CN101812218A - Reactive water-dispersed epoxy resin emulsion and preparation method thereof - Google Patents
Reactive water-dispersed epoxy resin emulsion and preparation method thereof Download PDFInfo
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- CN101812218A CN101812218A CN201010150306.7A CN201010150306A CN101812218A CN 101812218 A CN101812218 A CN 101812218A CN 201010150306 A CN201010150306 A CN 201010150306A CN 101812218 A CN101812218 A CN 101812218A
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Abstract
The invention relates to a water-based epoxy resin emulsion which comprises the following components by weight percent: 100 percent of epoxy resin, 5-35 percent of reactive water-dispersed epoxy resin emulsifying agent, 0-1 percent of surface active agent, 0-70 percent of cosolvent, 0-4 percent of flocculant and the balance of water. The surface active agent comprises one or more of sodium dodecyl benzene sulfonate, lauryl sodium sulfate and lauryl potassium sulfate, the cosolvent comprises one or more of propylene glycol monomethyl ether, ethylene glycol monomethylether, ethylene glycol monomethyl ether and acetonyl acetone; and the flocculant comprises one or more of acetic acid and crylic acid. The invention also discloses a preparation method of the water-based epoxy resin emulsion and a synthesis method of the reactive water-dispersed epoxy resin emulsifying agent. The invention greatly enriches the variety of the epoxy resin emulsions, expands the application field of the water-based epoxy resin emulsion, simplifies the production process of the water-based epoxy resin emulsion, and provides a wide prospect for replacing the water-based epoxy resin emulsion with a solvent epoxy resin emulsion in the practical application.
Description
Technical field
The present invention relates to a kind of aqueous epoxy coating and preparation method thereof, especially relate to a kind of reactive water-dispersed epoxy resin emulsion and preparation method thereof, belong to the chemistry painting industry technology.
Background technology
Resins, epoxy is a kind of important thermosetting resin kind, because it has excellent physical and mechanical properties, electrical insulation capability, resistance to chemical corrosion, heat-resisting and adhesiveproperties, shrinking percentage is low, the hardness height, wear resistance is good, has been widely used in industrial circles such as chemical industry, water conservancy, traffic, machinery, electronics, household electrical appliances, automobile and aerospace at present.
Traditional solvent epoxy varnish system contains a large amount of volatile organic compounds (VOC) or hazardous air pollutants (HAP), not only environment is caused severe contamination, and is also very big to the harm of human health.Along with the development of society, people are urgent strict day by day to requirement on environmental protection, and the attention rate of mankind itself's health is promoted day by day, and the research of Resins, epoxy, development and application are just towards low/VOC free and HAP, and energy-conservation, directions such as ecology develop.
Compare with traditional solvent epoxy varnish system, the epoxy-resin systems that with water is dispersion medium has no atmospheric pollution, nontoxic, do not fire, advantages such as the constructing operation performance is good, the security in storage, transportation and the use also greatly improve, therefore, become the focus of Chinese scholars and application engineer research and development in recent years, promoted Study on Water Epoxy Resin Painting and exploitation.But, in the existing openly aqueous epoxy resin emulsion production technique, still there are problems:
A, add the aqueous epoxy resin emulsion that emulsifying agent makes by mechanical process, poor stability, film-forming properties is not good enough, add emulsifying agent after curing to film water-fast, the chemical resistant properties influence is bigger;
B, chemic modified method prepare aqueous epoxy resin emulsion, though obtained certain progress, but complex manufacturing, cost height (US 4315044), stability of emulsion is not good enough, and (US 5244856, CN 1891772A), rated epoxy narrow range (CN101177479A, US 5605605, only at low molecular weight liquid epoxy), the deficiency that has aspects such as (CN1415680A) of a large amount of cosolvent in the system has all greatly limited the widespread use of aqueous epoxy resin emulsion in national product and life.
Summary of the invention
Purpose of the present invention: be intended to propose a kind of universal efficient, pollution-free, aqueous epoxy resin emulsion of low/VOC free and HAP and preparation method thereof.
The reactive water-dispersed epoxy resin emulsion that the present invention proposes, it is by Resins, epoxy, the reactive water-dispersed epoxy resin emulsifying agent, tensio-active agent, cosolvent, flocculation agent and water are formed,
Above-mentioned each component with respect to the weight percent of Resins, epoxy is: Resins, epoxy 100%, and reactive water-dispersed epoxy resin emulsifying agent 5-35%, tensio-active agent 0-1%, cosolvent 0-70%, flocculation agent 0-4%, all the other are water.
