CN101117390B - Method for preparing aqueous epoxy emulsion - Google Patents
Method for preparing aqueous epoxy emulsion Download PDFInfo
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- CN101117390B CN101117390B CN2007100596698A CN200710059669A CN101117390B CN 101117390 B CN101117390 B CN 101117390B CN 2007100596698 A CN2007100596698 A CN 2007100596698A CN 200710059669 A CN200710059669 A CN 200710059669A CN 101117390 B CN101117390 B CN 101117390B
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Abstract
The present invention relates to a method for preparation of waterborne epoxy emulsion. Specific techniques are as follows. (1) Tween-series emulsifier and bisphenol-A epoxy resin produce reactive emulsifier in ring opening reaction under the function of catalysts; (2) the outcome of (1) and cationic surfactant are blended evenly to prepare composite emulsifier; (3) thinner gets adopted to dilute epoxy resin for the sake of lowering the viscidity, then the offspring of (1) is dropped into epoxy resin to prepare waterborne epoxy emulsion by using the method of phase conversion; (4) water is dropped into the outcome of (3) and waterborne epoxy emulsion is prepared after the mixing for a period of time. Waterborne epoxy emulsion has the properties below. Firstly, centrifugal stability reaches 2,000 turns per minute and no delamination happens within thirty minutes; secondly, emulsion remains unbroken and not delaminated within six months; thirdly, the average granular diameter is less than 1 um; last, water can be added for dilution and unbroken emulsion.
Description
Technical field
The invention belongs to technical field of macromolecules, be specifically related to a kind of method for preparation of waterborne epoxy emulsion.
Background technology
Development and new theory and the rules consciousness of people along with the coating Science and Technology have proposed more and more high requirement to environmental protection.Because the organic solvent that traditional solvent based coating evaporates has brought serious adverse consequences to topsoil and HUMAN HEALTH, therefore to low VOC, efficiently, energy-conservation, ecological direction develops, research and development environment-friendly type high performance coating has become the common recognition of coating circle, also is the inevitable outlet of coatings industry development.Resins, epoxy is because its excellent performance, spy such as good as sticking power, that chemical resistant properties is good, solvent resistance is excellent, hardness is high, wear resistance is good has obtained using widely particularly aspect the application of paints at aspects such as military, civilian, industrial maintenances, and 40% Resins, epoxy is used for coating in the worldwide at present.Resins, epoxy itself is water insoluble, can not directly add water and carry out emulsification, must introduce hydrophilic segment or add hydrophilic component to make in molecular chain, and Resins, epoxy is made the technology path that emulsion is tool using value.
Emulsifying agent is a kind of tensio-active agent, and its structure and hydrophile-lipophile balance value are the major influence factors of its emulsifying property of decision, must select suitable emulsifying agent just can obtain the emulsion of excellent in stability.Therefore, emulsifying agent is the key ingredient of preparation Resins, epoxy water miscible liquid.For Resins, epoxy, the available emulsifying agent has multiple, according to different non-reactive emulsifier, the response type epoxy resin emulsifying agent two big classes of can being divided into again of its structure and performance.Non-reacted epoxy resin emulsifying agent is generally some general tensio-active agents, and this class emulsifying agent does not contain the group of epoxy group(ing) and easy and epoxy reaction usually, does not participate in last curing reaction, mainly plays emulsifying effect.The emulsion particle that this method obtains is thick, out-of-shape, size distribution broad.Reactive emulsifier is a kind of emulsification function that has, and has the tensio-active agent of reactive functional groups simultaneously.Adopt Resins, epoxy building-up reactions type emulsifying agent, make the hydrophobic part of Resins, epoxy, can satisfy the structure and similar as far as possible this principle of character of the hydrophobic part and the oil phase of emulsifying agent, thereby obtain emulsifying effectiveness preferably as emulsifying agent.Simultaneously in curing reaction, it can also participate in film forming with the amine curing reaction, forms cross-linked network structure, tensio-active agent is fixed on to film firmly, like this dialysis, this free problem with regard to effectively having overcome tensio-active agent.Generally about 13%, the emulsifying agent consumption is excessive must to exert an influence to the curing performance of emulsion the consumption of reactive emulsifier in the document of being reported at present, and the content that therefore how to reduce emulsifying agent remains further to be studied.
