CN103172797B - 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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- CN103172797B CN103172797B CN201310080975.5A CN201310080975A CN103172797B CN 103172797 B CN103172797 B CN 103172797B CN 201310080975 A CN201310080975 A CN 201310080975A CN 103172797 B CN103172797 B CN 103172797B
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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 of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure and preparation method and the powder coating containing this prepolymer.
Background technology
Powder coating, as the environment friendly coated package material just grown up nearest decades, has that coating efficiency is high, protective and an advantage such as decorate properties is good, receives the extensive attention in the world, thus obtains 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, primarily of acrylic resin and corresponding solidifying agent formulated.
Acrylic powder coating is a kind of high-decoration, high weatherability coating, there is 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 furnishing fields such as automobile, refrigerator, electric fan, washing machine, be the high-grade powder coating developed rapidly after epoxy powder coating and polyester type powder paint.
The production of powder coating, be exactly by solid materialss such as resin, solidifying agent, pigment, filler and auxiliary agents, mixing machine is added not using under the ambient condition such as solvent or water in formula ratio ratio, forcing machine melting mixing is quantitatively added to after abundant blending dispersion, then on compressing tablet cooler, thin slice is pressed into, cooling is broken into flake, enter the broken rear cyclonic separation of air classifying abrasive dust again, the meal separated obtains finished product after vibratory screening apparatus sieves, and fine powder is reclaimed by bag filter, whole production process is a physical process, substantially 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 pulverize → carefully pulverizes and sieves → quality inspection packaging → product.It is that technical process is long that traditional powder coating manufactures main drawback, and facility investment is large, wastes man-hour, wastes energy, the drawbacks such as serious dust pollution.And at present, the production Multi-purpose mechanical breaking method of the powder coating of China manufactures, the fine spherical powder with microsuspending method synthesis with inierpeneirating network structure is few.
Summary of the invention
The object of this invention is to provide a kind of prepolymer of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure and preparation method and the powder coating containing this prepolymer.
The technical solution used in the present invention is:
A prepolymer for Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure, it is made up of following raw material: the organic solvent of the water of 300-500 part, the vibrin of 40-60 part, mix monomer, 65-85 part, the initiator of 0.1-0.5 part, the dispersion agent of 1-10 part, the stablizer of 1-10 part; Wherein, described mix monomer is made up 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 one in methyl methacrylate, vinylbenzene, vinyl toluene, vinyl cyanide, methyl acrylate.
Described soft monomer is at least one in butyl acrylate, ethyl propenoate, Octyl acrylate, Ethyl acrylate.
Described function monomer is hydroxyethyl methylacrylate, at least one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410, glycidyl methacrylate, N hydroxymethyl acrylamide, Viscoat 295.
Described vibrin is the saturated polyester resin containing end carboxyl and side carboxyl or the one contained in the saturated polyester resin of terminal hydroxy group and pendant hydroxyl group.
Described dispersion agent is at least one in aniorfic surfactant, cationic surfactant, amphoterics, nonionic surface active agent.
Described dispersion agent is at least one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10, OP-40, MS-1.
Described initiator is at least one in Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, di-isopropyl peroxydicarbonate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Described stablizer is at least one in gelatinum, gelatine, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 1793, carboxymethyl cellulose.
A preparation method for the prepolymer of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure, comprises the following steps:
1) mix monomer to be mixed with initiator, then by vibrin organic solvent dissolution, by above both mix and obtain oil-phase solution;
2) water, dispersion agent, stablizer are mixed to obtain aqueous phase solution;
3) mixed with aqueous phase solution by oil-phase solution, carry out sufficient back flow reaction, removing organic solvent, is cooled to room temperature, obtained mixed solution is carried out filtration washing, obtains product.
A kind of powder coating, it is made up of prepolymer, solidifying agent, color stuffing, other coatings additive(s)s.
The invention has the beneficial effects as follows: the present invention adopts micro-suspension IPN polymerization process, obtains the performed polymer of size tunable, and this performed polymer building-up process is pollution-free.
Specifically: the present invention adopts micro-suspension IPN polymerization process, directly obtain size tunable, narrow diameter distribution the spherical powder coating performed polymer of stable dispersion can be kept in depositing, eliminate the processing step of plasticizing mixing in traditional preparation methods and mechanical disintegration, for suitability for industrialized production saves the energy, the over-all properties of film can be significantly improved.The synthesis of this powder coating prepolymer resin take water as dispersion medium, micro-poison, harmless, pollution-free, belongs to Environmentally friendly coatings resin, has the wide prospect of marketing.
Accompanying drawing explanation
Fig. 1 is the optical microscope photograph (magnification: 200 ×) of the resinous powder particles that embodiment 1 is obtained by microsuspension.
Fig. 2 is the infrared spectrogram of prepolymer resin prepared by embodiment 1.