Reactive water-dispersed epoxy resin emulsifying agent wherein, be by polyglycol ether, linking agent, Resins, epoxy, synthetic under the effect of catalyst I and catalyst I I, in above-mentioned each component, the mass ratio of polyglycol ether and linking agent is 5.0: 40-40: 5.0, the mass ratio of polyglycol ether and Resins, epoxy is 1: 1-1: 25, the consumption of catalyst I is the 0.001-0.01% of system gross weight, the consumption of catalyst I I is the 0.001-0.01% of system gross weight, and the concrete synthetic method of this emulsifying agent is as follows:
With polyglycol ether, linking agent and diethylene glycol diethyl ether join and have heating, reflux, and in the reactor of devices such as stirrings, heat temperature raising is to 120-125 ℃, be stirred to abundant dissolving after, adding catalyst I, stirring reaction 3-4 hour; Be cooled to 75-80 ℃ then, add Resins, epoxy and catalyst I I, insulation continues reaction 2-3 hour; Behind the stopped reaction, underpressure distillation removes the diethylene glycol diethyl ether that desolvates, and cooling gets liquid, or grey or faint yellow paste reactive water-dispersed epoxy resin emulsifying agent.
As preferably, in the above-mentioned reactive water-dispersed epoxy resin emulsifying agent building-up process, the mass ratio of polyglycol ether and linking agent is 5.0: 40-40: 5.0.
As preferably, in the above-mentioned reactive water-dispersed epoxy resin emulsifying agent building-up process, polyglycol ether is selected from the polyoxyethylene glycol that molecular weight is 1000-6000, one or more in polypropylene glycol and the polytetramethylene glycol.
As preferably, in the above-mentioned reactive water-dispersed epoxy resin emulsifying agent building-up process, the linking agent diacid of selecting oneself, one or more in the para-amino benzoic acid; Also can select other polyprotonic acid for use, the polyprotonic acid derivative that amino or sulfydryl replace, one or more in acid anhydrides and the anhydride ester derivs.
As preferably, in the above-mentioned reactive water-dispersed epoxy resin emulsifying agent building-up process, Resins, epoxy is selected from the Racemic glycidol ether type epoxy that molecular weight is 380-3300, one or more in phthalic acid 2-glycidyl Resins, epoxy and the p-aminophenol three-glycidyl Resins, epoxy.
As preferably, in the above-mentioned reactive water-dispersed epoxy resin emulsifying agent building-up process, catalyst I is a tosic acid.
As preferably, in the above-mentioned reactive water-dispersed epoxy resin emulsifying agent building-up process, catalyst I I is selected from one or more in triphenyl phosphorus and triphenyl phosphatization hydrogen and the benzyldimethylamine.
The aqueous epoxy resin emulsion that the present invention proposes is by Resins, epoxy, by above-mentioned reactive water-dispersed epoxy resin emulsifying agent, tensio-active agent, cosolvent, flocculation agent and water are formed, above-mentioned each component with respect to the weight percent of Resins, epoxy is: Resins, epoxy 100%, reactive water-dispersed epoxy resin emulsifying agent 5-35%, tensio-active agent 0-1%, cosolvent 0-70%, flocculation agent 0-4%, all the other are water.The phase reversion method is adopted in the preparation of this aqueous epoxy resin emulsion, realizes by at a high speed even matter dispersion machine, and concrete preparation method is as follows:
Tensio-active agent and flocculation agent are added in the entry, stir, make it abundant dissolving; With Resins, epoxy (as being solid, then needing heating and melting), reactive water-dispersed epoxy resin emulsifying agent (as being solid, then needing heating and melting) and cosolvent add above-mentioned system, are stirred to mix; Equivalent adds an amount of water successively in above-mentioned system, and stirs, and getting solid content is 30-65%, and cosolvent content is lower than 30% the uniform and stable aqueous epoxy resin emulsion of oyster white.
As preferably, in the above-mentioned aqueous epoxy resin emulsion preparation process, Resins, epoxy is selected from molecular weight and is lower than 3300 Racemic glycidol ether type epoxy, adjacent (or, or to) phthalic acid 2-glycidyl Resins, epoxy, dimeracid 2-glycidyl Resins, epoxy, diaminodiphenylmethane four glycidyl epoxy resins, one or more in p-aminophenol three-glycidyl Resins, epoxy and the triglycidyl group tricarbimide Resins, epoxy.
