阅读说明：本技术 一种环氧树脂乳化剂及其制备方法和应用 (Epoxy resin emulsifier and preparation method and application thereof ) 是由 周江明 夏新年 李婧婧 杨聪 张琪 于 2019-10-16 设计创作，主要内容包括：本发明公开了一种环氧树脂乳化剂及其制备方法和应用,将环氧树脂加热至30～50℃后,在搅拌条件下,加入含叔胺盐的水溶液并升温至70～120℃反应,即得环氧树脂乳化剂,该环氧树脂乳化剂在室温下可以将环氧树脂乳化成稳定乳液,乳液和汉森水性固化剂6870配合制成清漆,具有表面光滑,涂膜透明,硬度高,涂膜附着力强,耐腐蚀等优点。该环氧树脂乳化剂制备方法简单,仅需一步完成,反应条件温和,易于控制,原料易得,成本低,适用于工业化生产。(The invention discloses an epoxy resin emulsifier and a preparation method and application thereof, wherein epoxy resin is heated to 30-50 ℃, and then added with aqueous solution containing tertiary amine salt under the condition of stirring and heated to 70-120 ℃ for reaction to obtain the epoxy resin emulsifier, the epoxy resin emulsifier can emulsify the epoxy resin into stable emulsion at room temperature, and the emulsion is matched with Hansen waterborne curing agent 6870 to prepare varnish, and the varnish has the advantages of smooth surface, transparent coating, high hardness, strong coating adhesion, corrosion resistance and the like. The preparation method of the epoxy resin emulsifier is simple, only needs one step, has mild reaction conditions, is easy to control, has easily obtained raw materials and low cost, and is suitable for industrial production.)

1. A preparation method of an epoxy resin emulsifier is characterized by comprising the following steps: heating the epoxy resin to 30-50 ℃, adding an aqueous solution containing tertiary amine salt under the condition of stirring, and heating to 70-120 ℃ for reaction to obtain the epoxy resin.

2. The method for preparing the epoxy resin emulsifier according to claim 1, wherein the method comprises the following steps: the epoxy resin comprises at least one of bisphenol A epoxy resin E51, bisphenol F epoxy resin YDF165, bisphenol F epoxy resin YDF170, novolac epoxy resin F51 and novolac epoxy resin F54.

3. The method for preparing the epoxy resin emulsifier according to claim 1, wherein the method comprises the following steps: the tertiary amine salt comprises at least one of trimethylamine hydrochloride, triethylamine hydrochloride and triethylamine sulfate.

4. The method for preparing an epoxy resin emulsifier according to any one of claims 1 to 3, wherein the method comprises the following steps: the mass of the tertiary amine salt is 1-50% of the mass of the epoxy resin.

5. The method for preparing the epoxy resin emulsifier according to claim 1, wherein the method comprises the following steps: the reaction time is 2-8 h.

6. The method for preparing the epoxy resin emulsifier according to claim 5, wherein the method comprises the following steps: the reaction time is 3-5 h.

7. An epoxy resin emulsifier is characterized in that: the preparation method of the compound is as described in any one of claims 1 to 6.

8. Use of the epoxy resin emulsifier according to claim 7, wherein: is applied to the preparation of waterborne epoxy resin emulsion.

9. Use of an epoxy resin emulsifier according to claim 8, characterized in that: and (3) uniformly stirring the epoxy resin emulsifier and the epoxy resin, and adding water to prepare the water-based epoxy resin emulsion.

10. Use of an epoxy resin emulsifier according to claim 9, characterized in that: the epoxy resin comprises at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and novolac epoxy resin.

11. Use of an epoxy resin emulsifier according to claim 9 or 10, characterized in that: the mass ratio of the epoxy resin to the epoxy resin emulsifier is 100: 10-100: 100.

12. use of an epoxy resin emulsifier according to claim 11, characterized in that: the mass ratio of the epoxy resin to the epoxy resin emulsifier is 100: 10-100: 50.

13. use of an epoxy resin emulsifier according to claim 9, characterized in that: the solid content of the water-based epoxy resin emulsion is 50-70%.

Technical Field

The invention relates to an epoxy resin emulsifier, in particular to an emulsifier obtained by modifying epoxy resin with tertiary amine, and also relates to a preparation method of the epoxy resin emulsifier and application of the epoxy resin emulsifier in preparation of a water-based epoxy resin emulsion, belonging to the technical field of epoxy coating.

