CN114230692A - Composite inorganic photoinitiator using full spectrum and preparation method and application thereof - Google Patents
Composite inorganic photoinitiator using full spectrum and preparation method and application thereof Download PDFInfo
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- CN114230692A CN114230692A CN202111632056.5A CN202111632056A CN114230692A CN 114230692 A CN114230692 A CN 114230692A CN 202111632056 A CN202111632056 A CN 202111632056A CN 114230692 A CN114230692 A CN 114230692A
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- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000001228 spectrum Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 10
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical group [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical group C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- -1 ester polyol Chemical class 0.000 claims description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000007517 lewis acids Chemical group 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 10
- 239000003513 alkali Substances 0.000 claims 1
- 239000012074 organic phase Substances 0.000 abstract description 6
- 239000010954 inorganic particle Substances 0.000 abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 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 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- FXCSCTVYEKPPDO-UHFFFAOYSA-N (2-ethenylphenyl)-phenylmethanone Chemical compound C=CC1=CC=CC=C1C(=O)C1=CC=CC=C1 FXCSCTVYEKPPDO-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
Abstract
The invention discloses a composite inorganic photoinitiator utilizing a full spectrum, which comprises a solvent, a solid part and deionized water, wherein the mass ratio of the solvent to the solid part is 1/10-3/10; the mass ratio of the deionized water/(the solvent and the solid parts) is 4/10-8/10, and the solid parts are prepared from the following raw materials in percentage by mass: 10-60 Wt% of precursor, 0.1-10 Wt% of catalyst, 0.1-10 Wt% of polyalcohol, 5-60 Wt% of resin monomer, 0.1-10 Wt% of inorganic base, 0.1-20 Wt% of functional monomer containing vinyl unsaturated group, 5-50 Wt% of pH regulator and 1-65 Wt% of polymerizable micromolecule photoinitiator. The composite inorganic photoinitiator can be better dispersed in an organic phase, so that the function of the inorganic photoinitiator is exerted, and after curing, inorganic particles are more tightly combined with the organic phase, so that the composite inorganic photoinitiator has better curing performance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a composite inorganic photoinitiator utilizing a full spectrum.
Background
A photoinitiator is a substance that absorbs radiation energy and undergoes an excitation to produce a photochemical change that produces a reactive intermediate (radical or cation) that has the ability to initiate polymerization. The existing photocuring technology uses a large amount of photoinitiator with relatively small molecular mass, and in the photocuring process of the photoinitiator, residual quantity and photolysis products are easy to migrate to the surface of a product to generate certain smell and even toxicity, so that the application of the photoinitiator in the aspects of food packaging, medical treatment and health care is limited. The nano material has excellent characteristics of surface interface effect, quantum size effect, macroscopic quantum tunneling effect and the like, so that the nano material has wide application prospect and commercial value. However, the nano material has small particle size, large specific surface area and a large amount of hydroxyl groups, so that the nano material has high surface energy, is easy to agglomerate and is not easy to disperse in organisms, and the actual application effect of the nano material is influenced. Therefore, many documents improve the dispersibility and compatibility of the nanomaterial in an organic system by performing surface modification on the nanomaterial.
The research on inorganic-organic composite photoinitiators is rarely carried out in China. The prior patent discloses a photoinitiator used as an initiator and a nano filler, which comprises a polyhedral oligomeric silsesquioxane (POSS) part and a photoinitiator part, wherein the preparation of the photoinitiator requires preparation of POSS with halogen elements on side chains in the first step, but the halogenation reaction conditions of POSS are strict (argon atmosphere and ice bath environment), the process is complicated, the introduction of halogen elements in the synthesis process causes potential toxicity of the final product, and the photoinitiator capable of reacting and grafting with POSS-X (X represents halogen elements) is limited. The prior art also discloses SiO2The preparation method of the nano particle surface graft polymer type photoinitiator comprises the first step of halogenating Si-OH into Si-Cl by thionyl chloride, the raw material thionyl chloride has high toxicity, and Si-The halogenation reaction conditions of OH are strict (no water environment is needed), and the photoinitiator capable of reacting and grafting with Si-Cl is limited, so that the selection of the photoinitiator is limited.
