CN101177479B - Method for preparing self-emulsification aqueous epoxy resin emulsion - Google Patents
Method for preparing self-emulsification aqueous epoxy resin emulsion Download PDFInfo
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Abstract
The invention relates to a method for preparing self-emulsifying aqueous epoxy resin emulsion, which is characterized in that the emulsion is made through the following two steps: (1) introducing hydrophilic groups to both ends of the main chain and the side chain through chain extending and grafting reaction to form aqueous epoxy resin; (2) Adding water to the produced aqueous epoxy resin and aqueous epoxy resin emulsion is obtained through self-emulsifying reaction. The self-emulsifying aqueous epoxy resin emulsion has excellent water dispersibility and processability. After film-forming by the firming agent, the self-emulsifying aqueous epoxy resin emulsion has excellent decoration effect and certain flexibility.
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, along with improving constantly of science and technology development and people's living standard, more and more higher for environmental protection requirement, relevant rules are strict day by day, corresponding therewith, coating system just develops towards high-performance, oligosaprobic direction, and environmentally friendly water-borne coatings will progressively substitute traditional in the past solvent based coating in the coming years.Resins, epoxy has obtained using widely relating to military affairs, civilian each department of national economy because of its excellent physical and mechanical performance, particularly in the coatings industry field, uses particularly extensive.In order more effectively to substitute common solvent epoxy varnish coating, the paint field people development research of aqueous epoxy resins is constantly made progress, present modal aqueous epoxy resins 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 inherent limitation own: production unit have relatively high expectations (need high-speed dispersion equipment), and particle diameter is bigger, and stability in storage and application performance are all undesirable.
Disclose in the United States Patent (USP) 6225376 by dimethylcyclohexylamine polyoxy alkane alkene has been introduced in the Resins, epoxy main chain, formed the method for self-emulsification aqueous epoxy resin.Its shortcoming is, domesticly is not easy to obtain suitable polyoxy alkane alkene polymer.United States Patent (USP) 5655605 has been introduced polyetheramine Jeffamine 2000 is inserted with the tetramethylolmethane is in many epoxy polymers at center, forms the method for the aqueous epoxy resins of self-emulsifying.Its advantage is that this resin crosslinks density is higher, is not bisphenol A-type but shortcoming is described Resins, epoxy, so antiseptic power is not as bisphenol A-type.The method that United States Patent (USP) 5750595 proposes is, utilizes poly glycol monomethyl ether and urethane monomer to react, and by the salt acid treatment, makes residual NCO group be reduced into NH
2Group again with the bisphenol A type epoxy resin grafting, forms self-emulsification aqueous epoxy resin.The shortcoming of this invention is complicated process of preparation, needs HCl to handle, and is difficult for scale operation.United States Patent (USP) 6143809 utilizes HNO
3Hydroxyl oxygen in the poly glycol monomethyl ether is changed into carboxyl, carry out the partial esterification reaction with bisphenol A type epoxy resin again, form the aqueous epoxy resins of self-emulsifying.The shortcoming of this invention is complicated process of preparation equally, needs to use dense HNO
3Carry out oxidation, corrodibility is big.
Summary of the invention
The present invention is directed to the more above-mentioned disadvantages that exist among the present aqueous epoxy resins preparation method, use the method for low-molecular-weight liquid epoxies by chemical modification, a certain amount of hydrophilic radical is incorporated on the main chain and side chain of resin through two-step reaction, make resin itself have certain wetting ability, thereby can be dispersed in the water well.Zhi Bei aqueous epoxy resin emulsion particle diameter is less by this method, and stability in storage is better, and the snappiness of paint film also is improved simultaneously.
The present invention is achieved in that to be that the preparation method of described self-emulsification aqueous epoxy resin emulsion is characterised in that, this emulsion was made by following two steps:
(1) on the main chain two ends of Resins, epoxy and side chain, introduces hydrophilic radical by the chain extension graft reaction, make aqueous epoxy resins;
(2) admixture water in the aqueous epoxy resins of making obtains aqueous epoxy resin emulsion by the self-emulsifying reaction.
