CN103965730B - A kind of zero VOC release water paint and preparation method thereof - Google Patents
A kind of zero VOC release water paint and preparation method thereof Download PDFInfo
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- CN103965730B CN103965730B CN201410218830.1A CN201410218830A CN103965730B CN 103965730 B CN103965730 B CN 103965730B CN 201410218830 A CN201410218830 A CN 201410218830A CN 103965730 B CN103965730 B CN 103965730B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003973 paint Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 112
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 239000004816 latex Substances 0.000 claims abstract description 7
- 229920000126 latex Polymers 0.000 claims abstract description 7
- 239000002023 wood Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 94
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 42
- 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
- 238000003756 stirring Methods 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 18
- 239000003995 emulsifying agent Substances 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
- 239000003999 initiator Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 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
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004017 vitrification Methods 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012875 nonionic emulsifier Substances 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000012874 anionic emulsifier Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 230000001804 emulsifying effect Effects 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
- 239000002562 thickening agent Substances 0.000 claims description 4
- -1 γ-(methacryloxy) propyl Chemical group 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 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- IVPWAZDCYGWSCL-UHFFFAOYSA-N C(C(=C)C)(=O)OC(CC[Si](OC)(OC)C)O Chemical compound C(C(=C)C)(=O)OC(CC[Si](OC)(OC)C)O IVPWAZDCYGWSCL-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-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
- 239000000758 substrate Substances 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 compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 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
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 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
- 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
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002464 physical blending Methods 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 208000031737 Tissue Adhesions Diseases 0.000 abstract 1
- 239000012855 volatile organic compound Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- LMVLVUPTDRWATB-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-ol Chemical compound CO[Si](C)(OC)CCCO LMVLVUPTDRWATB-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 3
- 238000003860 storage 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
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000005070 ripening Effects 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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 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
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 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
- 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
- 238000010924 continuous production Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000008398 formation water 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
- 238000002372 labelling Methods 0.000 description 1
- 229940058352 levulinate Drugs 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of environmentally friendly a kind of zero VOC release water paint and preparation method thereof.Adopt low Tg latex A and high glass transition temperature emulsion B physical blending by a certain percentage as basic film forming matter, only needing to add a small amount of coalescents when preparing water-borne wood coating can good filming, the low in raw material price of this water-borne wood coating, preparation technology is simple, and paint film has the permeability of excellence, glossiness, resistance to water and tissue adhesion performance simultaneously.
Description
Technical field:
The present invention relates to water paint of a kind of environmentally friendly zero VOC release room-temperature self crosslinking and preparation method thereof, belong to water-borne wood coating field.
Background technology:
Acrylic ester aquosity coating is with water for dispersion diluent, and excellent Water-borne Acrylic Coating must possess the performance that can compare favourably with traditional solvent based coating, and meets VOC (VOC) Abgasgesetz of various countries' increasingly stringent.China definition VOC in " environmental labelling product technology require water paint " (HJ/T201-2005) that promulgate for 2005 is the amount of all volatile organic compound in unit volume coating than water.Coating industry specifies, the VOC content coating lower than 30g/L belongs to low VOC coatings, and VOC content then belongs to Diamond Search coating less than 1g/L.
For reducing the VOC content in water paint, it is possible to select low film formation temperature emulsion, or use the coalescents of low VOC.CN141405A adopts the pure acrylate polymer emulsion of a kind of nucleocapsid structure to be film forming matter (mass percent 30～55%), add color stuffing (20～35%), water (5～20%), defoamer, dispersant, thickening agent and other auxiliary agent, obtain the super environmental protection latex paint of a kind of Diamond Search release, there is high temperature do not after-tack, low temperature can film forming, the VOC advantage close to zero, but its freeze-thaw stability is poor.CN103201346A discloses the levulinate coalescents of a kind of monohydroxy aliphatic alcohol with 10-20 carbon atom, there is the advantage that low VOC discharges, film forming efficiency is high, but it is relatively costly and film formation time is longer, limit the application in low-VOC aqueous coating field.US20010031362 discloses a kind of aqueous epoxy resins and organosilan double-component low VOC coatings, but its construction is inconvenient, and raw material is costly.
