CN103965730A - Aqueous coating material with ultralow VOC (Volatile Organic Compound) release and preparation method thereof - Google Patents
Aqueous coating material with ultralow VOC (Volatile Organic Compound) release and preparation method thereof Download PDFInfo
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- CN103965730A CN103965730A CN201410218830.1A CN201410218830A CN103965730A CN 103965730 A CN103965730 A CN 103965730A CN 201410218830 A CN201410218830 A CN 201410218830A CN 103965730 A CN103965730 A CN 103965730A
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- 238000000576 coating method Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011248 coating agent Substances 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000012855 volatile organic compound Substances 0.000 title abstract description 25
- 239000000839 emulsion Substances 0.000 claims abstract description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims description 94
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 41
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 35
- 238000004132 cross linking Methods 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 21
- 125000003368 amide group Chemical group 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 150000001336 alkenes Chemical class 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000004945 emulsification Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- -1 γ-(methacryloxy) propyl Chemical group 0.000 claims description 10
- 238000004581 coalescence Methods 0.000 claims description 9
- 239000003973 paint Substances 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012874 anionic emulsifier Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000004816 latex Substances 0.000 claims description 6
- 229920000126 latex Polymers 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012875 nonionic emulsifier Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 5
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000008719 thickening Effects 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- MORMPWNLQJTSOT-UHFFFAOYSA-L disodium;4-dodecyl-2-(4-sulfonatophenoxy)benzenesulfonate Chemical compound [Na+].[Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C(OC=2C=CC(=CC=2)S([O-])(=O)=O)=C1 MORMPWNLQJTSOT-UHFFFAOYSA-L 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical class CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical class CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical class CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- CASPZMCSNJZQMV-UHFFFAOYSA-N ethane;2-methyloxirane Chemical compound CC.CC1CO1 CASPZMCSNJZQMV-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
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Chemical class CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-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
- 230000035699 permeability Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004017 vitrification Methods 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000004160 Ammonium persulphate Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 235000019395 ammonium persulphate Nutrition 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 238000002464 physical blending Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 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 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229940058352 levulinate Drugs 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to an environmental-friendly aqueous coating material with ultralow VOC (Volatile Organic Compound) release and a preparation method thereof. An emulsion A with low vitrification temperature and an emulsion A with high vitrification temperature are adopted to be physically blended according to a certain ratio, so as to serve as a basic film-forming substance; during the preparation of the aqueous woodenware coating material, good film forming can be achieved by only adding a small amount of film forming assistant, the aqueous woodenware coating material is low in raw material cost and simple in preparation process, and meanwhile, a coating film has excellent permeability, glossiness, water resistance and adhesion resistance.
Description
Technical field:
The present invention relates to a kind of environmentally friendly ultralow VOC and discharge water-borne coatings of room-temperature self crosslinking and preparation method thereof, belong to water-borne wood coating field.
Background technology:
Acrylic ester aquosity coating is taking water as disperseing thinner, and excellent Water-borne Acrylic Coating must possess the performance that can compare favourably with traditional solvent based coating, and meets VOC (volatile organic compounds) Abgasgesetz of various countries' increasingly stringent.China in " environmental labelling product technical requirements---the water-borne coatings " within 2005, promulgated (HJ/T201-2005) in definition VOC be the amount of all volatile organic compound in unit volume coating in addition of dewatering.Coating industry regulation, VOC content belongs to low VOC coatings lower than the coating of 30g/L, and VOC content is less than 1g/L and belongs to zero VOC coating.
For reducing the VOC content in water-borne coatings, can select low film formation temperature emulsion, or use the film coalescence aid of low VOC.It is filmogen (mass percent 30～55%) that CN141405A adopts a kind of pure acrylate polymer emulsion of nucleocapsid structure, add color stuffing (20～35%), water (5～20%), defoamer, dispersion agent, thickening material and other auxiliary agent, obtain the super environmental protection latex paint that a kind of zero VOC discharges, having high temperature does not after-tack, low temperature can film forming, VOC approaches zero advantage, but its freeze-thaw stability is poor.CN103201346A discloses the levulinate film coalescence aid of the monohydroxy fatty alcohol of a kind of 10-20 of having carbon atom, have advantages of that low VOC discharges, film forming efficiency is high, but its cost is higher and film formation time is longer, limit the application in low-VOC aqueous coating field.US20010031362 discloses a kind of aqueous epoxy resins and the two component low VOC coatings of organosilane, but its construction is inconvenient, and raw material is comparatively expensive.
