CN101429267B - Preparation and uses of epoxy/acrylic acid hybridisation emulsion - Google Patents
Preparation and uses of epoxy/acrylic acid hybridisation emulsion Download PDFInfo
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Abstract
The invention provides a method for preparing an epoxy/ acrylic acid hybrid emulsion capable of being dried at a normal temperature, and application of the epoxy/ acrylic acid hybrid emulsion. The method comprises the following steps: firstly, an acrylic acid and an alkyl acrylate monomer are used to prepare a seed emulsion; secondly, an alkyl acrylate solution of epoxy resin is subjected to pre-emulsification; and thirdly, a pre-emulsified liquid is dripped into the seed emulsion, and the mixture is subjected to emulsion polymerization continuously to prepare the epoxy/ acrylic acid hybrid emulsion. Compared with the chemical modification methods such as graft copolymerization, esterification and modification of free radicals, the method has low reaction temperature and simple technique;and the prepared emulsion does not contain an organic solvent and has superior water resistance and solvent resistance. The hybrid emulsion prepared by the method can be used for preparing water-soluble self-dried coating; and the coating is quick to dry, has good adhesion, particularly greatly improves the water resistance and the solvent resistance, and can be widely applied to coating in the fields of metallic anticorrosion, buildings, wooden ware and so on.
Description
Technical field
The present invention relates to polymeric material field, but be a kind of preparation method and the application in the coating preparation thereof of epoxy/acrylic acid hybridisation emulsion of Air drying.The emulsion of utilizing this method to make can be widely used in the manufacturing of water-borne coatingss such as anti-corrosion of metal, building and woodenware.
Background technology
Along with improving constantly and environmental regulation constantly sound of in short supply day by day, common people's environmental consciousness of petroleum resources, coating industry develops to the low direction of polluting and saving resource.Water-borne coatings is a dispersion medium with water, does not fire, not quick-fried, safe in utilization, convenient, and the environment friendly of this uniqueness and security make water-borne coatings become one of important directions of coating development.
Water-base resin or polymer emulsion as the water-borne coatings film forming matter have decisive influence to coating property.It is thermoplastic that common ACRYLIC EMULSION mostly is greatly, and sticking power, water tolerance, solvent resistance are bad, so people adopt the whole bag of tricks that it is carried out modification, wherein relatively effective means is an epoxy resin modification.
Existing epoxy resin modification ACRYLIC EMULSION mainly adopts physical blending and two kinds of technologies of chemical copolymerization.
Physical blending is with ACRYLIC EMULSION and epoxy emulsion mechanically mixing, and chemical reaction does not take place between the two, and the emulsion film forming of this blend is inhomogeneous, and water tolerance improves limited.
Chemical copolymerization has two kinds of methods, a kind of is the free radical grafting copolymerization method, Resins, epoxy is dissolved in the wetting ability mixed solvents such as butanols and alcohol ether, under 110-120 ℃ to wherein dripping carboxylic polymerisable monomer, on the Resins, epoxy molecule segment, connect carboxyl, add amine then graft resin is neutralized, add water and stir, make water-base epoxy/acrylic resin, US4212781 utilizes this method to prepare water-base epoxy/acrylic resin exactly.
Another kind method is the esterification copolymerization method, with esterification copolymerization (esterification temperature is usually at 170 ℃) such as Resins, epoxy elder generation and lipid acid, adds the amine neutralization then, adds water to stir, and the water-base epoxy ester resin that makes is exactly this method as US4963602.
More than two kinds of chemical copolymerization methods make water-base epoxy/acrylic resin and water-base epoxy ester resin in contain hydrophilic organic solvent more than at least 20%, and lean on and vinylformic acid in-COOH after emulsification, resinous acid value is generally greater than 40mgKOH, therefore the wetting ability of paint film is very strong, usually need add amino resin and make amine baking varnish again, and can not be used for Air drying coating.
