CN105237777A - Preparation method of silicon modified waterborne epoxy resin - Google Patents
Preparation method of silicon modified waterborne epoxy resin Download PDFInfo
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- CN105237777A CN105237777A CN201510706229.1A CN201510706229A CN105237777A CN 105237777 A CN105237777 A CN 105237777A CN 201510706229 A CN201510706229 A CN 201510706229A CN 105237777 A CN105237777 A CN 105237777A
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- epoxy resin
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 72
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 53
- 239000010703 silicon Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- -1 aminopropyl Chemical group 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- 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 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 4
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 229960004488 linolenic acid Drugs 0.000 claims description 4
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002632 lipids Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 229920000620 organic polymer Polymers 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation method of silicon modified waterborne epoxy resin. The preparation method comprises the following steps: (1) modifying organosilicon with a silane coupling agent to prepare silica sol; and (2) carrying a reaction between silica sol and waterborne epoxy resin under the action of a catalyst, and adding a neutralizer to prepare silicon modified waterborne epoxy resin. By combining silica sol and water-borne epoxy resin by a chemical bond, the silicon modified waterborne epoxy resin with excellent performance is obtained. The silicon modified waterborne epoxy resin is a novel resin coating having excellent properties of both an organic polymer and an inorganic material. The silicon modified waterborne epoxy resin is a combination of an organic polymer and an inorganic phase at the nanoscale, producing a strong interfacial interaction between the organic polymer and the inorganic phase. The prepared silicon modified waterborne epoxy resin has superior organic and inorganic properties, has characteristics of high strength, high toughness, good adhesive force, good high temperature resistance, good ageing resistance and the like, and overcomes performance defects of traditional waterborne epoxy resin.
Description
Technical field
The present invention relates to water-borne coatings field, particularly relate to the preparation method of a kind of dryness and the good silicon modified aqueous epoxy resin of weathering resistance.
Background technology
It is good that epoxy resin has sticking power, and adhesive power is strong, and chemical-resistant is outstanding waits good characteristic, in paint field extensive application.Conventional epoxies great majority are insoluble in water; therefore execute a large amount of organic solvent of man-hour requirement to dilute; the volatilization of organic solvent can cause serious threat to the health of environment protection and people; therefore aqueous epoxy resins liking more and more by people, but aqueous epoxy resins self dryness, weathering resistance difference limit its application.Silicon modified epoxy resin coating prepared by domestic and international most of researchist is all the method adopting physical mixed, although the easy easy enforcement of method, stability is bad, easily produces precipitation.
By silicon sol, in the mode of chemical bond, modification is carried out to aqueous epoxy resins, obtained silicon modified aqueous epoxy resin, possess the good characteristic of organic coating film and inorganic coating film simultaneously, the dryness of aqueous epoxy resins, weathering resistance and shock-resistance are obtained and effectively improves.Therefore, the research of silicon modified aqueous epoxy resin is to the application performance improving aqueous epoxy resins, and preparation infant industry coating has important directive significance.
Summary of the invention
Instant invention overcomes shortcoming of the prior art, provide a kind of preparation method of silicon modified aqueous epoxy resin, possess inorganics and organic good characteristic, its stability is fine, and film dryness is good, hardness is high, and film has excellent resistance to acids and bases and ageing resistance simultaneously.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A preparation method for silicon modified aqueous epoxy resin, comprises the following steps:
(1) silicon sol is prepared with silane coupler modified organosilicon;
(2) epoxy resin of described silicon sol and Water-borne modification is reacted under the effect of catalyzer, then add neutralizing agent, prepare silicon modified aqueous epoxy resin.
Further, described silicon sol is grafted on the epoxy resin of Water-borne modification in the mode of chemical bond.
Further, described silicon sol is by unformed SiO
2microparticulate is formed afterwards in water, and particle diameter is between 1 ~ 100nm, and wherein the quality of silicon sol accounts for 2% ~ 50% of modified epoxy.
Further, the chemical general formula of described silane coupling agent is R1-Si (OR)
3, wherein OR is the alkoxyl group of hydrolysis, R
1for aminopropyl, vinyl, methyl or epoxy group(ing).
Further, described organosilicon is the mixing of one or more of methyltrimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, tetraethoxy and dimethyldiethoxysilane, described neutralizing agent be silica-based phosphoric acid ester, sodium bicarbonate, sodium-acetate, trisodium phosphate, sodium carbonate, ammoniacal liquor, triethylamine, dimethylethanolamine one or more.
Further, the epoxy resin of described Water-borne modification is by lipid acid and epoxy resin generation esterification, obtain epoxy ester resin, and add solvent cut, then add acrylicacidandesters class monomer and vinyl monomer under the effect of initiator, to cause it carry out radical polymerization, thus introduce polar group.