Disclosure of Invention
The invention mainly solves the technical problem of providing a composite inorganic photoinitiator utilizing full spectrum, a preparation method and application thereof, wherein the composite inorganic photoinitiator can be better dispersed in an organic phase so as to exert the function of the inorganic photoinitiator, and inorganic particles are more tightly combined with the organic phase after curing, so that the composite inorganic photoinitiator has better curing performance.
In order to solve the technical problems, the invention adopts a technical scheme that: providing a composite inorganic photoinitiator utilizing a full spectrum, wherein the photoinitiator comprises a solvent, a solid part and deionized water, and the mass ratio of the solvent to the solid part is 1/10-3/10; the mass ratio of the deionized water/(the solvent and the solid parts) is 4/10-8/10, and the solid parts are prepared from the following raw materials in percentage by mass:
the functional monomer containing the alkene unsaturated group is at least one of (methyl) acrylic acid, (methyl) acrylamide, allyl amine, styrene, acrylate and methacrylate;
the resin monomer is bisphenol A glycidyl methacrylate.
Further, the precursor is tetraisopropyl titanate.
The polyol is at least one of polyester polyol, polycarbonate polyol and rosin ester polyol.
Further, the inorganic base is at least one of potassium hydroxide, sodium hydroxide and lithium hydroxide.
Further, the pH value regulator is sodium carbonate, sodium bicarbonate, ammonia water, triethylamine or dimethylethanolamine.
Further, the catalyst is a lewis acid or lewis base.
A preparation method of a composite inorganic photoinitiator utilizing full spectrum comprises the steps of firstly adding a polymerizable micromolecule photoinitiator and a monomer containing an alkene unsaturated group into a solution dissolved with a precursor, polymerizing under the action of polyalcohol, and introducing a photoinitiation group into a polymer; then adding inorganic base, catalyst and resin monomer into the reaction system to carry out grafting reaction, thereby introducing unsaturated double bonds into the molecular structure of the polymer; and (3) adjusting the pH value of the system to be more than 7 by using a pH regulator, and adding deionized water under stirring to obtain the composite inorganic photoinitiator utilizing the full spectrum.
An application of the composite inorganic photoinitiator in photocuring.
The invention has the beneficial effects that:
(1) the preparation method has the advantages of simple operation, cheap and easily obtained raw materials and mild reaction conditions;
(2) the composite inorganic photoinitiator can be better dispersed in an organic phase, so that the function of the inorganic photoinitiator is exerted, and after curing, inorganic particles are more tightly combined with the organic phase, so that the composite inorganic photoinitiator has better curing performance.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.
Example 1:
the solvent is propylene glycol methyl ether, and the dosage of the propylene glycol methyl ether is 20 percent of the solid part;
80 percent of deionized water/(solvent + solid part)
The implementation steps are as follows: putting tetraisopropyl titanate into a four-mouth bottle, adding propylene glycol methyl ether to dissolve the tetraisopropyl titanate, heating to 100 ℃, dropwise adding 2959, acrylic acid, styrene and butyl acrylate under the action of polyester polyol, dropwise adding the mixture for two hours, keeping the temperature at 110 ℃ for two hours, then adding lithium hydroxide, adding bisphenol A glycidyl methacrylate and tetrabutylammonium bromide after 10 minutes, reacting for 5 hours, cooling to 40 ℃, adding sodium carbonate to adjust the pH value to be more than 7, then dropwise adding deionized water under the stirring of the rotating speed of 800r/min, emulsifying, and finally preparing the composite inorganic photoinitiator using the full spectrum.
