CN115677909B - Hydroxy acrylic ester resin dispersoid and preparation method and application thereof - Google Patents
Hydroxy acrylic ester resin dispersoid and preparation method and application thereof Download PDFInfo
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- -1 Hydroxy acrylic ester Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011347 resin Substances 0.000 title claims abstract description 15
- 229920005989 resin Polymers 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 174
- 239000011259 mixed solution Substances 0.000 claims abstract description 72
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 31
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 51
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 2
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 claims description 2
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 2
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 7
- 230000005611 electricity Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 102100026735 Coagulation factor VIII Human genes 0.000 description 8
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000012972 dimethylethanolamine Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002396 Polyurea Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009974 thixotropic effect Effects 0.000 description 3
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241001093575 Alma Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Abstract
The invention provides a hydroxy acrylic resin dispersoid, a preparation method and application thereof. The method comprises the following steps: mixing an acrylic ester monomer, styrene and methacrylic acid to form a monomer mixed solution I, mixing the acrylic ester monomer and acrylic acid to form a monomer mixed solution II, and mixing the acrylic ester monomer, a crosslinking monomer and a functional monomer to form a monomer mixed solution III; adding a kettle bottom solvent, heating, adding a monomer mixed solution I, and adding an initiator; adding a monomer mixed solution II and an initiator; neutralizing by adding a neutralizing agent, and adding water to disperse to obtain a hydroxy acrylic acid dispersion A; and adding the hydroxy acrylic acid dispersion A into a reaction kettle, adding the monomer mixed solution III, and adding an initiator to obtain the target hydroxy acrylic acid ester resin dispersion. The hydroxy acrylic resin dispersoid prepared by the process has excellent aluminum powder orientation performance when preparing aluminum powder paint, and is particularly suitable for preparing high-aluminum powder orientation silver powder paint in the fields of pen electricity and the like.
Description
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to a hydroxy acrylic resin dispersoid and a preparation method and application thereof.
Background
The water-based paint can avoid serious environmental pollution caused by solvent-based paint to a great extent, and is a necessary trend of development of the current paint industry under the current environmental protection policy. The aqueous hydroxy acrylic acid dispersoid has the excellent performances of high gloss, good weather resistance, color retention, gloss retention and the like, and is widely applied to the fields of high-grade coatings including the field of automobile coatings.
The silver paint (also called aluminum paint) is characterized in that aluminum powder is dispersed in resin as a raw material, in the process of forming a paint film, a flaky aluminum powder structure forms a parallel arrangement structure in the paint film, and under irradiation, the paint film presents a stronger metal flashing effect, so that a coating layer presents a metal texture, a nonmetallic material can be endowed with a metal appearance, and the silver paint has been widely applied to the application fields of 3C electronics, hubs, burglary-resisting doors, automobiles and the like at present. The solvent-based silver powder coating is very mature in application, and in contrast, the development of silver powder arrangement technology in the water-based coating is not mature, and the problems of poor aluminum powder arrangement, low glossiness and low fullness of the existing dispersion metallic paint on the market exist, so how to improve the silver powder arrangement of the water-based coating is a problem which needs to be solved in the industry at present.
The patent CN111040560 provides an industrial aluminum powder directional aqueous dispersion and a preparation method thereof, and the molecular chain has better thixotropic property and anchor aluminum powder orientation by introducing a reactive polyurea prepolymer, an amido functional monomer and a hydrophobic association type functional monomer. The method has the advantages that more functional monomers are used, the reactive polyurea prepolymer is required to be synthesized in advance, the process is complex, the control is difficult, and the use of the reactive polyurea prepolymer is limited to a certain extent. Patent CN106478860A provides an aqueous acrylic resin with excellent aluminum powder directionality, preparation and coating thereof, wherein the aluminum powder directionality effect is obtained by introducing functional monomers such as an amido acrylic monomer, an epoxy acrylic monomer, a phosphate acrylic monomer, an amino acrylic monomer and the like, the formula design is complex, the control of an industrial process is difficult, and the cost performance of the resin is low.