Summary of the invention:
The object of the invention is with the A emulsion of low Tg and the B emulsion physical blending according to a certain percentage of high glass transition temperature, when the mass ratio of A emulsion in blending emulsion is higher than 50% time, prepare the required film coalescence aid consumption of water-miscible paint lower than 2% of quality of the emulsion, the water-miscible paint VOC burst size making is less than 20g/L or is zero, provide a kind of environmentally friendly ultralow VOC to discharge water-borne coatings of room-temperature self crosslinking and preparation method thereof, cost of material is cheap, preparation and construction technology are simple, there is excellent permeability, glossiness and water tolerance, and hardness and the resistance to blocking of coating are improved.
A kind of ultralow VOC of the present invention discharges the water-borne coatings of room-temperature self crosslinking, the blending emulsion that comprises A, two kinds of polymer emulsions of B is filmogen, it is characterized in that A, two kinds of polymer emulsions of B are the emulsion that second-order transition temperature is different, the second-order transition temperature of A emulsion is-30 DEG C～30 DEG C, and the second-order transition temperature of B emulsion is 50 DEG C～100 DEG C.Wherein polymer emulsion A is acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contains carboxyl or the multipolymer of the vinyl monomer of amide group;
Polymer B emulsion is acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contains carboxyl or the multipolymer of the vinyl monomer of amide group;
The solid content of A, two kinds of polymer emulsions of B is 30%～55%, and latex A and the mass ratio of emulsion B in water-borne coatings are 1:1～4:1.
Further, acrylic acid or the like hard monomer is a kind of in following material or their combination: methyl methacrylate, Tert-butyl Methacrylate, isobornyl methacrylate, isobornyl acrylate;
Acrylic acid or the like soft monomer is a kind of in following material or their combination: n-butyl acrylate, isobutyl acrylate, vinylformic acid isopentyl ester, ethyl acrylate;
Alkene class cross-linking monomer is a kind of in following material or their combination: diacetone-acryloamide(DAA), acetoacetoxyethyl methacrylate, vinyltriethoxysilane, γ-(methacryloxy) propyl trimethoxy silicane, 3-(methacryloxy) propyl group methyl dimethoxysilane, vinyltrimethoxy silane, methacrylate based Trimethoxy silane;
The vinyl monomer that contains carboxyl or amide group is a kind of in following material or their combination: vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide.
Polymer emulsion A adopts following method preparation:
1) in the reactor of nitrogen protection, under agitation condition, add successively water, emulsifying agent, acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contain carboxyl or the mixture of the vinyl monomer of amide group carries out emulsification, heating in water bath to 50～90 DEG C, add initiator initiated polymerization to obtain seed emulsion, initiator need be mixed with initiator solution, and the reaction times is 0.5～1 hour;
2) acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer, the vinyl monomer that contains carboxyl or amide group, water and emulsifying agent are joined respectively in the reactor that mechanical stirring device is housed and carry out pre-emulsification dispersion, the pre-emulsification time is 0.5～2 hour;
3) toward step 1) seed emulsion in drip step 2) pre-emulsion and the initiator solution that obtain, time for adding is 1～3 hour;
4) after dropwising, slaking reaction 2～4 hours, is then down to temperature of reaction below 40 DEG C, adds pH adjusting agent to regulate ph value of emulsion to 7～9, with 200 mesh filter screens filtration dischargings, makes copolymer emulsion A;
Wherein step 1) in seed emulsion all kinds of monomer masses be respectively 5%～25% of monomer total mass separately, step 2) all kinds of monomer masses are respectively 95%～75% of monomer total mass separately in pre-emulsion; Acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contain carboxyl or the mass ratio of the vinyl monomer of amide group is: 30～60:40～70:3～8:2～5.
