CN1063770C - Organosilicon modified propenoic acid emulsion paint - Google Patents
Organosilicon modified propenoic acid emulsion paint Download PDFInfo
- Publication number
- CN1063770C CN1063770C CN97106714A CN97106714A CN1063770C CN 1063770 C CN1063770 C CN 1063770C CN 97106714 A CN97106714 A CN 97106714A CN 97106714 A CN97106714 A CN 97106714A CN 1063770 C CN1063770 C CN 1063770C
- Authority
- CN
- China
- Prior art keywords
- unsaturated
- acid
- emulsion paint
- organosilicon modified
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000839 emulsion Substances 0.000 title claims abstract description 22
- 239000003973 paint Substances 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- -1 polysiloxane Polymers 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001282 organosilanes Chemical class 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- OWUTVCVPEOXXHD-UHFFFAOYSA-N trimethoxy(prop-1-enyl)silane Chemical compound CO[Si](OC)(OC)C=CC OWUTVCVPEOXXHD-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 230000032683 aging Effects 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 1
- 229920006305 unsaturated polyester Polymers 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 239000004816 latex Substances 0.000 description 13
- 229920000126 latex Polymers 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920006243 acrylic copolymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000004159 Potassium persulphate Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 description 4
- 229920013701 VORANOL™ Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 208000031639 Chromosome Deletion Diseases 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to organosilicon modified acrylic acid emulsion paint which is prepared from 1 to 20 wt% of organosilicon monomers with unsaturated polyester double bonds, 1 to 20 wt% of unsaturated acid, 40 to 97 wt% of unsaturated monomers and 1 to 20 wt% of hydroxy silicone. The organosilicon modified acrylic acid emulsion paint has the characteristics of good water resistance performance, good dirt resistance performance, good water prevention performance and good ageing resistance performance, is superior to pure acrylic acid series paint, and can be used in paint production.
Description
The present invention relates to organosilicon modified propenoic acid emulsion paint.
With the multipolymer of (methyl) vinylformic acid and ester thereof is that the coating of main film forming substance is referred to as acrylic coating.Acrylic acid series coating look shallow, and film is plentiful, and physical strength is good, become the important coating variety of a class.But its pollution resistance, water-repellancy is not good enough, and weathering resistance is also good inadequately, and polysiloxane just in time can remedy this defective.The surface daub on a wall of metal building sheet material, the hard supercoat of frostings such as synthetic glass, polycarbonate not only requires coating gloss, and color and luster is good, and the physical strength height also requires it to have good antifouling, dustproof, ageing resistance.People have proposed vinylformic acid-organosilicon coating for this reason, this coating is the length of collection acrylic coating and organosilicon coating, by a certain amount of organosilicon of introducing functional group on acrylic resin macromolecular main chain and side chain, utilize the Si-O covalent bond energy to be 108kcal/mol, than common C-C bond energy big (83kcal/mol), to heat, stable to light, be not subject to action of ultraviolet light and the characteristic of deterioration, improved the weathering resistance of acrylic coating greatly, and it is good also to have coating adhesion, the water tolerance excellence, the over-all properties that paint film is full.For obtaining this acid-organosilicon crylic acid coating, early stage, people's mixed and modified method commonly used is mixed with acrylic resin and silicone resin, reaches the modification purpose.But silicone resin and other resin compatible are not good enough, and this modified effect can not be lasting, and after long-time the use, silicone ingredients can slowly disappear from the film surface.Often adopt chemical modification to make the organosilicon modified crylic acid resin coating of excellent performance in recent years.For example US3468836 reacts with acrylate copolymer that contains hydroxyl and polysiloxane; JP58-154766, JP59-20360 obtain containing the siloxanes of acrylic acid groups earlier, and the method with the unsaturated monomer copolymerization prepares again.Aforesaid method obtains solvent type resin all by solution polymerization, owing to leave solvent in the product, can cause environmental pollution, and consumes energy, so limited its application.JP51-146525, JP54-3512 have narrated with the polysiloxane that contains unsaturated group and other vinyl monomer method of emulsion polymerization in water, but the polymer-modified stability of emulsion that obtains is not good enough, easily separates, coacervation.