Disclosure of Invention
Based on the technical problems existing in the background art, the invention aims at providing a preparation method of a hydroxy acrylic resin dispersoid, which can realize high-gloss, high-fullness and high-metal texture aluminum paint and can improve the adhesive force of the aluminum paint to a substrate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method of preparing a hydroxy acrylate resin dispersion, the method comprising the steps of:
s1: mixing an acrylic ester monomer, styrene and methacrylic acid to form a monomer mixed solution I, wherein the acrylic ester monomer contains at least one hydroxy acrylic ester monomer; mixing an acrylic ester monomer and acrylic acid to form a monomer mixed solution II, wherein the acrylic ester monomer contains at least one hydroxy acrylic ester monomer; mixing an acrylic ester monomer, a crosslinking monomer and a functional monomer to form a monomer mixed solution III;
s2: adding a kettle bottom solvent into a reaction kettle, heating to a polymerization temperature, adding a monomer mixed solution I, adding an oil-soluble initiator, and preserving heat; adding a monomer mixed solution II, adding an oil-soluble initiator, and preserving heat;
s3: neutralizing by adding a neutralizing agent, and adding water to disperse to obtain a hydroxy acrylic acid dispersion A;
s4: adding the hydroxy acrylic acid dispersion A into a reaction kettle, heating, adding the monomer mixed solution III, adding the water-soluble initiator, preserving heat, and filtering to obtain the target hydroxy acrylic acid ester resin dispersion.
The method comprises the steps of firstly obtaining a dispersion structure with an inner layer containing relative weak acid methacrylic acid and an outer layer containing relative strong acid acrylic acid through a solution polymerization process, and then polymerizing an acrylic acid monomer mixed solution containing a crosslinking monomer onto the dispersion through an emulsion polymerization process to realize a shell structure with high shell hardness, micro crosslinking and large molecular weight. The structure achieves a hydroxy acrylic resin dispersion with a glass transition temperature greater than 50 ℃ and a weight average molecular weight greater than 20,000. The dispersion has the advantages that through the polymer structure designed by the acid distribution, when the pH value is adjusted by adding the neutralizer into the formula system, the high thixotropic dispersion can be obtained, meanwhile, the quick-drying performance is improved through the high molecular weight obtained by the emulsion polymerization process, the aluminum powder structure is easier to orient in the film forming process of a paint film, and the high-gloss, high-fullness and high-metal texture aluminum powder paint can be realized because of the low molecular weight structure of the solution polymerization part. Meanwhile, functional monomers are introduced into the shell layer to enhance the stability of the emulsion by introducing an anhydride structure, meanwhile, the thixotropic property of the emulsion is further enhanced by introducing the hydrophobicity of the polyisobutylene and the polybutadiene, so that the high-orientation property of the aluminum paint is obtained.
In the invention, the mass part content of each component in the monomer mixed solution I in S1 is as follows: 55.5-79% of acrylate monomer, 20-40% of styrene and 1-4.5% of methacrylic acid, wherein the hydroxyl acrylate monomer accounts for 5-15%, preferably 8-12% of the total mass of the monomer mixture I.
In the invention, the mass part content of each component in the monomer mixed solution II in S1 is as follows: 80-92% of acrylate monomer and 8-20% of acrylic acid, wherein the hydroxyl acrylate monomer accounts for 10-25%, preferably 10-20% of the total mass of the monomer mixed solution II.
In the invention, the mass part content of each component in the monomer mixed solution III in S1 is as follows: 95-98% of acrylate monomer, 0.5-2.0% of crosslinking monomer and 0.5-3.0% of functional monomer, based on the total mass of the monomer mixed solution III.
In the invention, the functional monomer in the monomer mixed solution III in the S1 is one or more of polybutadiene maleic anhydride, polyisobutylene succinic anhydride and polyisobutylene maleic anhydride.
In the invention, the crosslinking monomer in the monomer mixture III in the S1 is one or more of ethylene glycol dimethacrylate, 1, 4-butanediol methacrylate, 1, 6-hexanediol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate and allyl methacrylate.
In the invention, the acrylic ester monomer in the monomer mixed solution I and the monomer mixed solution II in the S1 is selected from one or more of methyl (methyl) acrylate, butyl (methyl) acrylate and isooctyl (methyl) acrylate.
In the invention, the hydroxy acrylic ester monomer in the monomer mixture I and the monomer mixture II in the S1 is selected from one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.