According to the present invention, relate to the preparation of described self-emulsification aqueous epoxy resin emulsion need with the starting material component comprise:
Component title consumption, quality %
Liquid bisphenol A epoxide resin 50～65
Catalyst A 0.05～0.3
Dihydroxyphenyl propane 3～11
Poly-dihydric alcohol glycidyl ether 4.1～4.5
Isocyanic ester 6.2～6.8
Polyoxyethylene glycol monoether 12.6～21.6
Catalyst B 0.03～1.0
1-Methoxy-2-propyl acetate 7～7.6
Described here bisphenol A epoxide resin is selected from a kind of among E-50, E-51, E-44, the E-42 or several; The polyoxyethylene glycol monoether is that an end of molecular chain contains active hydrogen group, and the other end does not contain the polyethyleneglycol derivative of active hydrogen group, and the group that contains reactive hydrogen of indication is selected from a kind of in hydroxyl, carboxyl, the amino here; The group that does not contain reactive hydrogen is selected from a kind of in methoxyl group, butoxy, the epoxy group(ing); Described isocyanic ester is selected from a kind of among HDI, TDI, MDI, the IPDI or several; Described catalyst A is an alkali catalyst, is selected from a kind of in benzyldimethylamine, tributylamine, the triphenylamine or several; Described catalyst B is the organic tin catalyzer, is selected from a kind of in dibutyl tin laurate, dibutyltin diacetate, the stannous octoate or several.
According to the inventive method, the concrete preparation process of aqueous epoxy resin emulsion is as follows:
The first step, in Resins, epoxy, introduce hydrophilic radical by the chain extension graft reaction, make aqueous epoxy resins, comprise following three reaction process: (1) makes bisphenol A epoxide resin, dihydroxyphenyl propane and poly-dihydric alcohol glycidyl ether carry out addition reaction under the effect of catalyst A, temperature of reaction is 140～200 ℃, and the reaction times is 3～7h; (2) make isocyanic ester and polyoxyethylene glycol monoether carry out addition reaction under the catalyst B effect, temperature of reaction is 30～80 ℃, and the reaction times is 2～8h; (3) under the catalyst B effect, control reaction temperature is 40～90 ℃, and the reaction times is 2～8h, and (1) reaction product and (2) reaction product are interacted, and makes aqueous epoxy resins;
Above-mentioned (1)～(3) reaction process is with chemical general formula schematically as follows:
In second step, the self-emulsifying reaction is about to deionized water and joins in the aqueous epoxy resins that is generated by above-mentioned (3) reaction, by the self-emulsifying reaction, obtains aqueous epoxy resin emulsion.
This self-emulsification aqueous epoxy resin emulsion has excellent water dispersible and processibility, and after reacting film-forming, demonstrate good decoration effect and have certain snappiness with solidifying agent, be a kind of splendid preparation water-borne coatings base material.
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
(1) will be heated to 90 ℃ with dihydroxyphenyl propane 11.4g after the liquid epoxies E-50 95g drying treatment, stir, adding polypropylene glycol glycidyl ether DY3601 (Vantico company product) company then produces) 7g and triphenyl phosphorus 0.17g, slowly be heated to 150 ℃, after significantly the heating phenomenon finishes near treating 160 ℃, be warming up to 190 ℃ with 1h.Slowly cool to 150 ℃ then, add 1-Methoxy-2-propyl acetate 12.8g, backflow 1h, stopped reaction, stand-by.
(2) liquid macrogol monomethyl ether 230g is added in the four-hole reaction flask, add catalyzer dibutyl tin laurate 0.2g, drip HDI100g, reaction is no more than 70 ℃.Behind the reaction 3h, stopped reaction, stand-by.