Embodiment
A prepolymer for Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure, it is made up of following raw material: the organic solvent of the water of 300-500 part, the vibrin of 40-60 part, mix monomer, 65-85 part, the initiator of 0.1-0.5 part, the dispersion agent of 1-10 part, the stablizer of 1-10 part; Wherein, described mix monomer is made up of the hard monomer of 35-40 part, the soft monomer of 5-15 part, the function monomer of 5-10 part.
Preferably, a prepolymer for Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure, it is made up of following raw material: the aromatic hydrocarbons organic solvent of the water of 300-500 part, the vibrin of 40-60 part, mix monomer, 65-85 part, the initiator of 0.1-0.5 part, the dispersion agent of 1-10 part, the stablizer of 1-10 part; Wherein, described mix monomer is made up 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 vibrin is used aromatic hydrocarbons organic solvent dissolution, by above both mix and obtain oil-phase solution;
2) aqueous phase solution is mixed to obtain at water, dispersion agent, stablizer;
3) mixed with aqueous phase solution by oil-phase solution, carry out sufficient back flow reaction, removing organic solvent, is cooled to room temperature, obtained mixed solution is carried out filtration washing, obtains product.
Preferred further, the preparation method of this prepolymer, comprises the following steps:
1) mix monomer is mixed with initiator, then vibrin is used aromatic hydrocarbons organic solvent dissolution, by above both mix and obtain oil-phase solution;
2) aqueous phase solution is mixed to obtain at water, dispersion agent, stablizer;
3) oil-phase solution and aqueous phase solution are carried out in a kettle. being uniformly mixed 0.5-1.5h at 50-70 DEG C, then at 70-85 DEG C, be uniformly mixed 1.5-2.5h, then at 85-95 DEG C, stir 0.8-1.2h; Finally access prolong, at 90-100 DEG C, stir 0.8-1.2h, by toluene distillation out.Mixed solution to room temperature, then is carried out filtration washing, after drying by last cooling down.
Corresponding powder coating made by the prepolymer that above-mentioned further preferred version can be utilized to prepare, cooperation solidifying agent, color stuffing, other coatings additive(s)s.
Described vibrin is the saturated polyester resin containing end carboxyl and side carboxyl or the one contained in the saturated polyester resin of terminal hydroxy group and pendant hydroxyl group; Preferably, the model of described vibrin is: CPE-2070 or P9332TG; Make solidifying agent containing the saturated polyester resin triglycidyl isocyanurate (TGIC) of end carboxyl and side carboxyl and hydroxyalkyl amide (HAA), the saturated polyester resin closure carbimide containing terminal hydroxy group and pendant hydroxyl group makees solidifying agent.
In the present invention, described hard monomer is at least one in methyl methacrylate, vinylbenzene, vinyl toluene, vinyl cyanide, methyl acrylate; Described soft monomer is at least one in butyl acrylate, ethyl propenoate, Octyl acrylate, Ethyl acrylate; Described function monomer is hydroxyethyl methylacrylate, at least one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410, glycidyl methacrylate, N hydroxymethyl acrylamide, Viscoat 295; Described dispersion agent is at least one in aniorfic surfactant, cationic surfactant, amphoterics, nonionic surface active agent; Preferably, described dispersion agent is at least one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10, OP-40, MS-1.Described initiator is at least one in Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, di-isopropyl peroxydicarbonate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Described stablizer is at least one in gelatinum, gelatine, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 1793, carboxymethyl cellulose.
Below in conjunction with specific embodiment, most the present invention is described further:
embodiment 1:
The prepolymer resin of poly-third olefin(e) acid ester ∕ 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 Hong Yi 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: first by vinylbenzene, methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate and azo-bis-isobutyl cyanide mixing, make initiator dissolve and obtain component A.Then vibrin CPE-2070 to be poured in toluene into heating for dissolving at 60 DEG C and obtains B component, by A, B two component be uniformly mixed that to make oil-phase solution stand-by;
Pour water into reactor, dispersion agent, stablizer to be added in reactor and stir and make it dissolve, be heated to 70 DEG C; Then oil-phase solution is poured in reactor, first at 70 DEG C of reaction 1.5h, then at 85 DEG C of reaction 2.5h, then at 90 DEG C of reaction 1h, finally accesses water distilling apparatus, at 100 DEG C, react 1h, by toluene distillation out; Last cooling down places 24h, mixed solution is carried out filtration washing, namely obtains acrylate/polyester resin powder coating performed polymer after oven dry.
Fig. 1 is the optical microscope photograph (magnification: 200 ×) of prepolymer resin powder particle prepared by the present embodiment.
Fig. 2 is the infrared spectrogram of prepolymer resin prepared by the present embodiment.
After tested, the second-order transition temperature of this performed polymer is 60 DEG C.
embodiment 2:
The prepolymer resin of poly-third olefin(e) acid ester ∕ vibrin inierpeneirating network structure, its each component proportion is (consumption is mass parts): deionized water 350, toluene 80, mix monomer 50, vibrin P9332TG(Zhejiang brilliance chemical industry) 50, auxiliary agent 10.