In the invention, the oil-soluble initiator S2 is selected from one or more of di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate and tert-amyl peroxy-2-ethylhexanoate; preferably, the amount of the oil-soluble initiator added after the monomer mixed solution I is 0.8-2.0% of the mass of the monomer mixed solution I, and the amount of the oil-soluble initiator added after the monomer mixed solution II is 0.5-1.5% of the mass of the monomer mixed solution II.
In the invention, the solvent S2 is one or more selected from solvent oil, propylene glycol butyl ether, ethylene glycol butyl ether, dipropylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether; preferably, the solvent is present in a ratio of 5 to 20% based on the total mass of monomer mixtures I, II and III.
In the invention, the monomer mixed solution I is added dropwise, the dropwise adding time is 2-5 hours, and the monomer mixed solution II is added dropwise, wherein the dropwise adding time is 0.5-3 hours.
In the present invention, the polymerization temperature of S2 is 80 to 160℃and preferably 100 to 145 ℃.
In the invention, the neutralizing agent S3 is selected from one or more of triethanolamine, ethanolamine, diethanolamine, triethylamine and N, N-dimethylethanolamine; preferably, the neutralizing agent is present in a ratio of 1% to 6% based on the total mass of monomer mixtures I, II and III.
In the invention, the water-soluble initiator S4 is selected from one or more of ammonium persulfate, sodium persulfate and potassium persulfate; preferably, the water-soluble initiator is added after the monomer mixed solution III is added in an amount of 0.1 to 0.8 percent of the mass of the monomer mixed solution III.
In the invention, the ratio of the monomer mixed liquid I in the S2 is 50-75%, the ratio of the monomer mixed liquid II in the S4 is 15-30%, and the ratio of the monomer mixed liquid III in the S4 is 10-20% based on the total mass of the monomer mixed liquids I, II and III.
In the present invention, the temperature of the temperature rise in S4 is 70 to 90℃and preferably 80 to 90 ℃.
In the invention, the monomer mixed solution III of the S4 is added dropwise, and the dropwise adding time is 0.5-1.0 hour.
In the invention, the glass transition temperature of the hydroxy acrylic resin in the hydroxy acrylic resin dispersion of S4 is more than 50 ℃, and the weight average molecular weight is more than 20,000.
It is another object of the present invention to provide a hydroxyacrylate resin dispersion.
The hydroxy acrylic resin dispersoid prepared by the preparation method. The glass transition temperature of the hydroxy acrylic resin in the hydroxy acrylic resin dispersoid is more than 50 ℃, and the weight average molecular weight is more than 20,000.
It is a further object of the present invention to provide the use of a hydroxyacrylate resin dispersion.
The use of the hydroxy acrylic resin dispersion is prepared by the preparation method or the hydroxy acrylic resin dispersion, and the dispersion is used for water-based silver powder coating.
The silver powder coating also comprises at least one of the following components: wetting agent, defoamer, aqueous aluminum powder, PH regulator, dispersant, orientation agent and film forming auxiliary agent, and can be matched with isocyanate curing agent and amino resin curing agent. Other components and amounts of the aqueous silver powder coating may be selected and adjusted by those skilled in the art using techniques commonly used in the art.
Compared with the prior art, the invention has the following positive effects:
(1) The silver powder has excellent orientation performance, can obtain higher metal flashing effect, and the FI value can reach more than 18;
(2) The obtained silver paint has excellent storage stability and no layering in more than 6 months; the method comprises the steps of carrying out a first treatment on the surface of the
(3) The adhesive force on nonpolar substrates such as PP is better, and the adhesive is particularly suitable for the fields such as pen electricity and the like.
Detailed Description
The following examples will further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and should also include any other known modifications within the scope of the claims.
Weight average molecular weight determination: number average molecular weight testing was performed using GPC (gel permeation chromatography, agilent 1260Infinity II). The glass transition temperature was measured by DSC (TA DSC 250). Aluminum powder alignment effect evaluation was characterized by FI (FLOP INDEX metal flake dynamic INDEX) values and tested by X-Rite MA68II in America. Adhesion test criteria the test was carried out using a PP (polypropylene) substrate (no surface treatment), the hundred-cell adhesion test method (GB 1720-1989). Paint film gloss was tested using a BGD 516/3 gloss meter. The stability test uses visual inspection for delamination.