For overcoming the defective that above-mentioned document exists, the purpose of this invention is to provide a kind of new organosilicon modified propenoic acid emulsion paint, this latex coating has water tolerance, pollution resistance, the characteristics that water-repellancy, resistance to deterioration are all good.The objective of the invention is to realize by following technical scheme: a kind of organosilicon modified propenoic acid emulsion paint comprises by weight percentage:
(a) contain the organosilane monomer 1～20% of unsaturated double-bond, organosilane monomer is selected from least a or its mixture in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane, the gamma-methyl allyl acyloxypropyl trimethoxysilane;
(b) unsaturated acid 1～20%, and unsaturated acid is selected from vinylformic acid, methacrylic acid or its mixture;
(c) unsaturated monomer 40～97%, and unsaturated monomer is selected from least two kinds or its mixture in methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide, acrylamide, dimethylaminoethyl acrylate methyl ammonia ethyl ester, the glycidyl methacrylate; (d) the hydroxyl polysiloxane 1～20%;
Be to carry out letex polymerization under 70～90 ℃ earlier by the composition (a) and (b) and (c), gained multipolymer and composition (d) reacted down at 70～90 ℃ obtain in temperature.
In the technique scheme by weight percentage the preferable range of unsaturated acid be 2～8%, the preferable range of hydroxyl polysiloxane is 1～10%.
Above-mentioned hydroxyl polysiloxane is taken off ethanol again and is made by the dimethyldiethoxysilane hydrolysis.Concrete steps: having prolong, in the four-necked bottle of Dropping feeder, adding dimethyldiethoxysilane, 732
#The type Zeo-karb is warming up to 60 ℃, begins to reflux, and drips the water of metering subsequently, finishes in 0.5～1 hour, is warming up to 70～80 ℃, keeps 2～3 hours.Leach 732
#Resin boils off ethanol again, obtains the hydroxyl polysiloxane of the about 10cp of viscosity.
The preparation of organosilicon modified propenoic acid emulsion paint of the present invention is the emulsion copolymerization by vinyl monomer, obtains with the reaction of hydroxyl polysiloxane again.The letex polymerization temperature is 70～90 ℃, and its technology is: with deionized water, compound emulsifying agent adds in the reactor, be warming up to 70～90 ℃, add partial monosomy and water-based initiator, drip remaining monomer and water-based initiator subsequently, added in 2～3 hours, equality of temperature is kept reaction 2 hours again.Add silicon alcohol condensation catalyst and hydroxyl polysiloxane then, keep reaction 2 hours, be cooled to below 50 ℃, regulate pH value to 8～9 with ammoniacal liquor.After 200 order net filtrations must be with the blue light emulsion.Hydroxyl polysiloxane and silicon alcohol condensation catalyst also can just add before emulsion copolymerization begins.
Above-mentioned compound emulsifying agent is composited by anion surfactant and nonionic surface active agent, anion surfactant such as sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, consumption 0.5～3%: nonionic surface active agent such as polyoxyethylene phenolic ether in the ninth of the ten Heavenly Stems, Voranol EP 2001, polyoxyethylene sorbitol acid anhydride oleic acid ester, polyoxyethylene sorbitol acid anhydride stearate etc., consumption 1～8%.
The water-based initiator adopts persulphate, as Potassium Persulphate, and ammonium persulphate, consumption 0.2～3%.Silicon alcohol condensation catalyst such as dibutyl tin dilaurate, dibutyl tin acetate, tetrabutyl titanate etc., consumption 0.05～5%.