Polymer emulsion B adopts following method preparation:
1) in the reactor of nitrogen protection, under agitation condition, the mixture of the vinyl monomer that add successively water, emulsifying agent, acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer, contains carboxyl or amide group carries out emulsification, heating in water bath to 50～90 DEG C, add initiator initiated polymerization to obtain seed emulsion, initiator need be mixed with initiator solution, and the reaction times is 0.5～1 hour;
2) acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer, the vinyl monomer that contains carboxyl or amide group, water and emulsifying agent are joined respectively in the reactor that mechanical stirring device is housed and carry out pre-emulsification dispersion, the pre-emulsification time is 0.5～2 hour;
3) toward step 1) seed emulsion in drip step 2) pre-emulsion and the initiator solution that obtain, time for adding is 1～3 hour;
4) after dropwising, slaking reaction 2～4 hours, is then down to temperature of reaction below 40 DEG C, adds pH adjusting agent to regulate ph value of emulsion to 7～9, with 200 mesh filter screens filtration dischargings, makes copolymer emulsion B;
Wherein step 1) in seed emulsion all kinds of monomer masses be respectively 5%～25% of monomer total mass separately, step 2) all kinds of monomer masses are respectively 95%～75% of monomer total mass separately in pre-emulsion; Acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contain carboxyl or the mass ratio of the vinyl monomer of amide group is: 60～90:10～30:3～8:0.5～5.
Synthetic copolymer latex A, B emulsifying agent used are anionic emulsifier, nonionic emulsifier or anionic emulsifier and the nonionic emulsifier one in composite, and consumption is synthesis step 1) seed emulsion and synthesis step 2) in pre-emulsion all kinds of monomer total masses 1%～3%.Wherein anionic emulsifier is: one or several in disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, allyl group polyethoxye sulfonate, sulfosuccinate synthetics; Nonionic emulsifier is: the one in polyoxyethylene octylphenol ether, epoxy ethane-epoxy propane copolyether, polyoxyethylene 20 sorbitan monostearate.
Synthetic copolymer latex A, B pH adjusting agent used are the one in ammoniacal liquor, 2-amino-2-methyl-1-propanol, sodium bicarbonate.
The invention provides the preparation method that the ultralow VOC of a kind of room-temperature self crosslinking discharges water-borne coatings, taking A, two kinds of polymer emulsion physical blendings of B as filmogen, add respectively one or more of defoamer, base material wetting agent, film coalescence aid, flow agent, wetting dispersing agent, thickening material, in white paint preparation, also need to add pigment auxiliary agent, disperse to make water-borne wood coating, wherein the total weight part of A, B polymer emulsion is 60%～90%.
The present invention proposes to be synthesized by the polymerization of seed emulsion semi-continuous process respectively A emulsion and the B emulsion of different glass temperature, wherein A emulsion is the low Tg soft emulsion that contains normal temperature crosslinked group and contain carboxyl or amide group functional group, and B emulsion is the high glass transition temperature hard emulsion that contains normal temperature crosslinked group and contain carboxyl or amide group functional group.Then by A emulsion and B emulsion physical blending according to a certain percentage, and with the composite formation water-borne coatingss such as auxiliary agent.A, B emulsion have good consistency, polymer emulsion A can give the MFT that mixed emulsion is lower (minimum film-forming temperature) and self-crosslinking reaction occurs in the time of film forming, do not use film coalescence aid or use minute quantity film coalescence aid to get final product good filming, polymer emulsion B adds hardness and the resistance to blocking that can improve water-miscible paint paint film, the blend of A, B emulsion makes paint film have excellent permeability, glossiness, water tolerance, and coating hardness and resistance to blocking are improved.
