CN106084241A - A kind of preparation method and applications of aqueous acrylic modified epoxy ester resin - Google Patents
A kind of preparation method and applications of aqueous acrylic modified epoxy ester resin Download PDFInfo
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- CN106084241A CN106084241A CN201610369627.3A CN201610369627A CN106084241A CN 106084241 A CN106084241 A CN 106084241A CN 201610369627 A CN201610369627 A CN 201610369627A CN 106084241 A CN106084241 A CN 106084241A
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- 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
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- 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
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- 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
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract
The invention discloses the preparation method of aqueous acrylic modified epoxy ester resin, and the epoxy ester resin prepared by utilization is prepared for coating.Use secondary esterification technique to carry out acrylic acid modified to epoxy resin, for the first time esterification enclose that one epoxide group of epoxy resin prevents it below acrylic acid modified during two epoxide groups open reaction simultaneously and cyclization gel reaction occur；Acrylate copolymer after the second time esterification in secondary esterification technique is employing prepolymerization in the present invention reacts with the epoxy resin of pre-esterification, has increased considerably the carboxyl-content after graft reaction, thus has improve the Water-borne modification degree of product.
Description
Technical field
The present invention relates to a kind of Water-borne modification epoxy ester resin field, especially a kind of aqueous acrylic modified epoxy ester resin
Preparation method and application in coating.
Technical background
Water paint is low due to its consumption of organic solvent, both can alleviate the consumption to petroleum resources, can be greatly lowered again
VOC emission, it has also become the study hotspot of various environment-friendly type coatings.The Water-borne modification of resin is by introducing polar group in system
Implement, the hydraulic performance declines such as the adhesive force of solidification coating, resistance to water, film strength can be made accordingly.Therefore, how tree is being improved
The while that fat being water miscible, ensure that the solidification high performance adhesive force of coating, resistance to water, film strength are water paint industrialization
Key issue.In recent years, patent (CN1474838A) discloses one and prepares waterborne acrylic modified alkyd resins: first prepare
A kind of sulfonate alkyd resin product, then prepares a kind of acrylated fatty acid product, finally both products suitably
React under polymerizing condition.This kind of product solves the dry problem of alkyd resin, but owing to its ester group is not protected,
Being easily broken off degrading in aqueous environment, therefore resistance to water or poor, bin stability need to improve.Patent
(CN1375535A) disclosing and synthesized by core-shell emulsion technology a kind of with alkyd resin as core, acrylic polymer is shell
Self-emulsifying nanometer emulsion.This emulsion is successfully realized acrylic polymer " parcel " of alkyd resin ester group, thus
Solve the storage stability of single aqueous alkyd resin, but this technique preparation process is complex and is only
Strength problem after solving the resistance to water problem of water-base resin and not improving resin film forming, in order to enable water-base resin
In the face of harsher applied environment expand application, the mechanical strength after its film forming must also be improved further.Patent
(CN101864044A) a kind of aqueous acrylic modified epoxy ester resin of addressing use nucleocapsid structure technology by vinyl-based or
The polymer overmold that acrylic monomer obtains through polyreaction in esterification after epoxy resin outside, prevent the ester group of inside
It is hydrolyzed, but nucleocapsid structure technology preparation technology is relatively complicated, the higher development being unfavorable for market of production cost, and be coated with
Each physical performance index such as film-strength does not the farthest reach solvent-borne type standard.Therefore, aqueous acrylic modified epoxy ester is developed at present
The task of top priority of resin is to possess excellent adhesion, high hydrolysis resistance increasing substantially water miscible the preparing of epoxy resin simultaneously
Property, the high-performance water-basedization resin of high film strength, be further prepared into water paint on this basis.
Summary of the invention
It is an object of the invention to overcome existing Water-borne modification resin the solidification adhesive force of coating, resistance to water, film strength etc.
The shortcoming of hydraulic performance decline, it is provided that a kind of have highly-water-soluble, excellent adhesion, high hydrolytic resistance, the high-performance of high film strength concurrently
Aqueous acrylic modified epoxy ester resin and water paint thereof, make Water-borne modification resin and coating energy while reducing environmental pollution
Enough performances excellent in the face of harsher applied environment performance.