Also there is the people that the esterification copolymerization is improved to reduce the acid number of resin,, obtains a resin that acid esters is lower with esterification copolymerization such as Resins, epoxy and lipid acid earlier, as the stratum nucleare of modified resin as ZL 01114997.3; Add acrylic monomer continuation polymerization then and obtain the higher relatively shell of acid number; Add the amine neutralization at last, add water and stir, can obtain the water-base resin of average acid number 20mgKOH.The water-base epoxy ester resin of this nucleocapsid structure can prepare self-drying paint, but because self acid number is still higher, water tolerance and antiseptic property are still not so good; And complicated process of preparation, the temperature of reaction height makes resin and also contains 8% left and right sides hydrophilic organic solvent.
The hybridisation emulsion polymerization is a kind of emulsion polymerization technology that occurred in recent years, at first modified resin is dissolved in the acrylic ester monomer, again with the pre-emulsification of this solution, carries out polymerization according to the technology of letex polymerization then.Hybridisation emulsion is aggregated on the technology the same with the conventional emulsion polymerization, but it has realized letex polymerization and modification simultaneously, and on this meaning, polymer emulsion modified new way has been opened up in the hybridisation emulsion polymerization, and its technology is economically feasible more.
Summary of the invention
The object of the present invention is to provide a kind of water-base epoxy/acrylic acid hybridisation emulsion.
Another object of the present invention provides the preparation method of this epoxy/acrylic acid hybridisation emulsion.This method temperature of reaction is low, and the emulsion that makes does not contain organic solvent, can be used for Air drying.
Another purpose of the present invention is to utilize resulting water-base epoxy/acrylic acid hybridisation emulsion to prepare aqueous self-drying coating.
Epoxy/acrylic acid hybridisation emulsion of the present invention is formed by following material cooperation.
Raw-material weight part
Resins, epoxy 2-20
Acrylic Acid Monomer and alkyl acrylate monomer 20-50
Emulsifying agent 2-5
Initiator 0.1-0.6
Neutralizing agent 0.2-1.0
Deionized water 50-60
Described Resins, epoxy is bisphenol A type epoxy resin, and epoxy equivalent (weight) is 185-833, preferable range 196-500.The trade mark commonly used comprises E54, E51, E44, E20, E12 etc.2-20 part of content of epoxy resin.
Described Acrylic Acid Monomer be selected from following one or more: vinylformic acid, methacrylic acid.
Alkyl acrylate monomer be selected from following one or more: methyl acrylate, butyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl methacrylate.
Described initiator comprises water soluble starter and oil-soluble initiator.
Water soluble starter be selected from following one or more: Ammonium Persulfate 98.5, Potassium Persulphate.
Oil-soluble initiator be selected from following one or more: benzoyl peroxide, azo two isobutyls are fine, cumyl hydroperoxide etc.
The present invention adopts mixed initiator, and what preparation was adopted during seed emulsion is water soluble starter, make seed emulsion after, what adopt when proceeding polymerization is oil-soluble initiator, initiator amount is 0.2-1.0 part.
Described emulsifying agent comprises anionic emulsifier, nonionic emulsifier and polymerizable emulsifier three classes.
Described anionic emulsifier can make the polymeric emulsion particle less usually, for example sodium lauryl sulphate, sodium laurylsulfonate, sodium vinyl sulfonate, Sodium dodecylbenzene sulfonate etc.;
Described nonionic emulsifier has fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether etc.;
Polymerizable emulsifier is meant and contains the emulsifying agent that can carry out the group of radical polymerization in the molecular structure, for example vinyl alkylphenol-polyethenoxy sulfonate, vinyl alkyl phosphate, allyl ethers hydroxyl sulfoacid sodium etc.This class emulsifying agent not only can carry out emulsification to monomer, and participates in polymerization in the emulsion polymerization process, is embedded in the emulsion particle surface, can reduce the total consumption of emulsifying agent, thereby improves the water tolerance and the sticking power of filming.
Described neutralizing agent be selected from following one or more: ammoniacal liquor, triethylamine, N, N-dimethylethanolamine.
The preparation method of epoxy/acrylic acid hybridisation emulsion of the present invention:
(1). 30-40 part water, 0.5-2 part emulsifier for mixing evenly are warming up to 40-60 ℃, add 5-10 part vinylformic acid and alkyl acrylate mix monomer, continue to be warming up to 70-80 ℃, add 0.05-0.2 part initiator, be obvious blue light until emulsion; Dropwise 5-10 part vinylformic acid and alkyl acrylate mix monomer dropwise insulation 30 minutes, make seed emulsion.
