CN102675859A - Ultrahigh molecular weight single-component waterborne epoxy resin emulsion and preparation method thereof - Google Patents
Ultrahigh molecular weight single-component waterborne epoxy resin emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses ultrahigh molecular weight single-component waterborne epoxy resin emulsion. The epoxy resin emulsion comprises 100 percent of modified epoxy resin, 5 to 35 percent of efficient emulsifier, 0 to 1 percent of surfactant, 0 to 70 percent of cosolvent and the balance of water; the modified epoxy resin comprises ultrahigh molecular weight epoxy resin, polyglycol ether, amphiphilic compound, isocyanate, sealing agent and catalyst; the ultrahigh molecular weight epoxy resin is bisphenol A epoxy resin of which the epoxide equivalent is more than 2,000; and the efficient emulsifier comprises ultrahigh molecular weight epoxy resin, polyether, organic silicon and catalyst. A preparation method for the epoxy resin emulsion comprises three steps, namely modification of the ultrahigh molecular weight epoxy resin, preparation of the efficient emulsifier and water adding emulsification.
Description
Technical field
The present invention relates to a kind of aqueous epoxy resin emulsion technology of preparing, single-component water-based epoxy resin latex of especially a kind of ultra-high molecular weight and preparation method thereof belongs to chemistry painting industry and matrix material manufacturing technology.
Background technology
Epoxy resin 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; Hardness is high, and 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.
Among the preparation technology of existing openly aqueous epoxy resin emulsion; Prepared aqueous epoxy resins is mainly two components; Middle lower molecular weight (EEW＜1100) aqueous epoxy resin emulsion; Be mainly used in building field, it is the dipping that about 2000 product is used for spun glass that a small amount of epoxy equivalent (weight) is only arranged.These products are mainly two components because the molecular weight of epoxy resin is low, and working life is short; Use inconvenience; And the paint film flexibility that makes, shock-resistance and Corrosion Protection are poor, can only be used for the lower water-based anticorrosion of steel structure priming paint of requirement and use; Wider in the building field use at present, still can not satisfy the technological urgent need of high-performance water-based epoxy protective system and treating compound fully.
Summary of the invention
The object of the invention: be intended to propose a kind of method for preparing the single-component water-based epoxy resin latex of ultra-high molecular weight (EEW>2000), the resin of preparing have the disperse phase particle diameter little, be evenly distributed, stability is high; The paint film antiseptic property is excellent, good, the strong adhesion of snappiness; Compare with low molecular weight epoxy, the composite material interface bonding force of processing is strong, makes goods mechanical property and ageing-resistant performance be greatly improved.Compare with two component epoxy, use more easyly, efficient is higher.
The single-component water-based epoxy resin latex of this ultra-high molecular weight that the present invention proposes is characterized in that: it comprises modified epoxy, efficient emulsifying agent, tensio-active agent, cosolvent and water;
Said single-component water-based epoxy resin latex is formed by following weight percent: the ultra epoxy resin 100% of modification, efficient emulsifying agent 5-35%, tensio-active agent 0-1%, cosolvent 0-70%, suitable quantity of water;
Described modified epoxy comprises: ultra-high molecular weight epoxy resin, polyglycol ether, amphiphilic compound, isocyanic ester, encapsulant and catalyzer; In described modified epoxy: the mass ratio of ultra-high molecular weight epoxy resin and polyglycol ether is 8:1 ~ 1:1; The mass ratio of ultra-high molecular weight epoxy resin and amphiphilic compound is 4:1 ~ 1:1; The mass ratio of ultra-high molecular weight epoxy resin and isocyanic ester is 10:3 ~ 10:4; The mass ratio of ultra-high molecular weight epoxy resin and encapsulant is 15:1 ~ 15:2, and catalyst consumption is the 0.01-0.1 of modified epoxy resin system gross weight;
Described ultra-high molecular weight epoxy resin is epoxy equivalent (weight) greater than 2000 bisphenol A type epoxy resin;
Described efficient emulsifying agent comprises ultra-high molecular weight epoxy resin, polyethers, organosilicon and catalyzer; Wherein ultra-high molecular weight epoxy resin and organosilyl mass ratio are 5:1 ~ 1:1, and the mass ratio of ultra-high molecular weight epoxy resin and polyethers is 6:1 ~ 6:4, and catalyst consumption is the 0.01-0.1 of efficient emulsifier system gross weight;
Described tensio-active agent is an X 2073, a kind of or two kinds and two or more mixtures in sodium lauryl sulphate and the dodecyl sulphate potassium;
Described cosolvent comprises propylene glycol monomethyl ether, ethylene glycol ethyl ether, a kind of or two kinds and two or more mixtures in EGME and the diacetone;
Described encapsulant is a kind of or two kinds and the two or more mixture in hexanolactam, phenol or the methyl ethyl ketoxime;
Described catalyzer is one or more the mixture in 2-ethyl-4-methylimidazole, triphenyl phosphorus, triphenyl phosphatization hydrogen or the benzyldimethylamine.