To achieve these goals, the technical scheme that the application uses is as follows:
A kind of preparation method of aqueous acrylic modified epoxy ester resin, specific as follows: (1) is that 1:1 takes according to mol ratio
Bisphenol A type epoxy resin and monoacid or binary acid, with n-butyl alcohol and propylene glycol monomethyl ether volume ratio as 1:2～the mixture of 2:1
As solvent, the epoxy resin prepolymer esterification products obtained for catalyst through esterification with dimethylethanolamine, catalyst
Consumption is the 1%～2% of bisphenol A type epoxy resin quality；
(2) α-methacrylic acid, methyl methacrylate and n-butyl acrylate are taken according to mass ratio 1:1:1～3:1:1,
Using n-butyl alcohol, propylene glycol monomethyl ether, butyl acetate volume ratio as 1:1:1～the mixture of 2:2:1 is as solvent, and azo two is different
Butyronitrile as chain-transferring agent, is copolymerized the acrylic compounds performed polymer obtained, initiator as initiator, n-dodecyl mereaptan
It is the 1%～2.5% of α-methacrylic acid quality with the consumption of chain-transferring agent；
(3) epoxy resin prepolymer esterification products prepared by 20～40 parts of steps (1), 40～70 parts of steps are taken according to weight portion
(2) the acrylic compounds performed polymer prepared, carries out esterification, the consumption of dimethylethanolamine under conditions of dimethylethanolamine
For the 1%～2% of epoxy resin prepolymer esterification products quality, neutralized dose is neutralized to neutrality, the concentration with 5～15 parts be 5～
The polyvinyl alcohol water solution mixing of 15%, the product obtained after eventually passing Water-borne modification process.
The present invention uses secondary esterification technique to carry out acrylic acid modified to epoxy resin, and esterification encloses ring for the first time
During one epoxide group of epoxy resins prevents its acrylic acid modified below, two epoxide groups are opened reaction simultaneously and are sent out
Generate ring gel reaction；In the present invention, the second time esterification in secondary esterification technique is that the acrylic acid after using prepolymerization gathers
Compound reacts with the epoxy resin of pre-esterification, has increased considerably the carboxyl-content after graft reaction, thus has improve product
The Water-borne modification degree of thing.
Described bisphenol A type epoxy resin is one or more in E-12, E-14, E-20.
Described monoacid or binary acid be the one in n-caproic acid, caprylic acid, M-phthalic acid, decanedioic acid, adipic acid or
Several.
Described nertralizer is one or more in ammonia, triethylamine and dimethylethanolamine.
Described polyvinyl alcohol water solution be after polyvinyl alcohol 1799 mixes with water under the conditions of 85 DEG C stirring and dissolving 6 hours
Prepare.Polyvinyl alcohol is a kind of good water soluble polymer of symmetry, has good drying and forming-film performance, and polyvinyl alcohol
At certain temperature (100～150 DEG C), the ability of rapid crystallization, the polyvinyl alcohol film resistance to water after crystallization is possessed between long-chain
Energy, mechanical strength, adhesive force all increase substantially, and what these performances Water-borne modification naval stores just was short of.The present invention will
Polyvinyl alcohol water solution mixes mutually with modified epoxy ester resin so that this product in use film, baking are dried
Afterwards, it is possible to possess high performance resistance to water, mechanical strength, adhesive force；
The application of described aqueous acrylic modified epoxy ester resin, is coated with preparing aqueous acrylic modified epoxy ester resin
Application in terms of material；
The coating of described aqueous acrylic modified epoxy ester resin, including following component, aqueous acrylic modified epoxy
Ester resin 60～75 parts；Deionized water 5～10 parts；Color stuffing 15～20 parts；Auxiliary agent 1～2 parts of compositions, stir through sufficiently mixing
Mix and form.
Described color stuffing be calcium carbonate, calcined kaolin, titanium dioxide, Griffith's zinc white., chrome yellow, white carbon black, ferrum oxide, pthalocyanine blue,
One or more compositions in phthalocyanine green.
Described auxiliary agent is aqueous defoamer, by polydimethylsiloxane, N, N '-stearoyl ethylenediamine, the one of white carbon
Or multiple composition.
Multiple color stuffing and auxiliary combination that the present invention uses use, and optimize mixing color and auxiliary agent using effect, make
The color of coating is more preferable with flow leveling.
Detailed description of the invention
In order to be more fully understood that the present invention, describe technical scheme in detail with instantiation below, but this
Invention is not limited thereto.