This step also can once add the vinylformic acid and the alkyl acrylate mix monomer of 10-20 part, adds initiator then and carries out polymerization and make seed emulsion.
(2). in the preparation seed emulsion, with 10-30 part alkyl acrylate monomer dissolving 2-20 part Resins, epoxy, add 0.05-0.55 part initiator, 1-3 part emulsifying agent, 0.1-0.5 part neutralizing agent and 20-30 part water then, carry out emulsification, obtain pre-emulsion with the high-shear emulsifying dispersion machine.
(3). in seed emulsion, drip pre-emulsion at 70-85 ℃, proceed letex polymerization, after letex polymerization is finished, be incubated 2 hours.
(4). the gained emulsion is cooled to 20-30 ℃, under whipped state, adds 0.1-0.5 part neutralizing agent and stir evenly, just obtain epoxy/acrylic acid hybridisation emulsion.
With the epoxy/acrylic acid hybridisation emulsion is the coating of base-material, comprises the epoxy/acrylic acid hybridisation emulsion of 25-50% weight percentage, proper assistant, pigment, filler and water.
With epoxy/acrylic acid hybridisation emulsion among the present invention is the preparation method for coating of base-material:
(1) dispersion agent, defoamer are dispersed in the water, adding pigment, filler stir evenly, and are dispersed to fineness through the sand mill grinding and meet the requirements, and make mill base.
(2) under whipped state, in epoxy/acrylic acid hybridisation emulsion, dose film coalescence aid, mill base, thickening material and PH conditioning agent successively and stir, obtain water-borne coatings.
After the epoxy/acrylic acid hybridisation emulsion film forming drying that the present invention makes, in the Resins, epoxy in epoxy group(ing) and (methyl) vinylformic acid-crosslinking reaction takes place, greatly improved the water tolerance of paint film, anti-solvent scouring, resisted staining property in COOH.
The present invention is used anionic emulsifier with nonionic emulsifying agent, adopt the emulsifying agent instead of part conventional emulsifier that has polymerizable double bond, to obtain the less emulsion of particle diameter and to keep emulsion-stabilizing, has reduced emulsifying agent to the water-proof disadvantageous effect of paint film.
The present invention adopts water soluble starter and oil-soluble initiator way of combining, has improved monomeric transformation efficiency.The present invention is more or less the same with the conventional emulsion polymerization on technology, but it has realized letex polymerization and modification, and its technology is economically feasible more, has opened up polymer emulsion modified new way.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) 80g water, 0.4g sodium laurylsulfonate and 0.1g polyoxyethylene octylphenol ether are stirred, be warming up to 50 ℃, add 10.2g methyl methacrylate and 5.6g butyl acrylate and 1.2g methacrylic acid, continue to be warming up to 70-80 ℃; Add 0.15g ammonium persulfate aqueous solution (being dissolved in the 20 gram water), be obvious blue light until emulsion; Drip the mix monomer of 10.2g methyl methacrylate and 5.6g butyl acrylate and 1.2g methacrylic acid, drip insulation 30 minutes, make seed emulsion.
(2) in the preparation seed emulsion, with 52g methyl methacrylate and 26g butyl acrylate mix monomer dissolving 12g E-51 Resins, epoxy, add 0.6g benzoyl peroxide initiator, 0.3g sodium laurylsulfonate and 1.2g polyoxyethylene octylphenol ether, 1.2g vinyl alkyl phosphate, 0.6g N then, N-dimethylethanolamine and 50g water, carry out emulsification with the high-shear emulsifying dispersion machine, obtain pre-emulsion.
(3) in seed emulsion, drip pre-emulsion at 70-85 ℃, proceed letex polymerization, after letex polymerization is finished, be incubated 2 hours.
(4) the gained emulsion is cooled to 20-30 ℃, adds an amount of N under whipped state, the N-dimethylethanolamine is adjusted to 8.0-9.0 with the emulsion pH value, just obtains epoxy/acrylic acid hybridisation emulsion.