Embodiment
Embodiment 1:
(1) preparation of copolymer emulsion A
By 212.9g methyl methacrylate, 227.4g butyl acrylate, 4.8g methacrylic acid, 9.6g Methacrylamide, 14.4g diacetone-acryloamide(DAA) and 9.6g3-(methacryloxy) propyl group methyl dimethoxysilane, 0.72g EF-810,0.56g DSB, 0.25g PE-6100,0.5g NaHCO
3add successively in the 2L reactor with whipping appts with 327.6g deionized water, open and stir pre-emulsification dispersion 1 hour.
In the 2L reactor that whipping appts is housed, add successively 6.48g EF-810,5.04g DSB, 2.27gPE-6100,0.5g NaHCO
3, 218.4g deionized water, 11.2g methyl methacrylate, 11.97g butyl acrylate, 0.3g methacrylic acid, 0.5g Methacrylamide, 0.8g diacetone-acryloamide(DAA), 0.5g3-(methacryloxy) propyl group methyl dimethoxysilane, open and stir and pass into nitrogen 30min, heating in water bath to 80 DEG C, add successively containing the 10g aqueous solution of 0.25g ammonium persulphate, containing the 10g aqueous solution of 0.25g sodium bisulfite with containing the 10g aqueous solution initiated polymerization of 0.13g FF6M, the reaction times is 30 minutes.
After seed emulsion preparation finishes, simultaneously by pre-emulsion, splash into reactor containing the 50g aqueous solution of 0.25g ammonium persulphate with containing the 50g aqueous solution of 0.25g sodium bisulfite, time for adding is 2 hours.After finishing, dropping is incubated slakings 2 hours at 80 DEG C, after being incubated, cool the temperature to below 40 DEG C, add 0.45g AMP-95 to regulate ph value of emulsion to 8.5, add with 20g deionized water mixing 7.8g adipic dihydrazide, stir after 15 minutes with 200 order filter-cloth filtering dischargings.
The design solid content of copolymer emulsion A is 42%, and second-order transition temperature is 10 DEG C.
(2) preparation of copolymer emulsion B
By 423.7g methyl methacrylate, 48.0g butyl acrylate, 2.4g methacrylic acid, 4.8g Methacrylamide, 9.6g3-(methacryloxy) propyl group methyl dimethoxysilane, 0.72g EF-810,0.56gDSB, 0.25g PE-6100,0.5g NaHCO
3add successively in the 2L reactor with whipping appts with 327.6g deionized water, open and stir pre-emulsification dispersion 1 hour.
In the 2L reactor that whipping appts is housed, add successively 6.48g EF-810,5.04g DSB, 2.27gPE-6100,0.5g NaHCO
3, 218.4g deionized water, 22.3g methyl methacrylate, 2.5g butyl acrylate, 0.1g methacrylic acid, 0.2g Methacrylamide, 0.5g3-(methacryloxy) propyl group methyl dimethoxysilane, open and stir and pass into nitrogen 30min, heating in water bath to 80 DEG C, add successively containing the 10g aqueous solution of 0.25g ammonium persulphate, containing the 10g aqueous solution of 0.25g sodium bisulfite with containing the 10g aqueous solution initiated polymerization of 0.13g FF6M, the reaction times is 30 minutes.
After seed emulsion preparation finishes, simultaneously by pre-emulsion, splash into reactor containing the 50g aqueous solution of 0.25g ammonium persulphate with containing the 50g aqueous solution of 0.25g sodium bisulfite, time for adding is 2 hours.After dropping finishes, 80 DEG C of insulation slakings 2 hours, after being incubated, cool the temperature to below 40 DEG C, add 0.45g AMP-95 to regulate ph value of emulsion to 8.5, stir after 15 minutes with 200 order filter-cloth filtering dischargings.
The design solid content of copolymer emulsion B is 42%, and second-order transition temperature is 80 DEG C.
(3) preparation of the clear priming paint of aqueous wooden ware
In 500ml beaker, add 55.5g copolymer emulsion A and 18.5g copolymer emulsion B, open and stir 1600rpm stirring 10 minutes, add successively 0.2g base material wetting agent TEGO-500,0.4g defoamer BYK-024, improve stirring velocity to 3000rpm dispersion 15 minutes, reduce stirring velocity to 1600rpm, add successively 7g water, 0.33g pH adjusting agent AMP-95 and 0.3g thickening material PUR40, disperse after 15 minutes, with 200 order filter-cloth filtering dischargings, to make varnish type water-borne wood coating.