Table 1 raw materials and sources for preparing hydroxy acrylate resin dispersions
Example 1
Preparing monomer mixed solution I, monomer mixed solution II and monomer mixed solution III.
30g of BCS was added to a 1L reactor containing heating means, condensing means and stirring means and heated to 138℃and, when the initial charge had risen to 138℃the following monomer mix I was started to drop uniformly: 40g MMA, 20g BA, 10g EHA, 56.25g BMA, 12.5g HEMA, 100g ST, 11.25g MAA and 5g DTBP for 2 hours, and after the monomer mixture was completely added dropwise, the mixture was kept at this temperature for 20 minutes, and then the following monomer mixture II was uniformly added dropwise: 70g of MMA, 30.5g of BA, 37.5g of HEMA, 12g of AA and 0.75g of DTBP for 3 hours, and after the monomer mixture is completely dripped, the temperature is kept for 10 minutes, then 5.6g of DMEA is added and stirred for 20 minutes, and then the mixture is dispersed with 520g of pure water for 10 minutes to obtain a hydroxy acrylic resin dispersion A.
The hydroxy acrylic resin dispersion A obtained above was added to a 1L reactor containing a heating device, a condensing device and a stirring device and heated to 88℃and, when the initial mass had risen to 85℃the following monomer mixture III was started to drop uniformly: 60g MMA, 39g BMA, 0.5g EGDMA, 0.5g polybutadiene maleic anhydride and 0.1g APS, wherein the dripping time is 1.0h, the temperature is kept for 20min after the dripping is finished, and then the mixture is filtered and discharged to obtain the hydroxy acrylic resin dispersoid.
Example 2
Preparing monomer mixed solution I, monomer mixed solution II and monomer mixed solution III.
90g of Pnb are introduced into a 1L reactor comprising a heating device, a condensing device and a stirring device and heated to 100℃and, when the initial charge has risen to 100℃the following monomer mixture I) is homogeneously dropped: 110g MMA, 30g BA, 20g EHA, 80g BMA, 56.25g HPA, 75g ST, 3.75g MAA and 3g TBPO, for 5 hours, and after the monomer mixture was added dropwise, it was kept at this temperature for 1.0 hour, and then the following monomer mixture II was uniformly dropped: 40g MMA, 12.5g BA, 7.5g HPA, 15g AA and 1.125g TBPO were added dropwise for 0.5 hour, and after the monomer mixture was completely added dropwise, it was kept at this temperature for 1 hour, then 29g TEOA was added and stirred for 20 minutes, and then dispersed with 520g pure water for 10 minutes to obtain a hydroxyacrylic acid resin dispersion A.
The hydroxy acrylic resin dispersion A obtained above was added to a 1L reactor containing a heating device, a condensing device and a stirring device and heated to 75℃and when the initial mass had risen to 85℃the following monomer mix III was started to drop uniformly: 40g MMA, 7.5g BMA, 1g ALMA, 1.5g polyisobutene maleic anhydride and 0.4g KPS, the dripping time is 30min, the temperature is kept for 30min after the dripping is finished, and then the material is filtered and discharged to obtain the hydroxy acrylic resin dispersoid.
Example 3
Preparing monomer mixed solution I, monomer mixed solution II and monomer mixed solution III.
50g of BCS was added to a 1L reactor containing heating means, condensing means and stirring means and heated to 140℃and, when the initial charge had risen to 140℃the following monomer mix I was started to drop uniformly: 100g MMA, 25.25g BA, 60g BMA, 32.5g HEMA, 97.5g ST, 9.75g MAA and 3.9g DTBP for 3 hours, and after the monomer mixture was completely added dropwise, the mixture was kept at this temperature for 30 minutes, and then the following monomer mixture II was uniformly added dropwise: 50g of MMA, 19g of BA, 15g of HEMA, 16g of AA and 1g of DTBP for 1.0 hour, and after the monomer mixture is completely dripped, the temperature is kept for 30 minutes, 17.3g of DMEA is added and stirred for 20 minutes, and then the mixture is dispersed with 520g of pure water for 10 minutes, so that a hydroxy acrylic resin dispersion A is obtained.
