CN103172797A - Polyacrylate/polyester resin prepolymer in interpenetration network structure, method for preparing same and powdery coating with same - Google Patents
Polyacrylate/polyester resin prepolymer in interpenetration network structure, method for preparing same and powdery coating with same Download PDFInfo
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- CN103172797A CN103172797A CN2013100809755A CN201310080975A CN103172797A CN 103172797 A CN103172797 A CN 103172797A CN 2013100809755 A CN2013100809755 A CN 2013100809755A CN 201310080975 A CN201310080975 A CN 201310080975A CN 103172797 A CN103172797 A CN 103172797A
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Abstract
The invention discloses a polyacrylate/polyester resin prepolymer in an interpenetration network structure. The prepolymer is prepared from the following raw materials: water, a polyester resin, mixed monomers, an organic solvent, an initiating agent, a dispersing agent and a stabilizing agent, wherein the mixed monomers comprise a hard monomer, a soft monomer and a functional monomer. A method for preparing the prepolymer comprises the following steps of: (1) mixing the mixed monomers with the initiating agent, dissolving the polyester resin in an organic solvent, and mixing the mixture of the mixed monomers and the initiating agent with the dissolved polyester resin uniformly to obtain an oil-phase solution; (2) mixing the water, the dispersing agent and the stabilizing agent uniformly to obtain a water-phase solution; and (3) mixing the oil-phase solution and the water-phase solution, carrying out refluxing reaction, removing a solvent, decreasing the temperature to room temperature, filtering an obtained mixed solution, and washing to obtain a product of reaction. A powdery coating is prepared from the prepolymer, a curing agent, a pigment filler and other coating additives. The prepolymer with a controllable particle size is prepared by adopting the micro-suspension interpenetration polymerization method, thus no pollution can be caused in the process of synthesizing the prepolymer.
Description
Technical field
The present invention relates to a kind of prepolymer and preparation method of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure and contain the powder coating of this prepolymer.
Background technology
Powder coating is as the environment friendly coated package material that just grows up decades recently, has that coating efficiency is high, protective and an advantage such as decorate properties is good, has been subject to the extensive attention in the world, thus the acquisition sustained and rapid development.Powder coating comprises the various series product such as epoxy polyester (mixing) type, epoxy type, polyester type, polyurethane-type, and acrylic powder coating is one of them important kind, and is mainly formulated by acrylic resin and corresponding solidifying agent.
Acrylic powder coating is a kind of high-decoration, high weatherability coating, has good ageing resistance, erosion resistance, wear resistance, outside durabitity, guarantor's light tint retention and higher mechanical property, suppleness and hardness, can be widely used in the high-grade decoration such as automobile, refrigerator, electric fan, washing machine field, be the high-grade powder coating that develops rapidly after epoxy powder coating and polyester type powder paint.
the production of powder coating, be exactly with resin, solidifying agent, pigment, the solid materials such as filler and auxiliary agent, add mixing machine in the formula ratio ratio not using under the ambient conditions such as solvent or water, through fully quantitatively being added to the forcing machine melting mixing after blending dispersion, then be pressed into thin slice on the compressing tablet cooler, cooling be broken into laminar, advance again the broken rear cyclonic separation of air classifying abrasive dust, the meal of separating obtains finished product after vibratory screening apparatus sieves, and fine powder reclaims by bag filter, whole production process is a physical process, basically there is not chemical reaction.The technological process of production is as follows: resin, solidifying agent, pigment, additive etc. → pre-mixing → melt extrude → compressing tablet pulverizing → fine powder is broken to sieve → and quality inspection packing → product.It is that technical process is long that traditional powder coating is made main drawback, and facility investment is large, wastes man-hour, waste energy, and the serious drawbacks such as dust pollution.And at present, the production Multi-purpose mechanical breaking method of the powder coating of China is made, and synthesizes the fine spherical powder with inierpeneirating network structure with microsuspending method few.
Summary of the invention
The purpose of this invention is to provide a kind of prepolymer and preparation method of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure and contain the powder coating of this prepolymer.
The technical solution used in the present invention is:
A kind of prepolymer of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure, it is to be made by following raw material: the dispersion agent of the organic solvent of the vibrin of the water of 300-500 part, 40-60 part, mix monomer, 65-85 part, the initiator of 0.1-0.5 part, 1-10 part, the stablizer of 1-10 part; Wherein, described mix monomer is comprised of the hard monomer of 35-40 part, the soft monomer of 5-15 part, the function monomer of 5-10 part.
Described hard monomer is at least a in methyl methacrylate, vinylbenzene, vinyl toluene, vinyl cyanide, methyl acrylate.
Described soft monomer is at least a in butyl acrylate, ethyl propenoate, Octyl acrylate, Ethyl acrylate.