The polyglycol ether that uses in the said modified epoxy is the polyoxyethylene glycol of molecular weight as 1000-6000, W 166, a kind of in the polytetramethylene glycol or be the multipolymer of polyglycol ether; Or be in the molecular chain one or both ends by one or more the mixture in the polyglycol ether of amino or carboxyl substituted and the multipolymer thereof.
The amphiphilic compound that uses in the said modified epoxy is a kind of or two kinds and two or more mixtures in SULPHOSUCCINIC ACID ESTER, diethylolamine, the trolamine.
The isocyanic ester that uses in the described modified epoxy is the toluene di-iso-cyanide ester ester, '-diphenylmethane diisocyanate, a kind of or two kinds and two or more mixtures in the isophorone diisocyanate.
The organosilicon that uses in the described modified epoxy is one or more the mixture in triethoxyl silane, tetramethyl-dihydro base sily oxide, SWS-F 221, octamethylcyclotetrasiloxane, ring five YSR 3286s.
Described low molecular weight epoxy resin emulsions, the addition of its cosolvent are the 0-10% of weight epoxy;
The single-component water-based epoxy resin latex of said ultra-high molecular weight, its preparation method comprise the preparation of the modification of ultra-high molecular weight epoxy resin, efficient emulsifying agent and add three steps of emulsifying water:
Wherein: the synthetic of described modified epoxy is with polyglycol ether, joins in the reactor drum that has heating, backflow, whipping appts, and heat temperature raising is to 120-125 ° of C; After being stirred to abundant dissolving; Vacuum hydro-extraction 30min is cooled to 75-80 ° of C then, adds isocyanic ester and catalyzer; Insulation continues reaction 2-3 hour; Add epoxy resin and amphiphilic compound, be warming up to 100-105 ° of C insulation reaction 2 hours, be cooled to 75-80 ° of C and add methyl ethyl ketoxime; Continue reaction 1 hour, add remaining epoxy, in 60-75 ° of C insulation 30min; Cooling gets light yellow thickness modified epoxy;
The compound method of said efficient emulsifying agent is: polyethers is joined in the reactor drum that has heating, refluxing and stirring device, feed nitrogen and stirring, heat temperature raising is to the 70-80 ° of excessive organosilicon of C dropping; React after 4 hours; Add epoxy resin, be warming up to 100 ° of C, reacted 3 hours; Cooling gets the efficient emulsifying agent of faint yellow thickness;
Adding the emulsifying water process is: with the ultra-high molecular weight epoxy resin of modification, efficient emulsifying agent and tensio-active agent add in the reactor drum, stir and heat up; When treating that pressure reaches 0.4Mpa; Start the high-shear dispersion machine, it carried out preparatory emulsification, subsequently to pre-emulsified resin emulsion through the processing that homogenizes of at a high speed even matter dispersion machine; Getting solid content is 30-65%, and cosolvent content is lower than 30% the uniform and stable single-component water-based epoxy resin latex of oyster white.
The solid content of said aqueous epoxy resin emulsion is 40 ~ 60%.
The present invention has synthesized a kind of modified epoxy, contains the reactive group of stable existence under the room temperature in this modified epoxy, and only crosslinking reaction takes place reactive group ability deblocking under temperature condition.Cooperate efficient emulsifying agent; Contain amphiphilic chemical substance in this emulsifying agent structure; In the epoxy resin emulsion process, emulsifying agent respectively with water and epoxy resin effect, on two-phase interface, produce strong adsorption; Prevent the dispersion particle cohesion, therefore can form highly stable single-component water-based epoxy resin latex.