Summary of the invention
The method for preparation of waterborne epoxy emulsion that the present invention proposes is to utilize the phase reversion method to adopt the method for preparation of waterborne epoxy emulsion of reactive emulsifier, and concrete technology is as follows:
(1) ring-opening reaction takes place and prepares reaction emulsifier in twain series emulsifier and bisphenol A type epoxy resin under catalyst action.
(2) product and cats product uniform mixing in (1) are prepared composite emulsifier.
(3) adopt thinner that Resins, epoxy is diluted,, (1) step product is added drop-wise in the Resins, epoxy, utilize the phase reversion legal system to be equipped with aqueous epoxy emulsion to reduce its viscosity.
(4) in (3) product, drip water, continue to stir for some time and prepare aqueous epoxy emulsion.
In the described step (1), the synthetic used catalyzer of modified epoxy is a boron trifluoride diethyl etherate, and its consumption is about 1～4% of a weight epoxy.
In the described step (1), adopt bisphenol A type epoxy resin, oxirane value adopts tween-80 at 0.2-0.51mol/100g, 60,20 with Resins, epoxy prepared in reaction New-type emulsifier.
In the described step (1), the mol ratio of hydroxyl and epoxy group(ing) is 1 in the reaction system of tween and Resins, epoxy: 0.5-0.6: 1.1, and temperature of reaction is 80～110 ℃, the reaction times is 6～7h.
In the described step (2), the cats product of employing is a sodium lauryl sulphate, and its consumption is the 0.27-0.52% of weight epoxy.
In the described step (2), the consumption of New-type emulsifier is the 5-9% of weight epoxy.
In the described step (3),, add the monocycle oxygen thinner of its 10-18% weight,, add the monocycle oxygen thinner of its 3-7% weight low-molecular-weight epoxy resin to high molecular expoxy resin.
Adopt monocycle oxygen-butyl glycidyl ethers that Resins, epoxy is diluted in the described step (3).
The aqueous epoxy resin emulsion that the present invention proposes by Resins, epoxy through reactive emulsifier and cats product emulsification, prepare by phase inversion technique, this reaction emulsifier has hydrophilic twain series emulsifier to react the New-type emulsifier that generation, end group are respectively epoxy group(ing) and hydroxyl in the presence of catalyzer by Resins, epoxy with it.Adopt Resins, epoxy building-up reactions type emulsifying agent, can satisfy the structure and similar as far as possible this principle of character of the hydrophobic part and the oil phase of emulsifying agent, thereby obtain emulsifying effectiveness preferably.Simultaneously because the special construction of reactive emulsifier, it can also participate in film forming with the amine curing reaction in curing reaction, form cross-linked network structure, tensio-active agent is fixed on films firmly, like this dialysis, this free problem with regard to effectively having overcome tensio-active agent; In addition cats product and reactive emulsifier are mixed into total body burden that composite emulsifier can effectively reduce emulsifying agent by a certain percentage, can also obtain the aqueous epoxy emulsion of excellent property simultaneously.
The performance of gained aqueous epoxy emulsion:
(1) centrifugal stability: 2000 rev/mins, 30 minutes not stratified
(2) stability in storage: not breakdown of emulsion layering of emulsion in 6 months
(3) median size:＜1 μ m
(4) can thin up and breakdown of emulsion not
Embodiment
Further describe the present invention below by the truth example.
Embodiment 1
(1) preparation of New-type emulsifier
On four neck flasks, be equipped with whipping appts, thermometer and towards nitrogen conduit, flask heats in water-bath, (oxirane value is 0.2mol/100g with 120g tween-80 and 51g (0.102mol epoxy group(ing)) Resins, epoxy E-20,) the adding flask, feed the nitrogen excluding air, be heated to 70 ℃ then, add the 0.51g boron trifluoride diethyl etherate again, temperature of reaction system rises.Control reaction temperature is 110 ℃, and sustained reaction made New-type emulsifier in 6 hours.
