CN101838396A - Method for preparing self-emulsifying water borne epoxy emulsion - Google Patents
Method for preparing self-emulsifying water borne epoxy emulsion Download PDFInfo
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- CN101838396A CN101838396A CN200910047801A CN200910047801A CN101838396A CN 101838396 A CN101838396 A CN 101838396A CN 200910047801 A CN200910047801 A CN 200910047801A CN 200910047801 A CN200910047801 A CN 200910047801A CN 101838396 A CN101838396 A CN 101838396A
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Abstract
The invention relates to a method for preparing a self-emulsifying water borne epoxy emulsion, which is characterized by comprising the steps of: respectively opening an epoxy ring of epoxide resin and introducing a hydrophilic group into a main chain by a two-step reaction; and preparing the self-emulsifying water borne epoxy emulsion by chain extension and grafting and self-emulsification. The obtained self-emulsifying water borne epoxy emulsion has high solid content and excellent water dispersion and processability. After the self-emulsifying water borne epoxy emulsion is cured with amino resin into a film, the paint film is flat, smooth and tough and has strong adhesive attraction, no toxicity, water resistance and excellent corrosion resistance. After being dried, the film has low shrinkage rate.
Description
Technical field
The present invention relates to a kind of preparation method of polymer water miscible liquid, specifically, relate to a kind of preparation method of self-emulsification aqueous epoxy resin emulsion, this emulsion can be used as the basic raw material of preparation water-borne coatings.
Background technology
In recent years, more and more higher for environmental protection requirement, impel coating system to develop towards high-performance, oligosaprobic direction, progressively substituting solvent based coating in the past with water-borne coatings in the coming years has become inevitable trend.Resins, epoxy is because its excellent mechanical and physical performance, all obtained using widely at aspects such as military, civilian, industrial maintenances, particularly aspect application of paints.For better replace solvents type epoxy coating system, research to water-base epoxy constantly makes progress, present modal water-base epoxy obtains by outer emulsive mode, promptly in the presence of emulsifying agent, make resin dispersion at aqueous phase with external force, but this method has itself inherent limitation: production unit is had relatively high expectations (needing high-speed dispersion equipment), and particle diameter is bigger, and stability in storage and application performance are all undesirable.
Summary of the invention
The present invention is intended to overcome some disadvantages that present aqueous epoxy resins exists, and adopts the solid epoxy of macromolecule, by the method for chemical modification, through two-step reaction, a certain amount of hydrophilic radical is incorporated on the main chain and side chain of resin.Make resin itself have certain wetting ability, thereby can well be dispersed in the water.Zhi Bei aqueous epoxy emulsion by this method, particle diameter is less, the solid content height, stability in storage is good, and paint film adhesion is strong, the shrinking percentage behind the dried coating film is low.
The preparation method of a kind of self-emulsified aqueous epoxy emulsion of the present invention, it is characterized in that the oxirane ring of Resins, epoxy being opened and on main chain, introduced hydrophilic radical respectively by two-step reaction, by chain extension grafting and self-emulsifying, the preparation self-emulsified aqueous epoxy emulsion, in weight part, the overall recipe ingredient of preparation feedback comprises:
Solid bisphenol A epoxy resin 20-40
Peroxide catalyst A 0.5-2.0
Vinylformic acid 2.3-2.4
Vinylbenzene 3.3-3.4
Acrylic ester compound 4.0-16.0
Butyl glycol ether 12.6-21.6
Ammoniacal liquor or aminated compounds 1.0-3.0
Phosphoric acid 0.03-0.3
Deionized water 18-26.
The entire reaction general formula is following, and (in the formula, A represents initiator; M represents acrylic monomer):
In above-mentioned prescription, described solid bisphenol A epoxy resin is selected from one or more among E-20, E-12, E-06 and the E-03.Described peroxide catalyst is selected from di-t-butyl peroxide, peroxidized t-butyl perbenzoate, peroxidation-3,3, the 5-tri-methyl hexanoic acid tert-butyl ester, peroxide acid tert-amyl acetate, peroxidation acetic acid tert-pentyl ester and 3, one or more in two (tert-pentyl peroxide) ethyl butyrates of 3-.Described acrylic ester compound is selected from one or more in allyl acrylate (AA), methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA) and the butyl acrylate (BA).Described aminated compounds is selected from one or more in dimethylethanolamine and the trolamine.
The preparation method of described self-emulsified aqueous epoxy emulsion comprises the following steps:
The first step: preparation aqueous epoxy resins.