Background

The epoxy coating has excellent mechanical property, corrosion resistance, bonding property and chemical stability, is widely applied to corrosion-resistant coatings, industrial floor coatings and the like, but the current leading products are mainly solvent type, contain organic solvents which are inflammable, explosive and volatile, cause environmental pollution when in use, and have more or less toxicity. In recent 10 years, in order to meet the requirement of environmental protection, the waterborne epoxy resin has been widely developed. For example, chinese patent application No. CN201711431253.4, application No. 2017.12.26 discloses a process for preparing a self-emulsifying aqueous epoxy synthetic emulsion, which comprises preparing an aqueous epoxy resin emulsion from polyethylene glycol, acid anhydride, 2, 4-diphenylmethane diisocyanate and epoxy resin, and has the disadvantages of multiple preparation steps, long reaction time, and the like. Chinese patent (application No. CN201810134466.9, application No. 2018.02.09) discloses a preparation method of an epoxy resin emulsifier and water-based epoxy resin, which comprises the steps of preparing the epoxy resin emulsifier and the water-based epoxy resin by using polyethylene glycol, diethanol amine, N-dimethyl ethanolamine, ethylene bromide and the epoxy resin, wherein the ethylene bromide is used as a raw material during preparation, and the raw material is volatile and toxic and is harmful to human health. At present, the domestic water-based epoxy resin is stored and transported in an emulsion state, the problems of storage and transportation stability and transportation cost exist, and compared with imported products, the water-based epoxy coating on the market at present has larger difference in performance. Therefore, the development of the room-temperature self-emulsifiable water-based epoxy resin has important practical significance and wide application prospect, and is an urgent requirement for national economic construction.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the epoxy resin emulsifier which can emulsify epoxy resin into stable emulsion at room temperature, and the epoxy resin emulsifier is matched with water-based epoxy emulsion prepared from epoxy resin and hansen water-based curing agent 6870 to prepare varnish, and has the advantages of smooth dry film surface, transparent coating film, high hardness, strong coating film adhesion, corrosion resistance and the like.

The invention also aims to provide a preparation method of the epoxy resin emulsion, which is completed by only one step of reaction, has mild reaction conditions, easy control, easily obtained raw materials, no need of organic solvent, low cost and suitability for industrial production.

The third purpose of the invention is to provide the application of the epoxy resin emulsifier in preparing the waterborne epoxy resin with good dispersion stability and excellent film-forming property.

In order to achieve the technical purpose, the invention provides a preparation method of an epoxy resin emulsifier, which comprises the steps of heating epoxy resin to 30-50 ℃, adding a tertiary amine salt-containing aqueous solution under the stirring condition, and heating to 70-120 ℃ for reaction to obtain the epoxy resin emulsifier.

The key point of the invention is that tertiary amine salt is used as a modifier of the epoxy resin, tertiary amine and epoxy functional groups generate ring-opening reaction, and tertiary amine salt reacts to generate quaternary ammonium salt with epoxy functional groups, so that the epoxy resin is endowed with stronger hydrophilic performance, and the electrochemical performance of the water-based coating film can be improved by utilizing the anti-corrosion performance of the quaternary ammonium salt.

The emulsifier is obtained by modifying epoxy resin, has good matching property with the epoxy resin, and solves the defects that the phenomena of blushing, foaming, even shedding and the like easily occur when the conventional emulsifier is introduced into an epoxy resin curing system in the prior art.

Preferably, the epoxy resin comprises at least one of bisphenol A epoxy resin E51, bisphenol F epoxy resin YDF165, bisphenol F epoxy resin YDF170, novolac epoxy resin F51 and novolac epoxy resin F54.

In a preferred embodiment, the tertiary amine salt includes at least one of trimethylamine hydrochloride, triethylamine hydrochloride and triethylamine sulfate.

In a preferable embodiment, the mass of the tertiary amine salt is 1% to 50% of the mass of the epoxy resin.

In the preferable scheme, the reaction time is 2-8 h, and the more preferable reaction time is 3-5 h.

The emulsifier has strong emulsifying capacity, and can emulsify the liquid epoxy resin at room temperature; because the epoxy resin is prepared by taking the epoxy resin as a raw material, the epoxy resin has the advantages of excellent compatibility with the epoxy resin and the like; the raw materials are liquid raw materials, and the modified emulsifier is still in a liquid state.

The invention also provides application of the epoxy resin emulsifier in preparation of the water-based epoxy resin emulsion.

In a preferable scheme, the epoxy resin emulsifier and the epoxy resin are uniformly stirred, and then water is added to prepare the water-based epoxy resin emulsion.

Preferably, the epoxy resin comprises at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and novolac epoxy resin.

In a preferred scheme, the mass ratio of the epoxy resin to the epoxy resin emulsifier is 100: 10-100: 100, respectively; the more preferable mass ratio is 100: 10-100: 50.

in a preferable scheme, the solid content of the water-based epoxy resin emulsion is 50-70%.