Operating procedure is simple, and production cost is low, and emulsifying power is high, and generally is applicable to the Racemic glycidol ether type epoxy of ultra-high molecular weight.Single-component water-based epoxy resin latex particle diameter through the present invention's preparation is little, is evenly distributed, and good stability can be used as the basic raw material for preparing aqueous epoxide resin paint.
Embodiment
Further specify the present invention through embodiment below, but the present invention never only is confined to these embodiment.
The single-component water-based epoxy resin latex of ultra-high molecular weight that the present invention proposes is characterized in that: it comprises modified ultra-high molecular mass epoxy resin, efficient emulsifying agent, tensio-active agent, cosolvent and water;
Said single-component water-based epoxy resin latex is formed by following weight percent: the ultra epoxy resin 100% of modification, efficient emulsifying agent 5-35%, tensio-active agent 0-1%, cosolvent 0-70%, suitable quantity of water;
Described modified epoxy comprises: ultra-high molecular weight epoxy resin, polyglycol ether, amphiphilic compound, isocyanic ester, encapsulant and catalyzer; In described modified epoxy: the mass ratio of ultra-high molecular weight epoxy resin and polyglycol ether is 8:1 ~ 1:1; The mass ratio of ultra-high molecular weight epoxy resin and amphiphilic compound is 4:1 ~ 1:1; The mass ratio of ultra-high molecular weight epoxy resin and isocyanic ester is 10:3 ~ 10:4; The mass ratio of ultra-high molecular weight epoxy resin and encapsulant is 15:1 ~ 15:2, and catalyst consumption is the 0.01-0.1 of modified epoxy resin system gross weight;
Described ultra-high molecular weight epoxy resin is epoxy equivalent (weight) greater than 2000 bisphenol A type epoxy resin;
Described efficient emulsifying agent comprises ultra-high molecular weight epoxy resin, polyethers, organosilicon and catalyzer; Wherein ultra-high molecular weight epoxy resin and organosilyl mass ratio are 5:1 ~ 1:1, and the mass ratio of ultra-high molecular weight epoxy resin and polyethers is 6:1 ~ 6:4, and catalyst consumption is the 0.01-0.1 of efficient emulsifier system gross weight;
Described tensio-active agent is an X 2073, a kind of or two kinds and two or more mixtures in sodium lauryl sulphate and the dodecyl sulphate potassium;
Described cosolvent comprises propylene glycol monomethyl ether, ethylene glycol ethyl ether, a kind of or two kinds and two or more mixtures in EGME and the diacetone;
Described encapsulant is a kind of or two kinds and the two or more mixture in hexanolactam, phenol or the methyl ethyl ketoxime;
Described catalyzer is one or more the mixture in 2-ethyl-4-methylimidazole, triphenyl phosphorus, triphenyl phosphatization hydrogen or the benzyldimethylamine.
The polyglycol ether that uses in the said modified epoxy is the polyoxyethylene glycol of molecular weight as 1000-6000, W 166, a kind of in the polytetramethylene glycol or be the multipolymer of polyglycol ether; Or be in the molecular chain one or both ends by one or more the mixture in the polyglycol ether of amino or carboxyl substituted and the multipolymer thereof.
The amphiphilic compound that uses in the said modified epoxy is a kind of or two kinds and two or more mixtures in SULPHOSUCCINIC ACID ESTER, diethylolamine, the trolamine.
The isocyanic ester that uses in the described modified epoxy is the toluene di-iso-cyanide ester ester, '-diphenylmethane diisocyanate, a kind of or two kinds and two or more mixtures in the isophorone diisocyanate.
The organosilicon that uses in the described modified epoxy is one or more the mixture in triethoxyl silane, tetramethyl-dihydro base sily oxide, SWS-F 221, octamethylcyclotetrasiloxane, ring five YSR 3286s.