Embodiment 2
(1) 80g water, 0.4g sodium vinyl sulfonate and 0.1g polyoxyethylene nonylphenol ether are stirred, be warming up to 50 ℃, add 9.48g methyl methacrylate and 6.32g butyl acrylate and 1.2g methacrylic acid, continue to be warming up to 70-80 ℃; Add 0.15g persulfate aqueous solution (being dissolved in the 20 gram water), be obvious blue light until emulsion; Drip the mix monomer of 9.48g methyl methacrylate and 6.32g butyl acrylate and 1.2g methacrylic acid, drip insulation 30 minutes, make seed emulsion.
(2) in the preparation seed emulsion, with 46.8g methyl methacrylate and 31.2g butyl acrylate mix monomer dissolving 12g E-51 Resins, epoxy, add 0.6g benzoyl peroxide initiator, 0.3g sodium vinyl sulfonate and 1.2g polyoxyethylene nonylphenol ether, 1.2g vinyl alkyl phosphate, 0.6g N then, N-dimethylethanolamine and 50g water, carry out emulsification with the high-shear emulsifying dispersion machine, obtain pre-emulsion.
(3) in seed emulsion, drip pre-emulsion at 70-85 ℃, proceed letex polymerization, after letex polymerization is finished, be incubated 2 hours.
(4) the gained emulsion is cooled to 20-30 ℃, under whipped state, adds an amount of triethylamine, the emulsion pH value is adjusted to 8.0-9.0, just obtain epoxy/acrylic acid hybridisation emulsion.
Embodiment 3
(1) 80g water, 0.4g sodium laurylsulfonate and 0.1g polyoxyethylene nonylphenol ether are stirred, be warming up to 50 ℃, add 10.2g methyl methacrylate and 5.6g butyl acrylate and 1.2g methacrylic acid, continue to be warming up to 70-80 ℃; Add 0.15g persulfate aqueous solution (being dissolved in the 20 gram water), be obvious blue light until emulsion; Drip the mix monomer of 10.2g methyl methacrylate and 5.6g butyl acrylate and 1.2g methacrylic acid, drip insulation 30 minutes, make seed emulsion.
(2) in the preparation seed emulsion, with 52g methyl methacrylate and 20.2g butyl acrylate and 5.8g Propylene glycol monoacrylate mix monomer dissolving 12g E-51 Resins, epoxy, add the fine initiator of 0.6g azo two isobutyls, 0.3g sodium laurylsulfonate and 1.2g polyoxyethylene nonylphenol ether, 1.2g vinyl alkylphenol-polyethenoxy sulfonate, 0.6g N then, N-dimethylethanolamine and 50g water, carry out emulsification with the high-shear emulsifying dispersion machine, obtain pre-emulsion.
(3) in seed emulsion, drip pre-emulsion at 70-85 ℃, proceed letex polymerization, after letex polymerization is finished, be incubated 2 hours.
(4) the gained emulsion is cooled to 20-30 ℃, adds an amount of N under whipped state, the N-dimethylethanolamine is adjusted to 8.0-9.0 with the emulsion pH value, just obtains epoxy/acrylic acid hybridisation emulsion.
Embodiment 4
(1) 80g water, 0.4g sodium vinyl sulfonate and 0.1g polyoxyethylene octylphenol ether are stirred, be warming up to 50 ℃, add 10.2g methyl methacrylate and 5.6g butyl acrylate and 1.2g methacrylic acid, continue to be warming up to 70-80 ℃; Add 0.15g ammonium persulfate aqueous solution (being dissolved in the 20 gram water), be obvious blue light until emulsion; Drip the mix monomer of 10.2g methyl methacrylate and 5.6g butyl acrylate and 1.2g methacrylic acid, drip insulation 30 minutes, make seed emulsion.
