CN108570132B - Hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin - Google Patents
Hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin Download PDFInfo
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- CN108570132B CN108570132B CN201710142499.3A CN201710142499A CN108570132B CN 108570132 B CN108570132 B CN 108570132B CN 201710142499 A CN201710142499 A CN 201710142499A CN 108570132 B CN108570132 B CN 108570132B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1472—Fatty acids
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Abstract
The invention provides a hybrid emulsion synthesis formula of epoxy ester resin aqueous dispersion and acrylic resin, which comprises the following components in parts by weight: 5-90 parts of epoxy ester resin aqueous dispersion, 1-50 parts of acrylic monomer, 0-7 parts of emulsifier, 0-2 parts of pH value regulator, 0.05-7 parts of initiator and 0-60 parts of water. The invention carries out hybridization polymerization on the epoxy ester resin and the acrylic resin, so that the obtained resin emulsion combines the advantages of the two resins, overcomes the defects of the two resins, and has the characteristics of high solid content, low viscosity, quick drying, good film forming property, high glossiness, aging resistance and good salt spray resistance.
Description
Technical Field
The invention relates to the technical field of water-based paint, in particular to a hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin.
Background
At present, single-component self-drying water-based paint products mainly comprise two types, namely alkyd resin synthesized by a solvent method and aqueous dispersion of epoxy ester resin, and have the advantages of good low-temperature film-forming property, good gloss and salt mist resistance, and the defects of serious hydrolysis in water, poor aging resistance, limitation of resin viscosity, small molecular weight, film formation by oxidation crosslinking, slow drying speed and low solid content; the other is an acrylic emulsion synthesized by an emulsion polymerization method, the molecular weight of the acrylic emulsion is very large, the acrylic emulsion has the characteristics of high solid content and low viscosity, and the acrylic emulsion has good dryness and aging resistance, but has poor low-temperature film-forming property and poor salt spray resistance.
Disclosure of Invention
The invention aims to overcome the defects of the two resins and provides a hybrid emulsion of an epoxy ester resin aqueous dispersion and an acrylic resin, so as to realize high solid content, low viscosity, quick drying, good film forming property, glossiness, aging resistance and salt spray resistance of the resin.
In one aspect, the invention provides a hybrid emulsion of an epoxy ester resin aqueous dispersion and an acrylic resin, wherein the hybrid emulsion comprises the following components in parts by weight: 5-90 parts of epoxy ester resin aqueous dispersion, 1-50 parts of acrylic monomer, 0-7 parts of emulsifier, 0-2 parts of pH value regulator, 0.05-7 parts of initiator and 0-60 parts of water.
Further, in the hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin, the synthetic formula comprises the following components in parts by weight: 20-80 parts of epoxy ester resin aqueous dispersion, 2-40 parts of acrylic monomers, 0.01-5 parts of emulsifier, 0-1 part of pH value regulator, 0.1-5 parts of initiator and 5-40 parts of water.
In the hybrid emulsion of the aqueous epoxy ester resin dispersion and the acrylic resin, the acrylic monomer is at least one of styrene, meth (acrylic acid), methyl methacrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycidyl methacrylate.
Further, in the hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin, the initiator is potassium persulfate, ammonium persulfate, azodiisobutyronitrile, benzoyl peroxide, tert-butyl peroxybenzoate, lauroyl peroxide, benzoyl peroxide/sucrose, tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/sodium metabisulfite, benzoyl peroxide/N, N-dimethylaniline, ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/rongalite, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/N, N-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, sodium persulfate, sodium hydrogen sulfite, sodium hydrogen, One or two of persulfate/mercaptan, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride and cumene hydroperoxide/tetraethylene imine.
In the hybrid emulsion of the epoxy ester resin water dispersion and the acrylic resin, the emulsifier is at least one of carboxylate, alkyl sulfate, sulfonate and polyoxyethylene carboxylate, polyol carboxylate, polyoxyethylene alkyl ether and ethoxy alcohol with HLB value of 9-14.
Further, in the hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin, the epoxy ester resin aqueous dispersion comprises the following components in parts by weight: 15-40 parts of epoxy resin, 11-40 parts of fatty acid, 2-8 parts of acrylic monomer, 4.5-35 parts of acrylate monomer, 0-0.1 part of catalyst, 0.6-2 parts of initiator content, 20-40 parts of solvent, 5-15 parts of neutralizer, 1-5 parts of drier and 100 parts of water.
Furthermore, in the hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin, the catalyst is organic tin or zinc catalyst; the neutralizing agent is at least one of triethylamine, N-dimethylethanolamine and methylmorpholine; the drier is cobalt, zirconium, zinc, calcium drier or their composition.
Further, in the hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin, the catalyst is zinc oxide or zinc naphthenate.
Further, in the hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin, the initiator is one or two of benzoic peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, di-tert-amyl peroxide and tert-butyl peroxy-2-ethylhexanoate (amyl).
