. a kind of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 6, feature
It is that the free radical photo-initiation includes but is not limited to 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxycyclohexylphenyl
Ketone, 2,4,6- trimethylbenzoy-dipheny phosphine oxides, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) benzene
Base] -1- acetone, benzophenone, 4- methyl benzophenone, one of 4- (dimethylamino)-benzoic acid-(2- ethyl) own ester or
It is several；The cation light initiator includes but is not limited to diazonium salt, diaryl iodonium salt, triaryl sulfonium salts, alkyl sulfide
One or more of salt, iron arene salt, sulfonyloxy ketone and triaryl silicon oxygen ether；The thermal initiator includes but does not limit to
In potassium peroxydisulfate, ammonium persulfate, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile,
One or more of azobisisoheptonitrile；The curing agent includes but is not limited to diethylene triamine, aromatic polyamine, double
One of cyanogen diamine, boron trifluoride, ethanedioic acid, phthalic anhydride, hydroquinone, ethylene glycol, 1,4- succinimide mercaptans are several
Kind；The catalyst includes but is not limited to n-propylamine, triethylamine, n,N-diisopropylethylamine, 4-dimethylaminopyridine, triphen
One or more of base phosphine.
8. a kind of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 1, feature
It is that the polymerization inhibitor includes but is not limited to 4- metoxyphenol, hydroquinone or 1,4-benzoquinone；The wetting agent includes but not
It is confined to propylene glycol or glycerol；The antioxidant includes but is not limited to DBPC 2,6 ditertiary butyl p cresol, butylhydroxy fennel
Ether or tert-butyl hydroquinone；The levelling agent includes but is not limited to dimethyl silicone polymer or polyacrylate；It is described to disappear
Infusion includes but is not limited to silicone emulsion, the fatty acid ester compounded object of higher alcohols, polyoxyethylene polyoxypropylene pentaerythrite ether, gathers
Ethylene oxide polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxyethylene polyoxypropylene glycerin ether or dimethyl silicone polymer；It is described
Rheology modifier includes but is not limited to fumed silica or castor oil derivative；The adhesion promoter includes but not office
It is limited to silane coupling agent or titanate coupling agent.
9. a kind of preparation method of organic-inorganic hybrid molecule composite material with high refraction coefficient described in claim 1,
It is characterized in that key step is as follows:
A) according to the ratio, metal oxygen cluster compound and its derivative, the activated monomer containing phenoxy group, polymerizable active group are weighed
Monomer or oligomer, solidification adjuvant, additive, it is spare；
B) metal oxygen cluster compound and its derivative are dissolved in the activated monomer containing phenoxy group, obtain clear solution；
C) monomer or oligomer for containing polymerizable active group will be added in clear solution obtained by step b), solidify adjuvant,
After additive, aggregated and/or crosslinking curing obtains the hybrid inorganic-organic composite material with high refraction coefficient.
10. a kind of preparation of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 9
Method, it is characterised in that the cured mode is the group of one or more of ultraviolet light irradiation, electron beam irradiation, heating
It closes.
11. a kind of preparation of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 9
Method, it is characterised in that the preparation method of the zirconium oxygen cluster compound and its derivative, key step are as follows:
1) organic acid containing aromatic rings is dissolved in the alcohols or organic acid containing aromatic rings, prepares solution A；By water
It is dissolved in the alcohols or organic acid containing aromatic rings, prepares solution B；
2) alkoxide compound of metal zirconium is added in solution A, is uniformly mixed, form solution C；
3) solution B is added dropwise under stirring conditions in solution C, forms homogeneous solution D；
4) acquired solution D is transferred to autoclave sealing, is heated to temperature 190-230 degree, the pressure rise in kettle is arrived
1.4-2.0MPa, heat preservation and 2-6 hour of dwell time, reaction terminate；
5) the heated rotary evaporation purification of gained crude product in autoclave obtained by step 4) is removed into solvent and other is not joined
The surface modifier for adding reaction obtains the suspended things of white or the sediment of white, as zirconium oxygen cluster compound and its derivative
Object.
12. a kind of preparation of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 9
Method, it is characterised in that the alkyl oxide of the metal zirconium, with formula M (OR)nIt indicates, wherein M represents metal zr element, R
Alkyl is represented, n represents the ligancy for corresponding to metal zr element.
13. a kind of preparation of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 9
Method, it is characterised in that the molar ratio of zirconium atom is 1/1 to 6/1 in the alkyl oxide of the reactants water and metal zirconium.
14. a kind of preparation of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 9
Method, it is characterised in that the refraction coefficient n of the surface modifier itself20 D≥1.52。
15. a kind of preparation of organic-inorganic hybrid molecule composite material with high refraction coefficient according to claim 9
Method, it is characterised in that the content of the catalyst and the surface modifier of auxiliary accounts for the alkyl oxide of metal zirconium and surface changes
The 0%-10% of the total weight of property agent.
16. the optical material comprising the organic-inorganic hybrid molecule composite material described in claim 1 with high refraction coefficient,
Opto-electronic device or functional paint.
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