Described low molecular weight epoxy resin emulsions, the addition of its cosolvent are the 0-10% of weight epoxy;
The single-component water-based epoxy resin latex of said ultra-high molecular weight, its preparation method comprise the preparation of the modification of ultra-high molecular weight epoxy resin, efficient emulsifying agent and add three steps of emulsifying water:
Wherein: the synthetic of described modified epoxy is with polyglycol ether, joins in the reactor drum that has heating, backflow, whipping appts, and heat temperature raising is to 120-125 ° of C; After being stirred to abundant dissolving; Vacuum hydro-extraction 30min is cooled to 75-80 ° of C then, adds isocyanic ester and catalyzer; Insulation continues reaction 2-3 hour; Add epoxy resin and amphiphilic compound, be warming up to 100-105 ° of C insulation reaction 2 hours, be cooled to 75-80 ° of C and add methyl ethyl ketoxime; Continue reaction 1 hour, add remaining epoxy, in 60-75 ° of C insulation 30min; Cooling gets light yellow thickness modified epoxy;
The compound method of said efficient emulsifying agent is: polyethers is joined in the reactor drum that has heating, refluxing and stirring device, feed nitrogen and stirring, heat temperature raising is to the 70-80 ° of excessive organosilicon of C dropping; React after 4 hours; Add epoxy resin, be warming up to 100 ° of C, reacted 3 hours; Cooling gets the efficient emulsifying agent of faint yellow thickness;
Adding the emulsifying water process is: with the ultra-high molecular weight epoxy resin of modification, efficient emulsifying agent and tensio-active agent add in the reactor drum, stir and heat up; When treating that pressure reaches 0.4Mpa; Start the high-shear dispersion machine, it carried out preparatory emulsification, subsequently to pre-emulsified resin emulsion through the processing that homogenizes of at a high speed even matter dispersion machine; Getting solid content is 30-65%, and cosolvent content is lower than 30% the uniform and stable single-component water-based epoxy resin latex of oyster white.
The solid content of said aqueous epoxy resin emulsion is 40 ~ 60%.
The performance of the single-component water-based epoxy resin latex of ultra-high molecular weight through the present invention preparation:
Epoxy equivalent (weight): 2000-4000
Viscosity: 2000-10000cp.s (25 ° of C);
Solid content: 50% ± 5;
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.
The preparation of the single-component water-based epoxy resin latex of embodiment 1E-03
A. modification E-03 epoxy resin is synthetic
The 218g cetomacrogol 1000 is joined in the reactor drum, is heated to 120-125 ° of C, be stirred to abundant dissolving after, vacuum hydro-extraction 30min; Be cooled to 75-80 then, add the 40g tolylene diisocyanate, insulation reaction 3 hours; Add 225g E-03 epoxy resin and 17g SULPHOSUCCINIC ACID ESTER, be warming up to 100-105 ° of C insulation reaction 2 hours, be cooled to 75-80 ° of C and add 28g; Methyl ethyl ketoxime continues reaction 1 hour, adds residue 290g epoxy resin; In 60-75 ° of C insulation 30min, cooling gets light yellow thickness modified epoxy.
B. the preparation of efficient emulsifying agent
The 240g polyethers joined have heating, reflux, in the reactor drum of devices such as stirring; Feed nitrogen and stirring, heat temperature raising reacts after 4 hours to 70-80 ° of C dropping 80g octamethylcyclotetrasiloxane; Add 300g epoxy resin, be warming up to 100 ° of C, reacted 3 hours; Cooling gets light yellow viscous liquid
The preparation of the single-component water-based epoxy resin latex of C.E-03 ultra-high molecular weight
With 100g modification E-03 epoxy resin, the efficient emulsifying agent of 15g adds in the high-pressure reactor, after stirring, under the whipped state; With 115g water, 15g diacetone and 0.5g tensio-active agent add in the above-mentioned system, heat up; When treating that pressure rises to 0.4Mpa, start the high-shear dispersion machine, in advance emulsification 90min; Obtain milky white liquid, pre-emulsified emulsion must the single-component water-based epoxy resin latex of E-06 ultra-high molecular weight through processings that homogenize of at a high speed even matter mulser.
The technical indicator of the single-component water-based epoxy resin latex of E-03 ultra-high molecular weight:
Viscosity: 2000-3000cp.s (25 ° of C);
Solid content: 47%;
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.