(1) solid bisphenol A epoxy resin, butyl glycol ether and phosphoric acid are carried out addition reaction, temperature of reaction is 90～110 ℃, and the reaction times is 3～5 hours;
(2) adopt reaction product, vinylformic acid, vinylbenzene, acrylic ester compound, butyl glycol ether and ammoniacal liquor or the aminated compounds of (1) under the effect of peroxide catalyst A, to carry out addition reaction, temperature of reaction is 135～155 ℃, reaction times is 2～4 hours, prepares aqueous epoxy resins;
Butyl glycol ether consumption in the step (1) accounts for the 85-90 weight % of its total amount, and the butyl glycol ether consumption in the step (2) accounts for the 10-15 weight % of its total amount,
Second step: the self-emulsifying reaction, deionized water is added in the aqueous epoxy resins that is generated by (2), obtain aqueous epoxy emulsion.
Advantage according to the self-emulsified aqueous epoxy emulsion of the inventive method preparation is, high solids content is arranged, excellent water dispersible and processibility, behind the aminoresin film-forming, paint film is smooth, smooth, tough and tensile, strong adhesion, nontoxic, water-fast, antiseptic property is good, the dried coating film post-shrinkage ratio is low.
Embodiment
Come the present invention is further described in detail with embodiment below, but the present invention is in no way limited to these embodiment.
Embodiment 1
The first step: preparation aqueous epoxy resins.
(1) solid epoxy E-03 240g, butyl glycol ether 153g and phosphoric acid 2g are added in the four-hole reaction flask, be heated to 90 ℃, stir, react after 3.5 hours, stopped reaction, stand-by.
(2) with vinylformic acid 23g, vinylbenzene 32g, methyl methacrylate 32g, butyl glycol ether 22g, butyl acrylate 11g, peroxidized t-butyl perbenzoate 7g and N, N-dimethylethanolamine 23g is placed on and drips in the pipe, and is stand-by.
The reaction product 395g of (1) is added in the four-hole reaction flask, then drip the reaction product 151g of (2) in this reaction flask, control reaction temperature is no more than 160 ℃, reacts after 3.5 hours, is cooled to 70 ℃, obtains aqueous epoxy resins.
Second step: self-emulsifying reaction.Drip deionized water 260g in above-mentioned product water epoxy resin, finish the self-emulsifying reaction, obtain aqueous epoxy emulsion, its median size is 0.100 μ m.
Embodiment 2
The first step: preparation aqueous epoxy resins.
(1) solid epoxy E-1212g, butyl glycol ether 7.5g and phosphoric acid 0.1g are added in the four-hole reaction flask, be heated to 90 ℃, stir, react after 3.5 hours, stopped reaction, stand-by.
(2) with vinylformic acid 1.2g, vinylbenzene 1.6g, methyl methacrylate 1.6g, butyl glycol ether 1.1g, butyl acrylate 0.5g, peroxidized t-butyl perbenzoate 0.4g and N, N-dimethylethanolamine 1.2g is placed on and drips in the pipe, and is stand-by.
The reaction product 20.5g of (1) is added in the four-hole reaction flask, then drip the reaction product 7.6g of (2) in this reaction flask, control reaction temperature is no more than 160 ℃, reacts after 3.5 hours, is cooled to 70 ℃, obtains aqueous epoxy resins.
Second step: the self-emulsifying reaction, in above-mentioned final product, drip deionized water 9g, finish the self-emulsifying reaction, obtain aqueous epoxy emulsion, its median size is 0.100 μ m.
Claims (6)
1. the preparation method of a self-emulsified aqueous epoxy emulsion, it is characterized in that the oxirane ring of Resins, epoxy being opened and on main chain, introduced hydrophilic radical respectively by two-step reaction, by chain extension grafting and self-emulsifying, the preparation self-emulsified aqueous epoxy emulsion, in weight part, the overall recipe ingredient of preparation feedback comprises:
Solid bisphenol A epoxy resin 20-40
Peroxide catalyst A 0.5-2.0
Vinylformic acid 2.3-2.4
Vinylbenzene 3.3-3.4
Acrylic ester compound 4.0-16.0
Butyl glycol ether 12.6-21.6
Ammoniacal liquor or aminated compounds 1.0-3.0
Phosphoric acid 0.03-0.3
Deionized water 18-26.
2. the preparation method of self-emulsified aqueous epoxy emulsion according to claim 1 is characterized in that described solid bisphenol A epoxy resin is selected from one or more among E-20, E-12, E-06 and the E-03.
3. the preparation method of self-emulsified aqueous epoxy emulsion according to claim 1, it is characterized in that described peroxide catalyst A is selected from di-t-butyl peroxide, peroxidized t-butyl perbenzoate, peroxidation-3,3, the 5-tri-methyl hexanoic acid tert-butyl ester, peroxide acid tert-amyl acetate, peroxidation acetic acid tert-pentyl ester and 3, one or more in two (tert-pentyl peroxide) ethyl butyrates of 3-.
4. the preparation method of self-emulsified aqueous epoxy emulsion according to claim 1 is characterized in that described acrylic ester compound is selected from one or more in allyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate and the butyl acrylate.