Embodiment 1
The bisphenol A epoxide resin that mol ratio is 1:1 is placed in there-necked flask with monoacid or binary acid, adds equal matter
The n-butyl alcohol that volume ratio is 1:2～2:1 of amount and propylene glycol monomethyl ether are as solvent, and dimethylethanolamine is as catalyst,
The consumption of catalyst is the 1%～2% of bisphenol A type epoxy resin quality, by constant temperature blender with magnetic force control temperature be 90～
115 DEG C, mixing speed is that 600r/min carries out esterification, and system acid number is down to during 5mgKOH/g be reaction end.Additionally,
The α-methacrylic acid of certain mass ratio, methyl methacrylate are placed in another there-necked flask with n-butyl acrylate,
Add the volume ratio of equal quality be the n-butyl alcohol of 1:1:1～2:2:1, propylene glycol monomethyl ether, butyl acetate as solvent, and
Azodiisobutyronitrile is α-first as initiator, n-dodecyl mereaptan as the consumption of chain-transferring agent, initiator and chain-transferring agent
The 1%～2.5% of base acrylic acid quality, using constant flow pump to control rotating speed is 70r/min, is added dropwise to built-in by acrylic monomers etc.
In the there-necked flask of solvent, reaction temperature 70～95 DEG C, time for adding 1.5～3.5h, afterwards constant temperature 1～3h.Then, will make
Epoxy resin prepolymer esterification products and acrylic product be placed in there-necked flask, using dimethylethanolamine as catalyst
Carrying out second step esterification, the consumption of catalyst is the 1%～2% of epoxy resin prepolymer esterification products quality, controls reaction temperature
Degree is 90～115 DEG C, the response time 80～100min.The two step esterification reaction products ultimately generated are acrylated epoxy tree
Fat, adds nertralizer and is neutralized to neutrality, mix with the polyvinyl alcohol water solution of a certain amount of 5～15% and be sufficiently mixed, add water dilute
Releasing to amount of solid content is 70%, is high-performance water-based acrylic modified epoxy ester resin；
Take this resin 60～75 parts successively with 15～20 parts of color stuffings, 5～10 parts of deionized waters, 1～2 part of auxiliary agent through overcharging
The mix and blend divided, obtains high-performance water-based acrylic modified epoxy ester resin coating.
Embodiment 2.
By bisphenol A epoxide resin E-20 that mol ratio is 1:1 and caprylic acid totally 30 parts be placed in there-necked flask, add equal
The volume ratio of quality be n-butyl alcohol and the propylene glycol monomethyl ether of 1:2 as solvent, and dimethylethanolamine is as catalyst, catalysis
The consumption of agent is the 1% of bisphenol A type epoxy resin quality, and controlling temperature by constant temperature blender with magnetic force is 105 DEG C, mixing speed
Carrying out esterification for 600r/min, system acid number is down to during 5mgKOH/g be reaction end.Additionally, be 2:1 by mass ratio:
The α-methacrylic acid of 1, methyl methacrylate and n-butyl acrylate totally 60 parts be placed in another there-necked flask, add
The volume ratio of isodose be the n-butyl alcohol of 1:1:1, propylene glycol monomethyl ether, butyl acetate as solvent, and azodiisobutyronitrile make
For initiator, n-dodecyl mereaptan is α-methacrylic acid quality as the consumption of chain-transferring agent, initiator and chain-transferring agent
1%, using constant flow pump to control rotating speed is 70r/min, is added dropwise in the there-necked flask of built-in solvent by acrylic monomers etc., reaction
Temperature 85 DEG C, time for adding 2h, afterwards constant temperature 2h.Then, by the epoxy resin prepolymer esterification products made and acrylic
Product is placed in there-necked flask, carries out second step esterification using dimethylethanolamine as catalyst, and the consumption of catalyst is
The 2% of epoxy resin prepolymer esterification products quality, controlling reaction temperature is 105 DEG C, response time 90min.Two steps ultimately generated
Esterification reaction product is acrylic modified epoxy resin, adds triethylamine and is neutralized to neutrality, water-soluble with the polyvinyl alcohol of 5 part 10%
Liquid mixing is sufficiently mixed, then add a certain amount of enter water to be diluted to amount of solid content be 70%, obtain high-performance water-based acrylic acid modified
Epoxy ester resin；
Take this resin 70 parts to pass through fully with 17 parts of titanium dioxides, 7 parts of deionized waters, 1.5 parts of polydimethylsiloxane successively
Mix and blend, obtain high-performance water-based acrylic modified epoxy ester resin coating.
