CN104311797A - Preparation method of water-based epoxy resin emulsion - Google Patents
Preparation method of water-based epoxy resin emulsion Download PDFInfo
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- CN104311797A CN104311797A CN201410579407.4A CN201410579407A CN104311797A CN 104311797 A CN104311797 A CN 104311797A CN 201410579407 A CN201410579407 A CN 201410579407A CN 104311797 A CN104311797 A CN 104311797A
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Abstract
The invention relates to a preparation method of water-based epoxy resin emulsion. The preparation method comprises the following steps of (1) preparing chemical modified epoxy resin: heating epoxy resin pre-dissolved by adopting n-butyl alcohol to 60-80 DEG C, dripping lactic acid and a catalyst under the stirring condition, slowly raising the temperature to 80-100 DEG C after the dripping is finished, reacting for 2-4 hours, cooling to 65-85 DEG C, and adding adipic acid to obtain modified epoxy resin; (2) preparing the water-based epoxy resin: under continuous stirring at the temperature of 65-70 DEG C, dripping triethanolamine into the modified epoxy resin, carrying out neutralization and salification on carboxyl groups, adding deionized water, and discharging to obtain the water-based epoxy resin. The preparation method has the advantages that the type and the used amount of a modifying agent are optimized, and bisphenol A-type epoxy resin is chemically modified by adopting environment-friendly chemical materials with wide source, namely lactic acid and adipic acid, are adopted as the modifying agents; the preparation process is simple, the materials are environmental friendly and are wide in source; the preparation method is suitable for large-scale production is achieved, the cost is reduced, and the prepared water-based epoxy resin is emulsion with a certain epoxy value and particle diameter and stable water dispersibility.
Description
Technical field
The present invention relates to a kind of preparation method of aqueous epoxy resin emulsion, belong to aqueous epoxy resins field.
Background technology
Epoxy resin (Epoxy Resin) refers in a molecular structure, containing two or more epoxide groups, and under suitable chemical reagent and suitable condition, can form the compound general name of three-dimensional cross-linked netted cured article.Epoxy resin, as one of three large interchangeable heat thermosetting resins, has excellent processing performance, mechanical property and physicals, is widely used in the fields such as mechano-electronic, aerospace, traffic and building.In current worldwide, the epoxy resin of 40% is used for coating, and most of epoxy resin is all water insoluble, so epoxypaint major part conventional is at present all solvent type.And the shortcomings such as organic solvent is inflammable, explosive, poisonous, contaminate environment bring inconvenience to accumulating and construction.Along with the progress of society and people to environmental quality requirement improve constantly and various countries' environmental protection standard, regulation constantly perfect, the environmental friendliness green chemical and the material that do not contain or contain less volatile organic matter (VOC) and air noxious pollutant (HAP) are subject to extensive concern, the aqueous epoxy resins of environment-friendly type just arises at the historic moment, and be more and more subject to people's attention, developed rapidly.
It is the stable dispersion of joining in the dispersion medium of external phase that aqueous epoxy resins (waterborne epoxy resin, WER) refers to that epoxy resin is dispersed in the form of particulate or drop with water.Current preparation Water-borne modification epoxy resin mainly contains following several method: additional emulsifying agent method, chemic modified method and solidifying agent emulsion process etc.Chemic modified method is also referred to as self-emulsification, utilize the hydrogen isoreactivity reactive group on the epoxy group(ing) of epoxy resin, secondary hydroxyl and methyne, pass through chemical reaction, other hydrophilic radical or segment (amino, carboxyl, ester group etc.) are incorporated in epoxy molecule skeleton, make it have the amphipathic characteristic of hydrophilic and oleophilic, thus there is the performance of surfactant-like, improve its water-dispersion performance.Chemic modified method can be divided into again amido reaction method, carboxyl reaction method and Graft Method.
But the kind of properties-correcting agent is a lot, the water-soluble epoxy resin properties-correcting agent on market is due to aspects such as formula and complete processings, and emulsion glossiness is bad, and opalescence is not strong.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of aqueous epoxy resin emulsion, its technological process is simple, raw material environmental protection and wide material sources, is suitable for scale operation, the aqueous epoxy resins of preparation has certain oxirane value and particle diameter, has the emulsion of superior water dispersibility.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of preparation method of aqueous epoxy resin emulsion, comprises the following steps:
Step (1) preparative chemistry modified epoxy: be heated to 60 ~ 80 DEG C by adopting propyl carbinol epoxy resin solvent in advance, drip lactic acid and catalyzer under agitation, after dropwising, slowly be warming up to 80 ~ 100 DEG C, 65 ~ 85 DEG C are cooled to after reaction 2 ~ 4h, add hexanodioic acid and be obtained by reacting modified epoxy, molar ratio 1:0.2 ~ 0.4 of the epoxy group(ing) in its epoxy resin and lactic acid, described hexanodioic acid molar weight is 1.5 times of the molar weight of lactic acid;
Step (2) prepares aqueous epoxy resins: under 50 ~ 70 DEG C of Keep agitation, in modified epoxy, be added dropwise to trolamine, and in carrying out carboxyl and salify, add deionized water, discharging obtains aqueous epoxy resin emulsion.