Further, in the hybrid emulsion of the epoxy ester resin water dispersion and the acrylic resin, the solvent is at least one of diethylene glycol butyl ether, dipropylene glycol butyl ether, n-butanol, ethylene glycol monobutyl ether, propylene glycol butyl ether, propylene glycol methyl ether, ethanol, isopropyl alcohol and sec-butyl alcohol.
The main body of the embodiment of the invention is a hybrid emulsion of epoxy ester resin and acrylic resin, wherein the aqueous dispersion of the epoxy ester has the advantages of good low-temperature film-forming property, high glossiness and good salt spray resistance, and has the disadvantages of serious hydrolysis in water, poor aging resistance, limitation of resin viscosity, small molecular weight (generally thousands), film formation by oxidation crosslinking, slow drying speed and low solid content; the acrylic emulsion has the characteristics of high solid content and low viscosity due to the very large molecular weight of molecules, generally tens of thousands to hundreds of thousands, has better quick drying property and aging resistance, but has poor low-temperature film forming property and poor salt spray property.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
The invention provides a hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin, which comprises the following components in parts by weight: 5-90 parts of epoxy ester resin aqueous dispersion, 1-50 parts of acrylic monomer, 0-7 parts of emulsifier, 0-2 parts of pH value regulator, 0.05-7 parts of initiator and 0-60 parts of water. Preferably, the weight parts of each component in the formula are as follows: 20-80 parts of epoxy ester resin aqueous dispersion, 2-40 parts of acrylic monomers, 0.01-5 parts of emulsifier, 0-1 part of pH value regulator, 0.1-5 parts of initiator and 5-40 parts of water.
Wherein: the epoxy resin aqueous dispersion is a product obtained by modifying epoxy resin with fatty acid and acrylic ester. The epoxy ester resin aqueous dispersion formula comprises the following components in parts by weight: 15-40 parts of epoxy resin, 11-40 parts of fatty acid, 2-8 parts of acrylic monomer, 4.5-35 parts of acrylate monomer, 0-0.1 part of catalyst, 0.6-2 parts of initiator content, 20-40 parts of solvent, 5-15 parts of neutralizer, 1-5 parts of drier and 100 parts of water. Preferably, the epoxy ester resin aqueous dispersion formula comprises the following components in parts by weight: 19-35 parts of epoxy resin, 12-27 parts of fatty acid, 2-4 parts of acrylic monomer, 5-30 parts of acrylate monomer, 0-0.08 part of catalyst, 0.6-1.6 parts of initiator, 20-30 parts of solvent, 5-10 parts of neutralizer, 1-5 parts of drier and 150 parts of water 100.
The epoxy resin in the epoxy ester resin aqueous dispersion formulation can be an A-type epoxy resin, and preferably one or two epoxy resins with epoxy equivalent weights in the range of 500-3000. For example, at least one of E12 type epoxy resin, E03 type epoxy resin, E14 type epoxy resin, and E51 type epoxy resin.
The fatty acid used for modifying the epoxy resin can be unsaturated fatty acid, and specifically can be one or more of linoleic acid, tall oil acid and dehydrated ricinoleic acid.
The acrylic monomer used for modifying the epoxy resin is one or two of acrylic acid and methacrylic acid.
The acrylate monomer can be one or more of styrene, methyl methacrylate, butyl (meth) acrylate, isobornyl methacrylate, hydroxyethyl (meth) acrylate and glycidyl methacrylate.
The catalyst is organic tin or zinc catalyst, preferably, the catalyst can be one of zinc oxide and zinc naphthenate. The initiator is one or two of peroxybenzoic acid, tert-butyl peroxybenzoate, di-tert-butyl peroxide, di-tert-amyl peroxide and tert-butyl peroxy-2-ethyl hexanoate (amyl ester).
The neutralizing agent is one or more of triethylamine, N-dimethylethanolamine and methylmorpholine.
The drier is cobalt, zirconium, zinc, calcium, barium drier or their composition. Wherein, the drier cobalt and zirconium are used as main drier which can be added independently, and zinc or calcium is used as auxiliary drier which is mixed with the main drier according to the mass ratio of (0-5) to 1, such as cobalt-zinc mixed drier, cobalt-barium-zinc drier, etc.
The solvent is one or more of diethylene glycol butyl ether, dipropylene glycol butyl ether, n-butanol, ethylene glycol monobutyl ether, propylene glycol butyl ether, propylene glycol methyl ether, ethanol, isopropanol and sec-butyl alcohol.
The acrylic monomer in the formulation of the hybrid emulsion provided in this embodiment may be acrylic and its esters. Specifically, the acrylic monomer is at least one selected from the group consisting of styrene, (meth) acrylic acid, methyl methacrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycidyl methacrylate. It is to be noted that (meth) acrylic acid includes methacrylic acid and acrylic acid, butyl (meth) acrylate includes butyl methacrylate and butyl acrylate, isobornyl (meth) acrylate includes isobornyl methacrylate and isobornyl acrylate, ethyl (meth) acrylate includes ethyl methacrylate and ethyl acrylate, hydroxyethyl (meth) acrylate includes hydroxyethyl methacrylate and hydroxyethyl acrylate, and hydroxypropyl (meth) acrylate includes hydroxypropyl methacrylate and hydroxypropyl acrylate.