Embodiment 3.
Bisphenol A epoxide resin E-20 that mol ratio is 1:1 and adipic acid are placed in there-necked flask totally 40 parts, add equal
The volume ratio of quality be n-butyl alcohol and the propylene glycol monomethyl ether of 2:1 as solvent, and dimethylethanolamine is as catalyst, catalysis
The consumption of agent is the 2% of bisphenol A type epoxy resin quality, and controlling temperature by constant temperature blender with magnetic force is 90 DEG C, mixing speed
Carrying out esterification for 600r/min, system acid number is down to during 5mgKOH/g be reaction end.Additionally, be 1:1 by mass ratio:
The α-methacrylic acid of 1, methyl methacrylate and n-butyl acrylate totally 70 parts be placed in another there-necked flask, add
The volume ratio of equal quality be the n-butyl alcohol of 2:2:1, propylene glycol monomethyl ether, butyl acetate as solvent, and azodiisobutyronitrile
As initiator, n-dodecyl mereaptan is α-methacrylic acid quality as the consumption of chain-transferring agent, initiator and chain-transferring agent
2.5%, use constant flow pump control rotating speed be 70r/min, acrylic monomers etc. is added dropwise in the there-necked flask of built-in solvent,
Reaction temperature 70 DEG C, time for adding 3.5h, afterwards constant temperature 3h.Then, by the epoxy resin prepolymer esterification products made and acrylic acid
Type of Collective product is placed in there-necked flask, carries out second step esterification using dimethylethanolamine as catalyst, catalyst
Consumption is the 2% of epoxy resin prepolymer esterification products quality, and controlling reaction temperature is 90 DEG C, response time 100min.Ultimately generate
Two step esterification reaction products be acrylic modified epoxy resin, add triethylamine and be neutralized to neutrality, with the 10% of 10 parts poly-
Vinyl alcohol aqueous solution mixing is sufficiently mixed, and being diluted with water to amount of solid content is 70%, obtains high-performance water-based acrylic acid modified ring
Oxygen ester resin；
Take this resin 60 parts to pass through sufficiently with 15 parts of calcium carbonate, 5 parts of deionized waters, 1 part of polydimethylsiloxane successively
Mix and blend, obtains high-performance water-based acrylic modified epoxy ester resin coating.
Embodiment 4.
By bisphenol A epoxide resin E-20 that mol ratio is 1:1 and SA totally 20 parts be placed in there-necked flask, add equal
The volume ratio of quality be n-butyl alcohol and the propylene glycol monomethyl ether of 1:1.5 as solvent, and dimethylethanolamine is as catalyst, urges
The consumption of agent is the 1.3% of bisphenol A type epoxy resin quality, and controlling temperature by constant temperature blender with magnetic force is 115 DEG C, stirring
Speed is that 600r/min carries out esterification, and system acid number is down to during 5mgKOH/g be reaction end.Additionally, by mass ratio be
The α-methacrylic acid of 3:1:1, methyl methacrylate and n-butyl acrylate totally 50 parts be placed in another there-necked flask, then
Add the volume ratio of isodose be the n-butyl alcohol of 1.3:1.3:1, propylene glycol monomethyl ether, butyl acetate as solvent, and azo two
Isopropyl cyanide is Alpha-Methyl propylene as initiator, n-dodecyl mereaptan as the consumption of chain-transferring agent, initiator and chain-transferring agent
The 1.5% of acid quality, using constant flow pump to control rotating speed is 70r/min, and acrylic monomers etc. is added dropwise to three mouthfuls of built-in solvent
In flask, reaction temperature 95 DEG C, time for adding 1.5h, afterwards constant temperature 1h.Then, by the epoxy resin prepolymer esterification products made with
Acrylic product is placed in there-necked flask, carries out second step esterification using dimethylethanolamine as catalyst, urges
The consumption of agent is the 1.3% of epoxy resin prepolymer esterification products quality, and controlling reaction temperature is 115 DEG C, response time 80min.
The two step esterification reaction products ultimately generated are acrylic modified epoxy resin, add triethylamine and are neutralized to neutrality, with 10 parts
The polyvinyl alcohol water solution mixing of 5% is sufficiently mixed, and being diluted with water to amount of solid content is 70%, obtains high-performance water-based acrylic acid
Modified epoxy ester resin；
Take this resin 75 parts successively with 20 parts of Griffith's zinc white .s, 10 parts of deionized waters, 2 parts of N, N '-stearoyl ethylenediamines through overcharging
The mix and blend divided, obtains high-performance water-based acrylic modified epoxy ester resin coating.