Summary of the invention:
It is an object of the invention to the B emulsion physical blending according to a certain percentage of the A emulsion with low Tg and high glass transition temperature, when in blending emulsion, the mass ratio of A emulsion is higher than 50%, needed for preparing water paint, coalescents consumption is lower than the 2% of quality of the emulsion, the water paint VOC burst size prepared less than 20g/L or is zero, water paint of a kind of environmentally friendly zero VOC release room-temperature self crosslinking and preparation method thereof is provided, low in raw material price, preparation and construction technology are simple, there is the permeability of excellence, glossiness and resistance to water, and improve hardness and the resistance to blocking of coating.
The water paint of a kind of zero VOC of the present invention release room-temperature self crosslinking, blending emulsion including two kinds of polymer emulsions of A, B is film forming matter, it is characterized in that two kinds of polymer emulsions of A, B are the emulsion that vitrification point is different, the vitrification point of A emulsion is-30 DEG C～30 DEG C, and the vitrification point of B emulsion is 50 DEG C～100 DEG C.Wherein polymer emulsion A is acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the copolymer containing carboxyl or the vinyl monomer of amide groups；
Polymer B emulsion is acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the copolymer containing carboxyl or the vinyl monomer of amide groups；
The solid content of two kinds of polymer emulsions of A, B is 30%～55%, and latex A and emulsion B mass ratio in water paint are 1:1～4:1.
Further, acrylic compounds hard monomer is a kind of in following material or their combination: methyl methacrylate, Tert-butyl Methacrylate, isobornyl methacrylate, isobornyl acrylate；
Acrylic compounds soft monomer is a kind of in following material or their combination: n-butyl acrylate, Isobutyl 2-propenoate, isoamyl acrylate, acrylic acid-2-ethyl caproite；
Alkene class cross-linking monomer is a kind of in following material or their combination: N-[2-(2-methyl-4-oxopentyl), acetoacetoxyethyl methacrylate, VTES, γ-(methacryloxy) propyl trimethoxy silicane, 3-(methacryloxy) hydroxypropyl methyl dimethoxysilane, vinyltrimethoxy silane, methacrylate based trimethoxy silane；
Vinyl monomer containing carboxyl or amide groups is a kind of in following material or their combination: acrylic acid, methacrylic acid, methylene-succinic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-butoxy methyl acrylamide.
Polymer emulsion A adopts following method to prepare:
1) in the reactor of nitrogen protection; under stirring condition; it is sequentially added into water, emulsifying agent, acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the mixture containing carboxyl or the vinyl monomer of amide groups and carries out emulsifying; heating in water bath is to 50～90 DEG C; adding initiator causes polymerization to obtain seed emulsion; initiator need to be configured to initiator solution, and the response time is 0.5～1 hour；
2) by acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer, being added separately to equipped with carrying out pre-emulsification dispersion in the reactor of mechanical stirring device containing the vinyl monomer of carboxyl or amide groups, water and emulsifying agent, the pre-emulsification time is 0.5～2 hour；
3) toward step 1) seed emulsion in dropping step 2) pre-emulsion that obtains and initiator solution, time for adding is 1～3 hour；
4) after dropwising, slaking reaction 2～4 hours, then reaction temperature is down to less than 40 DEG C, adds pH adjusting agent and regulate ph value of emulsion to 7～9, filter discharging with 200 mesh filter screens, prepare copolymer emulsion A；
Wherein step 1) in seed emulsion all kinds of monomer masses respectively each monomer gross mass 5%～25%, step 2) in pre-emulsion all kinds of monomer masses respectively each monomer gross mass 95%～75%；The mass ratio of acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the vinyl monomer containing carboxyl or amide groups is: 30～60:40～70:3～8:2～5.
