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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
modified epoxy
ester resin
epoxy ester
resin
acrylic modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610369627.3A
Other languages
Chinese (zh)
Inventor
孙光明
孙文俊
王庆军
谢吉星
武林华
李丽
段洪东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Qilu Paint Co Ltd
Original Assignee
Shandong Qilu Paint Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Qilu Paint Co Ltd filed Critical Shandong Qilu Paint Co Ltd
Priority to CN201610369627.3A priority Critical patent/CN106084241A/en
Publication of CN106084241A publication Critical patent/CN106084241A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02Macromolecular 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
    • C08G81/024Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/14Polycondensates modified by chemical after-treatment
    • C08G59/1433Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/14Polycondensates modified by chemical after-treatment
    • C08G59/1433Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/14Polycondensates modified by chemical after-treatment
    • C08G59/1494Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D187/00Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)

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

A kind of preparation method and applications of aqueous acrylic modified epoxy ester resin
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.
CN201610369627.3A 2016-05-30 2016-05-30 A kind of preparation method and applications of aqueous acrylic modified epoxy ester resin Pending CN106084241A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610369627.3A CN106084241A (en) 2016-05-30 2016-05-30 A kind of preparation method and applications of aqueous acrylic modified epoxy ester resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610369627.3A CN106084241A (en) 2016-05-30 2016-05-30 A kind of preparation method and applications of aqueous acrylic modified epoxy ester resin

Publications (1)

Publication Number Publication Date
CN106084241A true CN106084241A (en) 2016-11-09

Family

ID=57230915

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610369627.3A Pending CN106084241A (en) 2016-05-30 2016-05-30 A kind of preparation method and applications of aqueous acrylic modified epoxy ester resin

Country Status (1)

Country Link
CN (1) CN106084241A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106634382A (en) * 2016-12-23 2017-05-10 珠海市立州涂料有限公司 Environment-friendly anticorrosion quick-drying type primer-topcoat integrated air-dry paint and preparation method thereof
CN107236424A (en) * 2017-06-07 2017-10-10 山东益利油漆有限公司 A kind of aqueous vehicle bridge anticorrosive paint and preparation method thereof
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
CN111944377A (en) * 2020-08-24 2020-11-17 江苏华夏制漆科技有限公司 Multifunctional water-based epoxy acrylic resin composition and preparation method thereof
CN112979889A (en) * 2021-03-25 2021-06-18 西北永新涂料有限公司 Waterborne acrylic modified epoxy ester resin and preparation method and application thereof
CN115010937A (en) * 2022-06-24 2022-09-06 安徽尚德轨道设备制造有限公司 Ternary composite resin and preparation method of waterproof coating thereof
CN115895402A (en) * 2022-11-17 2023-04-04 安徽工业大学 Heat dissipation coating material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106634382A (en) * 2016-12-23 2017-05-10 珠海市立州涂料有限公司 Environment-friendly anticorrosion quick-drying type primer-topcoat integrated air-dry paint and preparation method thereof
CN106634382B (en) * 2016-12-23 2019-08-20 珠海市立州水性涂料有限公司 A kind of bottom surface unification self-drying paint of environment friendly corrosion protection quick-dry type and preparation method thereof
CN107236424A (en) * 2017-06-07 2017-10-10 山东益利油漆有限公司 A kind of aqueous vehicle bridge anticorrosive paint and preparation method thereof
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
CN110408296B (en) * 2019-08-09 2021-01-26 江苏海晟涂料有限公司 High-solid-content water-based ship anticorrosive paint and preparation method thereof
CN111944377A (en) * 2020-08-24 2020-11-17 江苏华夏制漆科技有限公司 Multifunctional water-based epoxy acrylic resin composition and preparation method thereof
CN112979889A (en) * 2021-03-25 2021-06-18 西北永新涂料有限公司 Waterborne acrylic modified epoxy ester resin and preparation method and application thereof
CN115010937A (en) * 2022-06-24 2022-09-06 安徽尚德轨道设备制造有限公司 Ternary composite resin and preparation method of waterproof coating thereof
CN115895402A (en) * 2022-11-17 2023-04-04 安徽工业大学 Heat dissipation coating material and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN106084241A (en) A kind of preparation method and applications of aqueous acrylic modified epoxy ester resin
CN101914185B (en) Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom
CN103613702B (en) A kind of water-soluble multifunctional acrylic matting resin and preparation method thereof
CN101585899B (en) Cationic modified epoxy resin emulsion and preparation method and application thereof
CN104761685A (en) Preparation method of waterborne acrylic modified saturated polyester resin
CN103555115B (en) A kind of galvanized sheet coating and preparation method thereof
CN104356320B (en) Waterborne epoxy ester-acrylic hybrid resin and preparation method thereof
CN102134294B (en) High-covering-power styrene-acrylate emulsion, synthesis method thereof and use thereof in aqueous printing ink
CN101280035A (en) Wet-rub resistant styrene-acrylic emulsion and preparation thereof
CN103709885A (en) Water-based environment-friendly modified alkyd wood paint
CN102993442A (en) Aqueous acrylic acid modified epoxy ester emulsion and its preparation method
CN103540217B (en) The double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked and its preparation method
CN104744639A (en) Preparation method of organic silicon modified normal-temperature multiple self-crosslinked epoxy resin emulsion
CN104031516A (en) Water-based glass winebottle baking varnish and preparation method thereof
CN105713155A (en) Preparation method of polymer material for paper cultural relic protection and application thereof
CN105732909B (en) A kind of preparation method of acrylic polysiloxane water-based emulsion
CN102140295A (en) Composite emulsion for water-based plastic base paint and preparation method of composite emulsion
CN104293062A (en) Aqueous soft biomass anti-fouling paint and preparation method thereof
CN104497813A (en) Nitrocellulose-modified low-temperature quick-drying unsaturated polyester primer and preparation method thereof
CN106221569A (en) A kind of high adhesion force acrylic resin paint and preparation method thereof
CN109467638A (en) Diamond Search, hydroxyl acrylic aqueous dispersion of polyester modification and preparation method thereof
CN102492100A (en) Water-dispersed fluorine-containing hydroxyl acrylic-epoxy ester heterozygous body resin and coating thereof
CN101671955B (en) Oily canvas coating and manufacture method thereof
CN104497811B (en) Alkali-washable UV (ultraviolet) paint for mobile phone glass screens and preparation method thereof
CN102719179B (en) High solid low VOC (volatile organic compounds) environment-friendly aluminum paint and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20161109