In the present invention, introduce the unsaturated acid molecule, make and introduced numerous strong hydrophilicity groups in the latex coating that makes, increased the stability of latex coating.Introduce hard monomer, make latex coating that good hardness of film, photostabilization arranged, improved the minimum film-forming temperature of latex as methyl methacrylate.Introduce soft monomer, increased the snappiness of coating as butyl acrylate, sticking power, water tolerance has reduced the film-forming temperature of latex.Introduce unsaturated acid and the organosilane monomer that contains unsaturated double-bond, for above-mentioned unsaturated monomer provides cross-linking set, thus crosslinking curing after coating can be heated.Because during the latex film forming, siloxanes generally is enriched in the multipolymer surface, therefore introduce the water resistance that the hydroxyl polysiloxane has improved latex coating greatly.
In the latex coating of the present invention, owing to contain the component of the organosilane monomer that is equivalent to unsaturated double-bond, unsaturated acid, unsaturated monomer, hydroxyl polysiloxane, therefore water tolerance, pollution resistance, the water-repellancy performance of this latex coating obviously are better than pure acrylic acid coating, have obtained effect preferably.This latex coating has satisfactory stability simultaneously, and can reach more than 1 year storage period.
The invention will be further elaborated below by embodiment.[embodiment 1]
Have prolong, Dropping feeder, in the four-hole boiling flask of stirring, thermometer, adding entry 154 grams, sodium lauryl sulphate 1 gram, Voranol EP 2001 3 grams, Potassium Persulphate 0.4 gram is heated to 75 ℃.Drip vinyltrimethoxy silane 5 grams, vinylformic acid 3 grams, methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams added in 2 hours, kept reaction 2 hours in 75 ℃.Add dibutyl tin dilaurate 0.3 gram then, drip hydroxyl polysiloxane 3 grams,, be cooled to below 50 ℃, regulate pH value to 8～9,, must be with blue light organosilicon-modified acrylic copolymer emulsion through 200 order net filtrations with ammoniacal liquor in 75 ℃ of reactions 2 hours.Yield 98.1%, solid content 40%.[embodiment 2]
Vinyltriethoxysilane 15 grams, methyl methacrylate 38 grams, butyl methacrylate 43 grams, other prescription and technology are identical with embodiment 1.Get the organosilicon-modified acrylic copolymer emulsion, its yield 98.6%, solid content 40.1%.[embodiment 3]
Mix monomer is by vinyltrimethoxy silane 3 grams, and methacrylic acid 5 restrains, methyl methacrylate 44 grams, and butyl acrylate 48 grams, glycidyl methacrylate 6 grams mix, and other prescription and technology are identical with embodiment 1.Get the organosilicon-modified acrylic copolymer emulsion, its yield 99.2%, solid content 40.2%.[embodiment 4]
Glycidyl methacrylate is used Jia Jibingxisuanβ-Qiang Yizhi instead in the mix monomer, and other prescription and technology are identical with embodiment 3.Get the organosilicon-modified acrylic copolymer emulsion, its yield 99.3%, solid content 40.5%.[embodiment 5]
In four-hole boiling flask, add deionized water 154 grams, sodium lauryl sulphate 1 gram, Voranol EP 2001 3 grams, hydroxyl polysiloxane 10 grams, dibutyl tin dilaurate 0.3 gram, Potassium Persulphate 0.4 gram is warming up to 75 ℃.Drip vinyltrimethoxy silane 5 grams, vinylformic acid 3 grams, methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams added in 2 hours, kept reaction 2 hours in 75 ℃ again.Be cooled to below 50 ℃, regulate pH value to 8～9 with ammoniacal liquor.Get the organosilicon-modified acrylic copolymer emulsion, its yield 99.2%, solid content 40.7%.[comparative example 1]
In four-hole boiling flask, add deionized water 154 grams, sodium lauryl sulphate 1 gram, Voranol EP 2001 3 grams, Potassium Persulphate 0.4 gram, be warming up to 75 ℃, dropwise addition of acrylic acid 3 restrains then, methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams, added in 2 hours, and kept reaction 2 hours in 75 ℃ again.Get the acrylic copolymer emulsion.[comparative example 2]
Mix monomer is vinyltrimethoxy silane 5 grams, vinylformic acid 3 grams, and methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams, other prescription and technology are identical with comparative example 1.