Polymer emulsion B adopts following method to prepare:
1) in the reactor of nitrogen protection; under stirring condition; be sequentially added into water, emulsifying agent, acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer, mixture containing carboxyl or the vinyl monomer of amide groups carry out emulsifying; heating in water bath is to 50～90 DEG C; adding initiator causes polymerization to obtain seed emulsion; initiator need to be configured to initiator solution, and the response time is 0.5～1 hour；
2) by acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer, being added separately to equipped with carrying out pre-emulsification dispersion in the reactor of mechanical stirring device containing the vinyl monomer of carboxyl or amide groups, water and emulsifying agent, the pre-emulsification time is 0.5～2 hour；
3) toward step 1) seed emulsion in dropping step 2) pre-emulsion that obtains and initiator solution, time for adding is 1～3 hour；
4) after dropwising, slaking reaction 2～4 hours, then reaction temperature is down to less than 40 DEG C, adds pH adjusting agent and regulate ph value of emulsion to 7～9, filter discharging with 200 mesh filter screens, prepare copolymer emulsion B；
Wherein step 1) in seed emulsion all kinds of monomer masses respectively each monomer gross mass 5%～25%, step 2) in pre-emulsion all kinds of monomer masses respectively each monomer gross mass 95%～75%；The mass ratio of acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the vinyl monomer containing carboxyl or amide groups is: 60～90:10～30:3～8:0.5～5.
Emulsifying agent used by synthetic copolymer latex A, B be anionic emulsifier, nonionic emulsifier or anionic emulsifier and nonionic emulsifier composite in one, consumption is synthesis step 1) seed emulsion and synthesis step 2) in pre-emulsion the 1%～3% of all kinds of monomer gross masses.Wherein anion emulsifier is: one or several in disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, allylpolyethoxy sulfonate, sulfosuccinate synthetic；Nonionic emulsifier is: the one in OPEO, epoxy ethane-epoxy propane copolyether, polyoxyethylene 20 sorbitan monostearate.
PH adjusting agent used by synthetic copolymer latex A, B is the one in ammonia, 2-amino-2-methyl-1-propanol, sodium bicarbonate.
The preparation method that the invention provides a kind of room-temperature self crosslinking zero VOC release water paint, with two kinds of polymer emulsion physical blendings of A, B for film forming matter, be separately added into defoamer, substrate wetting agents, coalescents, levelling agent, wetting dispersing agent, thickening agent one or more, also need to add pigment auxiliary agent in prepared by white paint, dispersion prepare water-borne wood coating, wherein A, B polymer emulsion total weight portion be 60%～90%.
The present invention proposes respectively by the A emulsion of seed emulsion semi-continuous process polymerization synthesis different glass temperature and B emulsion, wherein A emulsion is containing normal temperature crosslinked group and the low Tg soft emulsion containing carboxyl or amido functionality, and B emulsion is containing normal temperature crosslinked group and the high glass transition temperature hard emulsion containing carboxyl or amido functionality.Then by A emulsion and B emulsion physical blending according to a certain percentage, and with the composite formation water paints such as auxiliary agent.A, B emulsion has the good compatibility, polymer emulsion A can give the relatively low MFT of mixed emulsion (minimum film formation temperature) and self-crosslinking reaction occurs when film forming, do not use coalescents or use minute quantity coalescents to get final product good filming, the addition of polymer emulsion B can improve hardness and the resistance to blocking of water paint paint film, the blended of A, B emulsion makes paint film have the permeability of excellence, glossiness, resistance to water, and coating hardness and resistance to blocking are improved.
Detailed description of the invention
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 N-[2-(2-methyl-4-oxopentyl) and 9.6g3-(methacryloxy) hydroxypropyl methyl dimethoxysilane, 0.72gEF-810,0.56gDSB, 0.25gPE-6100,0.5gNaHCO3It is sequentially added in the 2L reactor with agitating device with 327.6g deionized water, opens stirring pre-emulsification and disperse 1 hour.