A, B emulsion described in embodiment 2-9 are that from the preparation difference of embodiment 1 composition of emulsifying agent is different with consumption, and other condition is consistent with embodiment 1 with technique, and concrete emulsifying agent composition and consumption are in table 1.A, B emulsion described in embodiment 10-16 are that from the preparation difference of embodiment 1 composition of monomer is different with consumption, and other condition is consistent with embodiment 1 with technique, and concrete monomer ratio is in table 2.
Table 1: embodiment 2
-9A, the synthetic emulsifying agent composition used of B emulsion and consumption
In table, EF-810 is sulfosuccinate synthetics, DSB is disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, SE-10N is allyl group polyethoxye sulfonate, LF-4 is sulfo-succinic acid salt mixture, OP-10 polyoxyethylene octylphenol ether, Tween-60 is polyoxyethylene 20 sorbitan monostearate, and PE-6100 is propylene oxide-oxyethane copolyether.
Table 2: embodiment 10-16A emulsion is synthesized monomer ratio used
Embodiment 10-16B emulsion is synthesized monomer ratio used
In table, MMA is methyl methacrylate, BA is butyl acrylate, MAA is methacrylic acid, AA is vinylformic acid, and MAM is Methacrylamide, and AM is acrylamide, DAAM is diacetone-acryloamide(DAA), KH-571 is 3-(methacryloxy) propyl group methyl dimethoxysilane, and A-151 is vinyltriethoxysilane, and A-174 is γ-(methacryloxy) propyl trimethoxy silicane.
A, B emulsion described in embodiment 17-22 are that from the difference of embodiment 1 allocation proportion of emulsifying agent in seed emulsion and pre-emulsion is different, and other condition is consistent with embodiment 1 with technique, and wherein emulsifying agent allocation proportion is in table 3.
Table 3: embodiment 17-22A, the synthetic emulsifying agent allocation proportion used of B emulsion
The g of unit
Table 4: embodiment 1-22 copolymer emulsion property indices test result
Note: sampling and measuring when transformation efficiency finishes for reaction; Calcium ion stability testing method is that in the emulsion of 16ml, to add 4ml massfraction be 0.5% calcium chloride water, room temperature left standstill after 48 hours, observed whether breakdown of emulsion, layering and separate out small-particle agglutinating matter of emulsion, if be difficult phenomenon, Calcium ion stability is passed through, otherwise does not pass through.
Embodiment 23-33 is that water-borne wood coating water tolerance, glossiness, hardness, resistance to blocking, 50 DEG C of stability in storage test results are prepared in A, the blend of B emulsion different ratios.
Table 5: water-borne coatings property indices test result is prepared in embodiment 23-33A, the blend of B emulsion different ratios
Note: embodiment 26 and embodiment 30 add the film coalescence aid DPnB of 2% mass parts in the time preparing water-borne coatings; 50 DEG C of stability in storagies are tested as to add 60g water-borne coatings in 100ml transparent plastic bottle, are positioned in 50 DEG C of baking ovens after sealing, observe water-borne coatings can stably stored until occur that sedimentation, layering, gel separate out the time of phenomenon, in sky.
Embodiment 34-38: the preparation of aqueous wooden ware based white primer
In 200ml beaker, add the wetting dispersing agent BYK-190 of 17g water, 7.5g, under 1200rpm stirring velocity, stir 10 minutes, add 75g rutile titanium dioxide and 0.5g anti-settling agent BYK-420, under 2000rpm stirring velocity, disperse, while reaching below 30 μ m by Hegman grind gage test fineness, stop stirring, the white slurry making is waited until use.