(2) in the preparation seed emulsion, with 52g methyl methacrylate and 26g butyl acrylate mix monomer dissolving 6g E-20 Resins, epoxy, dissolve fully until E-20 Resins, epoxy, add the fine initiator of 0.6g azo two isobutyls, 0.3g sodium vinyl sulfonate and 1.2g polyoxyethylene octylphenol ether, 1.2g vinyl alkylphenol-polyethenoxy sulfonate, 0.6g N then, N-dimethylethanolamine and 50g water, carry out emulsification with the high-shear emulsifying dispersion machine, obtain pre-emulsion.
(3) in seed emulsion, drip pre-emulsion at 70-85 ℃, proceed letex polymerization, after letex polymerization is finished, be incubated 2 hours.
(4) the gained emulsion is cooled to 20-30 ℃, adds an amount of N under whipped state, the N-dimethylethanolamine is adjusted to 8.0-9.0 with the emulsion pH value, just obtains epoxy/acrylic acid hybridisation emulsion.
Embodiment 5
(1) 80g water, 0.4g sodium laurylsulfonate and 0.1g fatty alcohol-polyoxyethylene ether are stirred, be warming up to 50 ℃, add 20.4g methyl methacrylate and 10.2g butyl acrylate and 2.4g methacrylic acid, continue to be warming up to 70-80 ℃; Add 0.15g persulfate aqueous solution (being dissolved in the 20 gram water), be obvious blue light, make seed emulsion until emulsion.
(2) in the preparation seed emulsion, with 52g methyl methacrylate and 20.8g butyl acrylate and 5.2g Hydroxyethyl acrylate mix monomer dissolving 6g E-44 Resins, epoxy, add 0.6g benzoyl peroxide initiator, 0.3g sodium laurylsulfonate and 1.2g fatty alcohol-polyoxyethylene ether, 1.2g vinyl alkyl phosphate, 0.6g N then, N-dimethylethanolamine and 50g water, carry out emulsification with the high-shear emulsifying dispersion machine, obtain pre-emulsion.
(3) in seed emulsion, drip pre-emulsion at 70-85 ℃, proceed letex polymerization, after letex polymerization is finished, be incubated 2 hours.
(4) the gained emulsion is cooled to 20-30 ℃, adds an amount of N under whipped state, the N-dimethylethanolamine is adjusted to 8.0-9.0 with the emulsion pH value, just obtains epoxy/acrylic acid hybridisation emulsion.
Embodiment 6
(1) 80g water, 0.4g sodium laurylsulfonate and 0.1g fatty alcohol-polyoxyethylene ether are stirred, be warming up to 50 ℃, add 10.2g methyl methacrylate and 5.6g butyl acrylate and 1.2g methacrylic acid, continue to be warming up to 70-80 ℃; Add 0.15g ammonium persulfate aqueous solution (being dissolved in the 20 gram water), be obvious blue light until emulsion; Drip the mix monomer of 10.2g methyl methacrylate and 5.6g butyl acrylate and 1.2g methacrylic acid, drip insulation 30 minutes, make seed emulsion.
(2) in the preparation seed emulsion, with 52g methyl methacrylate and 26g butyl acrylate mix monomer dissolving 18g E-51 Resins, epoxy, add 0.6g benzoyl peroxide initiator, 0.3g sodium laurylsulfonate and 1.2g fatty alcohol-polyoxyethylene ether, 1.2g vinyl alkyl phosphate, 0.6g N then, N-dimethylethanolamine and 50g water, carry out emulsification with the high-shear emulsifying dispersion machine, obtain pre-emulsion.
(3) in seed emulsion, drip pre-emulsion at 70-85 ℃, proceed letex polymerization, after polymerization is finished, be incubated 2 hours.
(4) the gained emulsion is cooled to 20-30 ℃, under whipped state, adds an amount of triethylamine, the emulsion pH value is adjusted to 8.0-9.0, just obtain epoxy/acrylic acid hybridisation emulsion.
Embodiment 7
The preparation of water-base epoxy/vinylformic acid iron oxide red anti-corrosion primer:
(1) 0.3 part of dispersion agent, 0.2 part of defoamer are dispersed in 25 parts of water, add 15 parts of iron oxide reds, 5 parts of zinc phosphates, 2 parts of aluminium triphosphates, 10 parts of process whites, 8 parts of talcum powder, stir evenly, grind through sand mill and be dispersed to fineness≤50 μ m, make the iron oxide red slurry.