It is sequentially added into 6.48gEF-810,5.04gDSB, 2.27gPE-6100,0.5gNaHCO in equipped with the 2L reactor of agitating device3, 218.4g deionized water, 11.2g methyl methacrylate, 11.97g butyl acrylate, 0.3g methacrylic acid, 0.5g Methacrylamide, 0.8g N-[2-(2-methyl-4-oxopentyl), 0.5g3-(methacryloxy) hydroxypropyl methyl dimethoxysilane, open stirring and pass into nitrogen 30min, heating in water bath is to 80 DEG C, being sequentially added into the 10g aqueous solution containing 0.25g Ammonium persulfate., the 10g aqueous solution containing 0.25g sodium sulfite and the 10g aqueous solution initiated polymerization containing 0.13gFF6M, the response time is 30 minutes.
Pre-emulsion, the 50g aqueous solution containing 0.25g Ammonium persulfate. and the 50g aqueous solution containing 0.25g sodium sulfite are instilled reactor after terminating by seed emulsion preparation simultaneously, and time for adding is 2 hours.It is incubated ripening 2 hours at 80 DEG C after completion of dropwise addition, less than 40 DEG C are cooled the temperature to after being incubated, add 0.45gAMP-95 and regulate ph value of emulsion to 8.5, add with 20g deionized water mixing 7.8g adipic dihydrazide, with 200 order filter-cloth filtering dischargings after stirring 15 minutes.
The design solid content of copolymer emulsion A is 42%, and vitrification point 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) hydroxypropyl methyl dimethoxysilane, 0.72gEF-810,0.56gDSB, 0.25gPE-6100,0.5gNaHCO3It is sequentially added in the 2L reactor with agitating device with 327.6g deionized water, opens stirring pre-emulsification and disperse 1 hour.
It is sequentially added into 6.48gEF-810,5.04gDSB, 2.27gPE-6100,0.5gNaHCO in equipped with the 2L reactor of agitating device3, 218.4g deionized water, 22.3g methyl methacrylate, 2.5g butyl acrylate, 0.1g methacrylic acid, 0.2g Methacrylamide, 0.5g3-(methacryloxy) hydroxypropyl methyl dimethoxysilane, open stirring and pass into nitrogen 30min, heating in water bath is to 80 DEG C, being sequentially added into the 10g aqueous solution containing 0.25g Ammonium persulfate., the 10g aqueous solution containing 0.25g sodium sulfite and the 10g aqueous solution initiated polymerization containing 0.13gFF6M, the response time is 30 minutes.
Pre-emulsion, the 50g aqueous solution containing 0.25g Ammonium persulfate. and the 50g aqueous solution containing 0.25g sodium sulfite are instilled reactor after terminating by seed emulsion preparation simultaneously, and time for adding is 2 hours.It is incubated ripening 2 hours at 80 DEG C after completion of dropwise addition, after being incubated, cools the temperature to less than 40 DEG C, add 0.45gAMP-95 and regulate ph value of emulsion to 8.5, with 200 order filter-cloth filtering dischargings after stirring 15 minutes.
The design solid content of copolymer emulsion B is 42%, and vitrification point is 80 DEG C.
(3) preparation of the clear priming paint of aqueous wooden ware
500ml beaker adds 55.5g copolymer emulsion A and 18.5g copolymer emulsion B, open stirring 1600rpm to stir 10 minutes, it is sequentially added into 0.2g substrate wetting agents TEGO-500,0.4g defoamer BYK-024, improve mixing speed to disperse 15 minutes to 3000rpm, reduce mixing speed to 1600rpm, it is sequentially added into 7g water, 0.33gpH regulator AMP-95 and 0.3g thickening agent PUR40, with 200 order filter-cloth filtering dischargings after disperseing 15 minutes, makes varnish type water-borne wood coating.
From the preparation of embodiment 1, A, B emulsion described in embodiment 2-9 is distinctive in that the composition of emulsifying agent and consumption are different, other condition is consistent with embodiment 1 with technique, and concrete emulsifying agent composition and consumption are in Table 1.From the preparation of embodiment 1, A, B emulsion described in embodiment 10-16 is distinctive in that the composition of monomer and consumption are different, other condition is consistent with embodiment 1 with technique, and concrete monomer ratio is in Table 2.