In 500ml beaker, add 60g polymer emulsion A and 20g polymer emulsion B, open and stir 1600rpm stirring 10 minutes, add successively 0.5g defoamer BYK-024, 0.6g defoamer TEGO-902W, 0.2g flow agent BYK-346, 1.0g deionized water, rotating speed is increased to 3000rpm to be disperseed 30 minutes, add 1.0g silicon-dioxide flatting silica under 3000rpm, to disperse 30 minutes, rotating speed is down to 1600rpm, add successively 5.0g deionized water, the cured auxiliary agent MD2000 of 2.0g, 0.1g flow agent BYK-333 dispersed with stirring 15 minutes, add successively 0.3gpH conditioning agent AMP-95, 2.0g auxiliary rheological agents R212, under 1600rpm, dispersed with stirring added 23g to starch in vain after 15 minutes, continue to stir after 15 minutes with 200 order filter-cloth filtering dischargings.
Table 6: water-borne coatings property indices test result is prepared in embodiment 34-37A, the blend of B emulsion different ratios
Note: embodiment 26 and embodiment 30 add the film coalescence aid DPnB of 2% mass parts in the time preparing water-borne coatings; 50 DEG C of stability in storagies are tested as to add 60g water-borne coatings in 100ml transparent plastic bottle, are positioned in 50 DEG C of baking ovens after sealing, observe water-borne coatings can stably stored until occur that sedimentation, layering, gel separate out the time of phenomenon, in sky.
Claims (7)
1. ultralow VOC discharges a water-borne coatings, it is characterized in that comprising A, two kinds of acrylic polymer emulsions of B; A, two kinds of polymer emulsions of B are the emulsion that second-order transition temperature is different, and the second-order transition temperature of A emulsion is-30 DEG C～30 DEG C, and the second-order transition temperature of B emulsion is 50 DEG C～100 DEG C; Wherein polymer emulsion A is acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contains carboxyl or the multipolymer of the vinyl monomer of amide group;
Polymer emulsion B is acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contains carboxyl or the multipolymer of the vinyl monomer of amide group;
The solid content of A, two kinds of polymer emulsions of B is 30%～55%, and latex A and the mass ratio of emulsion B in water-borne coatings are 1:1～4:1.
2. discharge water-borne coatings according to the ultralow VOC of claim 1, it is characterized in that, acrylic acid or the like hard monomer is one or several in following material: methyl methacrylate, Tert-butyl Methacrylate, isobornyl methacrylate, isobornyl acrylate;
Acrylic acid or the like soft monomer is one or several in following material: n-butyl acrylate, isobutyl acrylate, vinylformic acid isopentyl ester, ethyl acrylate;
Alkene class cross-linking monomer is one or several in following material: diacetone-acryloamide(DAA), acetoacetoxyethyl methacrylate, vinyltriethoxysilane, γ-(methacryloxy) propyl trimethoxy silicane, 3-(methacryloxy) propyl group methyl dimethoxysilane, vinyltrimethoxy silane, methacrylate based Trimethoxy silane;
The vinyl monomer that contains carboxyl or amide group is one or several in following material: vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide.
3. ultralow VOC according to claim 1 and 2 discharges water-borne coatings, it is characterized in that, low Tg polymer emulsion A adopts following method preparation:
1) in the reactor of nitrogen protection, under agitation condition, add successively water, emulsifying agent, acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contain carboxyl or the mixture of the vinyl monomer of amide group carries out emulsification, heating in water bath to 50～90 DEG C, add initiator initiated polymerization to obtain seed emulsion, initiator need be mixed with initiator solution, and the reaction times is 0.5～1 hour;
2) acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer, the vinyl monomer that contains carboxyl or amide group, water and emulsifying agent are joined respectively in the reactor that mechanical stirring device is housed and carry out pre-emulsification dispersion, the pre-emulsification time is 0.5～2 hour;
3) toward step 1) seed emulsion in drip step 2) pre-emulsion and the initiator solution that obtain, time for adding is 1～3 hour;
4) after dropwising, slaking reaction 2～4 hours, is then down to temperature of reaction below 40 DEG C, adds pH adjusting agent to regulate ph value of emulsion to 7～9, with 200 mesh filter screens filtration dischargings, makes copolymer emulsion A;
Wherein step 1) in seed emulsion all kinds of monomer masses be respectively 5%～25% of monomer total mass separately, step 2) all kinds of monomer masses are respectively 95%～75% of monomer total mass separately in pre-emulsion; Acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer, the mass ratio of vinyl monomer that contains carboxyl or amide group are: 30～60:40～70:3～8:2～5.