The initiator in the hybrid emulsion formulation is selected from the group consisting of potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, t-butyl peroxybenzoate, lauroyl peroxide, and redox initiators, such as benzoyl peroxide/sucrose, t-butyl hydroperoxide/rongalite, t-butyl hydroperoxide/sodium metabisulfite, benzoyl peroxide/N, N-dimethylaniline, ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/rongalite, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/N, N-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, sodium persulfate/sodium hydrogen sulfite, sodium hydrogen peroxide/sodium metabisulfite, sodium hydrogen peroxide/sodium hydrogen sulfite/sodium hydrogen, One or two of cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride and cumene hydroperoxide/tetraethylene imine.
The emulsifier in the formula of the hybrid emulsion is at least one of carboxylate, alkyl sulfate, sulfonate and polyoxyethylene carboxylate, polyol carboxylate, polyoxyethylene alkyl ether and ethoxy alcohol with HLB value of 9-14. Namely: the emulsifier in the embodiment of the present invention may be selected from at least one of anionic emulsifiers (such as carboxylates, alkylsulfates, and sulfonates) and nonionic emulsifiers having an HLB value of 9 to 14 (such as polyoxyethylene carboxylates, polyol carboxylates, polyoxyethylene alkyl ethers, and ethoxylated alcohols).
The pH adjusting agent in the formulation of the hybrid emulsion is any pH adjusting agent known to those skilled in the art, such as sodium bicarbonate, and the like.
The preparation method of the hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin provided by the invention comprises the following steps:
(1) preparation of epoxy ester aqueous dispersion: the first step is as follows: adding epoxy resin, fatty acid and catalyst in the epoxy ester water dispersion formula into a reaction kettle, stirring and heating to 170-210 ℃, preserving heat until the acid value of the material is less than 10mg KOH/g to obtain fatty acid modified epoxy resin, cooling to 80-160 ℃, and adding partial solvent in the formula for dilution to obtain epoxy ester resin for later use.
In specific implementation, 5-7 parts of xylene can be added into the reaction kettle, on one hand, the xylene can fully disperse the epoxy resin and the fatty acid in a reaction system; on the other hand, the water generated by the reaction is carried out by the circulating reflux of the dimethylbenzene, the reaction is promoted to be carried out in the forward direction, and when the acid value of the material is less than 10mg KOH/g, the dimethylbenzene can be pumped out by vacuum.
And secondly, adding part of initiator into the acrylic monomer and the acrylic monomer in the formula of the epoxy ester aqueous dispersion, uniformly mixing, dropwise adding the mixture into the fatty acid modified epoxy ester resin at the temperature of 110-150 ℃ for 2-4 hours, supplementing the initiator after the dropwise adding is finished until the conversion rate reaches more than 95%, adding a neutralizer and a drier into the reacted materials, uniformly stirring, and adding water while stirring for emulsification to obtain the epoxy ester aqueous dispersion. In specific implementation, the reaction temperature is determined according to different initiators, such as the reaction temperature of benzoyl peroxide and tert-butyl peroxybenzoate is 110-. After the dropwise addition is finished, an initiator can be supplemented until the conversion rate reaches more than 95%, the acid value of the obtained resin is 20-30mgKOH/g, at the moment, a neutralizing agent and a drier are added into a reaction system, the mixture is uniformly stirred, water is added while stirring for emulsification, the obtained emulsion has the pH of 8-10, the solid content of 30-40%, the fineness of below 25 mu m, and the acid value of the emulsion is 10-15 mgKOH/g.
In addition, a third step, namely a step of removing the solvent under reduced pressure, may be included: adding the epoxy ester aqueous dispersion into a container, heating to 30-70 ℃, gradually opening large vacuum, removing most of the solvent in the epoxy ester aqueous dispersion under a reduced pressure state, and adding water to adjust to proper solid content after the removal is finished. The obtained epoxy ester water dispersion contains 30-50% of solid, has an acid value of 10-15mgKOH/g, a VOC of below 7%, and has a pH value of 8-10.
(2) Acrylic monomer pre-emulsification step: at normal temperature, in a protective atmosphere, adding 0-90% of the epoxy ester aqueous dispersion, 50-100% of the emulsifier and 50-100% of water in the step (1) into a reaction vessel, mixing and dissolving 100% of the acrylic monomer and 50-100% of the initiator in the formula of the hybrid emulsion, adding into the reaction vessel, and stirring at high speed for 10-40 minutes to obtain the pre-emulsion of the acrylic monomer for later use. The acrylic monomer can be sufficiently emulsified by high-speed stirring to prepare for the next reaction.