Described function monomer is hydroxyethyl methylacrylate, at least a in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410, glycidyl methacrylate, N hydroxymethyl acrylamide, Viscoat 295.
Described vibrin be contain the saturated polyester resin of end carboxyl and side carboxyl or contain terminal hydroxy group and the saturated polyester resin of pendant hydroxyl group in a kind of.
Described dispersion agent is at least a in aniorfic surfactant, cationic surfactant, amphoterics, nonionic surface active agent.
Described dispersion agent is at least a in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10, OP-40, MS-1.
Described initiator is at least a in Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, di-isopropyl peroxydicarbonate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Described stablizer is at least a in gelatinum, gelatine, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 1793, carboxymethyl cellulose.
A kind of preparation method of prepolymer of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure comprises the following steps:
1) mix monomer is mixed with initiator, then with the vibrin organic solvent dissolution, with above both mix and obtain oil-phase solution;
2) water, dispersion agent, stablizer are mixed to get aqueous phase solution;
3) oil-phase solution is mixed with aqueous phase solution, carry out sufficient back flow reaction, remove organic solvent, be cooled to room temperature, resulting mixed solution is carried out filtration washing, namely get product.
A kind of powder coating, it is comprised of prepolymer, solidifying agent, color stuffing, other coatings additive(s)s.
The invention has the beneficial effects as follows: the present invention adopts little suspension IPN polymerization process, has obtained the controlled performed polymer of particle diameter, and this performed polymer building-up process is pollution-free.
Specifically: the present invention adopts little suspension IPN polymerization process, obtained directly that particle diameter is controlled, narrow diameter distribution, and can deposit the spherical powder coating performed polymer of middle maintenance stable dispersion, plasticizing mixing in traditional preparation method and the processing step of mechanical disintegration have been saved, save the energy for suitability for industrialized production, can significantly improve the over-all properties of filming.Synthesizing take water as dispersion medium of this powder coating prepolymer resin, little poison, harmless, pollution-free belongs to environmentally friendly coating resin, has the wide prospect of marketing.
Description of drawings
Fig. 1 is embodiment 1 by the optical microscope photograph of the resulting resinous powder particles of microsuspension (magnification: 200 *).
Fig. 2 is the infrared spectrogram of the prepolymer resin of embodiment 1 preparation.
Embodiment
A kind of prepolymer of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure, it is to be made by following raw material: the dispersion agent of the organic solvent of the vibrin of the water of 300-500 part, 40-60 part, mix monomer, 65-85 part, the initiator of 0.1-0.5 part, 1-10 part, the stablizer of 1-10 part; Wherein, described mix monomer is comprised of the hard monomer of 35-40 part, the soft monomer of 5-15 part, the function monomer of 5-10 part.
Preferably, a kind of prepolymer of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure, it is to be made by following raw material: the dispersion agent of the aromatic hydrocarbons organic solvent of the vibrin of the water of 300-500 part, 40-60 part, mix monomer, 65-85 part, the initiator of 0.1-0.5 part, 1-10 part, the stablizer of 1-10 part; Wherein, described mix monomer is comprised of the vinylbenzene of 5-15 part, the methyl methacrylate of 20-35 part, the butyl acrylate of 5-15 part, the hydroxyethyl methylacrylate of 5-10 part.
Use the raw material of this preferred version to make the method for this prepolymer, comprise the following steps:
1) mix monomer is mixed with initiator, then with vibrin aromatic hydrocarbons organic solvent dissolution, with above both mix and obtain oil-phase solution;
2) mix to get aqueous phase solution at water, dispersion agent, stablizer;
3) oil-phase solution is mixed with aqueous phase solution, carry out sufficient back flow reaction, remove organic solvent, be cooled to room temperature, resulting mixed solution is carried out filtration washing, namely get product.
Further preferred, the preparation method of this prepolymer comprises the following steps:
1) mix monomer is mixed with initiator, then with vibrin aromatic hydrocarbons organic solvent dissolution, with above both mix and obtain oil-phase solution;
2) mix to get aqueous phase solution at water, dispersion agent, stablizer;
3) oil-phase solution and aqueous phase solution are mixed 0.5-1.5h under 50-70 ℃ in reactor, then mix 1.5-2.5h under 70-85 ℃, then stir 0.8-1.2h under 85-95 ℃; Access at last prolong, stir 0.8-1.2h under 90-100 ℃, with toluene distillation out.Last cooling down is to room temperature, then mixed solution is carried out filtration washing, gets final product after drying.
Can utilize prepolymer, cooperation solidifying agent, color stuffing, other coatings additive(s)s of above-mentioned further preferred version preparation to make corresponding powder coating.