The hydroxy acrylic resin dispersion A obtained above was added to a 1L reactor containing a heating device, a condensing device and a stirring device and heated to 75℃and when the initial mass had risen to 85℃the following monomer mix III was started to drop uniformly: 50g MMA, 23.5g BMA, 0.75g EGDMA, 0.75g polybutadiene maleic anhydride and 0.375g APS, the dropwise addition time was 48min, the heat preservation was carried out for 1.0h after the dropwise addition was completed, and then the discharge was filtered to obtain a hydroxy acrylic resin dispersion.
Comparative example 1
Comparative example 1 differs from example 3 only in that the monomer is not reacted in the monomer mixture III.
Preparing monomer mixed solution I, monomer mixed solution II and monomer mixed solution III.
50g of BCS was added to a 1L reactor containing heating means, condensing means and stirring means and heated to 140℃and, when the initial charge had risen to 140℃the following monomer mix I was started to drop uniformly: 100g MMA, 25.25g BA, 60g BMA, 32.5g HEMA, 97.5g ST, 9.75g MAA and 3.9g DTBP for 3 hours, and after the monomer mixture was completely added dropwise, the mixture was kept at this temperature for 30 minutes, and then the following monomer mixture II was uniformly added dropwise: 50g of MMA, 19g of BA, 15g of HEMA, 16g of AA and 1g of DTBP for 1.0 hour, and after the monomer mixture is completely dripped, the temperature is kept for 30 minutes, 17.3g of DMEA is added and stirred for 20 minutes, and then the mixture is dispersed with 520g of pure water for 10 minutes, so that a hydroxy acrylic resin dispersion A is obtained.
The hydroxy acrylic resin dispersion A obtained above was added to a 1L reactor containing a heating device, a condensing device and a stirring device and heated to 75℃and when the initial mass had risen to 85℃the following monomer mix III was started to drop uniformly: 50g MMA, 23.5g BMA, 0.75g EGDMA and 0.375g APS, the dropwise addition time is 48min, the temperature is kept for 1.0h after the dropwise addition is completed, and then the material is filtered and discharged to obtain the hydroxy acrylic resin dispersoid.
Comparative example 2
Comparative example 2 differs from example 3 only in the absence of monomer mixture III.
Preparing monomer mixed solution I, monomer mixed solution II and monomer mixed solution III.
50g of BCS was added to a 1L reactor containing heating means, condensing means and stirring means and heated to 140℃and, when the initial charge had risen to 140℃the following monomer mix I was started to drop uniformly: 100g MMA, 25.25g BA, 60g BMA, 32.5g HEMA, 97.5g ST, 9.75g MAA and 3.9g DTBP for 3 hours, and after the monomer mixture was completely added dropwise, the mixture was kept at this temperature for 30 minutes, and then the following monomer mixture II was uniformly added dropwise: 50g of MMA, 19g of BA, 15g of HEMA, 16g of AA and 1g of DTBP for 1.0 hour, and after the monomer mixture is completely dripped, the temperature is kept for 30 minutes, 17.3g of DMEA is added and stirred for 20 minutes, and then the mixture is dispersed with 520g of pure water for 10 minutes, so that a hydroxy acrylic resin dispersion is obtained.
Aqueous silver paint coatings were prepared from the hydroxy acrylic resin dispersions obtained in the above examples and comparative examples, and the formulations are shown in table 2:
table 2 aqueous silver paint formulation
The preparation method comprises the following steps:
firstly, adding 4g of water, 8g of silver powder 1405L, 0.2g of BYK 192 and 4g of BCS into a dispersion tank in sequence, stirring for 20min at 800r/min, and standing at room temperature for soaking for 4h to obtain aqueous silver powder slurry for later use.
60g of a hydroxyacrylate resin dispersion was added, the pH was adjusted by adding 0.2g of DMEA, followed by sequentially adding 0.5g of TEGO 270, 0.1g of TEGO 902W, 20g of 3% RD, 1g of BYK8421, 1g of 50% TEGO 3060, 1g of 50% A308, and after stirring at 800r/min for 20 minutes, 16.2g of the aqueous silver powder paste obtained above was then added to obtain an aqueous silver powder paint A component.
80 percent (20 percent of PMA open-diluted) of isocyanate curing agent is added on the basis of the component A, and the mixture is stirred for 10 minutes at 800r/min to obtain the water-based silver powder coating for performance test.