Epoxy group(ing) in its epoxy resin of the present invention and molar ratio 1:0.2 ~ 0.4 of lactic acid, the molar ratio 1:0.3 of the epoxy group(ing) in preferred epoxy and lactic acid, described hexanodioic acid molar weight is 1.5 times of the molar weight of lactic acid.The aqueous epoxy resins prepared within the scope of this at epoxy resin and lactic acid and hexanodioic acid has superior water dispersible and glossiness, not only environmental protection in later stage use procedure, low irritant smell, and is easy to application.
Lactic acid (2 hydroxy propanoic acid) is extensively present in occurring in nature, is a kind of organic acid of having many uses, is mainly used in the industries such as food, medicine, makeup, weaving, leather and plastic optical fibre.Lactic acid can be used as the starting raw material of poly(lactic acid), produces the biological degradation plastics of a new generation.
Hexanodioic acid (adipic acid) is a kind of industrial significant di-carboxylic acid, and all play an important role in Chemical Manufacture, organic synthesis industry, medicine, lubricant manufacture etc., output shelter has the second in di-carboxylic acid.In Polymer Industry, hexanodioic acid is mainly used as the raw material of nylon66 fiber and engineering plastics, also for the production of various esters product, is also used as the raw material etc. of polyurethane elastomer.Pure lactic acid does not have toxicity, and its esters is also nontoxic so long as not heavy metallic salt, and hexanodioic acid has a little hormesis to eyes, skin and mucous membrane etc.
The invention has the beneficial effects as follows: the present invention optimizes kind and the consumption of properties-correcting agent, using originate widely environmental protective type chemical material acid and hexanodioic acid as properties-correcting agent, chemical modification bisphenol A type epoxy resin, preparation technology is simple, raw material environmental protection and wide material sources, be suitable for scale operation, reduce costs, the aqueous epoxy resins prepared has certain oxirane value and particle diameter, and has excellent water dispersible and the aqueous epoxy resin emulsion of stability.
On the basis of technique scheme, the present invention can also do following improvement.
The preparation method of a kind of aqueous epoxy resin emulsion of the present invention, more preferably described catalyzer is that N, N-diη-propyl methane amide is or/and N, N-diethylformamide.
The preparation method of a kind of aqueous epoxy resin emulsion of the present invention, more preferably, described catalyst levels is for epoxy resin massfraction 0.3 ~ 0.6%, is preferably 0.5%.Use N, N-diη-propyl methane amide and N, N-diethylformamide, N, the ratio of N-diη-propyl methane amide and N, N-diethylformamide is preferably 1:1, and not only consumption is few to use the catalyst combination of this proportional range, and in contrast to former catalyzer and substantially increase speed of response, energy-efficient.
The preparation method of a kind of aqueous epoxy resin emulsion of the present invention, more preferably, described epoxy resin is the bisphenol A type epoxy resin of low oxirane value, comprises E-20, E-14, E-12 and E-10 model.
The reaction mechanism of foundation of the present invention is: introduce hydrophilic radical-COOH with epoxy group(ing) generation ring-opening reaction a small amount of in a certain amount of lactic acid and hexanodioic acid and bisphenol A type epoxy resin, makes to retain epoxy group(ing) as much as possible in each molecular resin.Water-soluble or the water dispersible that on the one hand resin possessed, remain again a considerable amount of epoxy group(ing) on the other hand, the wetting ability of modified resin and reactive behavior is made to reach rational balance, thus overcome method of modifying in the past and be difficult to the contradiction that both get both, there is excellent using value, shown in the mechanism following formula (1) of concrete reaction.