Described vibrin be contain the saturated polyester resin of end carboxyl and side carboxyl or contain terminal hydroxy group and the saturated polyester resin of pendant hydroxyl group in a kind of; Preferably, the model of described vibrin is: CPE-2070 or P9332TG; The saturated polyester resin that contains end carboxyl and side carboxyl is made solidifying agent with triglycidyl isocyanurate (TGIC) and hydroxyalkyl amide (HAA), and the saturated polyester resin that contains terminal hydroxy group and pendant hydroxyl group is made solidifying agent with the closure carbimide.
In the present invention, described hard monomer is at least a in methyl methacrylate, vinylbenzene, vinyl toluene, vinyl cyanide, methyl acrylate; Described soft monomer is at least a in butyl acrylate, ethyl propenoate, Octyl acrylate, Ethyl acrylate; Described function monomer is hydroxyethyl methylacrylate, at least a in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410, glycidyl methacrylate, N hydroxymethyl acrylamide, Viscoat 295; Described dispersion agent is at least a in aniorfic surfactant, cationic surfactant, amphoterics, nonionic surface active agent; Preferably, described dispersion agent is at least a in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10, OP-40, MS-1.Described initiator is at least a in Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, di-isopropyl peroxydicarbonate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Described stablizer is at least a in gelatinum, gelatine, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 1793, carboxymethyl cellulose.
The present invention is described further below in conjunction with specific embodiment:
Embodiment 1:
The prepolymer resin of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure, its each component proportion is (consumption is mass parts): deionized water 400, toluene 70, mix monomer 50, vibrin CPE-2070(Longkou City great meaning molding powder company limited) 50, auxiliary agent 10;
Acrylic acid or the like mix monomer proportioning: hard monomer 35, soft monomer 10, function monomer 5;
Wherein, hard monomer vinylbenzene 10, methyl methacrylate 25; Soft monomer butyl acrylate 10; Function monomer hydroxyethyl methylacrylate 5.
Auxiliary agent: dispersion agent: sodium dodecylbenzenesulfonate 5, stablizer: polyvinyl alcohol 2.5, gelatinum 2.5;
Initiator: azo-bis-isobutyl cyanide 2.
The preparation method of this prepolymer resin: at first with vinylbenzene, methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate and azo-bis-isobutyl cyanide mix, and make the initiator dissolving obtain the A component.Then vibrin CPE-2070 is poured in toluene and obtain the B component 60 ℃ of lower heating for dissolving, A, B two components are mixed to make oil-phase solution stand-by;
Pour water into reactor, dispersion agent, stablizer are added in reactor and stir make its dissolving, be heated to 70 ℃; Then oil-phase solution is poured in reactor, at first at 70 ℃ of reaction 1.5h, then at 85 ℃ of reaction 2.5h, then at 90 ℃ of reaction 1h, accesses at last water distilling apparatus, react 1h under 100 ℃, with toluene distillation out; Last cooling down is placed 24h, and mixed solution is carried out filtration washing, namely gets acrylate/polyester resin powder coating performed polymer after oven dry.
Fig. 1 is the optical microscope photograph (magnification: 200 *) of the prepolymer resin powder particle of the present embodiment preparation.
Fig. 2 is the infrared spectrogram of the prepolymer resin of the present embodiment preparation.
After tested, the second-order transition temperature of this performed polymer is 60 ℃.
Embodiment 2:
Deionized water 350, toluene 80, mix monomer 50, vibrin P9332TG(Zhejiang brilliance chemical industry) 50, auxiliary agent 10 prepolymer resin of poly-the third olefin(e) acid ester ∕ vibrin inierpeneirating network structure, its each component proportion is (consumption is mass parts):.
Mix monomer proportioning: hard monomer 40, soft monomer 5, function monomer 5.
Wherein, hard monomer vinylbenzene 10, methyl methacrylate 30, soft monomer butyl acrylate 5, function monomer hydroxyethyl methylacrylate 5.
Auxiliary agent: dispersion agent: Sodium dodecylbenzene sulfonate 5, stablizer: polyvinyl alcohol 2.5, gelatinum 2.5;
Initiator: azo-bis-isobutyl cyanide 1.5.
The preparation method of this prepolymer resin: at first with vinylbenzene, methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate and azo-bis-isobutyl cyanide mix, make the initiator dissolving obtain the A component, then vibrin P9332TG is poured in toluene and obtain the B component 60 ℃ of lower heating for dissolving, A, B two components are mixed to make oil-phase solution stand-by.
Pour deionized water into reactor, dispersion agent, stablizer are added in reactor and stir make its dissolving, be heated to 70 ℃.Then oil-phase solution is poured in reactor, at first at 70 ℃ of reaction 1.5h, then at 85 ℃ of reaction 2.5h, then at 90 ℃ of reaction 1h, accesses at last water distilling apparatus, react 1h under 100 ℃, with toluene distillation out.Last cooling down is placed 24h, and mixed solution is carried out filtration washing, namely gets acrylate/polyester resin powder coating prepolymer resin after oven dry.