As preferably, in the above-mentioned aqueous epoxy resin emulsion preparation process, the consumption of reactive water-dispersed epoxy resin emulsifying agent is the 15-25% with respect to content of epoxy resin.
As preferably, be higher than 400 Resins, epoxy for molecular weight, in the preparation process of above-mentioned aqueous epoxy resin emulsion, the consumption of cosolvent is the 6-10% with respect to content of epoxy resin.
As preferably, be lower than 400 Resins, epoxy for molecular weight, in the preparation process of above-mentioned aqueous epoxy resin emulsion, can not add cosolvent.
As preferably, the solid content of above-mentioned aqueous epoxy resin emulsion is 40-60%.
As preferably, in the above-mentioned aqueous epoxy resin emulsion preparation process, cosolvent is the propylene glycol monomethyl ether that hypotoxic non-air is polluted.Also can adopt in ethylene glycol ethyl ether, ethylene glycol monomethyl ether and the diacetone with similar performance one or more.
As preferably, the content of cosolvent is the 0-10% with respect to the emulsion gross weight in the above-mentioned aqueous epoxy resin emulsion.
The performance of the aqueous epoxy resin emulsion by the present invention preparation:
Outward appearance: milky emulsion or blue colloidal solution
Disperse phase particle diameter :≤1 μ m
The centrifugal stability of emulsion: 4000rpm, 40min is not stratified
Stability in storage: not breakdown of emulsion layering of emulsion in 18 months
The present invention has synthesized a kind of reactive water-dispersed epoxy resin emulsifying agent, the epoxide group that contains hydrophilic diether linkage structure and close Resins, epoxy in this emulsifying agent structure, in the Resins, epoxy emulsion process, emulsifying agent respectively with water and Resins, epoxy effect, on two-phase interface, produce strong adsorption, prevent the dispersion particle cohesion, therefore can form highly stable epoxy resin latex.This reactive emulsifier end has epoxy group(ing), so emulsifying agent itself can react with epoxy curing agent, becomes a part of solidifying the back epoxy-resin systems, and the type emulsifying agent is different with adding, and this emulsifying agent is very little to the influence of film performance.Synthesizing of reactive water-dispersed epoxy resin emulsifying agent among the present invention, operating procedure is simple, production cost is low, the emulsifying power height, and generally be applicable to lower molecular weight and high-molecular weight Racemic glycidol ether type epoxy, the emulsification of glycidyl ester type epoxy resin and glycidyl amine type epoxy resin.Aqueous epoxy resin emulsion particle diameter by the present invention's preparation is little, be evenly distributed, good stability, can be used as the basic raw material of preparation aqueous epoxide resin paint, with suitable solidifying agent coupling, be widely used in Resins, epoxy industry ground slab, metal anti-corrosive paint, wood lacquer, aqueous binders, concrete or modifying mortar agent etc.
Embodiment
Further specify the present invention below by embodiment, but the present invention never only is confined to these embodiment.
Embodiment 1
Synthesizing of the preparation of water-based glycidyl ether type epoxy resin latex and respective reactivity water-dispersed epoxy resin emulsifying agent
A. reactive emulsifier is synthetic
With the 240g cetomacrogol 1000,35g hexanodioic acid and 300ml diethylene glycol diethyl ether join in the 1000ml three neck round-bottomed flasks, be heated to 120-125 ℃, after being stirred to abundant dissolving, diethylene glycol diethyl ether solution (3%) with the 10ml tosic acid in 5min is added drop-wise in this system, stirring reaction 3-4 hour.Be cooled to 75-80 ℃ then, add 360g Resins, epoxy E-51, after stirring, the acetone soln with the 10ml triphenyl phosphorus in 5min is added drop-wise in this reaction system, and insulation continues reaction 2-3 hour.Behind the stopped reaction, underpressure distillation removes the diethylene glycol diethyl ether that desolvates, and cooling gets faint yellow paste reactive water-dispersed epoxy resin emulsifying agent.
B. the preparation of water-based Racemic glycidol ether type epoxy E-51 emulsion
Synthetic reactive emulsifier among 120g Resins, epoxy E-51 and the above-mentioned A of 20g is joined in the 500ml three neck round-bottomed flasks, be warming up to 50 ℃, fully stir, to even.