4. ultralow VOC according to claim 1 and 2 discharges water-borne coatings, it is characterized in that, high glass transition temperature polymer emulsion B adopts following method preparation:
1) in the reactor of nitrogen protection, under agitation condition, the mixture of the vinyl monomer that add successively water, emulsifying agent, acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer, contains carboxyl or amide group carries out emulsification, heating in water bath to 50～90 DEG C, add initiator initiated polymerization to obtain seed emulsion, initiator need be mixed with initiator solution, and the reaction times is 0.5～1 hour;
2) acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer, the vinyl monomer that contains carboxyl or amide group, water and emulsifying agent are joined respectively in the reactor that mechanical stirring device is housed and carry out pre-emulsification dispersion, the pre-emulsification time is 0.5～2 hour;
3) toward step 1) seed emulsion in drip step 2) pre-emulsion and the initiator solution that obtain, time for adding is 1～3 hour;
4) after dropwising, slaking reaction 2～4 hours, is then down to temperature of reaction below 40 DEG C, adds pH adjusting agent to regulate ph value of emulsion to 7～9, with 200 mesh filter screens filtration dischargings, makes copolymer emulsion B;
Wherein step 1) in seed emulsion all kinds of monomer masses be respectively 5%～25% of monomer total mass separately, step 2) all kinds of monomer masses are respectively 95%～75% of monomer total mass separately in pre-emulsion; Acrylic acid or the like hard monomer, acrylic acid or the like soft monomer, alkene class cross-linking monomer and contain carboxyl or the mass ratio of the vinyl monomer of amide group is: 60～90:10～30:3～8:0.5～5.
5. according to the preparation method described in claim 3 or 4, it is characterized in that: synthetic copolymer latex A, B emulsifying agent used are anionic emulsifier, nonionic emulsifier or anionic emulsifier and the nonionic emulsifier one in composite, and consumption is synthesis step 1) seed emulsion and synthesis step 2) in pre-emulsion all kinds of monomer total masses 1%～3%; Wherein anionic emulsifier is: one or several in disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, allyl group polyethoxye sulfonate, sulfosuccinate synthetics; Nonionic emulsifier is: the one in polyoxyethylene octylphenol ether, epoxy ethane-epoxy propane copolyether, polyoxyethylene 20 sorbitan monostearate.
6. according to the preparation method described in claim 3 or 4, it is characterized in that: pH adjusting agent is the one in ammoniacal liquor, 2-amino-2-methyl-1-propanol, sodium bicarbonate.
7. a kind of ultralow VOC according to claim 1 discharges the preparation method of water-borne coatings, it is characterized in that: taking the mixed emulsion of polymer emulsion A, B as filmogen, add one or more auxiliary agents in defoamer, base material wetting agent, film coalescence aid, flow agent, thickening material, wetting dispersing agent, in white paint preparation, also need to add pigment auxiliary agent, disperse to make water-borne wood coating, wherein the total weight part of A, B polymer emulsion is 60%～90%.
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| CN104804562A (en) * | 2015-04-17 | 2015-07-29 | 湖南中汉高分子材料科技有限公司 | Anti-after-tack elastic acrylic aqueous dispersion and preparation method thereof |
| CN104927470A (en) * | 2015-07-17 | 2015-09-23 | 广东华兹卜化学工业有限公司 | Water-based thick-coated carpentry transparent base paint and preparation method thereof |
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| CN106543333B (en) * | 2016-10-27 | 2020-03-03 | 万华化学集团股份有限公司 | High-corrosion-resistance acrylic emulsion, preparation method thereof and water-based acrylic anticorrosive paint |
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