Product feature: external appearance characteristic is white powder, and form is spherical ellipse, particle diameter 5 ~ 30 μ m;
After testing, 60 ℃ of the second-order transition temperatures of this prepolymer resin;
With this prepolymer resin, solidifying agent, filler, that other auxiliary agents are made corresponding formula is as follows:
Performed polymer powder 2kg, solidifying agent TGIC 150g, filler barium sulfate 1.2kg, auxiliary agent: the sharp PV88 30g of wax powder Clariant PE520 30g, flow agent moral letter, optical brightener H701(come this Chinese workers in Hubei) 30g, st-yrax 30g.
The spraying method of this powder coating: electrostatic spraying.
Powder coating performed polymer powder and solidifying agent, filler, auxiliary agent are mixed, then cross net with 160 eye mesh screens.Electrostatic spraying is put baking oven into after to the aluminium sheet, and 200 ℃, heating 15min.
The character of paint film after the curing cross-linked film forming: hardness of film 4H, sticking power grade 2.
Claims (10)
1. the prepolymer of poly-third an olefin(e) acid ester ∕ vibrin inierpeneirating network structure, it is characterized in that: it is to be made by following raw material: the dispersion agent of the organic solvent of the vibrin of the water of 300-500 part, 40-60 part, mix monomer, 65-85 part, the initiator of 0.1-0.5 part, 1-10 part, the stablizer of 1-10 part; Wherein, described mix monomer is comprised of the hard monomer of 35-40 part, the soft monomer of 5-15 part, the function monomer of 5-10 part.
2. the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 1 is characterized in that: described hard monomer is at least a in methyl methacrylate, vinylbenzene, vinyl toluene, vinyl cyanide, methyl acrylate.
3. the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 1 is characterized in that: described soft monomer is at least a in butyl acrylate, ethyl propenoate, Octyl acrylate, Ethyl acrylate.
4. the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 1, it is characterized in that: described function monomer is hydroxyethyl methylacrylate, at least a in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410, glycidyl methacrylate, N hydroxymethyl acrylamide, Viscoat 295.
5. the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 1 is characterized in that: described vibrin be contain the saturated polyester resin of end carboxyl and side carboxyl or contain terminal hydroxy group and the saturated polyester resin of pendant hydroxyl group in a kind of.
6. the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 1 is characterized in that: described dispersion agent is at least a in aniorfic surfactant, cationic surfactant, amphoterics, nonionic surface active agent.
7. the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 6 is characterized in that: described dispersion agent is at least a in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10, OP-40, MS-1.
8. the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 1 is characterized in that: described initiator is at least a in Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, di-isopropyl peroxydicarbonate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Described stablizer is at least a in gelatinum, gelatine, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 1793, carboxymethyl cellulose.
9. the preparation method of the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure claimed in claim 1 is characterized in that: comprise the following steps:
1) mix monomer is mixed with initiator, then with the vibrin organic solvent dissolution, with above both mix and obtain oil-phase solution;
2) water, dispersion agent, stablizer are mixed to get aqueous phase solution;
3) oil-phase solution is mixed with aqueous phase solution, carry out sufficient back flow reaction, remove organic solvent, be cooled to room temperature, resulting mixed solution is carried out filtration washing, namely get product.
10. powder coating, it is characterized in that: it is comprised of prepolymer claimed in claim 1, solidifying agent, color stuffing, other coatings additive(s)s.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103881627A (en) * | 2014-03-20 | 2014-06-25 | 杨毅 | Foamed microporous acrylic emulsion |
| WO2015058685A1 (en) * | 2013-10-21 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Aqueous acrylic acid modified saturated polyester resin |
| CN109054533A (en) * | 2018-07-18 | 2018-12-21 | 陕西科技大学 | A kind of ternary IPN structural paint and preparation method thereof |
| CN111489720A (en) * | 2020-05-08 | 2020-08-04 | 雅歌乐器(漳州)有限公司 | Guitar production process |
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| CN101787239A (en) * | 2009-12-31 | 2010-07-28 | 广东银洋树脂有限公司 | Method for preparing environment-friendly powder coating resin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015058685A1 (en) * | 2013-10-21 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Aqueous acrylic acid modified saturated polyester resin |
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| CN103881627B (en) * | 2014-03-20 | 2016-08-17 | 杨毅 | Foaming microporous acrylic emulsion |
| CN109054533A (en) * | 2018-07-18 | 2018-12-21 | 陕西科技大学 | A kind of ternary IPN structural paint and preparation method thereof |
| CN111489720A (en) * | 2020-05-08 | 2020-08-04 | 雅歌乐器(漳州)有限公司 | Guitar production process |
| CN111489720B (en) * | 2020-05-08 | 2024-02-27 | 雅歌乐器(漳州)有限公司 | Guitar production process |
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