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: first by vinylbenzene, methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate and azo-bis-isobutyl cyanide mixing, initiator is dissolved and obtains component A, then vibrin P9332TG to be poured in toluene into heating for dissolving at 60 DEG C and obtains B component, by A, B two component be uniformly mixed that to make oil-phase solution stand-by.
Pour deionized water into reactor, dispersion agent, stablizer to be added in reactor and stir and make it dissolve, be heated to 70 DEG C.Then oil-phase solution is poured in reactor, first at 70 DEG C of reaction 1.5h, then at 85 DEG C of reaction 2.5h, then at 90 DEG C of reaction 1h, finally accesses water distilling apparatus, at 100 DEG C, react 1h, by toluene distillation out.Last cooling down places 24h, mixed solution is carried out filtration washing, namely obtains acrylate/polyester resin powder coating prepolymer resin after oven dry.
Product feature: external appearance characteristic is white powder, form is spherical ellipsoid, particle diameter 5 ~ 30 μm;
After testing, the second-order transition temperature 60 DEG C of this prepolymer resin;
With this prepolymer resin, solidifying agent, that corresponding formula made by filler, other auxiliary agents is as follows:
Performed polymer powder 2kg, solidifying agent TGIC 150g, filler barium sulfate 1.2kg, auxiliary agent: wax powder Clariant PE520 30g, flow agent moral believe sharp PV88 30g, optical brightener H701(Hubei carrys out this Chinese workers) 30g, st-yrax 30g.
The spraying method of this powder coating: electrostatic spraying.
Powder coating performed polymer powder is mixed with solidifying agent, filler, auxiliary agent, then crosses net with 160 eye mesh screens.Baking oven is put into, 200 DEG C, heating 15min after in electrostatic spraying to aluminium sheet.
The character of paint film after curing cross-linked film forming: hardness of film 4H, sticking power grade 2.
Claims (6)
1. a prepolymer for poly-third olefin(e) acid ester ∕ vibrin inierpeneirating network structure, is characterized in that: it is made up of following raw material: the organic solvent of the water of 300-500 part, the vibrin of 40-60 part, mix monomer, 65-85 part, the initiator of 0.1-0.5 part, the dispersion agent of 1-10 part, the stablizer of 1-10 part; Wherein, described mix monomer is made up 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 one in methyl methacrylate, vinylbenzene, vinyl toluene, vinyl cyanide, methyl acrylate; Described soft monomer is at least one in butyl acrylate, ethyl propenoate, Octyl acrylate, Ethyl acrylate; Described function monomer is hydroxyethyl methylacrylate, at least one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410, glycidyl methacrylate, N hydroxymethyl acrylamide, Viscoat 295; Described vibrin is the saturated polyester resin containing end carboxyl and side carboxyl or the one contained in the saturated polyester resin of terminal hydroxy group and pendant hydroxyl group.
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 dispersion agent is at least one in aniorfic surfactant, cationic surfactant, amphoterics, nonionic surface active agent.
3. the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 2, is characterized in that: described dispersion agent is at least one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10, OP-40, MS-1.
4. 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 one in Diisopropyl azodicarboxylate, benzoyl peroxide, lauroyl peroxide, di-isopropyl peroxydicarbonate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Described stablizer is at least one in gelatinum, gelatine, polyvinyl alcohol 1788, polyvinyl alcohol 1799, polyvinyl alcohol 1793, carboxymethyl cellulose.
5. the preparation method of the prepolymer of a kind of Ju Bing olefin(e) acid Zhi ∕ vibrin inierpeneirating network structure according to claim 1, is characterized in that: comprise the following steps:
1) mix monomer to be mixed with initiator, then by vibrin organic solvent dissolution, by above both mix and obtain oil-phase solution;
2) water, dispersion agent, stablizer are mixed to obtain aqueous phase solution;
3) mixed with aqueous phase solution by oil-phase solution, carry out sufficient back flow reaction, removing organic solvent, is cooled to room temperature, obtained mixed solution is carried out filtration washing, obtains product.
6. a powder coating, is characterized in that: it is made up of prepolymer according to claim 1, solidifying agent, color stuffing, other coatings additive(s)s.
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| CN103554381A (en) * | 2013-10-21 | 2014-02-05 | 北京金汇利应用化工制品有限公司 | Water-based acrylic acid modified saturated polyester resin and preparation method thereof |
| CN103881627B (en) * | 2014-03-20 | 2016-08-17 | 杨毅 | Foaming microporous acrylic emulsion |
| CN109054533B (en) * | 2018-07-18 | 2021-06-29 | 陕西科技大学 | Polymer coating and preparation method thereof |
| 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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| CN100430424C (en) * | 2006-10-24 | 2008-11-05 | 河北工业大学 | Process for preparing acrylate resin for powder paint |
| CN101787239B (en) * | 2009-12-31 | 2012-05-23 | 广东银洋树脂有限公司 | Method for preparing environment-friendly powder coating resin |
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