Divide ten equivalent to join successively in the above-mentioned system aqueous solution of 143g water and 3 gram acetic acid, at every turn after water injection after, be stirred well to evenly.Initially, resin viscosity can be big from little change in the flask, when the half of the water yield above Total Water, opposite turning point occurs, and system is changed to oil-in-water-type by water-in-oil emulsion, and the viscosity of system reduces with the adding of rate of water added.After all the water yield adds, obtain oyster white water-based Racemic glycidol ether type epoxy E-51 emulsion.
The performance of water-based Racemic glycidol ether type epoxy E-51 emulsion:
Viscosity: 600-800cp.s (25 ℃)
Solid content: 50%
Disperse phase particle diameter :≤1 μ m
The centrifugal stability of emulsion: 4000rpm, 40min is not stratified
Stability in storage: not breakdown of emulsion layering in 18 months
C. the preparation of water-based Racemic glycidol ether type epoxy E-06 emulsion
With 100g Resins, epoxy E-06, the synthetic reactive emulsifier joins in the 500ml three neck round-bottomed flasks among the above-mentioned A of 70g propylene glycol monomethyl ether and 20g, is warming up to 80 ℃, is stirred well to dissolving; After in 5min, being added drop-wise to 10ml sodium dodecyl benzene sulfonate aqueous solution (1%) in the system, fully stir, to mixing.
Divide ten equivalent to join successively in the above-mentioned system aqueous solution of 55g water and 5 gram acetic acid, at every turn after water injection after, be stirred well to evenly.Initially, resin viscosity can be big from little change in the flask, when the half of the water yield above Total Water, opposite turning point occurs, and system is changed to oil-in-water-type by water-in-oil emulsion, and the viscosity of system reduces with the adding of rate of water added.After all the water yield adds, obtain oyster white water-based Racemic glycidol ether type epoxy E-06 emulsion.
The performance of water-based Racemic glycidol ether type epoxy E-06 emulsion:
Viscosity: 5000-10000cp.s (25 ℃)
Solid content: 50%
Organic solvent: 29%
Disperse phase particle diameter :≤1.5 μ m
The centrifugal stability of emulsion: 4000rpm, 40min is not stratified
Stability in storage: not breakdown of emulsion layering in 12 months
Embodiment 2
Synthesizing of the preparation of water-based glycidyl ester type epoxy resin emulsion and respective reactivity water-dispersed epoxy resin emulsifying agent
A. reactive emulsifier is synthetic
With the 240g cetomacrogol 1000,35g hexanodioic acid and 300ml diethylene glycol diethyl ether join in the 1000ml three neck round-bottomed flasks, be heated to 120-125 ℃, after being stirred to abundant dissolving, diethylene glycol diethyl ether solution (3%) with the 10ml tosic acid in 5min is added drop-wise in this system, stirring reaction 3-4 hour.Be cooled to 70-80 ℃ then, add 300g phthalic acid 2-glycidyl Resins, epoxy, after stirring, the acetone soln with the 10ml triphenyl phosphorus in 5min is added drop-wise in this reaction system, and insulation continues reaction 2-3 hour.Behind the stopped reaction, underpressure distillation removes the diethylene glycol diethyl ether that desolvates, and cooling gets faint yellow paste reactive water-dispersed epoxy resin emulsifying agent.
B. the preparation of water-based glycidyl ester type epoxy resin emulsion
Synthetic reactive emulsifier among 120g phthalic acid 2-glycidyl Resins, epoxy and the above-mentioned A of 20g is joined in the 500ml three neck round-bottomed flasks, be warming up to 50 ℃, fully stir, to even.
Divide ten equivalent to join successively in the above-mentioned system aqueous solution of 143g water 3 gram acetic acid, at every turn after water injection after, be stirred well to evenly.Initially, resin viscosity can be big from little change in the flask, when the half of the water yield above Total Water, opposite turning point occurs, and system is changed to oil-in-water-type by water-in-oil emulsion, and the viscosity of system reduces with the adding of rate of water added.After all the water yield adds, obtain oyster white water-based phthalic acid 2-glycidyl epoxy resin latex.