Embodiment 5.
By bisphenol A epoxide resin E-20 that mol ratio is 1:1 and n-caproic acid totally 20 parts be placed in there-necked flask, add equal
The volume ratio of quality be n-butyl alcohol and the propylene glycol monomethyl ether of 1.5:1 as solvent, and dimethylethanolamine is as catalyst, urges
The consumption of agent is the 1.6% of bisphenol A type epoxy resin quality, and controlling temperature by constant temperature blender with magnetic force is 95 DEG C, stirring
Speed is that 600r/min carries out esterification, and system acid number is down to during 5mgKOH/g be reaction end.Additionally, by mass ratio be
The α-methacrylic acid of 2:1:1, methyl methacrylate and n-butyl acrylate totally 60 parts be placed in another there-necked flask, then
Add the volume ratio of isodose be the n-butyl alcohol of 1.6:1.6:1, propylene glycol monomethyl ether, butyl acetate as solvent, and azo two
Isopropyl cyanide is Alpha-Methyl propylene as initiator, n-dodecyl mereaptan as the consumption of chain-transferring agent, initiator and chain-transferring agent
The 2.0% of acid quality, using constant flow pump to control rotating speed is 70r/min, and acrylic monomers etc. is added dropwise to three mouthfuls of built-in solvent
In flask, reaction temperature 80 DEG C, time for adding 2h, afterwards constant temperature 2h.Then, the epoxy resin prepolymer esterification products and third will made
Olefin(e) acid Type of Collective product is placed in there-necked flask, carries out second step esterification using dimethylethanolamine as catalyst, catalysis
The consumption of agent is the 1.6% of epoxy resin prepolymer esterification products quality, and controlling reaction temperature is 95 DEG C, response time 90min.Finally
The two step esterification reaction products generated are acrylic modified epoxy resin, add triethylamine and are neutralized to neutrality, with the 5% of 15 parts
Polyvinyl alcohol water solution mixing is sufficiently mixed, and being diluted with water to amount of solid content is 70%, obtains high-performance water-based acrylic acid modified
Epoxy ester resin；
Take this resin 65 parts successively with 20 parts of chrome yellow, 10 parts of deionized waters, 2 parts of N, N '-stearoyl ethylenediamines and white carbon
Equal proportion mixture through sufficient mix and blend, obtain high-performance water-based acrylic modified epoxy ester resin coating.
Experimental example
High-performance water-based acrylic modified epoxy ester resin coating property is tested: the coating property to above example respectively
Test with the property indices after spraying film forming, baking.Its test result is shown in Table 1.
Table 1: each embodiment coating property test result
Claims (8)
1. the preparation method of an aqueous acrylic modified epoxy ester resin, it is characterised in that specifically comprise the following steps that
(1) it is that 1:1 takes bisphenol A type epoxy resin and monoacid or binary acid, with n-butyl alcohol and propylene glycol monomethyl ether according to mol ratio
It is 1:1 according to volume ratio 1:2～2:1 mixed liquor as the mass ratio of solvent, solvent and raw material, with dimethylethanolamine for catalysis
The epoxy resin prepolymer esterification products that agent obtains through esterification, the consumption of catalyst is the 1% of bisphenol A type epoxy resin quality
～2%；
(2) α-methacrylic acid, methyl methacrylate and n-butyl acrylate are taken according to mass ratio 1:1:1～3:1:1, with just
Butanol, propylene glycol monomethyl ether, butyl acetate according to volume ratio 1:1:1～2:2:1 mixed liquor as the quality of solvent, solvent and raw material
Than being 1:1, and azodiisobutyronitrile is as initiator, and n-dodecyl mereaptan as chain-transferring agent, is copolymerized and obtains
The consumption of acrylic compounds performed polymer, initiator and chain-transferring agent is the 1%～2.5% of α-methacrylic acid quality；
(3) epoxy resin prepolymer esterification products prepared by 20～40 parts of steps (1), 40～70 parts of step (2) systems are taken according to weight portion
Standby acrylic compounds performed polymer, carries out esterification under the catalysis of dimethylethanolamine, the consumption of dimethylethanolamine is epoxy
The 1%～2% of resin pre-esterification product quality, neutralized dose is neutralized to neutrality, the concentration with 5～15 parts be 5～15% poly-
Vinyl alcohol aqueous solution mixes, and obtains product after eventually passing Water-borne modification process.