(3) the reaction product 133.4g with above-mentioned (1) adds in the four-hole reaction flask, add catalyzer dibutyl tin laurate 0.15g, in reaction flask, drip the reaction product 35.9g of above-mentioned (2), temperature of reaction is no more than 70 ℃, behind the reaction 3.5h, add deionized water 30g, be cooled to 50 ℃, add deionized water 100g again.
So the median size of the aqueous epoxy resin emulsion of preparation is 0.319 μ m, and oxirane value is 0.12.
Embodiment 2
(1) will be heated to 90 ℃ with dihydroxyphenyl propane 61.5g after the liquid epoxies E-44 600g drying treatment, stir, add polypropylene glycol glycidyl ether DY3601 (Vantico company product) 37.8g and triphenyl phosphorus 1.5g then, slowly be heated to 150 ℃, after significantly the heating phenomenon finishes near treating 160 ℃, be warming up to 190 ℃ with 1h.Slowly cool to 150 ℃ then, add 1-Methoxy-2-propyl acetate 123.7g, backflow 1h, stopped reaction, stand-by.
(2) liquid macrogol monoglycidyl ether 500g is added in the four-hole reaction flask, add catalyzer dibutyl tin laurate 0.36g, drip 134.4g, reaction is no more than 70 ℃.Behind the reaction 3h, stopped reaction, stand-by.
(3) the reaction product 321.6g with (1) adds in the four-hole reaction flask, add catalyzer dibutyl tin laurate 0.3g, drip the reaction product 110g of (2) in reaction flask, temperature of reaction is no more than 70 ℃, behind the reaction 3.5h, add deionized water 110.5g, be cooled to 50 ℃, add deionized water 156.3g again, promptly obtain aqueous epoxy resin emulsion of the present invention, median size is 0.1-0.3 μ m, and oxirane value is 0.32.
In addition, if replace Resins, epoxy E-50 with epoxy resin E-44, the polyoxyethylene glycol monoglycidyl ether replaces poly glycol monomethyl ether can improve the dryness and the cross-linking density of aqueous epoxy resin emulsion.
Claims (1)
1. the preparation method of a self-emulsification aqueous epoxy resin emulsion is characterized in that, described emulsion is made as follows:
(1) will be heated to 90 ℃ with dihydroxyphenyl propane 11.4g after the liquid epoxies E-50 95g drying treatment, stir, add polypropylene glycol Racemic glycidol mystery DY3601 7g and triphenyl phosphorus 0.17g that Vantico company produces then, slowly be heated to 150 ℃, after significantly the heating phenomenon finishes near treating 160 ℃, be warming up to 190 ℃ with 1h, slowly cool to 150 ℃ then, add 1-Methoxy-2-propyl acetate 12.8g, backflow 1h, stopped reaction, stand-by;
(2) liquid macrogol monomethyl ether 230g is added in the four-hole reaction flask, add catalyzer dibutyl tin laurate 0.2g, drip HDI100g, reaction is no more than 70 ℃, behind the reaction 3h, and stopped reaction, stand-by;
(3) the reaction product 133.4g with above-mentioned (1) adds in the four-hole reaction flask, add catalyzer dibutyl tin laurate 0.15g, in reaction flask, drip the reaction product 35.9g of above-mentioned (2), temperature of reaction is no more than 70 ℃, behind the reaction 3.5h, add deionized water 30g, be cooled to 50 ℃, add deionized water 100g again, get the product self-emulsification aqueous epoxy resin emulsion; So the median size of the emulsification aqueous epoxy resin emulsion of preparation is 0.319 μ m, and oxirane value is 0.12.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP4025649A4 (en) * | 2019-09-04 | 2023-04-19 | Rhodia Operations | Self-emulsifying epoxy composition and the coating composition prepared from the same |