The performance of water-based phthalic acid 2-glycidyl epoxy resin latex:
Viscosity: 600-800cp.s (25 ℃)
Solid content: 50%
Disperse phase particle diameter :≤1 μ m
The centrifugal stability of emulsion: 4000rpm, 40min is not stratified
Stability in storage: not breakdown of emulsion layering of emulsion in 18 months
Embodiment 3
Synthesizing of the preparation of water-based glycidyl amine type epoxy resin emulsion and respective reactivity water-dispersed epoxy resin emulsifying agent
A. reactive emulsifier is synthetic
With the 240g cetomacrogol 1000,35g hexanodioic acid and 300ml diethylene glycol diethyl ether join in the 1000ml three neck round-bottomed flasks, be heated to 120-125 ℃, after being stirred to abundant dissolving, diethylene glycol diethyl ether solution (3%) with the 10ml tosic acid in 5min is added drop-wise in this system, stirring reaction 3-4 hour.Be cooled to 70-80 ℃ then, add 300g p-aminophenol three-glycidyl Resins, epoxy, after stirring, the acetone soln with the 10ml triphenyl phosphorus in 5min is added drop-wise in this reaction system, and insulation continues reaction 2-3 hour.Behind the stopped reaction, underpressure distillation removes the diethylene glycol diethyl ether that desolvates, and cooling gets faint yellow paste reactive water-dispersed epoxy resin emulsifying agent.
B. the preparation of water-based glycidyl amine type epoxy resin emulsion
Synthetic reactive emulsifier among 120g p-aminophenol three-glycidyl Resins, epoxy and the above-mentioned A of 20g is joined in the 500ml three neck round-bottomed flasks, be warming up to 50 ℃, fully stir, to even.
Divide ten equivalent to join successively in the above-mentioned system aqueous solution of 143g water 3 gram acetic acid, at every turn after water injection after, be stirred well to evenly.Initially, resin viscosity can be big from little change in the flask, when the half of the water yield above Total Water, opposite turning point occurs, and system is changed to oil-in-water-type by water-in-oil emulsion, and the viscosity of system reduces with the adding of rate of water added.After all the water yield adds, obtain oyster white water-based p-aminophenol three-glycidyl epoxy resin latex.
The performance of water-based p-aminophenol three-glycidyl epoxy resin latex:
Viscosity: 800-1000cp.s (25 ℃)
Solid content: 50%
Disperse phase particle diameter :≤1 μ m
The centrifugal stability of emulsion: 4000rpm, 40min is not stratified
Stability in storage: not breakdown of emulsion layering of emulsion in 18 months
The present invention is not limited to the method described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on present technique field personnel according to the present invention can change, technology related to the present invention and product that method such as reorganization obtains, all within protection scope of the present invention.
Claims (9)
1. reactive water-dispersed epoxy resin emulsion is characterized in that: it is by Resins, epoxy, the reactive water-dispersed epoxy resin emulsifying agent, and tensio-active agent, cosolvent, flocculation agent and water are formed,
Above-mentioned each component with respect to the weight percent of Resins, epoxy is: Resins, epoxy 100%, and reactive water-dispersed epoxy resin emulsifying agent 5-35%, tensio-active agent 0-1%, cosolvent 0-70%, flocculation agent 0-4%, all the other are water; Tensio-active agent wherein comprises Sodium dodecylbenzene sulfonate, one or more in sodium lauryl sulphate and the dodecyl sulphate potassium; Cosolvent wherein comprises propylene glycol monomethyl ether, ethylene glycol ethyl ether, one or more in ethylene glycol monomethyl ether and the diacetone; Flocculation agent wherein comprises acetic acid, one or more in the vinylformic acid.
2. reactive water-dispersed epoxy resin emulsion according to claim 1 is characterized in that: described water-dispersed epoxy resin emulsifying agent is by polyglycol ether, linking agent, and Resins, epoxy, synthetic reactive emulsifier under the effect of catalyst I and catalyst I I,
In above-mentioned each component, the mass ratio of polyglycol ether and linking agent is 5.0: 40-40: 5.0, the mol ratio of polyglycol ether and Resins, epoxy is 1: 1-1: 25, the consumption of catalyst I is the 0.001-0.01% of system gross weight, and the consumption of catalyst I I is the 0.001-0.01% of system gross weight.
3. according to claim 1 or 3 described reactive water-dispersed epoxy resin emulsions, it is characterized in that: described Resins, epoxy comprises the Racemic glycidol ether type epoxy, one or more in glycidyl ester type epoxy resin and the glycidyl amine type epoxy resin.