2. the preparation method of aqueous acrylic modified epoxy ester resin as claimed in claim 1, it is characterised in that described bis-phenol
A type epoxy resin is one or more in E-12, E-14, E-20.
3. the preparation method of aqueous acrylic modified epoxy ester resin as claimed in claim 1, it is characterised in that described unitary
Acid or binary acid are one or more in n-caproic acid, caprylic acid, M-phthalic acid, decanedioic acid, adipic acid.
4. the preparation method of aqueous acrylic modified epoxy ester resin as claimed in claim 1, it is characterised in that described neutralization
Agent is one or more in ammonia, triethylamine and dimethylethanolamine.
5. the preparation method of aqueous acrylic modified epoxy ester resin as claimed in claim 1, it is characterised in that described is poly-
Vinyl alcohol aqueous solution is that after polyvinyl alcohol 1799 mixes with water, under the conditions of 85 DEG C, stirring and dissolving prepares for 6 hours.
6. the application of aqueous acrylic modified epoxy ester resin, it is characterised in that preparing aqueous acrylic modified epoxy ester tree
Application in terms of grease coating material.
7. the application of aqueous acrylic modified epoxy ester resin as claimed in claim 6, it is characterised in that described aqueous third
The coating of olefin(e) acid modified epoxy ester resin, by the following component of weight portion, aqueous acrylic modified epoxy ester resin 60～75 parts；
Deionized water 5～10 parts；Color stuffing 15～20 parts；Auxiliary agent 1～2 parts of compositions, mix together through sufficiently.
8. the application of aqueous acrylic modified epoxy ester resin as claimed in claim 7, it is characterised in that described color stuffing is
One or more in calcium carbonate, calcined kaolin, titanium dioxide, Griffith's zinc white., chrome yellow, white carbon black, ferrum oxide, pthalocyanine blue, phthalocyanine green
Composition；Described auxiliary agent is aqueous defoamer, by polydimethylsiloxane, N, N '-stearoyl ethylenediamine, the one of white carbon or many
Plant composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851396A (en) * | 2009-06-12 | 2010-10-06 | 北京金汇利应用化工制品有限公司 | Waterborne epoxy ester resin composition and preparation method thereof and water-based paint prepared from same |
| CN101864044A (en) * | 2010-07-02 | 2010-10-20 | 湖南湘江涂料集团有限公司 | Aqueous acrylic modified epoxy ester resin and synthesizing method thereof |
| CN102504668A (en) * | 2011-11-18 | 2012-06-20 | 杭州传化涂料有限公司 | Water-based primer-topcoat synthetic anti-corrosive paint for coating automobile spare parts and preparation method thereof |
-
2016
- 2016-05-30 CN CN201610369627.3A patent/CN106084241A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851396A (en) * | 2009-06-12 | 2010-10-06 | 北京金汇利应用化工制品有限公司 | Waterborne epoxy ester resin composition and preparation method thereof and water-based paint prepared from same |
| CN101864044A (en) * | 2010-07-02 | 2010-10-20 | 湖南湘江涂料集团有限公司 | Aqueous acrylic modified epoxy ester resin and synthesizing method thereof |
| CN102504668A (en) * | 2011-11-18 | 2012-06-20 | 杭州传化涂料有限公司 | Water-based primer-topcoat synthetic anti-corrosive paint for coating automobile spare parts and preparation method thereof |
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| CN107828006A (en) * | 2017-10-26 | 2018-03-23 | 广东立得新材料科技有限公司 | A kind of preparation method of the high water-based acrylic resin of heat resistance and the product of acquisition |
| CN109135518A (en) * | 2018-08-31 | 2019-01-04 | 吉力水性新材料科技（珠海）有限公司 | A kind of aqueous acrylic modified epoxy ester lotion anticorrosive paint |
| CN110408296A (en) * | 2019-08-09 | 2019-11-05 | 江苏海晟涂料有限公司 | A kind of high solid content water marine anticorrosive paint and preparation method thereof |
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| CN115895402A (en) * | 2022-11-17 | 2023-04-04 | 安徽工业大学 | Heat dissipation coating material and preparation method and application thereof |
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Application publication date: 20161109 |