R representative in formula (1):
Aqueous epoxy resin emulsion prepared by the present invention is for preparing aqueous epoxide resin paint, and this coating has the following advantages: using water as dispersion medium, and the content not containing organic solvent or volatile organic compounds is lower, non-environmental-pollution; Good operation performance, service tool directly can clean with water, easy to operate, safety; To most of base material, there is good sticking power, and can with cement or sand-cement slurry with the use of; Can solidify in room temperature and moist environment, have rational set time, and ensure higher cross-linking density.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of epoxy resin and modified epoxy;
Embodiment
Be described principle of the present invention and feature below in conjunction with following examples, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
The preparation method of a kind of aqueous epoxy resin emulsion of the present invention, comprise the following steps: step 1: chemical modification epoxy resin: agitator is being housed, reflux exchanger, dropping funnel, in the 250ml four-hole boiling flask of thermometer, add with 20mL propyl carbinol bisphenol A type epoxy resin (E-20) 50g solvent in advance, slowly be warming up to 70 DEG C, take the N of a certain amount of lactic acid and 0.25g, the mixing solutions of N-diη-propyl methane amide is in constant pressure funnel, slowly flask is added dropwise under uniform stirring and constant temperature, about 0.5h dropwises, slowly be warmed up to 90 DEG C, 70 DEG C are cooled to after reaction 3h, add hexanodioic acid reaction 50min.Wherein: molar ratio 1:0.3 ~ 0.4 of the epoxy group(ing) in epoxy resin and lactic acid, described hexanodioic acid molar weight is 1.5 times of the molar weight of lactic acid;
Step 2: the preparation of aqueous epoxy resins: under 55 DEG C of Keep agitation conditions, adds trolamine (dropping to degree of neutralization 100%) in modified resin, in and salify after, add appropriate amount of deionized water, discharging obtains aqueous epoxy resins.
The technical indicator of aqueous epoxy resins prepared by embodiment 1:
Aqueous epoxy resins outward appearance: the blueing light emulsion of stable uniform
Oxirane value: 0.357
Aqueous dispersions particle diameter: 210nm
Embodiment 2
The preparation method of a kind of aqueous epoxy resin emulsion of the present invention, comprise the following steps: step 1: chemical modification epoxy resin: agitator is being housed, reflux exchanger, dropping funnel, in the 250ml four-hole boiling flask of thermometer, add with 20mL propyl carbinol bisphenol A type epoxy resin (E-14) 50g solvent in advance, slowly be warming up to 70 DEG C, take the composite catalyst (N of a certain amount of lactic acid and 0.15g, N-diη-propyl methane amide and N, N-diethylformamide configures with the mol ratio of 1:1) mixing solutions in constant pressure funnel, slowly flask is added dropwise under uniform stirring and constant temperature, about 0.5h dropwises, slowly be warmed up to 90 DEG C, 75 DEG C are cooled to after reaction 3h, add hexanodioic acid reaction 60min.Molar ratio 1:0.3 ~ 0.4 of the epoxy group(ing) in epoxy resin and lactic acid, described hexanodioic acid molar weight is 1.5 times of the molar weight of lactic acid;
Step 2: the preparation of aqueous epoxy resins: under 60 DEG C of Keep agitation, adds trolamine (dropping to degree of neutralization 100%) in modified resin, in and salify after, add appropriate amount of deionized water, discharging obtains aqueous epoxy resins.
The technical indicator of aqueous epoxy resins prepared by embodiment 2:
Aqueous epoxy resins outward appearance: the faint yellow emulsion of stable uniform
Oxirane value: 0.350
Aqueous dispersions particle diameter: 135nm
Embodiment 3
The preparation method of a kind of aqueous epoxy resin emulsion of the present invention, comprise the following steps: step 1: chemical modification epoxy resin: agitator is being housed, reflux exchanger, dropping funnel, in the 250ml four-hole boiling flask of thermometer, add with 20mL propyl carbinol bisphenol A type epoxy resin (E-10) 50g solvent in advance, slowly be warming up to 70 DEG C, take the N of a certain amount of lactic acid and 0.25g, the mixing solutions of N-diethylformamide is in constant pressure funnel, slowly flask is added dropwise under uniform stirring and constant temperature, about 0.5h dropwises, slowly be warmed up to 90 DEG C, 80 DEG C are cooled to after reaction 3h, add hexanodioic acid reaction 70min.Molar ratio 1:0.3 ~ 0.4 of the epoxy group(ing) in epoxy resin and lactic acid, described hexanodioic acid molar weight is 1.5 times of the molar weight of lactic acid;
Step 2: the preparation of aqueous epoxy resins: under 65 DEG C of Keep agitation, adds trolamine (dropping to degree of neutralization 100%) in modified resin, in and salify after, add appropriate amount of deionized water, discharging obtains aqueous epoxy resins.
The technical indicator of aqueous epoxy resins prepared by embodiment 3:
Aqueous epoxy resins outward appearance: the faint yellow emulsion of stable uniform
Oxirane value: 0.347
Aqueous dispersions particle diameter: 98nm
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a preparation method for aqueous epoxy resin emulsion, is characterized in that, comprises the following steps:
Step (1) preparative chemistry modified epoxy: be heated to 60 ~ 80 DEG C by adopting propyl carbinol epoxy resin solvent in advance, drip lactic acid and catalyzer under agitation, after dropwising, slowly be warming up to 80 ~ 100 DEG C, 65 ~ 85 DEG C are cooled to after reaction 2 ~ 4h, add hexanodioic acid and be obtained by reacting modified epoxy, molar ratio 1:0.2 ~ 0.4 of the epoxy group(ing) in its epoxy resin and lactic acid, described hexanodioic acid molar weight is 1.5 times of the molar weight of lactic acid;
Step (2), under 50 ~ 70 DEG C of Keep agitation, is added dropwise to trolamine in modified epoxy, and in carrying out carboxyl and salify, add deionized water, discharging obtains aqueous epoxy resins, and structural formula is shown below:
2. the preparation method of a kind of aqueous epoxy resin emulsion according to claim 1, it is characterized in that, described catalyzer is that N, N-diη-propyl methane amide is or/and N, N-diethylformamide.