(3) And (3) hybridizing the epoxy ester resin aqueous dispersion with acrylic resin: introducing nitrogen gas in a protective atmosphere, for example, in the whole reaction process, adding 5-20% of the pre-emulsion of the acrylic monomer obtained in the step (2), the rest of the emulsifier, the rest of the initiator and the water in the formula of the hybrid emulsion, the rest of the aqueous dispersion of the epoxy ester in the step (1) and the pH regulator in the formula of the hybrid emulsion into a reaction vessel, heating to 30-85 ℃ under the stirring state, reacting for 20-60 minutes, beginning to dropwise add the rest of the pre-emulsion in the step (2), wherein the dropwise adding time is 1-8 hours, supplementing the initiator in the dropwise adding process, and preserving the temperature at 50-90 ℃ for 1.5-6.5 hours after the dropwise adding is finished. The reaction speed can be effectively controlled by adding 5-20% of the acrylic monomer pre-emulsion, and the selected initiator contains a redox initiator and can initiate the reaction at a lower temperature, so that the reaction temperature can be controlled at 30-85 ℃, and the energy is saved. In order to make the reaction more complete, the initiator may be added at intervals, for example, 1 hour, depending on the actual conditions of the reaction.
In the above preparation method, the skilled person can select the process parameters in the hybridization process. In a preferred embodiment, in step (3), the temperature is raised to 75-85 ℃ while stirring, and the temperature is maintained at 80-85 ℃ after the addition. In another preferred embodiment, in step (3), the time for the incubation may be 2 to 5 hours.
In the preparation process of the epoxy ester water dispersion, the epoxy resin is modified by a certain amount of fatty acid, and after the drier is added, the epoxy ester water dispersion has better normal-temperature drying performance; acrylic acid (ester) is used for graft copolymerization, acrylic acid is used for neutralization to provide water solubility, and the acrylic acid is a copolymerization reaction, so that a water-soluble group is prevented from being separated from a main chain, and the resin is more stable after being hydrated.
The hybridization process adopts an emulsion polymerization method, no additional solvent is needed in the reaction process, and the preparation of low VOC (volatile organic solvent) environment-friendly products is facilitated; and the emulsion polymerization method can reduce the viscosity of the emulsion and improve the solid content of the emulsion, so that the solid content of the coating can be improved and volatile substances can be reduced in the process of manufacturing the coating, thereby saving energy. In addition, the introduction of (methyl) acrylic acid and ester thereof can adjust the glass transition temperature of the resin, thereby being capable of being made into a product with high glass transition temperature, high hardness and quick drying, and solving the problem that the water-based epoxy ester industrial paint is very slow to dry at normal temperature; in addition, because the epoxy ester resin dispersoid synthesized by a solvent method is grafted and hybridized with acrylic resin, the hybridized emulsion has good film-forming property and can be oxidized and crosslinked in the air, so that the final product is more compact than the paint film of the acrylic emulsion prepared by a common emulsion polymerization method, and has better water resistance and salt spray resistance.
The present invention is further illustrated by the following specific examples.
Example 1
(1) Adding 12280 g of epoxy resin E, 30 g of dehydrated ricinoleic acid, 200 g of tall oil acid and 0.5 g of zinc oxide into a reaction bottle, stirring and heating to 210 ℃ at 200-;
(2) mixing 22 g of acrylic acid and 100 g of methyl methacrylate, adding 5 g of tert-butyl peroxybenzoate, uniformly mixing, dripping into the above material for 2-3 hours, supplementing 5 g of tert-butyl peroxybenzoate for three times after dripping, and finally preserving heat for 3 hours to obtain acrylic acid and fatty acid modified epoxy resin;
(3) cooling the modified resin to 80 ℃, adding 55 g of triethylamine, 22 g of cobalt and zinc mixed drier, uniformly stirring, dripping 1000 g of distilled water at 40 ℃ into the resin, and emulsifying to obtain an epoxy ester aqueous dispersion;
(4) placing the emulsified emulsion into a three-mouth bottle, installing a vacuumizing device, controlling the temperature at 45-50 ℃, gradually opening the vacuum until a solvent flows out, collecting the amount of the removed solvent, detecting until the content of butanol in the emulsion is below 1%, and finally adjusting the solid content of the emulsion to 40-44% by using water;
(5) under the protection of nitrogen atmosphere, 400 g of the epoxy ester water dispersion prepared in the step, 2.2 g of emulsifier AS801 (a mixture of alkyl alcohol polyalkoxy sodium sulfate salt and polymers of methyl oxirane, ethylene oxide and mono (2-ethylhexyl) ether) and 40 g of water in the formula of the hybrid emulsion are added into a container, 60 g of methyl methacrylate and 0.8 g of azodiisobutyronitrile are firstly mixed and dissolved, and then the mixture is added into the container and stirred at high speed for 3 minutes to obtain a pre-emulsion of acrylic monomers;
(6) and (2) continuously introducing nitrogen into the reaction system, adding 100 g of the residual epoxy ester aqueous dispersion in the step (3), 8011 g of the emulsifier AS remaining in the formula of the hybrid emulsion, 0.08 g of ammonium persulfate, 0.1 g of sodium bicarbonate in the formula of the hybrid emulsion and 22 g of the acrylic monomer pre-emulsion prepared in the step (5) into a reaction bottle, heating to 80 ℃ while stirring, reacting for 30 minutes, beginning to dropwise add the acrylic monomer pre-emulsion remaining in the step (5), finishing dropwise adding within 1-2 hours, supplementing ammonium persulfate according to the specific conditions of the reaction in the dropwise adding process, keeping the temperature at 80 ℃ for 1.5-2 hours after completing dropwise adding, cooling to 40 ℃, and filtering to discharge. The solid content of the obtained emulsion is 50 percent, the viscosity is 35mPa.s, and after the emulsion is coated into a varnish film, the surface drying time is 30 minutes, the actual drying time is 10 hours, the glossiness is 98 percent, and the emulsion is water-resistant for 24 hours and salt spray resistant for 196 hours.