Further, described lipid acid is oleic acid, described oleic acid is synourin oil, oleum lini, soya-bean oil or tung oil, equivalent value is 200 ~ 300, described epoxy resin is bisphenol A type epoxy resin, molecular weight is between 800 ~ 3000, and described bisphenol A type epoxy resin is epoxy resin E-06, epoxy resin E-20 or epoxy resin E-12.
Further, described solvent is the mixed solvent of one or more of ethanol, Virahol, propyl carbinol, ethylene glycol monobutyl ether, propylene glycol, ethylene glycol diethyl ether, described Acrylic Acid Monomer, as one or more in n-butyl acrylate, β-dimethyl-aminoethylmethacrylate, vinylformic acid, methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, described vinyl monomer, can be vinylbenzene, vinyl acetate one or more.
Further, described initiator is that benzoyl peroxide or azo two isobutyl are fine, and the consumption of initiator is 1% ~ 6% of acrylic acid and propynoic acid ester class monomer and vinyl monomer weight.
Compared with prior art, the invention has the beneficial effects as follows:
The preparation method of a kind of silicon modified aqueous epoxy resin of the present invention, comprises the following steps: (1) prepares silicon sol with silane coupler modified organosilicon; (2) epoxy resin of described silicon sol and Water-borne modification is reacted under the effect of catalyzer, then add neutralizing agent, prepare silicon modified aqueous epoxy resin.Make the two combine with the form of chemical bond, obtain the silicon modified aqueous epoxy resin of excellent performance.Silicon modified aqueous epoxy resin is a kind of new type resin coating simultaneously having organic polymer and inorganic materials good characteristic, and it is that organic polymer and inorganic phase combine on nanoscale, makes to there is stronger interfacial interaction between the two.Silicon modified aqueous epoxy resin prepared by the present invention possesses organic and inorganic premium properties simultaneously, the characteristic such as have high strength, high tenacity, sticking power is good, high thermal resistance is good, ageing resistance is good, overcomes the defect in traditional aqueous epoxy resins performance.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1
Take Union carbide A-162 60 parts, dehydrated alcohol 64 parts, distilled water 20 parts and 3-triethoxysilyl-1-propylamine 20 parts, mix and be adjusted to acid system, at 50 ~ 75 DEG C, reacting 8h, namely obtain modified silicasol.
By epoxy resin E-06 (epoxy equivalent (weight) 800 ~ 3000) 70 parts, linolenic acid 50 parts and 1 part, zinc oxide carry out esterification at 220 DEG C, butyl glycol ether dilution is added after esterification completes, by n-butyl acrylate 12 parts after cooling, vinylbenzene 14 parts, (this experiment is synthesized for 8 parts, vinylformic acid and silicon sol 20 parts, admittedly containing 20%) mixing solutions slowly add, react under the effect of catalyzer benzoyl peroxide, after having reacted, silicon modified aqueous epoxy resin can be obtained.
Embodiment 2
Take Union carbide A-162 60 parts, dehydrated alcohol 64 parts, distilled water 20 parts and 3-triethoxysilyl-1-propylamine 20 parts, mix and be adjusted to acid system, at 50 ~ 75 DEG C, reacting 8h, namely obtain modified silicasol.
By epoxy resin E-06 (epoxy equivalent (weight) 800 ~ 3000) 70 parts, linolenic acid 50 parts and 1 part, zinc oxide carry out esterification at 220 DEG C, butyl glycol ether dilution is added after esterification completes, by n-butyl acrylate 12 parts after cooling, vinylbenzene 14 parts, (this experiment is synthesized for 8 parts, vinylformic acid and silicon sol 30 parts, admittedly containing 20%) mixing solutions slowly add, react under the effect of catalyzer benzoyl peroxide, after having reacted, silicon modified aqueous epoxy resin can be obtained.
Embodiment 3
Take Union carbide A-162 60 parts, dehydrated alcohol 54 parts, distilled water 22 parts and 3-triethoxysilyl-1-propylamine 22 parts, mix and be adjusted to acid system, at 50 ~ 75 DEG C, reacting 8h, namely obtain modified silicasol.
By epoxy resin E-06 (epoxy equivalent (weight) 800 ~ 3000) 70 parts, linolenic acid 30 parts and 1 part, zinc oxide carry out esterification at 220 DEG C, butyl glycol ether dilution is added after esterification completes, by n-butyl acrylate 18 parts after cooling, vinylbenzene 21 parts, (this experiment is synthesized for 12 parts, vinylformic acid and silicon sol 20 parts, admittedly containing 20%) mixing solutions slowly add, react under the effect of catalyzer benzoyl peroxide, after having reacted, silicon modified aqueous epoxy resin can be obtained.