5. the preparation method of self-emulsified aqueous epoxy emulsion according to claim 1 is characterized in that described aminated compounds is selected from one or more in dimethylethanolamine and the trolamine.
6. the preparation method of self-emulsified aqueous epoxy emulsion according to claim 1 is characterized in that described preparation method comprises the following steps:
By the composition proportioning of the described self-emulsified aqueous epoxy emulsion of claim 1,
The first step: preparation aqueous epoxy resins.
(1) solid bisphenol A epoxy resin, butyl glycol ether and phosphoric acid are carried out addition reaction, temperature of reaction is 90～110 ℃, and the reaction times is 3～5 hours;
(2) adopt reaction product, vinylformic acid, vinylbenzene, acrylic ester compound, butyl glycol ether and ammoniacal liquor or the aminated compounds of (1) under the effect of peroxide catalyst A, to carry out addition reaction, temperature of reaction is 135～155 ℃, reaction times is 2～4 hours, prepares aqueous epoxy resins;
Butyl glycol ether consumption in the step (1) accounts for the 85-90 weight % of its total amount, and the butyl glycol ether consumption in the step (2) accounts for the 10-15 weight % of its total amount,
Second step: self-emulsifying reaction.Deionized water is added in the aqueous epoxy resins that is generated by (2), obtain aqueous epoxy emulsion.
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| CN200910047801A CN101838396A (en) | 2009-03-19 | 2009-03-19 | Method for preparing self-emulsifying water borne epoxy emulsion |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146248A (en) * | 2011-04-08 | 2011-08-10 | 广州慧谷化学有限公司 | Acid resistance and high temperature resistance antiseptic waterborne coating for inner wall of pop can |
| CN102964535A (en) * | 2012-11-22 | 2013-03-13 | 上海涂料有限公司技术中心 | Preparation method and application of composite emulsion for alkali-resistant wine label coating |
| CN104356881A (en) * | 2014-12-10 | 2015-02-18 | 李永志 | Hydrophilic anti-mildew coating, |
| CN104356725A (en) * | 2014-12-10 | 2015-02-18 | 李永志 | Hydrophilic corrosion-resistant coating |
| WO2015058683A1 (en) * | 2013-10-21 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Water-based anti-corrosion resin |
| CN106118332A (en) * | 2016-07-19 | 2016-11-16 | 雷春生 | A kind of preparation method suppressing carbon dioxide corrosion coating |
| CN106634400A (en) * | 2015-10-31 | 2017-05-10 | 丹阳市海信涂料化工厂 | Technological method of preparation of self-emulsified waterborne epoxy coating |
| CN109206633A (en) * | 2018-08-10 | 2019-01-15 | 江苏宏源机电科技有限公司 | A kind of preparation method of aqueous epoxy emulsion |
-
2009
- 2009-03-19 CN CN200910047801A patent/CN101838396A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146248A (en) * | 2011-04-08 | 2011-08-10 | 广州慧谷化学有限公司 | Acid resistance and high temperature resistance antiseptic waterborne coating for inner wall of pop can |
| CN102146248B (en) * | 2011-04-08 | 2013-01-30 | 广州慧谷化学有限公司 | Acid resistance and high temperature resistance antiseptic waterborne coating for inner wall of pop can |
| CN102964535A (en) * | 2012-11-22 | 2013-03-13 | 上海涂料有限公司技术中心 | Preparation method and application of composite emulsion for alkali-resistant wine label coating |
| CN102964535B (en) * | 2012-11-22 | 2014-12-10 | 上海涂料有限公司技术中心 | Preparation method and application of composite emulsion for alkali-resistant wine label coating |
| WO2015058683A1 (en) * | 2013-10-21 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Water-based anti-corrosion resin |
| CN104356881A (en) * | 2014-12-10 | 2015-02-18 | 李永志 | Hydrophilic anti-mildew coating, |
| CN104356725A (en) * | 2014-12-10 | 2015-02-18 | 李永志 | Hydrophilic corrosion-resistant coating |
| CN106634400A (en) * | 2015-10-31 | 2017-05-10 | 丹阳市海信涂料化工厂 | Technological method of preparation of self-emulsified waterborne epoxy coating |
| CN106118332A (en) * | 2016-07-19 | 2016-11-16 | 雷春生 | A kind of preparation method suppressing carbon dioxide corrosion coating |
| CN106118332B (en) * | 2016-07-19 | 2018-05-01 | 河北晨阳工贸集团有限公司 | A kind of preparation method for suppressing carbon dioxide corrosion coating |
| CN109206633A (en) * | 2018-08-10 | 2019-01-15 | 江苏宏源机电科技有限公司 | A kind of preparation method of aqueous epoxy emulsion |
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Application publication date: 20100922 |