Example 2
(1) Adding epoxy resin E12175 g, dehydrated ricinoleic acid 28 g, linoleic acid 112 g and zinc naphthenate 0.1 g into a reaction bottle, stirring and heating to 205-210 ℃, reacting to an acid value of below 7mgKOH/g, cooling to 160 ℃, and adding ethylene glycol monobutyl ether 120 g. Keeping the temperature at 145-150 ℃ to obtain the fatty acid modified epoxy resin;
(2) mixing 21 g of acrylic acid and 90 g of methyl methacrylate, adding 3 g of di-tert-butyl peroxide, dripping into the above material for 3-4 hours after uniform mixing, adding 1 g of di-tert-butyl peroxide for three times after dripping, and finally keeping the temperature for 3 hours to obtain acrylic acid and fatty acid modified epoxy resin;
(3) cooling the modified resin to 80 ℃, adding 25 g of N, N-dimethylethanolamine, uniformly stirring, dripping 643 g of distilled water with the temperature of 40 ℃ into the resin, emulsifying to obtain epoxy ester water dispersion, and adjusting the solid content to 35%;
(4) under the protection of nitrogen atmosphere, taking 360 g of the epoxy ester aqueous dispersion prepared in the step, 2.2 g of emulsifier AEO-9 (ethoxy alcohol) in a hybrid emulsion formula, and 40 g of water, adding 40 g of methyl methacrylate, 2 g of isobornyl methacrylate and 0.65 g of azodiisobutyronitrile into a container, mixing and dissolving, and adding into the container to stir at high speed for 20 minutes to obtain a pre-emulsion of an acrylic monomer;
(5) and (2) continuously introducing nitrogen into the reaction system, adding 40 g of the residual epoxy ester aqueous dispersion in the step (3), 1 g of the residual emulsifier in the hybrid emulsion formula, 0.08 g of potassium persulfate and 10 g of water, 0.1 g of sodium bicarbonate in the hybrid emulsion formula and 20 g of the acrylic monomer pre-emulsion prepared in the step (4) into a reaction bottle, heating to 83 ℃ while stirring, reacting for 30 minutes, beginning to dropwise add the acrylic monomer pre-emulsion remaining in the step (4), finishing dropwise adding within 2-3 hours, supplementing potassium persulfate according to the specific conditions of the reaction in the dropwise adding process, keeping the temperature at 83 ℃ for 2-2.5 hours after dropwise adding, cooling to 40 ℃, filtering and discharging. The solid content of the obtained emulsion is 36 percent, the viscosity is 80mPa.s, after the emulsion is coated into a varnish film, the surface drying time is 20 minutes, the actual drying time is 2 hours, the glossiness is 95 percent, the water resistance is 72 hours, and the salt spray resistance is 96 hours.