3. the preparation method of a kind of aqueous epoxy resin emulsion according to claim 2, is characterized in that, N, N-diη-propyl methane amide and N, N-diethylformamide used in combination time, N, the mass ratio of N-diη-propyl methane amide and N, N-diethylformamide is 1:1.
4. a kind of preparation method of aqueous epoxy resin emulsion according to claim 1 or 2, it is characterized in that, the molar ratio 1:0.3 of the epoxy group(ing) in its epoxy resin and lactic acid, described hexanodioic acid molar weight is 1.5 times of the molar weight of lactic acid.
5. the preparation method of a kind of aqueous epoxy resin emulsion according to claim 2, it is characterized in that, described catalyst levels is 0.3 ~ 0.6% of epoxy resin massfraction.
6. a kind of preparation method of aqueous epoxy resin emulsion according to claim 1 or 2, it is characterized in that, described epoxy resin is the bisphenol A type epoxy resin of low oxirane value, comprises E-20, E-14, E-12 and E-10 model.
7. the purposes of aqueous epoxy resins in coating prepared of any one of Claims 1-4.
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| CN105017506A (en) * | 2015-07-21 | 2015-11-04 | 厦门双瑞船舶涂料有限公司 | Preparation method of modified epoxy resin |
| CN107761392A (en) * | 2017-11-10 | 2018-03-06 | 安徽翰联纺织有限公司 | Y3+The afterfinish method of the high-strength water process fabric of base, final finishing mechanism |
| CN109280341A (en) * | 2018-09-21 | 2019-01-29 | 佛山皖和新能源科技有限公司 | A kind of preparation method of epoxy resin base electromagnetic screen material |
| CN112029375A (en) * | 2020-08-17 | 2020-12-04 | 山东国铭球墨铸管科技有限公司 | Inorganic-organic hybrid polymer anticorrosive paint and preparation method thereof |
| CN113061232A (en) * | 2021-04-07 | 2021-07-02 | 安庆瑞泰化工有限公司 | Biomass polyacid modified epoxy emulsion and preparation method thereof |
| CN114198052A (en) * | 2021-11-08 | 2022-03-18 | 中国石油大学(华东) | Method for improving cementing strength of marine natural gas hydrate formation well cementation two-interface |
| CN117701112A (en) * | 2024-01-23 | 2024-03-15 | 中建国际工程有限公司 | Water-based building anti-corrosion coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017506A (en) * | 2015-07-21 | 2015-11-04 | 厦门双瑞船舶涂料有限公司 | Preparation method of modified epoxy resin |
| CN107761392A (en) * | 2017-11-10 | 2018-03-06 | 安徽翰联纺织有限公司 | Y3+The afterfinish method of the high-strength water process fabric of base, final finishing mechanism |
| CN109280341A (en) * | 2018-09-21 | 2019-01-29 | 佛山皖和新能源科技有限公司 | A kind of preparation method of epoxy resin base electromagnetic screen material |
| CN112029375A (en) * | 2020-08-17 | 2020-12-04 | 山东国铭球墨铸管科技有限公司 | Inorganic-organic hybrid polymer anticorrosive paint and preparation method thereof |
| CN113061232A (en) * | 2021-04-07 | 2021-07-02 | 安庆瑞泰化工有限公司 | Biomass polyacid modified epoxy emulsion and preparation method thereof |
| CN114198052A (en) * | 2021-11-08 | 2022-03-18 | 中国石油大学(华东) | Method for improving cementing strength of marine natural gas hydrate formation well cementation two-interface |
| CN114198052B (en) * | 2021-11-08 | 2024-05-28 | 中国石油大学(华东) | Method for improving cementing strength of two interfaces of marine natural gas hydrate stratum well cementation |
| CN117701112A (en) * | 2024-01-23 | 2024-03-15 | 中建国际工程有限公司 | Water-based building anti-corrosion coating and preparation method thereof |
| CN117701112B (en) * | 2024-01-23 | 2024-05-07 | 中建国际工程有限公司 | Water-based building anti-corrosion coating and preparation method thereof |
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Application publication date: 20150128 |