Table 1: embodiment 2-9A, B emulsion synthesis emulsifying agent composition used and consumption
In table, EF-810 is sulfosuccinate synthetic, DSB is disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, SE-10N is allylpolyethoxy sulfonate, LF-4 is sulfo-succinic acid salt mixture, OP-10 OPEO, Tween-60 is polyoxyethylene 20 sorbitan monostearate, and PE-6100 is propyleneoxide-ethyleneoxide copolyether.
Table 2: embodiment 10-16A emulsion synthesis monomer ratio used
Embodiment 10-16B emulsion synthesis monomer ratio used
In table, MMA is methyl methacrylate, BA is butyl acrylate, MAA is methacrylic acid, AA is acrylic acid, and MAM is Methacrylamide, and AM is acrylamide, DAAM is N-[2-(2-methyl-4-oxopentyl), KH-571 is 3-(methacryloxy) hydroxypropyl methyl dimethoxysilane, and A-151 is VTES, and A-174 is γ-(methacryloxy) propyl trimethoxy silicane.
A, B emulsion described in embodiment 17-22 is distinctive in that from embodiment 1 emulsifying agent allocation proportion 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, B emulsion synthesis emulsifying agent allocation proportion used
Unit g
Table 4: embodiment 1-22 copolymer emulsion property indices test result
Note: sampling and measuring when conversion ratio terminates for reaction；Calcium ion stability method of testing is that addition 4ml mass fraction is the calcium chloride water of 0.5% in the emulsion of 16ml, room temperature stood after 48 hours, observes emulsion whether breakdown of emulsion, layering and precipitates out little particle flocculation material, if being difficult upper phenomenon, Calcium ion stability is passed through, and does not otherwise pass through.
Embodiment 23-33 is that A, B emulsion different proportion is blended prepares water-borne wood coating resistance to water, glossiness, hardness, resistance to blocking, 50 DEG C of storage stability test results.
Table 5: embodiment 23-33A, B emulsion different proportion are blended prepares water paint property indices test result
Note: embodiment 26 and embodiment 30 add the coalescents DPnB of 2% mass parts when preparing water paint；The test of 50 DEG C of storage stabilities, for adding 60g water paint in 100ml transparent plastic bottle, is positioned in 50 DEG C of baking ovens after sealing, observe water paint can storage-stable until occurring that sedimentation, layering, gel precipitate out the time of phenomenon, in sky.
Embodiment 34-38: the preparation of aqueous wooden ware based white primer
200ml beaker adds the wetting dispersing agent BYK-190 of 17g water, 7.5g, stir 10 minutes under 1200rpm mixing speed, add 75g rutile titanium dioxide and 0.5g anti-settling agent BYK-420, disperse under 2000rpm mixing speed, testing when fineness reaches below 30 μm with Hegman grind gage and stop stirring, the white slurry prepared remains to use.
null500ml beaker adds 60g polymer emulsion A and 20g polymer emulsion B，Open stirring 1600rpm to stir 10 minutes，It is sequentially added into 0.5g defoamer BYK-024、0.6g defoamer TEGO-902W、0.2g levelling agent BYK-346、1.0g deionized water，Rotating speed is increased to 3000rpm disperse 30 minutes，Add 1.0g silicon dioxide flatting silica and disperse 30 minutes at 3,000 rpm，Rotating speed is down to 1600rpm，It is sequentially added into 5.0g deionized water、The cured auxiliary agent MD2000 of 2.0g、0.1g levelling agent BYK-333 dispersed with stirring 15 minutes，It is sequentially added into 0.3gpH regulator AMP-95、2.0g auxiliary rheological agents R212，Dispersed with stirring adds 23g and starches in vain after 15 minutes at 1600 rpm，Continue after stirring 15 minutes with 200 order filter-cloth filtering dischargings.
Table 6: embodiment 34-37A, B emulsion different proportion are blended prepares water paint property indices test result
Note: embodiment 26 and embodiment 30 add the coalescents DPnB of 2% mass parts when preparing water paint；The test of 50 DEG C of storage stabilities, for adding 60g water paint in 100ml transparent plastic bottle, is positioned in 50 DEG C of baking ovens after sealing, observe water paint can storage-stable until occurring that sedimentation, layering, gel precipitate out the time of phenomenon, in sky.