Example 3
(1) 175 g of the mixture of epoxy resin E12 and epoxy resin E03, 28 g of dehydrated ricinoleic acid, 112 g of linoleic acid and 0.1 g of the mixture of zinc oxide and zinc naphthenate are added into a reaction bottle, stirred and heated to 190 ℃ at 180 ℃ for reaction until the acid value is below 9mgKOH/g, and then cooled to 150 ℃ and 110 g of ethylene glycol butyl ether is added. Keeping the temperature at 130-135 ℃ to obtain the fatty acid modified epoxy resin;
(2) mixing 14 g of acrylic acid, 15 g of methyl methacrylate and 30 g of styrene, adding 3 g of di-tert-amyl peroxide, dripping the mixture into the above material for 3 to 4 hours after uniform mixing, supplementing 1 g of di-tert-butyl peroxide for three times after dripping, and finally preserving heat for 3 hours to obtain acrylic acid and fatty acid modified epoxy resin;
(3) cooling the modified resin to 80 ℃, adding 16 g of N, N-dimethylethanolamine, uniformly stirring, dripping 565 g of distilled water with the temperature of 40 ℃ into the resin, emulsifying to obtain an epoxy ester aqueous dispersion, and adjusting the solid content to 35%;
(4) under the protection of nitrogen atmosphere, 200 g of the epoxy ester aqueous dispersion prepared in the step, 2.2 g of emulsifier AS801 (a mixture of alkyl alcohol polyalkoxy sodium sulfate salt and polymers of methyl oxirane, ethylene oxide and mono (2-ethylhexyl) ether) and AEO-9 (ethoxylated alcohol) in a hybrid emulsion formula in a mass ratio of 2: 1), 40 g of water are added into a container, 40 g of methyl methacrylate and 0.8 g of azodiisobutyronitrile are mixed and dissolved firstly, and then are added into the container to be stirred at a high speed for 25 minutes, so that a pre-emulsion of acrylic monomers is obtained;
(5) and (2) continuously introducing nitrogen into the reaction system, adding 100 g of the residual epoxy ester aqueous dispersion in the step (3), 1 g of the residual emulsifier in the formula of the hybrid emulsion, 0.08 g of ammonium persulfate, 0.05 g of sodium bicarbonate in the formula of the hybrid emulsion and 20 g of the acrylic monomer pre-emulsion prepared in the step (4) into a reaction bottle, heating to 80 ℃ while stirring, reacting for 40 minutes, dropwise adding the residual acrylic monomer pre-emulsion in the step (4), finishing dropwise adding within 3-4 hours, supplementing ammonium persulfate according to the specific conditions of the reaction in the dropwise adding process, keeping the temperature at 80-85 ℃ for 3-3.5 hours after the dropwise adding is finished, cooling to 40 ℃, and filtering to discharge. The obtained emulsion has the solid content of 37.8 percent and the viscosity of 50mPa.s, and after the emulsion is coated into a varnish paint film, the surface drying time is 30 minutes, the actual drying time is 8 hours, the glossiness is 95 percent, the water resistance is 48 hours, and the salt spray resistance is 72 hours.
Example 4
(1) Adding 14100 g of epoxy resin E, 80 g of soya oil acid and 0.3 g of zinc oxide into a reaction bottle, stirring and heating to 190-200 ℃, reacting until the acid value is below 10mgKOH/g, cooling to 145 ℃, and adding 40 g of n-butyl alcohol. Keeping the temperature at 110-118 ℃ to obtain the fatty acid modified epoxy resin;
(2) mixing 8 g of acrylic acid and 30 g of methyl methacrylate, adding 1.5 g of a mixture of peroxybenzoic acid and tert-butyl peroxybenzoate, uniformly mixing, dripping into the above material for 2-3 hours, supplementing 1.5 g of tert-butyl peroxybenzoate for three times after dripping, and finally preserving heat for 3 hours to obtain acrylic acid and fatty acid modified epoxy resin;
(3) cooling the modified resin to 80 ℃, adding 15 g of N, N-dimethylethanolamine, uniformly stirring, dripping 265 g of distilled water of 40 ℃ into the resin, emulsifying to obtain an epoxy ester aqueous dispersion, and adjusting the solid content to 39%;
(4) under the protection of nitrogen atmosphere, 350 g of the epoxy ester aqueous dispersion prepared in the step, 3.5 g of emulsifier NP-10 (nonylphenol polyoxyethylene ether) in a hybrid emulsion formula and 30 g of water are added into a container, 100 g of methyl methacrylate and 5 g of azodiisobutyronitrile are firstly mixed and dissolved, and then are added into the container to be stirred at high speed for 30 minutes, so as to obtain pre-emulsion of acrylic monomers;
(5) and (2) continuously introducing nitrogen into the reaction system, adding 150 g of the residual epoxy ester aqueous dispersion in the step (3), 1.5 g of the residual emulsifier in the formula of the hybrid emulsion, 0.08 g of ammonium persulfate, 27 g of water, 0.04 g of sodium bicarbonate in the formula of the hybrid emulsion and 30 g of the pre-emulsion of the acrylic monomer prepared in the step (4) into a reaction bottle, heating to 70 ℃ while stirring, reacting for 45 minutes, beginning to dropwise add the pre-emulsion of the residual acrylic monomer in the step (4), finishing dropwise adding within 4-5 hours, supplementing ammonium persulfate according to the specific conditions of the reaction in the dropwise adding process, keeping the temperature at 70-75 ℃ for 4.5-5 hours after dropwise adding, cooling to 40 ℃, filtering and discharging. The solid content of the obtained emulsion is 45 percent, the viscosity is 30mPa.s, after the emulsion is coated into a varnish film, the surface drying time is 30 minutes, the actual drying time is 4 hours, the glossiness is 98 percent, and the emulsion is water-resistant for 24 hours and salt spray-resistant for 72 hours.