Example 2:
the solvent is ethylene glycol monobutyl ether, and the dosage of the solvent is 20 percent of the solid part;
deionized water/(solvent + solid) 70%
The implementation steps are as follows: putting tetraisopropyl titanate into a four-mouth bottle, adding ethylene glycol monobutyl ether to dissolve the tetraisopropyl titanate, heating to 110 ℃, dropwise adding acrylated benzophenone, methacrylic acid, styrene, methyl methacrylate and hydroxyethyl methacrylate under the action of polyester polyol, dropwise adding the mixture for two hours, then keeping the temperature at 110 ℃ for two hours, then adding potassium hydroxide, adding bisphenol A glycidyl methacrylate and tetrabutylammonium bromide after 10 minutes, reacting for 3 hours, cooling to 60 ℃, adding triethylamine to adjust the pH value to be more than 7, then dropwise adding deionized water under the stirring of the rotating speed of 600r/min, emulsifying, and finally obtaining the composite inorganic photoinitiator using the full spectrum.
Example 3:
the solvent is ethylene glycol monobutyl ether and isopropanol, and the dosage of the solvent is 30 percent of the solid;
deionized water/(solvent + solid) 60%
The implementation steps are as follows: putting an epoxy resin E-51 and a ring-opening product of myristic acid into a four-mouth bottle, adding ethylene glycol monobutyl ether and isopropanol to dissolve the epoxy resin E-51 and the ring-opening product, heating to 120 ℃, dropwise adding vinyl benzophenone, acrylated benzophenone, methacrylic acid, styrene, methyl acrylate and isobornyl acrylate under the action of polycarbonate polyol, dropwise adding for two hours, then preserving the temperature for two hours at 120 ℃, then adding sodium hydroxide, adding bisphenol A glycidyl methacrylate and tetramethyl ammonium bromide after 10 minutes, reacting for 4 hours, cooling to 50 ℃, adding ammonia water to adjust the pH value to be more than 7, then dropwise adding deionized water under stirring at the rotating speed of 600r/min, emulsifying, and finally preparing the composite inorganic photoinitiator using a full spectrum.
Example 4:
the solvent is propylene glycol monomethyl ether, and the dosage of the solvent is 15 percent of the solid;
deionized water/(solvent + solid) 65%
The implementation steps are as follows: putting tetraisopropyl titanate into a four-mouth bottle, adding propylene glycol monomethyl ether to dissolve the tetraisopropyl titanate, heating to 110 ℃, dropwise adding modified 2-carboxythianthrone, methacrylic acid, styrene, methyl methacrylate and ethyl acrylate under the action of rosin ester polyol, dropwise adding the modified 2-carboxythianthrone, the methacrylic acid, the styrene, the methyl methacrylate and the ethyl acrylate for two hours, then preserving the temperature for two hours at 110 ℃, then adding lithium hydroxide, adding bisphenol A glycidyl methacrylate and tetrabutylammonium bromide after 10 minutes, reacting for 4 hours, cooling to 60 ℃, adding sodium bicarbonate to adjust the pH value to be more than 7, then dropwise adding deionized water under the stirring of the rotating speed of 900r/min, emulsifying, and finally preparing the full-spectrum composite inorganic photoinitiator.
Example 5:
the solvent is ethylene glycol monobutyl ether, and the dosage of the solvent is 25 percent of the solid part;
deionized water/(solvent + solid) 65%
The implementation steps are as follows: putting tetraisopropyl titanate into a four-mouth bottle, adding ethylene glycol monobutyl ether to dissolve the tetraisopropyl titanate, heating to 120 ℃, dropwise adding acrylated camphorquinone, methacrylic acid, styrene, methyl methacrylate and isobornyl acrylate under the action of polycarbonate polyol, dropwise adding the mixture for two hours, keeping the temperature at 120 ℃ for two hours, then adding potassium hydroxide, adding bisphenol A glycidyl methacrylate and tetramethylammonium chloride after 10 minutes, reacting for 4 hours, cooling to 50 ℃, adding dimethylethanolamine to adjust the pH value to be more than 7, dropwise adding deionized water under the stirring of the rotating speed of 700r/min, emulsifying, and finally preparing the composite inorganic photoinitiator using the full spectrum.