The glossiness and FI value of the aqueous silver paint prepared by the hydroxy acrylic ester resin dispersion of each example and comparative example are tested, and the detection results are shown in Table 3:
TABLE 3 results of gloss and FI test of aqueous silver paint
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Tg | 70 | 65 | 55 | 68 | 43 |
| Mw | 36576 | 45218 | 26792 | 31964 | 15627 |
| Stability of | >6 months of | >6 months of | >6 months of | Layering for 3 months | Layering for 1 month |
| FI value | 21.56 | 20.12 | 20.32 | 13.84 | 9.85 |
| Adhesion to PP substrate | Level 0 | Level 0 | Level 0 | No adhesion | No adhesive force |
| Gloss (60 degree) | 93 | 90 | 92 | 70 | 88 |
Comparative example 1 differs from example 3 only in that the monomer is not reacted in the monomer mixture III, which gives a film having a lower FI value and at the same time no adhesion on the PP substrate.
Finally, it should be noted that the above embodiments are only described as preferred embodiments of the present invention, and not limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various modifications and improvements made to the technical solution of the present invention or equivalent substitutions should be made, all fall within the scope of the present invention as defined in the claims.
Claims (12)
1. A method of preparing a hydroxy acrylate resin dispersion, the method comprising the steps of:
s1: mixing an acrylic ester monomer, styrene and methacrylic acid to form a monomer mixed solution I, wherein the acrylic ester monomer contains at least one hydroxy acrylic ester monomer; mixing an acrylic ester monomer and acrylic acid to form a monomer mixed solution II, wherein the acrylic ester monomer contains at least one hydroxy acrylic ester monomer; mixing an acrylic ester monomer, a crosslinking monomer and a functional monomer to form a monomer mixed solution III;
s2: adding a kettle bottom solvent into a reaction kettle, heating to a polymerization temperature, adding a monomer mixed solution I, adding an oil-soluble initiator, and preserving heat; adding a monomer mixed solution II, adding an oil-soluble initiator, and preserving heat;
s3: neutralizing by adding a neutralizing agent, and adding water to disperse to obtain a hydroxy acrylic acid dispersion A;
s4: adding the hydroxy acrylic acid dispersion A into a reaction kettle, heating, adding the monomer mixed solution III, adding a water-soluble initiator, preserving heat, and filtering to obtain a target hydroxy acrylic acid ester resin dispersion;
wherein the functional monomer in the S1 is one or more of polybutadiene maleic anhydride, polyisobutylene succinic anhydride and polyisobutylene maleic anhydride.
2. The preparation method according to claim 1, wherein the mass part content of each component in the monomer mixture I of S1 is: 55.5-79% of acrylate monomer, 20-40% of styrene and 1-4.5% of methacrylic acid, wherein the hydroxyl acrylate monomer accounts for 5-15% of the total mass of the monomer mixed solution I;
and/or the mass part content of each component in the monomer mixed solution II in the S1 is as follows: 80-92% of acrylate monomer and 8-20% of acrylic acid, wherein the hydroxyl acrylate monomer accounts for 10-25% of the total mass of the monomer mixed solution II;
and/or the mass part content of each component in the monomer mixed solution III in the S1 is as follows: 95-98% of acrylate monomer, 0.5-2.0% of crosslinking monomer and 0.5-3.0% of functional monomer, based on the total mass of the monomer mixed solution III.
3. The preparation method according to claim 2, wherein the hydroxyl acrylate monomer in S1 accounts for 8-12% based on the total mass of the monomer mixture I;
and/or the hydroxyl acrylic ester monomer in S1 accounts for 10-20% based on the total mass of the monomer mixed solution II.
4. The preparation method according to claim 1 or 2, wherein the crosslinking monomer in the monomer mixture III in S1 is one or more of ethylene glycol dimethacrylate, 1, 4-butylene glycol methacrylate, 1, 6-hexanediol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate and allyl methacrylate;
and/or, the acrylic ester monomer in the monomer mixed solution I and the monomer mixed solution II in the S1 is selected from one or more of methyl (methyl) acrylate, butyl (methyl) acrylate and isooctyl (methyl) acrylate;
and/or, the hydroxy acrylate monomer in the monomer mixture I and the monomer mixture II in the S1 is selected from one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.