The preparation of the single-component water-based epoxy resin latex of embodiment 2E-06
A. modification E-06 epoxy resin is synthetic
The 218g cetomacrogol 1000 is joined in the reactor drum, is heated to 120-125 ° of C, be stirred to abundant dissolving after, vacuum hydro-extraction 30min; Be cooled to 75-80 then, add the 55g tolylene diisocyanate, insulation reaction 3 hours; Add 270g E-06 epoxy resin and 25g SULPHOSUCCINIC ACID ESTER, be warming up to 100-105 ° of C insulation reaction 2 hours, be cooled to 75-80 ° of C and add 33g; Methyl ethyl ketoxime continues reaction 1 hour, adds residue 250g epoxy resin; In 60-75 ° of C insulation 30min, cooling gets light yellow thickness modified epoxy.
B. the preparation of efficient emulsifying agent
The 240g polyethers joined have heating, reflux, in the reactor drum of devices such as stirring; Feed nitrogen and stirring, heat temperature raising reacts after 4 hours to 70-80 ° of C dropping 80g octamethylcyclotetrasiloxane; Add 300g epoxy resin, be warming up to 100 ° of C, reacted 3 hours; Cooling gets light yellow viscous liquid
The preparation of the single-component water-based epoxy resin latex of C.E-06 ultra-high molecular weight
With 100g modification E-06 epoxy resin, efficient emulsifying agent of 15g and tensio-active agent add in the high-pressure reactor, after stirring, under the whipped state; With 115g water, 15g diacetone and 0.5g tensio-active agent add in the above-mentioned system, heat up; When treating that pressure rises to 0.4Mpa, start the high-shear dispersion machine, in advance emulsification 90min; Obtain milky white liquid, pre-emulsified emulsion must the single-component water-based epoxy resin latex of E-06 ultra-high molecular weight through processings that homogenize of at a high speed even matter mulser.
The technical indicator of the single-component water-based epoxy resin latex of E-06 ultra-high molecular weight:
Viscosity: 2000-3000cp.s (25 ° of C);
Solid content: 47%;
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.
Claims (8)
1. single-component water-based epoxy resin latex of ultra-high molecular weight is characterized in that: it comprises modified epoxy, efficient emulsifying agent, tensio-active agent, cosolvent and water;
Said single-component water-based epoxy resin latex is formed by following weight percent: the ultra epoxy resin 100% of modification, efficient emulsifying agent 5-35%, tensio-active agent 0-1%, cosolvent 0-70%, suitable quantity of water;
Described modified epoxy comprises: ultra-high molecular weight epoxy resin, polyglycol ether, amphiphilic compound, isocyanic ester, encapsulant and catalyzer; In described modified epoxy: the mass ratio of ultra-high molecular weight epoxy resin and polyglycol ether is 8:1 ~ 1:1; The mass ratio of ultra-high molecular weight epoxy resin and amphiphilic compound is 4:1 ~ 1:1; The mass ratio of ultra-high molecular weight epoxy resin and isocyanic ester is 10:3 ~ 10:4; The mass ratio of ultra-high molecular weight epoxy resin and encapsulant is 15:1 ~ 15:2, and catalyst consumption is the 0.01-0.1 of modified epoxy resin system gross weight;
Described ultra-high molecular weight epoxy resin is epoxy equivalent (weight) greater than 2000 bisphenol A type epoxy resin;
Described efficient emulsifying agent comprises ultra-high molecular weight epoxy resin, polyethers, organosilicon and catalyzer; Wherein ultra-high molecular weight epoxy resin and organosilyl mass ratio are 5:1 ~ 1:1, and the mass ratio of ultra-high molecular weight epoxy resin and polyethers is 6:1 ~ 6:4, and catalyst consumption is the 0.01-0.1 of efficient emulsifier system gross weight;
Described tensio-active agent is an X 2073, a kind of or two kinds and two or more mixtures in sodium lauryl sulphate and the dodecyl sulphate potassium;
Described cosolvent comprises propylene glycol monomethyl ether, ethylene glycol ethyl ether, a kind of or two kinds and two or more mixtures in EGME and the diacetone;
Described encapsulant is a kind of or two kinds and the two or more mixture in hexanolactam, phenol or the methyl ethyl ketoxime;
Described catalyzer is one or more the mixture in 2-ethyl-4-methylimidazole, triphenyl phosphorus, triphenyl phosphatization hydrogen or the benzyldimethylamine.