(2) preparation of epoxy resin latex
In the 800ml beaker, add 180gE-20 Resins, epoxy, start dispersion machine and stir at a slow speed, add 32g butyl glycidyl ethers.After Resins, epoxy dissolves fully, add 9g New-type emulsifier, 0.486g sodium lauryl sulphate and 0.6g defoamer again, fully dispersed with stirring.
Progressively add 222g distilled water under high-speed stirring, descend suddenly up to the viscosity of system, this moment, system was the oil-in-water system from the water-in-oil system transition, and phase reversion has taken place, and continued high-speed stirring and made the stable epoxy resin latex of oyster white.
Solid content: 50%
Viscosity: about 417mPas
Epoxy equivalent (weight): 501
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
(3) preparation of bi-component aqueous epoxy resin paint film
First component: 751 solidifying agent second components: aqueous epoxy resin emulsion
The first component: the mixed of second component=1: 3.5 (weight ratio), stir by hand, be coated on the iron plate with brush.Form transparent film after the moisture evaporation, the performance of filming is:
| Project | Performance |
| Time of drying, surface drying/h did solid work/h pencil hardness wear resistance (750g/300r)/g ultimate compression strength/(Nmm -2) water tolerance (48h) alkali resistance (and 10%NaOH, 48h) acid resistance (10%HCl, 48h) oil-proofness (machine oil, 30d) | 1.5 17 1H＜0.02 50 no change no change no change no change |
Embodiment 2
(1) preparation of New-type emulsifier
On four neck flasks, be equipped with whipping appts, thermometer and towards nitrogen conduit, flask heats in water-bath, 110g Tween-60 and 34.7g (0.177mol epoxy group(ing)) Resins, epoxy E-51 (oxirane value is 0.51mol/100g) are added flask, feed the nitrogen excluding air, be heated to 70 ℃ then, add the 0.87g boron trifluoride diethyl etherate again, temperature of reaction system rises.Control reaction temperature is 95 ℃, and sustained reaction made New-type emulsifier in 6.5 hours.
(2) preparation of epoxy resin latex
In the 800ml beaker, add 115gE-51 Resins, epoxy, start dispersion machine and stir at a slow speed, add 11.5g butyl glycidyl ethers.After Resins, epoxy dissolves fully, add New-type emulsifier, 0.44g sodium lauryl sulphate and the 0.5g defoamer of 8.05g preparation again, fully dispersed with stirring.
Progressively add 90g distilled water under high-speed stirring, descend suddenly up to the viscosity of system, this moment, system was the oil-in-water system from the water-in-oil system transition, and phase reversion has taken place, and continued high-speed stirring about 10 minutes, made the stable epoxy resin latex of oyster white.
Solid content: 60%
Viscosity: about 532mPas
Epoxy equivalent (weight): 523
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The use of this epoxy emulsion:
The preparation of bi-component aqueous epoxy resin paint film
First component: 751 solidifying agent second components: aqueous epoxy resin emulsion
The first component: the mixed of second component=1: 3.5 (weight ratio), stir by hand, be coated on the iron plate with brush.Form transparent film after the moisture evaporation, the performance of filming is:
| Project | Performance |
| Time of drying, surface drying/h did solid work/h pencil hardness wear resistance (750g/300r)/g ultimate compression strength/(Nmm -2) water tolerance (48h) alkali resistance (and 10%NaOH, 48h) acid resistance (10%HCl, 48h) oil-proofness (machine oil, 30d) | 1.5 17 1H＜0.02 50 no change no change no change no change |
Embodiment 3
(1) preparation of New-type emulsifier
On four neck flasks, be equipped with whipping appts, thermometer and towards nitrogen conduit, flask heats in water-bath, 100g tween 20 and 63g (0.2772mol epoxy group(ing)) epoxy resin E-44 (oxirane value is 0.44mol/100g) are added flask, feed the nitrogen excluding air, be heated to 70 ℃ then, add the 2.5g boron trifluoride diethyl etherate again, temperature of reaction system rises.Control reaction temperature is 80 ℃, and sustained reaction made New-type emulsifier in 7 hours.
(2) preparation of epoxy resin latex
In the 800ml beaker, add 115gE-44 Resins, epoxy, start dispersion machine and stir at a slow speed, add 8.05g butyl glycidyl ethers.After Resins, epoxy dissolves fully, add New-type emulsifier, 0.6g sodium lauryl sulphate and the 0.5g defoamer of 10.35g preparation again, fully dispersed with stirring.