Claims (6)
1. a zero VOC release water paint, is characterized in that including two kinds of acrylic polymer emulsions of A, B；Two kinds of polymer emulsions of A, B are the emulsion that vitrification point is different, and the vitrification point of A emulsion is-30 DEG C～30 DEG C, and the vitrification point of B emulsion is 50 DEG C～100 DEG C；Wherein polymer emulsion A is acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the copolymer containing carboxyl or the vinyl monomer of amide groups；Acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer, mass ratio containing carboxyl or the vinyl monomer of amide groups be: 30～60:40～70:3～8:2～5；
Polymer emulsion B is acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the copolymer containing carboxyl or the vinyl monomer of amide groups；The mass ratio of acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the vinyl monomer containing carboxyl or amide groups is: 60～90:10～30:3～8:0.5～5；
The solid content of two kinds of polymer emulsions of A, B is 30%～55%, and latex A and emulsion B mass ratio in water paint are 1:1～4:1；
Wherein acrylic compounds hard monomer is one or several in following material: methyl methacrylate, Tert-butyl Methacrylate, isobornyl methacrylate, isobornyl acrylate；Acrylic compounds soft monomer is one or several in following material: n-butyl acrylate, Isobutyl 2-propenoate, isoamyl acrylate, acrylic acid-2-ethyl caproite；
Alkene class cross-linking monomer is one or several in following material: N-[2-(2-methyl-4-oxopentyl), acetoacetoxyethyl methacrylate, VTES, γ-(methacryloxy) propyl trimethoxy silicane, 3-(methacryloxy) hydroxypropyl methyl dimethoxysilane, vinyltrimethoxy silane, methacrylate based trimethoxy silane；
Vinyl monomer containing carboxyl or amide groups is one or several in following material: acrylic acid, methacrylic acid, methylene-succinic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide.
2. zero VOC according to claim 1 release water paint, is characterized in that described polymer emulsion A adopts following method to prepare:
1) in the reactor of nitrogen protection; under stirring condition; it is sequentially added into water, emulsifying agent, acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer and the mixture containing carboxyl or the vinyl monomer of amide groups and carries out emulsifying; heating in water bath is to 50～90 DEG C; adding initiator causes polymerization to obtain seed emulsion; initiator need to be configured to initiator solution, and the response time is 0.5～1 hour；
2) by acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer, being added separately to equipped with carrying out pre-emulsification dispersion in the reactor of mechanical stirring device containing the vinyl monomer of carboxyl or amide groups, water and emulsifying agent, the pre-emulsification time is 0.5～2 hour；
3) toward step 1) seed emulsion in dropping step 2) pre-emulsion that obtains and initiator solution, time for adding is 1～3 hour；
4) after dropwising, slaking reaction 2～4 hours, then reaction temperature is down to less than 40 DEG C, adds pH adjusting agent and regulate ph value of emulsion to 7～9, filter discharging with 200 mesh filter screens, prepare copolymer emulsion A；
Wherein step 1) in seed emulsion all kinds of monomer masses respectively each monomer gross mass 5%～25%, step 2) in pre-emulsion all kinds of monomer masses respectively each monomer gross mass 95%～75%.