The relevant properties of the composite inorganic photoinitiators using the full spectrum obtained in the various examples are as follows:
the above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications made by the present invention in the equivalent structure or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (8)
1. A composite inorganic photoinitiator utilizing a full spectrum, characterized in that:
the photoinitiator comprises a solvent, a solid part and deionized water, wherein the mass ratio of the solvent to the solid part is 1/10-3/10; the mass ratio of the deionized water/(the solvent and the solid parts) is 4/10-8/10, and the solid parts are prepared from the following raw materials in percentage by mass:
the functional monomer containing the alkene unsaturated group is at least one of (methyl) acrylic acid, (methyl) acrylamide, allyl amine, styrene, acrylate and methacrylate;
the resin monomer is bisphenol A glycidyl methacrylate.
2. The compound inorganic photoinitiator according to claim 1, wherein the compound inorganic photoinitiator has a full spectrum, and is characterized in that: the precursor is tetraisopropyl titanate.
3. The compound inorganic photoinitiator according to claim 1, wherein the compound inorganic photoinitiator has a full spectrum, and is characterized in that: the polyol is at least one of polyester polyol, polycarbonate polyol and rosin ester polyol.
4. The compound inorganic photoinitiator according to claim 1, wherein the compound inorganic photoinitiator has a full spectrum, and is characterized in that: the inorganic alkali is at least one of potassium hydroxide, sodium hydroxide and lithium hydroxide.
5. The compound inorganic photoinitiator according to claim 1, wherein the compound inorganic photoinitiator has a full spectrum, and is characterized in that: the pH value regulator is sodium carbonate, sodium bicarbonate, ammonia water, triethylamine or dimethylethanolamine.
6. The compound inorganic photoinitiator according to claim 1, wherein the compound inorganic photoinitiator has a full spectrum, and is characterized in that: the catalyst is a lewis acid or lewis base.
7. A preparation method of a composite inorganic photoinitiator using a full spectrum is characterized in that: firstly, adding a polymerizable micromolecule photoinitiator and a monomer containing an alkene unsaturated group into a solution in which a precursor is dissolved, polymerizing under the action of polyol, and introducing a photoinitiation group into a polymer; then adding inorganic base, catalyst and resin monomer into the reaction system to carry out grafting reaction, thereby introducing unsaturated double bonds into the molecular structure of the polymer; and (3) adjusting the pH value of the system to be more than 7 by using a pH regulator, and adding deionized water under stirring to obtain the composite inorganic photoinitiator utilizing the full spectrum.
8. Use of a composite inorganic photoinitiator according to claim 1 in photocuring using the full spectrum.
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| CN101186743A (en) * | 2007-11-16 | 2008-05-28 | 北京化工大学 | Ultraviolet light solidifying copolymer emulsion and preparation method thereof |
| CN101333278A (en) * | 2008-08-07 | 2008-12-31 | 北京化工大学 | Method for preparing water-soluble polymerisable macromolecule photoinitiator |
| CN105273157A (en) * | 2015-10-22 | 2016-01-27 | 广东工业大学 | UV (ultraviolet)-curable low-oxygen-polymerization-inhibition nano hybrid filler and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186743A (en) * | 2007-11-16 | 2008-05-28 | 北京化工大学 | Ultraviolet light solidifying copolymer emulsion and preparation method thereof |
| CN101333278A (en) * | 2008-08-07 | 2008-12-31 | 北京化工大学 | Method for preparing water-soluble polymerisable macromolecule photoinitiator |
| CN105273157A (en) * | 2015-10-22 | 2016-01-27 | 广东工业大学 | UV (ultraviolet)-curable low-oxygen-polymerization-inhibition nano hybrid filler and preparation method thereof |
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