Progressively add 202g distilled water under high-speed stirring, descend suddenly up to the viscosity of system, this moment, system was the oil-in-water system from the water-in-oil system transition, and phase reversion has taken place, and continued high-speed stirring and made the stable epoxy resin latex of oyster white.
Solid content: 40%
Viscosity: about 510mPas
Epoxy equivalent (weight): 482
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The use of this epoxy emulsion:
The preparation of bi-component aqueous epoxy resin paint film
First component: 751 solidifying agent second components: aqueous epoxy resin emulsion
The first component: the mixed of second component=1: 3.5 (weight ratio), stir by hand, be coated on the iron plate with brush.Form transparent film after the moisture evaporation, the performance of filming is:
| Project | Performance |
| Time of drying, surface drying/h did solid work/h pencil hardness wear resistance (750g/300r)/g ultimate compression strength/(Nmm -2) water tolerance (48h) alkali resistance (and 10%NaOH, 48h) acid resistance (10%HCl, 48h) oil-proofness (machine oil, 30d) | 1.5 17 1H＜0.02 50 no change no change no change no change |
Embodiment 4
(1) preparation of New-type emulsifier
On four neck flasks, be equipped with whipping appts, thermometer and towards nitrogen conduit, flask heats in water-bath, (oxirane value is 0.2mol/100g with 120g tween-80 and 51g (0.102mol epoxy group(ing)) Resins, epoxy E-20,) the adding flask, feed the nitrogen excluding air, be heated to 70 ℃ then, add the 0.51g boron trifluoride diethyl etherate again, temperature of reaction system rises.Control reaction temperature is 110 ℃, and sustained reaction made New-type emulsifier in 6 hours.
(2) preparation of epoxy resin latex
In the 800ml beaker, add 180gE-20 Resins, epoxy, start dispersion machine and stir at a slow speed, add 25.2g butyl glycidyl ethers.After Resins, epoxy dissolves fully, add 9g New-type emulsifier, 0.486g sodium lauryl sulphate and 0.6g defoamer again, fully dispersed with stirring.
Progressively add 200g distilled water under high-speed stirring, descend suddenly up to the viscosity of system, this moment, system was the oil-in-water system from the water-in-oil system transition, and phase reversion has taken place, and continued high-speed stirring about 15 minutes, made the stable epoxy resin latex of oyster white.
Solid content: 52%
Viscosity: about 417mPas
Epoxy equivalent (weight): 501
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
(3) preparation of bi-component aqueous epoxy resin paint film
First component: 751 solidifying agent second components: aqueous epoxy resin emulsion
The first component: the mixed of second component=1: 3.5 (weight ratio), stir by hand, be coated on the iron plate with brush.Form transparent film after the moisture evaporation, the performance of filming is:
| Project | Performance |
| Time of drying, surface drying/h did solid work/h pencil hardness wear resistance (750g/300r)/g ultimate compression strength/(Nmm -2) water tolerance (48h) alkali resistance (and 10%NaOH, 48h) acid resistance (10%HCl, 48h) oil-proofness (machine oil, 30d) | 1.5 17 1H＜0.02 50 no change no change no change no change |
Embodiment 5
(1) preparation of New-type emulsifier
On four neck flasks, be equipped with whipping appts, thermometer and towards nitrogen conduit, flask heats in water-bath, 100g tween 20 and 63g (0.2772mol epoxy group(ing)) epoxy resin E-44 (oxirane value is 0.44mol/100g) are added flask, feed the nitrogen excluding air, be heated to 70 ℃ then, add the 2.5g boron trifluoride diethyl etherate again, temperature of reaction system rises.Control reaction temperature is 80 ℃, and sustained reaction made New-type emulsifier in 7 hours.
(2) preparation of epoxy resin latex
In the 800ml beaker, add 115gE-44 Resins, epoxy, start dispersion machine and stir at a slow speed, add 5.75g butyl glycidyl ethers.After Resins, epoxy dissolves fully, add New-type emulsifier, 0.6g sodium lauryl sulphate and the 0.5g defoamer of 10.35g preparation again, fully dispersed with stirring.