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| CN101550226B (en) * | 2009-05-06 | 2011-04-27 | 上海电动工具研究所 | Method for preparing water soluble epoxy insulated resin in alkaline medium |
| CN101885832B (en) * | 2010-07-12 | 2012-10-03 | 中科院广州化灌工程有限公司 | Preparation and application of latent nonionic self-emulsifying epoxy curing agent |
| EP2415879A1 (en) * | 2010-08-06 | 2012-02-08 | LANXESS Deutschland GmbH | Compositions comprising at least one compound containing carbamoylsulfonate groups and their use as tanning agents |
| CN101955589A (en) * | 2010-08-31 | 2011-01-26 | 上海三瑞化学有限公司 | Diluent-free self-emulsifying waterborne epoxy resin emulsion and preparation method thereof |
| CN101974162B (en) * | 2010-08-31 | 2012-07-04 | 上海三瑞化学有限公司 | Low-VOC (Volatile Organic Compound) self-emulsifying solid epoxy resin water-based emulsion and preparation method thereof |
| CN102229701B (en) * | 2011-05-13 | 2012-07-04 | 湖南大学 | Non-ionic aqueous epoxy resin emulsion and its preparation method |
| CN102321252B (en) * | 2011-05-23 | 2013-07-24 | 天津大学 | Polyurea-modified self-emulsifying nano aqueous epoxy emulsion and preparation method thereof |
| CN102492360B (en) * | 2011-12-01 | 2014-01-29 | 常州光辉化工有限公司 | Solvent-free polyurethane wear-resistant terrace paint and preparation method thereof |
| CN103497617B (en) * | 2013-09-09 | 2016-04-20 | 肇庆学院 | A kind of preparation method of self-emulsifying cation epoxy emulsion |
| CN103554509B (en) * | 2013-10-28 | 2016-01-06 | 武汉工程大学 | A kind of self-emulsifiable non-ionic water-borne epoxy resin latex and preparation method thereof |
| CN104404829B (en) * | 2014-10-14 | 2017-01-25 | 陕西师范大学 | Flexibility agent and application thereof in expansion and flattening of huge historical photograph |
| CN104479136B (en) * | 2014-11-14 | 2017-02-22 | 江苏丰彩新型建材有限公司 | Nonionic epoxy emulsifier and preparation method thereof |
| CN104829846A (en) * | 2015-06-05 | 2015-08-12 | 洛阳市阳光涂料研究所 | Comb-shaped self-emulsifying nonionic type water-borne epoxy resin, water-borne epoxy resin emulsion and water-borne epoxy resin preparation method |
| CN105482094A (en) * | 2015-12-29 | 2016-04-13 | 江苏丰彩新型建材有限公司 | Non-ionic water-borne epoxy resin and preparation method thereof |
| CN105713181B (en) * | 2016-04-19 | 2018-08-14 | 江苏丰彩新型建材有限公司 | Water paint self-emulsifying epoxy resin emulsion and preparation method thereof |
| CN106589392B (en) * | 2016-12-29 | 2019-07-19 | 长兴化学工业(中国)有限公司 | A kind of highly branched chain response type liquid epoxies emulsifier and preparation method thereof |
| CN109942837A (en) * | 2019-03-19 | 2019-06-28 | 重庆鹏方路面工程技术研究院有限公司 | A kind of modified epoxy resin emulsion and preparation method thereof |
| CN111087607B (en) * | 2019-12-09 | 2022-12-06 | 湖南柯盛新材料有限公司 | Preparation method and application of self-emulsifying accelerant for epoxy colored sand |
| CN114605616B (en) * | 2020-12-03 | 2023-05-26 | 万华化学集团股份有限公司 | Quick-drying nonionic water-based epoxy curing agent, and preparation method and application thereof |
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| EP4025649A4 (en) * | 2019-09-04 | 2023-04-19 | Rhodia Operations | Self-emulsifying epoxy composition and the coating composition prepared from the same |
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