Get the tinplate of 50 * 120 * 0.2mm, polish repeatedly with No. 0 sand paper earlier, remove tin coating, use alcohol, acetone scrub again.The emulsion that obtains in the foregoing description and the comparative example evenly is applied on the tinplate, in 150 ℃ of dryings 10 minutes, smooth, bright filming.Film performance is as shown in table 1.
Table 1 film performance
| Latex | Sticking power (level) | Pencil hardness | Shock strength (Kg/cm) | Gloss (45 °) | Water tolerance | Water-repellancy |
| Embodiment 1 | ?1 | ?2H | ?50 | ?107 | Slight loss of gloss | High (contact angle＞90 °) |
| Embodiment 2 | ?1 | ?3H | ?50 | ?83 | No abnormal | High (contact angle＞90 °) |
| Embodiment 3 | ?1 | ?2H | ?50 | ?100 | Slight loss of gloss | High (contact angle＞90 °) |
| Embodiment 4 | ?1 | ?2H | ?50 | ?98 | No abnormal | High (contact angle＞90 °) |
| Embodiment 5 | ?1 | ?2H | ?50 | ?109 | No abnormal | High (contact angle＞90 °) |
| Comparative example 1 | ?1 | ?2H | ?50 | ?/ | Bubble is arranged, get rusty | Low (contact angle＜＜90 °) |
| Comparative example 2 | ?1 | ?2H | ?50 | ?/ | Bubble is arranged, get rusty | Low (contact angle＜＜90 °) |
With the latex coating that the foregoing description 1～5 makes, at room temperature left standstill no change 1 year.
The film performance testing method:
Sticking power: GB1720-79
Pencil hardness: GB6739-86
Shock strength: GB1732-79
Gloss: GB1743-79
Water tolerance: test plate (panel) in distilled water immersion 7 days, is observed coating and is changed under room temperature.
Water-repellancy: film to go up to drip and go up deionized water, estimate its contact angle size.The big expression water-repellancy of contact angle height.
Claims (3)
1, a kind of organosilicon modified propenoic acid emulsion paint comprises by weight percentage:
(a) contain the organosilane monomer 1～20% of unsaturated double-bond, organosilane monomer is selected from least a or its mixture in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane, the gamma-methyl allyl acyloxypropyl trimethoxysilane;
(b) unsaturated acid 1～20%, and unsaturated acid is selected from vinylformic acid, methacrylic acid or its mixture;
(c) unsaturated monomer 40～97%, and unsaturated monomer is selected from least two kinds or its mixture in methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide, acrylamide, dimethylaminoethyl acrylate methyl ammonia ethyl ester, the glycidyl methacrylate; (d) the hydroxyl polysiloxane 1～20%;
Be to carry out letex polymerization under 70～90 ℃ earlier by the composition (a) and (b) and (c), gained multipolymer and composition (d) reacted down at 70～90 ℃ obtain in temperature.
2, organosilicon modified propenoic acid emulsion paint according to claim 1 is characterized in that unsaturated acid is 2～8% by weight percentage.