Progressively add 202g distilled water under high-speed stirring, descend suddenly up to the viscosity of system, this moment, system was the oil-in-water system from the water-in-oil system transition, and phase reversion has taken place, and continued high-speed stirring and made the stable epoxy resin latex of oyster white.
Solid content: 40%
Viscosity: about 510mPas
Epoxy equivalent (weight): 496
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The use of this epoxy emulsion:
The preparation of bi-component aqueous epoxy resin paint film
First component: 751 solidifying agent second components: aqueous epoxy resin emulsion
The first component: the mixed of second component=1: 3.5 (weight ratio), stir by hand, be coated on the iron plate with brush.Moisture is waved
Form transparent film after sending out, the performance of filming is:
| Project | Performance |
| Time of drying, surface drying/h did solid work/h pencil hardness wear resistance (750g/300r)/g ultimate compression strength/(Nmm -2) water tolerance (48h) alkali resistance (and 10%NaOH, 48h) acid resistance (10%HCl, 48h) oil-proofness (machine oil, 30d) | 1.5 17 1H＜0.02 50 no change no change no change no change |
Embodiment 6
(1) preparation of New-type emulsifier
On four neck flasks, be equipped with whipping appts, thermometer and towards nitrogen conduit, flask heats in water-bath, (oxirane value is 0.2mol/100g with 120g tween-80 and 51g (0.102mol epoxy group(ing)) Resins, epoxy E-20,) the adding flask, feed the nitrogen excluding air, be heated to 70 ℃ then, add the 0.51g boron trifluoride diethyl etherate again, temperature of reaction system rises.Control reaction temperature is 110 ℃, and sustained reaction made New-type emulsifier in 6 hours.
(2) preparation of epoxy resin latex
In the 800ml beaker, add 180gE-20 Resins, epoxy, start dispersion machine and stir at a slow speed, add 18g butyl glycidyl ethers.After Resins, epoxy dissolves fully, add 9g New-type emulsifier, 0.486g sodium lauryl sulphate and 0.6g defoamer again, fully dispersed with stirring.
Progressively add 300g distilled water under high-speed stirring, descend suddenly up to the viscosity of system, this moment, system was the oil-in-water system from the water-in-oil system transition, and phase reversion has taken place, and continued high-speed stirring about 10 minutes, made the stable epoxy resin latex of oyster white.
Solid content: 41%
Viscosity: about 417mPas
Epoxy equivalent (weight): 497
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
(3) preparation of bi-component aqueous epoxy resin paint film
First component: 751 solidifying agent second components: aqueous epoxy resin emulsion
The first component: the mixed of second component=1: 3.5 (weight ratio), stir by hand, be coated on the iron plate with brush.Form transparent film after the moisture evaporation, the performance of filming is:
| Project | Performance |
| Time of drying surface drying/h | 1.5 |
| Do solid work/h pencil hardness wear resistance (750g/300r)/g ultimate compression strength/(Nmm -2) water tolerance (48h) alkali resistance (and 10%NaOH, 48h) acid resistance (10%HCl, 48h) oil-proofness (machine oil, 30d) | 17 1H＜0.02 50 no change no change no change no change |
The present invention is not limited to the technology 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 that method such as reorganization obtains, all within protection scope of the present invention.
Claims (4)
1. method for preparation of waterborne epoxy emulsion is characterized in that:
(1) ring-opening reaction takes place and prepares reaction emulsifier in tween emulsifier and bisphenol A type epoxy resin under the effect of catalyzer boron trifluoride diethyl etherate; The mol ratio of hydroxyl and epoxy group(ing) is 1 in the reaction system of tween and Resins, epoxy: 0.5-0.6: 1.1, and the boron trifluoride diethyl etherate consumption is 1～4% of a weight epoxy, and temperature of reaction is 80～110 ℃, and the reaction times is 6～7h;
(2) product and sodium lauryl sulphate uniform mixing in (1) are prepared composite emulsifier;
(3) adopt thinner that Resins, epoxy is diluted, (1) step product is added drop-wise in the Resins, epoxy, utilize the phase reversion legal system to be equipped with aqueous epoxy emulsion;
(4) in (3) product, drip water, continue to stir for some time and prepare aqueous epoxy emulsion.