Embodiment 4
Take the silicon modified aqueous epoxy resin 100 parts prepared by embodiment 2, dispersion agent 0.5 part, appropriate distilled water, titanium dioxide 65 parts, process white 135 parts, under homogenizer, disperse 30min, then add granulated glass sphere and grind, stop grinding to during fineness≤10 μm of coating, add distilled water adjusting viscosity, add flow agent, be coated on tinplate, obtained film.Table 1 shows film in dryness, resistance to acids and bases etc., all has excellent performance.
Table 1 film performance is tested
Last it is noted that these are only the preferred embodiments of the present invention; be not limited to the present invention; although with reference to embodiment to invention has been detailed description; for a person skilled in the art; it still can be modified to the technical scheme described in foregoing embodiments; or equivalent replacement is carried out to wherein portion of techniques feature; but it is within the spirit and principles in the present invention all; any amendment of doing, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for silicon modified aqueous epoxy resin, is characterized in that, comprises the following steps:
(1) silicon sol is prepared with silane coupler modified organosilicon;
(2) epoxy resin of described silicon sol and Water-borne modification is reacted under the effect of catalyzer, then add neutralizing agent, prepare silicon modified aqueous epoxy resin.
2. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 1, it is characterized in that, described silicon sol is grafted on the epoxy resin of Water-borne modification in the mode of chemical bond.
3. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 1, it is characterized in that, described silicon sol is by unformed SiO
2microparticulate is formed afterwards in water, and particle diameter is between 1 ~ 100nm, and wherein the quality of silicon sol accounts for 2% ~ 50% of modified epoxy.
4. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 1, it is characterized in that, the chemical general formula of described silane coupling agent is R1-Si (OR)
3, wherein OR is the alkoxyl group of hydrolysis, R
1for aminopropyl, vinyl, methyl or epoxy group(ing).
5. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 1, it is characterized in that, described organosilicon is the mixing of one or more of methyltrimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, tetraethoxy and dimethyldiethoxysilane, described neutralizing agent be silica-based phosphoric acid ester, sodium bicarbonate, sodium-acetate, trisodium phosphate, sodium carbonate, ammoniacal liquor, triethylamine, dimethylethanolamine one or more.
6. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 1, it is characterized in that, the epoxy resin of described Water-borne modification is by lipid acid and epoxy resin generation esterification, obtain epoxy ester resin, and add solvent cut, then add acrylicacidandesters class monomer and vinyl monomer under the effect of initiator, to cause it carry out radical polymerization, thus introduce polar group.
7. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 6, it is characterized in that, described lipid acid is oleic acid, described oleic acid is synourin oil, oleum lini, soya-bean oil or tung oil, equivalent value is 200 ~ 300, and described epoxy resin is bisphenol A type epoxy resin, and molecular weight is between 800 ~ 3000, described bisphenol A type epoxy resin is epoxy resin E-06, epoxy resin E-20 or epoxy resin E-12.
8. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 6, it is characterized in that, described solvent is the mixed solvent of one or more of ethanol, Virahol, propyl carbinol, ethylene glycol monobutyl ether, propylene glycol, ethylene glycol diethyl ether, described Acrylic Acid Monomer, as one or more in n-butyl acrylate, β-dimethyl-aminoethylmethacrylate, vinylformic acid, methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, described vinyl monomer, can be vinylbenzene, vinyl acetate one or more.
9. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 6; it is characterized in that; described initiator is that benzoyl peroxide or azo two isobutyl are fine, and the consumption of initiator is 1% ~ 6% of acrylic acid and propynoic acid ester class monomer and vinyl monomer weight.
10. the preparation method of a kind of silicon modified aqueous epoxy resin according to claim 6, it is characterized in that, take Union carbide A-162 60 parts, dehydrated alcohol 64 parts, distilled water 20 parts and 3-triethoxysilyl-1-propylamine 20 parts, mix and be adjusted to acid system, at 50 ~ 75 DEG C, react 8h, namely obtain modified silicasol;
By epoxy resin E-06 (epoxy equivalent (weight) 800 ~ 3000) 70 parts, linolenic acid 50 parts and 1 part, zinc oxide carry out esterification at 220 DEG C, butyl glycol ether dilution is added after esterification completes, by n-butyl acrylate 12 parts after cooling, vinylbenzene 14 parts, the mixing solutions of 8 parts, vinylformic acid and silicon sol 20 parts (solid content 20%) slowly adds, and reacts, can obtain silicon modified aqueous epoxy resin after having reacted under the effect of catalyzer benzoyl peroxide.