3, organosilicon modified propenoic acid emulsion paint according to claim 1 is characterized in that hydroxyl polysiloxane by weight percentage 1～10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106714A CN1063770C (en) | 1997-11-13 | 1997-11-13 | Organosilicon modified propenoic acid emulsion paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106714A CN1063770C (en) | 1997-11-13 | 1997-11-13 | Organosilicon modified propenoic acid emulsion paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1217361A CN1217361A (en) | 1999-05-26 |
| CN1063770C true CN1063770C (en) | 2001-03-28 |
Family
ID=5168930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106714A Expired - Fee Related CN1063770C (en) | 1997-11-13 | 1997-11-13 | Organosilicon modified propenoic acid emulsion paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1063770C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362048C (en) * | 2003-07-30 | 2008-01-16 | 宜通工程有限公司 | Polymeric colloidal sol compositon, aqueous colloidal sol composition, and its preparing method and use |
| CN101457112B (en) * | 2008-10-17 | 2011-03-30 | 芜湖力特尔涂料制造有限公司 | Automobile reflecting layer coating |
| CN101457111B (en) * | 2008-10-17 | 2011-06-15 | 芜湖力特尔涂料制造有限公司 | Reflecting layer coating |
| CN101457113B (en) * | 2008-10-17 | 2011-06-22 | 芜湖力特尔涂料制造有限公司 | Automobile reflecting layer coating |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103341C (en) * | 1999-11-09 | 2003-03-19 | 复旦大学 | Organosilicon modified acrylate latex with core-shell structure and its preparing process |
| CN1313550C (en) * | 2004-06-11 | 2007-05-02 | 中国石油天然气集团公司 | Acrylic resin paint for reflecting light and its production process |
| CN1305988C (en) * | 2005-09-23 | 2007-03-21 | 浙江大学 | Prepn of organosilicon modified pressure-sensitive acrylate adhesive |
| CN100410286C (en) * | 2006-06-07 | 2008-08-13 | 刘晓国 | Silicone modified polyacrylate and its prepn and application |
| DE102006037270A1 (en) | 2006-08-09 | 2008-02-14 | Wacker Chemie Ag | Self-dispersible silicone copolymers and process for their preparation and their use |
| CN101348611B (en) * | 2008-09-05 | 2010-12-29 | 中国海洋石油总公司 | Acroleic acid modified polysiloxane resin and coating thereof |
| CN101581045B (en) * | 2009-06-12 | 2011-06-08 | 辽宁恒星精细化工（集团）有限公司 | Elastic colorized printing paste and production method thereof |
| CN101649014B (en) * | 2009-09-22 | 2011-03-09 | 西北工业大学 | Method for preparing organosilicon modified styrene-methyl methacrylate copolymer emulsion at room temperature |
| CN102051011A (en) * | 2009-11-06 | 2011-05-11 | 3M创新有限公司 | Water-based floor wax composition |
| CN102492085A (en) * | 2011-12-06 | 2012-06-13 | 扬州大学 | Organosilicon-modified styrene-acrylic architectural waterproof latex and preparation method thereof |
| CN103525298B (en) * | 2013-09-24 | 2016-01-20 | 江苏荣昌新材料科技有限公司 | Thermostable anticorrosive coating and preparation method |
| CN104710891A (en) * | 2015-03-26 | 2015-06-17 | 常熟市优德爱涂料有限公司 | Novel water-based matted finishing varnish and preparation method thereof |
| CN108359338B (en) * | 2018-01-12 | 2020-01-14 | 雅图高新材料有限公司 | Self-leveling varnish capable of being sprayed at high viscosity and preparation method thereof |
| CN108842440B (en) * | 2018-06-26 | 2021-03-30 | 杭州新生印染有限公司 | Production process of flame-retardant blended fabric |
| CN111534184A (en) * | 2020-06-05 | 2020-08-14 | 郑希超 | Anti-fouling environment-friendly emulsion paint and preparation method thereof |
| CN114350258A (en) * | 2022-01-21 | 2022-04-15 | 宁国市茂发装饰材料有限公司 | Transparent waterproof antibacterial water-based paint and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51146525A (en) * | 1975-06-10 | 1976-12-16 | Shinetsu Chemical Co | Water hardening cement mixture |
| JPS6029903A (en) * | 1983-07-29 | 1985-02-15 | Sony Corp | Magnetic recording and reproducing device |