4. reactive water-dispersed epoxy resin emulsion according to claim 2, it is characterized in that: described polyglycol ether comprises polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, above-mentioned polyoxyethylene glycol ether copolymer, and in the molecular chain one or both ends by in the above-mentioned polyglycol ether of amino or carboxyl substituted and the multipolymer thereof one or more.
5. reactive water-dispersed epoxy resin emulsion according to claim 2 is characterized in that: described linking agent comprises polyprotonic acid, the polyprotonic acid derivative that amino or sulfydryl replace, one or more in acid anhydrides and the anhydride ester derivs.
6. reactive water-dispersed epoxy resin emulsion according to claim 2 is characterized in that: described catalyst I comprises tosic acid, one or more in thionamic acid and the tetrabutyl titanate.
7. reactive water-dispersed epoxy resin emulsion according to claim 3 is characterized in that: described catalyst I I comprises triphenylphosphine, one or more in triphenylphosphine hydrogen and the benzyldimethylamine.
8. reactive water-dispersed epoxy resin emulsion according to claim 1 is characterized in that: for described low molecular weight epoxy resin emulsions, the addition of its cosolvent is the 0-5% of weight epoxy; For described high molecular expoxy resin emulsion, the addition of its cosolvent is the 5-30% of weight epoxy.
9. reactive water-dispersed epoxy resin emulsion according to claim 1 is characterized in that: it comprises the preparation of the synthetic and aqueous epoxy resin emulsion of reactive water-dispersed epoxy resin emulsifying agent:
The synthetic method of described reactive water-dispersed epoxy resin emulsifying agent is: with polyglycol ether and linking agent under the effect of catalyst I, under 120-130 ℃, stirring reaction 3-4 hour; After question response was finished, system was cooled to 75-85 ℃, added Resins, epoxy and catalyst I I, continued reaction 2-3 hour, got the reactive water-dispersed epoxy resin emulsifying agent;
The phase reversion method is adopted in the preparation of described aqueous epoxy resin emulsion, realizes by at a high speed even matter dispersion machine, is specially: tensio-active agent and flocculation agent are added in the entry, stir, make it abundant dissolving; Resins, epoxy or heating back fused solid epoxy and cosolvent are joined in the reactive water-dispersed epoxy resin emulsifying agent, be stirred to and mix; Add entry successively, and stir, promptly get the oyster white aqueous epoxy resin emulsion.
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| CN102675859A (en) * | 2012-05-10 | 2012-09-19 | 上海富朗化工科技发展有限公司 | Ultrahigh molecular weight single-component waterborne epoxy resin emulsion and preparation method thereof |
| CN102675861A (en) * | 2012-05-10 | 2012-09-19 | 上海富朗化工科技发展有限公司 | Single-component water-based epoxy resin emulsion and preparation method thereof |
| CN105084844A (en) * | 2015-08-31 | 2015-11-25 | 武汉理工大学 | Epoxy resin emulsion modified cement-based patching material and preparation material thereof |
| CN107353773A (en) * | 2017-07-14 | 2017-11-17 | 湖南沃特邦恩新材料有限公司 | A kind of water corrosion-resistant epoxy paint containing graphene and preparation method and application |
| CN107603410A (en) * | 2017-10-13 | 2018-01-19 | 武汉工程大学 | Floor coatings aqueous epoxy resin emulsion and preparation method thereof |
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Cited By (5)
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| CN102675859A (en) * | 2012-05-10 | 2012-09-19 | 上海富朗化工科技发展有限公司 | Ultrahigh molecular weight single-component waterborne epoxy resin emulsion and preparation method thereof |
| CN102675861A (en) * | 2012-05-10 | 2012-09-19 | 上海富朗化工科技发展有限公司 | Single-component water-based epoxy resin emulsion and preparation method thereof |
| CN105084844A (en) * | 2015-08-31 | 2015-11-25 | 武汉理工大学 | Epoxy resin emulsion modified cement-based patching material and preparation material thereof |
| CN107353773A (en) * | 2017-07-14 | 2017-11-17 | 湖南沃特邦恩新材料有限公司 | A kind of water corrosion-resistant epoxy paint containing graphene and preparation method and application |
| CN107603410A (en) * | 2017-10-13 | 2018-01-19 | 武汉工程大学 | Floor coatings aqueous epoxy resin emulsion and preparation method thereof |
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