(2) under whipped state, in 32 parts of epoxy/acrylic acid hybridisation emulsions, dose 1.6 parts of film coalescence aid, 0.5 part successively and dodge iron oxide red slurry, 0.4 part of thickening material and 0.2 part of PH conditioning agent that corrosion inhibitor, 65.5 parts (1) step obtain and stir, obtain water-based iron oxide red anti-corrosion primer.
The paint film property index is as follows:
Table 1 water-base epoxy/vinylformic acid iron oxide red anti-corrosion primer performance
Embodiment 8
The preparation of water-base epoxy/vinylformic acid white anticorrosive finish paint:
(1) 0.3 part of dispersion agent, 0.2 part of defoamer are dispersed in 20 parts of water, add 22 parts of titanium dioxides, 8 parts of process whites, 7 parts of talcum powder, stir evenly, grind through sand mill and be dispersed to fineness≤30 μ m, make stock white.
(2) under whipped state, stock white, 0.3 part of thickening material and 0.2 part of PH conditioning agent that 2 parts of film coalescence aid of interpolation, 57.5 parts (1) step obtain in 40 parts of epoxy/acrylic acid hybridisation emulsions stirs successively, obtains the white anticorrosive finish paint.
The paint film property index is as follows:
Table 2 water-base epoxy/vinylformic acid antisepsis finishing paint performance
Claims (2)
1. epoxy/acrylic acid hybridisation emulsion is prepared by following material:
Raw-material weight part
Resins, epoxy 2-20
Acrylic Acid Monomer and alkyl acrylate monomer 20-50
Emulsifying agent 2-5
Initiator 0.2-0.6
Neutralizing agent 0.2-1.0
Deionized water 50-60
It is characterized in that the preparation method of described epoxy/acrylic acid hybridisation emulsion is:
(1). 30-40 part water, 0.5-2 part emulsifier for mixing evenly are warming up to 40-60 ℃, add 5-10 part vinylformic acid and alkyl acrylate mix monomer, continue to be warming up to 70-80 ℃, add 0.05-0.2 part initiator, be blue light until emulsion; Dropwise 5-10 part vinylformic acid and alkyl acrylate mix monomer dropwise insulation 30 minutes, make seed emulsion;
(2). in the preparation seed emulsion, with 10-30 part alkyl acrylate monomer dissolving 2-20 part Resins, epoxy, add 0.05-0.55 part initiator, 1-3 part emulsifying agent, 0.1-0.5 part neutralizing agent and 20-30 part water then, carry out emulsification, obtain pre-emulsion with the high-shear emulsifying dispersion machine;
(3). in seed emulsion, drip pre-emulsion at 70-85 ℃, proceed letex polymerization, after letex polymerization is finished, be incubated 2 hours;
(4). the gained emulsion is cooled to 20-30 ℃, under whipped state, adds 0.1-0.5 part neutralizing agent and stir evenly, just obtain epoxy/acrylic acid hybridisation emulsion;
Described Resins, epoxy is bisphenol A type epoxy resin, and epoxy equivalent (weight) is 185-833, specifically adopts Resins, epoxy E20, E12;
Described initiator comprises water soluble starter and oil-soluble initiator;
Described water soluble starter be selected from following one or more: Ammonium Persulfate 98.5, Potassium Persulphate;
Described oil-soluble initiator be selected from following one or more: benzoyl peroxide, Diisopropyl azodicarboxylate, cumyl hydroperoxide;
Described initiator adopts mixed initiator, and what adopt during the preparation seed emulsion is water soluble starter, make seed emulsion after, what adopt when proceeding polymerization is oil-soluble initiator;
Described emulsifying agent is a polymerizable emulsifier vinyl alkyl phosphate.
2. an aqueous self-drying coating is characterized in that, contains 25-50% epoxy/acrylic acid hybridisation emulsion as claimed in claim 1.
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| CN114044847B (en) * | 2021-11-18 | 2023-05-26 | 新旭新材料有限公司 | High-water-resistance and dirt-resistance acrylate emulsion and preparation method thereof |
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