2. method for preparation of waterborne epoxy emulsion as claimed in claim 1 is characterized in that described bisphenol A type epoxy resin, and oxirane value is at 0.2～0.51mol/100g.
3. method for preparation of waterborne epoxy emulsion as claimed in claim 1 is characterized in that described tween is tween 80, polysorbate60 or polysorbas20.
4. method for preparation of waterborne epoxy emulsion as claimed in claim 1 is characterized in that described sodium lauryl sulphate, and its consumption is 0.27～0.52% of a weight epoxy, and the consumption of reaction emulsifier is the 5-9% of weight epoxy.
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| CN2007100596698A CN101117390B (en) | 2007-09-18 | 2007-09-18 | Method for preparing aqueous epoxy emulsion |
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| CN2007100596698A CN101117390B (en) | 2007-09-18 | 2007-09-18 | Method for preparing aqueous epoxy emulsion |
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| CN101117390B true CN101117390B (en) | 2010-12-22 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775108B (en) * | 2010-03-26 | 2012-10-31 | 哈尔滨工业大学 | Synthesis of modified aqueous epoxy resin and method for preparing antiseptic rusty paint |
| CN102775948B (en) * | 2012-07-10 | 2014-12-03 | 亿利沙材料科技有限责任公司 | Hydrophilic epoxy resin binder and preparation method and application thereof |
| CN105001432A (en) * | 2015-07-28 | 2015-10-28 | 何肖凤 | Method for preparing water-borne epoxy resin emulsion |
| CN109181473B (en) * | 2018-08-09 | 2021-05-04 | 庆阳洲阳石油机械制造有限公司 | High-performance bi-component water-based anticorrosive paint and preparation method thereof |
| CN108865236A (en) * | 2018-08-15 | 2018-11-23 | 新疆水处理工程技术研究中心有限公司 | A kind of thick oil demulsifier and preparation method thereof |
| EP3904454B1 (en) * | 2018-12-29 | 2023-07-19 | Wanhua Chemical Group Co., Ltd. | Preparation method for emulsifier, emulsifier, aqueous epoxy resin dispersion and formulation method |
| CN110804371B (en) * | 2019-12-02 | 2021-11-19 | 苏州太湖电工新材料股份有限公司 | Self-emulsifying epoxy resin emulsion and preparation method and application thereof |
| CN112898733B (en) * | 2019-12-03 | 2023-08-11 | 南通星辰合成材料有限公司 | Water-based polyphenol type epoxy emulsion and preparation method thereof |
| CN111154379B (en) * | 2020-01-19 | 2022-03-22 | 南通大学 | Preparation method of waterborne epoxy resin emulsion containing nano wear-resistant material |
| CN116063631A (en) * | 2020-12-15 | 2023-05-05 | 苏州太湖电工新材料股份有限公司 | Preparation method of aqueous acrylic epoxy resin emulsion |
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| US6369139B1 (en) * | 1995-04-12 | 2002-04-09 | Crompton Corporation | Compositions of epoxysilane emulsion additives in waterbased reactive polymer dispersions and methods of preparation |
| CN1621425A (en) * | 2004-10-15 | 2005-06-01 | 上海市建筑科学研究院有限公司 | Self-emulsified aqueous epoxy emulsion and method for preparing same |
| CN1911920A (en) * | 2006-08-18 | 2007-02-14 | 中国科学院广州化学研究所 | 2-amino ethyl sulfonic acid modified water epoxy resin and its preparation method and water epoxy emulsion prepared from said water epoxy resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6369139B1 (en) * | 1995-04-12 | 2002-04-09 | Crompton Corporation | Compositions of epoxysilane emulsion additives in waterbased reactive polymer dispersions and methods of preparation |
| CN1621425A (en) * | 2004-10-15 | 2005-06-01 | 上海市建筑科学研究院有限公司 | Self-emulsified aqueous epoxy emulsion and method for preparing same |
| CN1911920A (en) * | 2006-08-18 | 2007-02-14 | 中国科学院广州化学研究所 | 2-amino ethyl sulfonic acid modified water epoxy resin and its preparation method and water epoxy emulsion prepared from said water epoxy resin |
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