3. zero VOC according to claim 1 release water paint, is characterized in that, described polymer emulsion B adopts following method to prepare:
1) in the reactor of nitrogen protection; under stirring condition; be sequentially added into water, emulsifying agent, acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer, mixture containing carboxyl or the vinyl monomer of amide groups carry out emulsifying; heating in water bath is to 50～90 DEG C; adding initiator causes polymerization to obtain seed emulsion; initiator need to be configured to initiator solution, and the response time is 0.5～1 hour；
2) by acrylic compounds hard monomer, acrylic compounds soft monomer, alkene class cross-linking monomer, being added separately to equipped with carrying out pre-emulsification dispersion in the reactor of mechanical stirring device containing the vinyl monomer of carboxyl or amide groups, water and emulsifying agent, the pre-emulsification time is 0.5～2 hour；
3) toward step 1) seed emulsion in dropping step 2) pre-emulsion that obtains and initiator solution, time for adding is 1～3 hour；
4) after dropwising, slaking reaction 2～4 hours, then reaction temperature is down to less than 40 DEG C, adds pH adjusting agent and regulate ph value of emulsion to 7～9, filter discharging with 200 mesh filter screens, prepare copolymer emulsion B；
Wherein step 1) in seed emulsion all kinds of monomer masses respectively each monomer gross mass 5%～25%, step 2) in pre-emulsion all kinds of monomer masses respectively each monomer gross mass 95%～75%.
4. the zero VOC release water paint according to Claims 2 or 3, it is characterized in that: the emulsifying agent used by synthetic copolymer latex A, B be anionic emulsifier, nonionic emulsifier or anionic emulsifier and nonionic emulsifier composite in one, consumption is synthesis step 1) seed emulsion and synthesis step 2) in pre-emulsion the 1%～3% of all kinds of monomer gross masses；Wherein anion emulsifier is: one or several in disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, allylpolyethoxy sulfonate, sulfosuccinate synthetic；Nonionic emulsifier is: the one in OPEO, epoxy ethane-epoxy propane copolyether, polyoxyethylene 20 sorbitan monostearate.
5. the zero VOC release water paint according to Claims 2 or 3, is characterized in that: pH adjusting agent is the one in ammonia, 2-amino-2-methyl-1-propanol, sodium bicarbonate.
6. the preparation method of a kind of zero VOC according to claim 1 release water paint, it is characterized in that: with the mixed emulsion of polymer emulsion A, B for film forming matter, add one or more auxiliary agents in defoamer, substrate wetting agents, coalescents, levelling agent, thickening agent, wetting dispersing agent, also need to add pigment auxiliary agent in prepared by white paint, dispersion prepare water-borne wood coating, wherein A, B polymer emulsion total percentage by weight be 60%～90%.
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| ES2763924T3 (en) * | 2014-08-20 | 2020-06-01 | Sun Chemical Corp | Printing inks and coating compositions for polyethylene coated panel |
| CN104804562B (en) * | 2015-04-17 | 2017-03-08 | 湖南中汉高分子材料科技有限公司 | One kind is anti-to after-tack elastomeric propylene sour water 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 |
| EP3325526B1 (en) * | 2015-07-20 | 2022-07-06 | Dow Global Technologies LLC | A coating additive |
| CN105418828A (en) * | 2015-12-18 | 2016-03-23 | 武汉华工图像技术开发有限公司 | Aqueous acrylic acid emulsion and preparation method thereof |
| CN105694650A (en) * | 2016-04-25 | 2016-06-22 | 韩志龙 | Preparation method of light-resistant water-based paint and adhesive |
| JP2020501935A (en) * | 2016-10-20 | 2020-01-23 | サン・ケミカル・コーポレーション | Water-based ink for shrinkable and non-shrinkable polymer films |
| 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 |
| CN107353757A (en) * | 2017-06-26 | 2017-11-17 | 界首市通泽建材销售有限公司 | A kind of acrylic ester aquosity coating of low VOC releases |
| CN109486331A (en) * | 2018-10-26 | 2019-03-19 | 江门市新会区明洋化工实业有限公司 | A kind of coating composition and preparation method thereof |
| CN111138979A (en) * | 2019-12-31 | 2020-05-12 | 杭州立威化工涂料有限公司 | Production process of water-based high-performance anti-tack highlight self-drying paint |
| CN112724772A (en) * | 2020-12-29 | 2021-04-30 | 广东绿色大地化工有限公司 | Composite modified acrylic amino water-based baking paint |
| CN114426791B (en) * | 2021-12-30 | 2023-04-07 | 广东美涂士建材股份有限公司 | Room-temperature crosslinking nano alloy coating and preparation method thereof |
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