Priority Applications (1)
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| CN106674441A (en) * | 2017-01-24 | 2017-05-17 | 湘江涂料科技有限公司 | Water-soluble acrylate modified epoxy ester resin and preparation method thereof |
| CN107382098A (en) * | 2017-06-28 | 2017-11-24 | 常州市鑫嘉生物科技有限公司 | A kind of glass fiber infiltration agent and preparation method thereof |
| CN109535652A (en) * | 2018-11-07 | 2019-03-29 | 北京科技大学 | The method for preparing hybrid material based on silicon/titanium complex sol modified epoxy |
| CN110079195A (en) * | 2019-05-24 | 2019-08-02 | 上海瀚岱化学有限公司 | A kind of aqueous epoxy resins composition and its application |
| CN110746917A (en) * | 2019-10-18 | 2020-02-04 | 李志兴 | Preparation method of high-temperature-resistant epoxy resin adhesive |
| CN110776849A (en) * | 2019-10-23 | 2020-02-11 | 烟台德邦科技有限公司 | Double-component high/low temperature resistant conductive adhesive and preparation method thereof |
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| CN111349377A (en) * | 2020-04-28 | 2020-06-30 | 中科院广州化学有限公司 | Organic silicon modified waterborne epoxy acrylate UV curing coating and preparation and application thereof |
| CN111690102A (en) * | 2020-07-02 | 2020-09-22 | 中山华明泰科技股份有限公司 | Preparation method and application of water-based acrylic resin for metal surface spraying |
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| CN104744645A (en) * | 2015-01-07 | 2015-07-01 | 北京金汇利应用化工制品有限公司 | Preparation method for high-resistance inorganic-organic composite modified acrylic epoxy ester resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104744645A (en) * | 2015-01-07 | 2015-07-01 | 北京金汇利应用化工制品有限公司 | Preparation method for high-resistance inorganic-organic composite modified acrylic epoxy ester resin |
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| CN106674441A (en) * | 2017-01-24 | 2017-05-17 | 湘江涂料科技有限公司 | Water-soluble acrylate modified epoxy ester resin and preparation method thereof |
| CN106674441B (en) * | 2017-01-24 | 2019-07-23 | 湘江涂料科技有限公司 | A kind of water-soluble acrylic modified epoxy ester resin and preparation method thereof |
| CN107382098A (en) * | 2017-06-28 | 2017-11-24 | 常州市鑫嘉生物科技有限公司 | A kind of glass fiber infiltration agent and preparation method thereof |
| CN107382098B (en) * | 2017-06-28 | 2020-01-14 | 珠海辉帛复合材料有限公司 | Glass fiber impregnating compound and preparation method thereof |
| CN109535652A (en) * | 2018-11-07 | 2019-03-29 | 北京科技大学 | The method for preparing hybrid material based on silicon/titanium complex sol modified epoxy |
| CN110079195A (en) * | 2019-05-24 | 2019-08-02 | 上海瀚岱化学有限公司 | A kind of aqueous epoxy resins composition and its application |
| CN110746917A (en) * | 2019-10-18 | 2020-02-04 | 李志兴 | Preparation method of high-temperature-resistant epoxy resin adhesive |
| CN110776849A (en) * | 2019-10-23 | 2020-02-11 | 烟台德邦科技有限公司 | Double-component high/low temperature resistant conductive adhesive and preparation method thereof |
| CN111018404A (en) * | 2019-12-02 | 2020-04-17 | 安徽富瑞雪化工科技股份有限公司 | Antifouling real stone paint and preparation method thereof |
| CN111349377A (en) * | 2020-04-28 | 2020-06-30 | 中科院广州化学有限公司 | Organic silicon modified waterborne epoxy acrylate UV curing coating and preparation and application thereof |
| CN111349377B (en) * | 2020-04-28 | 2021-10-19 | 中科院广州化学有限公司 | Organic silicon modified waterborne epoxy acrylate UV curing coating and preparation and application thereof |
| CN111690102A (en) * | 2020-07-02 | 2020-09-22 | 中山华明泰科技股份有限公司 | Preparation method and application of water-based acrylic resin for metal surface spraying |
| CN111690102B (en) * | 2020-07-02 | 2021-02-26 | 中山华明泰科技股份有限公司 | A kind of preparation method and application for spraying water-based acrylic resin on metal surface |
| CN117534997A (en) * | 2023-11-20 | 2024-02-09 | 擎天材料科技有限公司 | Water-based single-component epoxy resin coating and preparation method and application thereof |
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