| JPH01284513A (en) * | 1988-05-11 | 1989-11-15 | Chuo Rika Kogyo Kk | Acrylic emulsion composition |
| JPH09208643A (en) * | 1996-02-07 | 1997-08-12 | Toshiba Silicone Co Ltd | Modified polyorganosiloxane emulsion |
-
1997
- 1997-11-13 CN CN97106714A patent/CN1063770C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51146525A (en) * | 1975-06-10 | 1976-12-16 | Shinetsu Chemical Co | Water hardening cement mixture |
| JPS6029903A (en) * | 1983-07-29 | 1985-02-15 | Sony Corp | Magnetic recording and reproducing device |
| JPH01284513A (en) * | 1988-05-11 | 1989-11-15 | Chuo Rika Kogyo Kk | Acrylic emulsion composition |
| JPH09208643A (en) * | 1996-02-07 | 1997-08-12 | Toshiba Silicone Co Ltd | Modified polyorganosiloxane emulsion |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362048C (en) * | 2003-07-30 | 2008-01-16 | 宜通工程有限公司 | Polymeric colloidal sol compositon, aqueous colloidal sol composition, and its preparing method and use |
| CN101457112B (en) * | 2008-10-17 | 2011-03-30 | 芜湖力特尔涂料制造有限公司 | Automobile reflecting layer coating |
| CN101457111B (en) * | 2008-10-17 | 2011-06-15 | 芜湖力特尔涂料制造有限公司 | Reflecting layer coating |
| CN101457113B (en) * | 2008-10-17 | 2011-06-22 | 芜湖力特尔涂料制造有限公司 | Automobile reflecting layer coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1217361A (en) | 1999-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1063770C (en) | Organosilicon modified propenoic acid emulsion paint | |
| CN109868026B (en) | Organic silicon modified acrylate resin, preparation method thereof and hydrophobic weather-resistant slow-release modified acrylic resin coating | |
| KR0174804B1 (en) | Water-bae silicone-modified acrylate polymer emulsion | |
| CN101735379B (en) | Preparation method of self-drying low aliphatic chain oxosilane modified water-borne acrylic resin | |
| CN1887926A (en) | Silicone modified polyacrylate and its prepn and application | |
| CN1063769C (en) | Process for preparing organosilicon modified propenoic acid emulsion paint | |
| JPS62169861A (en) | Composition of resin containing silicon atom | |
| CN114015307B (en) | Single-component water-based acrylic acid strippable paint and preparation method and application thereof | |
| CN103992242A (en) | Fluorinated isocyanate and method for preparing fluorinated isocyanate-acrylate copolymer emulsion | |
| CN106947030A (en) | POSS base hydridization polyacrylate dispersions and preparation method and application | |
| CN1557850A (en) | Process for preparing organosilicon modified acrylic ester elastic emulsion | |
| CN1103341C (en) | Organosilicon modified acrylate latex with core-shell structure and its preparing process | |
| CN1281643C (en) | Silicofluoride containing acrylic copolyresin emulsion and paint | |
| CN1263546A (en) | Resin compositions for coatings | |
| CN1130437C (en) | Organosilicon modified acrylic ester emulsion | |
| CN1155635C (en) | Organosilicon grafted and mofiied acrylic ester copolymer emulsion | |
| CN1155637C (en) | Grafted-organosilicon modified acrylic ester copolymer emulsion | |
| CN1130436C (en) | Organosilicon-acrylic resin emulsion | |
| CN1354189A (en) | Stable organosilicon modified copolymer emulsion and its preparation method | |
| CN1155636C (en) | Grafted-organosilicon modified acrylic resin emulsion | |
| CN115093792A (en) | Antireflection coating liquid and preparation method thereof | |
| CN1137170C (en) | Organosilicon modified acrylic resin emulsion | |
| CN115124649B (en) | Real stone paint emulsion and preparation method and application thereof | |
| CN1155634C (en) | Organosilicon grafted and modified acrylic resin emulsion | |
| JP3473878B2 (en) | Water-based paint composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20010328 Termination date: 20111113 |