Example 5
(1) Adding 51100 g of epoxy resin E, 120 g of soya oil acid and 0.5 g of zinc oxide into a reaction bottle, stirring and heating to 200-210 ℃, reacting until the acid value is below 8mgKOH/g, cooling to 140 ℃, and adding 90 g of propylene glycol butyl ether. Keeping the temperature at 130-135 ℃ to obtain the fatty acid modified epoxy resin;
(2) mixing 14 g of acrylic acid and 30 g of styrene, adding 1.5 g of tert-butyl peroxy-2-ethylhexanoate, uniformly mixing, dripping into the above material for 2-3 hours, supplementing 1.5 g of tert-butyl peroxybenzoate for three times after dripping, and finally preserving heat for 3 hours to obtain acrylic acid and fatty acid modified epoxy resin;
(3) cooling the modified resin to 80 ℃, adding 18 g of N, N-dimethylethanolamine, uniformly stirring, dripping 400 g of distilled water with the temperature of 40 ℃ into the resin, emulsifying to obtain epoxy ester aqueous dispersion, and adjusting the solid content to 34%;
(4) under the protection of nitrogen atmosphere, taking 63 g of the epoxy ester aqueous dispersion prepared in the step, 3.5 g of emulsifier (AS801 (a mixture of alkyl alcohol polyalkoxy sulfate sodium salt and polymers of methyl ethylene oxide, ethylene oxide and mono (2-ethylhexyl) ether) and GS7815 (a mixture of natural phenol polyoxyethylene ether) in a hybrid emulsion formula in a mass ratio of 2: 1)), 50 g of a mixture of methyl methacrylate and butyl methacrylate, and 33 g of water, adding the mixture into a container, and stirring at a high speed for 35 minutes to obtain a pre-emulsion of acrylic monomers;
(5) and (3) continuously introducing nitrogen into the reaction system, adding 27 g of the residual epoxy ester aqueous dispersion in the step (3), 1.5 g of the residual emulsifier in the formula of the hybrid emulsion, 2.5 g of lauroyl peroxide, 0.08 g of sodium bicarbonate in the formula of the hybrid emulsion and 8 g of the pre-emulsion of the acrylic monomer prepared in the step (4) into a reaction bottle, heating to 75 ℃ while stirring, reacting for 50 minutes, starting to dropwise add the pre-emulsion of the residual acrylic monomer in the step (4), completing dropwise addition within 5-6 hours, supplementing lauroyl peroxide according to the specific conditions of the reaction in the dropwise addition process, keeping the temperature at 75-80 ℃ for 5-6.5 hours after the dropwise addition is completed, cooling to 40 ℃, filtering and discharging. The solid content of the obtained emulsion is 44.6 percent, the viscosity is 300mPa.s, and after the emulsion is coated into a varnish paint film, the surface drying time is 30 minutes, the actual drying time is 2 hours, the glossiness is 90 percent, the water resistance is 24 hours, and the salt spray resistance is 48 hours.
Example 6
(1) Adding 12250 g of epoxy resin E, 50 g of soya oil acid and 0.3 g of zinc oxide into a reaction bottle, stirring and heating to 180 ℃ under 170 ℃, reacting to an acid value below 9mgKOH/g, cooling to 138 ℃, and adding 108 g of n-butanol. Keeping the temperature at 110-118 ℃ to obtain the fatty acid modified epoxy resin;
(2) mixing 16 g of acrylic acid and 60 g of styrene, adding 1.5 g of tert-amyl peroxy-2-ethylhexanoate, uniformly mixing, dripping into the above material for 3-4 hours, supplementing 1.5 g of tert-butyl peroxybenzoate for three times after dripping, and finally preserving heat for 3 hours to obtain acrylic acid and fatty acid modified epoxy resin;
(3) cooling the modified resin to 80 ℃, adding 20 g of N, N-dimethylethanolamine, uniformly stirring, dripping 570 g of distilled water with the temperature of 40 ℃ into the resin, emulsifying to obtain epoxy ester aqueous dispersion, and adjusting the solid content to 35%;
(4) under the protection of nitrogen atmosphere, adding 63 g of the epoxy ester aqueous dispersion prepared in the above steps, 0.7 g of emulsifier GS7815 (natural phenol polyoxyethylene ether) in the formula of the hybrid emulsion and 10.5 g of methyl methacrylate into a container, and stirring at high speed for 40 minutes to obtain pre-emulsion of acrylic monomers;
(5) and (2) continuously introducing nitrogen into the reaction system, adding 37 g of the residual epoxy ester aqueous dispersion in the step (3), 0.3 g of the residual emulsifier in the formula of the hybrid emulsion, 0.12 g of benzoyl peroxide/N, N-dimethylaniline, 0.1 g of sodium bicarbonate in the formula of the hybrid emulsion and 8 g of the pre-emulsion of the acrylic monomer prepared in the step (4) into a reaction bottle, heating to 30 ℃ while stirring, reacting for 60 minutes, beginning to dropwise add the pre-emulsion of the residual acrylic monomer in the step (4), dropwise adding for 6 to 8 hours, supplementing benzoyl peroxide/N, N-dimethylaniline according to the specific conditions of the reaction in the dropwise adding process, preserving the temperature for 3.5 to 5 hours at 45 to 50 ℃, cooling to 40 ℃, filtering and discharging. The solid content of the obtained emulsion is 40.8 percent, the viscosity is 50mPa.s, and after the emulsion is coated into a varnish paint film, the surface drying time is 30 minutes, the actual drying time is 10 hours, the glossiness is 98 percent, the water resistance is 24 hours, and the salt spray resistance is 120 hours.