2. the single-component water-based epoxy resin latex of ultra-high molecular weight as claimed in claim 1; It is characterized in that: the polyglycol ether that uses in the said modified epoxy is the polyoxyethylene glycol of molecular weight as 1000-6000; W 166, a kind of in the polytetramethylene glycol or be the multipolymer of polyglycol ether; Or be in the molecular chain one or both ends by one or more the mixture in the polyglycol ether of amino or carboxyl substituted and the multipolymer thereof.
3. the single-component water-based epoxy resin latex of ultra-high molecular weight as claimed in claim 1 is characterized in that: the amphiphilic compound that uses in the said modified epoxy is a kind of or two kinds and two or more mixtures in SULPHOSUCCINIC ACID ESTER, diethylolamine, the trolamine.
4. the single-component water-based epoxy resin latex of ultra-high molecular weight as claimed in claim 1; It is characterized in that: the isocyanic ester that uses in the described modified epoxy is the toluene di-iso-cyanide ester ester; '-diphenylmethane diisocyanate, a kind of or two kinds and two or more mixtures in the isophorone diisocyanate.
5. the single-component water-based epoxy resin latex of ultra-high molecular weight as claimed in claim 1 is characterized in that: the organosilicon that uses in the described modified epoxy is one or more the mixture in triethoxyl silane, tetramethyl-dihydro base sily oxide, SWS-F 221, octamethylcyclotetrasiloxane, ring five YSR 3286s.
6. the single-component water-based epoxy resin latex of ultra-high molecular weight as claimed in claim 1 is characterized in that: for described low molecular weight epoxy resin emulsions, the addition of its cosolvent is the 0-10% of weight epoxy;
7. like the single-component water-based epoxy resin latex of the said ultra-high molecular weight of claim 1-5, its preparation method comprises the preparation of the modification of ultra-high molecular weight epoxy resin, efficient emulsifying agent and adds three steps of emulsifying water:
Wherein: the synthetic of described modified epoxy is with polyglycol ether, joins in the reactor drum that has heating, backflow, whipping appts, and heat temperature raising is to 120-125 ° of C; After being stirred to abundant dissolving; Vacuum hydro-extraction 30min is cooled to 75-80 ° of C then, adds isocyanic ester and catalyzer; Insulation continues reaction 2-3 hour; Add epoxy resin and amphiphilic compound, be warming up to 100-105 ° of C insulation reaction 2 hours, be cooled to 75-80 ° of C and add methyl ethyl ketoxime; Continue reaction 1 hour, add remaining epoxy, in 60-75 ° of C insulation 30min; Cooling gets light yellow thickness modified epoxy;
The compound method of said efficient emulsifying agent is: polyethers is joined in the reactor drum that has heating, refluxing and stirring device, feed nitrogen and stirring, heat temperature raising is to the 70-80 ° of excessive organosilicon of C dropping; React after 4 hours; Add epoxy resin, be warming up to 100 ° of C, reacted 3 hours; Cooling gets the efficient emulsifying agent of faint yellow thickness;
Adding the emulsifying water process is: with the ultra-high molecular weight epoxy resin of modification, efficient emulsifying agent and tensio-active agent add in the reactor drum, stir and heat up; When treating that pressure reaches 0.4Mpa; Start the high-shear dispersion machine, it carried out preparatory emulsification, subsequently to pre-emulsified resin emulsion through the processing that homogenizes of at a high speed even matter dispersion machine; Getting solid content is 30-65%, and cosolvent content is lower than 30% the uniform and stable single-component water-based epoxy resin latex of oyster white.
8. like the single-component water-based epoxy resin latex of the said ultra-high molecular weight of claim 7, it is characterized in that: the solid content of said aqueous epoxy resin emulsion is 40 ~ 60%.
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| CN103772638A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Polyurethane-structure-modified bisphenol F epoxy resin composite, as well as preparation and application thereof |
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| CN103772638B (en) * | 2012-10-26 | 2016-05-04 | 中国石油化工股份有限公司 | By bisphenol F epoxy resin composition and preparation and the application of polyurethane structural modification |
| CN103788322B (en) * | 2012-10-26 | 2016-09-14 | 中国石油化工股份有限公司 | The bisphenol A epoxide resin compositions modified by polyurethane structural and preparation thereof and application |
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Application publication date: 20120919 |