5. The preparation method according to claim 1, wherein the oil-soluble initiator S2 is one or more selected from the group consisting of di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate and tert-amyl peroxy-2-ethylhexanoate;
and/or the solvent in S2 is selected from one or more of solvent oil, propylene glycol butyl ether, ethylene glycol butyl ether, dipropylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether;
and/or, dropwise adding the monomer mixed solution I in the step S2 for 2-5 hours, and dropwise adding the monomer mixed solution II for 0.5-3 hours;
and/or the polymerization temperature of S2 is 80-160 ℃.
6. The preparation method according to claim 5, wherein the amount of the oil-soluble initiator added after the addition of the monomer mixed solution I in S2 is 0.8-2.0% of the mass of the monomer mixed solution I, and the amount of the oil-soluble initiator added after the addition of the monomer mixed solution II is 0.5-1.5% of the mass of the monomer mixed solution II;
and/or the polymerization temperature of S2 is 100-145 ℃.
7. The method according to claim 1, wherein the neutralizing agent of S3 is one or more selected from the group consisting of triethanolamine, ethanolamine, diethanolamine, triethylamine, and N, N-dimethylethanolamine.
8. The method of claim 7, wherein the neutralizing agent is 1% -6% by weight of the total mass of the monomer mixture I, II and III.
9. The method of claim 1, wherein S4 the water-soluble initiator is selected from one or more of ammonium persulfate, sodium persulfate, and potassium persulfate;
and/or S2 the ratio of the monomer mixed solution I is 50-75%, the ratio of the monomer mixed solution II is 15-30%, and S4 the ratio of the monomer mixed solution III is 10-20% based on the total mass of the monomer mixed solutions I, II and III;
and/or, the temperature of the temperature rise in the step S4 is 70-90 ℃;
and/or dropwise adding the monomer mixed solution III in the step S4, wherein the dropwise adding time is 0.5-1.0 hour;
and/or, the glass transition temperature of the hydroxy acrylic resin in the hydroxy acrylic resin dispersion of S4 is more than 50 ℃, and the weight average molecular weight is more than 20,000.
10. The preparation method according to claim 9, wherein the amount of the water-soluble initiator added after the addition of the monomer mixed solution III in S4 is 0.1-0.8% of the mass of the monomer mixed solution III;
and/or, the temperature of the temperature rise in the step S4 is 80-90 ℃.
11. A hydroxyacrylate resin dispersion prepared by the method of any one of claims 1-10.
12. Use of the hydroxyacrylate resin dispersion prepared by the preparation method of any one of claims 1 to 10 or the hydroxyacrylate resin dispersion of claim 11 for an aqueous silver powder coating.
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| JP2011057891A (en) * | 2009-09-11 | 2011-03-24 | Dic Corp | Method for producing aqueous polymer dispersion for coating material and dispersion thereof |
| CN107434842A (en) * | 2016-05-26 | 2017-12-05 | 万华化学集团股份有限公司 | A kind of core shell structure Hydroxylated acrylic resin emulsion and its preparation method and application |
| CN107805291A (en) * | 2017-11-14 | 2018-03-16 | 武汉双键开姆密封材料有限公司 | A kind of water-based hydroxyl acrylic acid dispersion and preparation method |
| CN108264643A (en) * | 2017-12-19 | 2018-07-10 | 万华化学（宁波）有限公司 | A kind of copolymer p, water-borne dispersions resin and its application in water paint |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011057891A (en) * | 2009-09-11 | 2011-03-24 | Dic Corp | Method for producing aqueous polymer dispersion for coating material and dispersion thereof |
| CN107434842A (en) * | 2016-05-26 | 2017-12-05 | 万华化学集团股份有限公司 | A kind of core shell structure Hydroxylated acrylic resin emulsion and its preparation method and application |
| CN107805291A (en) * | 2017-11-14 | 2018-03-16 | 武汉双键开姆密封材料有限公司 | A kind of water-based hydroxyl acrylic acid dispersion and preparation method |
| CN108264643A (en) * | 2017-12-19 | 2018-07-10 | 万华化学（宁波）有限公司 | A kind of copolymer p, water-borne dispersions resin and its application in water paint |
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