It can be seen that the hybrid emulsions obtained in examples 1-6 all have the characteristics of high solid-to-low viscosity, fast drying, good film forming property, high gloss, good water and salt spray resistance, for example, the hybrid emulsions and aqueous epoxy resin dispersions of examples 1, 2 and 6 were separately tested under the same test conditions as the existing aqueous acrylic emulsions, and the results are shown in the following table:
from the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the hybrid emulsion of the epoxy ester resin dispersoid and the acrylic resin, prepared by the invention, integrates the advantages of the epoxy ester dispersoid and the acrylic resin emulsion, overcomes the defects of the epoxy ester dispersoid and the acrylic resin emulsion, and has the characteristics of high solid content, low viscosity, quick drying, good film forming property, high glossiness, good aging resistance and good salt spray resistance.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. The hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin is characterized in that the synthetic formula comprises the following components in parts by weight: 5-90 parts of epoxy ester resin aqueous dispersion, 1-50 parts of acrylic monomers, 0-7 parts of emulsifier, 0-2 parts of pH value regulator, 0.05-7 parts of initiator and 0-60 parts of water; the epoxy ester resin aqueous dispersion formula comprises the following components in parts by weight: 15-40 parts of epoxy resin, 11-40 parts of fatty acid, 2-8 parts of acrylic monomer, 4.5-35 parts of acrylate monomer, 0-0.1 part of catalyst, 0.6-2 parts of initiator content, 20-40 parts of solvent, 5-15 parts of neutralizer, 1-5 parts of drier and 100 parts of water.
2. The hybrid emulsion of the epoxy ester resin aqueous dispersion and the acrylic resin as claimed in claim 1, wherein the synthetic formula comprises the following components in parts by weight: 20-80 parts of epoxy ester resin aqueous dispersion, 2-40 parts of acrylic monomers, 0.01-5 parts of emulsifier, 0-1 part of pH value regulator, 0.1-5 parts of initiator and 5-40 parts of water.
3. The hybrid emulsion of an aqueous epoxy ester resin dispersion and an acrylic resin according to claim 1, wherein the acrylic monomer is (meth) acrylic acid; the acrylate monomer is at least one of styrene, methyl methacrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and glycidyl methacrylate.
4. The hybrid emulsion of an aqueous epoxy ester resin dispersion and an acrylic resin according to claim 1, wherein the initiator is potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, tert-butyl peroxybenzoate, lauroyl peroxide, benzoyl peroxide/sucrose, tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/sodium metabisulfite, benzoyl peroxide/N, N-dimethylaniline, ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/rongalite, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide/N, N-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, sodium persulfate, sodium hydrogen sulfite, One or two of potassium persulfate/silver nitrate, persulfate/mercaptan, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride and cumene hydroperoxide/tetraethylene imine.
5. The hybrid emulsion of an aqueous epoxy ester resin dispersion and an acrylic resin according to claim 1, wherein the emulsifier is at least one of carboxylates, alkyl sulfates, sulfonates, and polyoxyethylene carboxylates, polyol carboxylates, polyoxyethylene alkyl ethers, and ethoxylated alcohols having an HLB value of 9-14.
6. The hybrid emulsion of the aqueous epoxy ester resin dispersion and the acrylic resin according to claim 1, wherein the epoxy resin is a bisphenol a type epoxy resin; the catalyst is organic tin or zinc catalyst; the neutralizing agent is at least one of triethylamine, N-dimethylethanolamine and methylmorpholine; the drier is cobalt, zirconium, zinc, calcium drier or their composition.
7. The hybrid emulsion of an aqueous epoxy ester resin dispersion and an acrylic resin according to claim 1, wherein the catalyst is zinc oxide or zinc naphthenate.
8. The hybrid emulsion of the aqueous epoxy ester resin dispersion and the acrylic resin as claimed in claim 1, wherein the initiator is one or two of benzoic peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, di-tert-amyl peroxide and tert-butyl peroxy-2-ethylhexanoate (amyl).
9. The hybrid emulsion of the aqueous epoxy ester resin dispersion and the acrylic resin according to claim 1, wherein the solvent is at least one of diethylene glycol butyl ether, dipropylene glycol butyl ether, n-butanol, ethylene glycol butyl ether, propylene glycol methyl ether, ethanol, isopropyl alcohol, and sec-butyl alcohol.
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