The specific preparation method of the epoxy resin emulsifier comprises the following steps: heating epoxy resin at 40 ℃, adding a tertiary amine salt solution under the stirring condition, then heating, keeping the temperature at 70-120 ℃ for reaction, and obtaining the epoxy resin emulsifier after the reaction is finished.

The preparation method of the water-based epoxy resin comprises the steps of mixing the epoxy resin with an epoxy resin emulsifier, and uniformly stirring by using a sand grinding stirring dispersion machine to obtain a substance A; adding deionized water into the A substance under high-speed stirring to prepare water-based epoxy resin; the water addition time was 20 minutes; the solid content of the water-based epoxy resin is about 60 percent.

Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:

the epoxy resin emulsifier can emulsify epoxy resin into stable emulsion at normal temperature, and the water-based epoxy resin varnish prepared from the epoxy resin emulsifier and the epoxy resin has the advantages of smooth surface of a dry film, transparent coating film, high hardness, strong adhesion of the coating film, corrosion resistance and the like.

The preparation method of the epoxy resin emulsifier provided by the invention is completed by only one-step reaction, is mild in reaction condition, easy to control, easy to obtain raw materials and low in cost, and is suitable for industrial production.

The epoxy resin emulsifier is particularly suitable for preparing the waterborne epoxy resin with good dispersion stability and excellent film-forming property.

Detailed Description

For better understanding of the present invention, the following examples are given to illustrate the technical solution of the present invention, but the present invention is not limited thereto:

example 1:

a preparation method of an epoxy resin emulsifier comprises the following steps: 50g of epoxy resin E51 is put into a reaction bottle, stirred, heated to 40 ℃, added with 8.85g of triethylamine hydrochloride solution, heated to 90 ℃ and kept reacting for 5 hours to prepare the epoxy resin emulsifier.

Example 2:

a preparation method of an epoxy resin emulsifier comprises the following steps: 50g of epoxy resin F51 is put into a reaction bottle, stirred, heated to 40 ℃, added with 11.96g of triethylamine sulfate solution, heated to 70 ℃ and kept reacting for 8 hours to prepare the epoxy resin emulsifier.

Example 3:

a preparation method of an epoxy resin emulsifier comprises the following steps: 50g of epoxy resin YDF-165 is put into a reaction bottle, stirred, heated to 40 ℃, then added with 6.4g of trimethylamine hydrochloride solution, heated to 120 ℃ and kept reacting for 3 hours to prepare the epoxy resin emulsifier.

Example 4

A preparation method of the water-based epoxy resin comprises the following steps:

the first step is as follows: mixing 150g of epoxy resin E51 with the epoxy resin emulsifier described in example 1, and uniformly stirring by using a sand-grinding stirring disperser to obtain a substance A;

and secondly, dropwise adding 130 g of deionized water into the substance A within 20min while stirring, and continuously stirring for 40-60min after dropwise adding is finished to obtain the milky water-based epoxy resin.

Through the test: the water-based epoxy emulsion prepared in the embodiment 4 is matched with a Hansen water-based curing agent 6870 to prepare varnish, the surface of a water-based epoxy resin varnish film is smooth, and the varnish film is transparent; the pencil hardness is 4H, and the coating adhesion is 0 grade; soaking in 3.5% saline water for 48 hr without whitening, foaming, dropping, and discoloration; the electrochemical alternating current impedance value of the membrane soaked in 3.5% saline water for 48 hours reaches 1.881 multiplied by 10⁷Ω。

Example 5:

a preparation method of the water-based epoxy resin comprises the following steps:

the first step is as follows: mixing 150g of epoxy resin F51 with the epoxy resin emulsifier described in example 2, and uniformly stirring by using a sand-grinding stirring disperser to obtain a substance A;

the second step is that: and (3) dropwise adding 130 g of deionized water into the waterborne epoxy resin within 20min, stirring while dropwise adding, and continuously stirring for 40-60min after dropwise adding is finished to obtain the milky waterborne epoxy resin.

Through the test: the water-based epoxy emulsion prepared in the example 5 is matched with a Hansen water-based curing agent 6870 to prepare varnish, and the water-based epoxy varnish has smooth film surface and transparent film; the pencil hardness is 6H, and the coating adhesion is 0 grade; soaking in 3.5% saline water for 48 hr without whitening, foaming, dropping, and discoloration; the electrochemical alternating current impedance value of the membrane soaked in 3.5% saline water for 48 hours reaches 6.998 multiplied by 10⁷Ω。

Example 6:

a preparation method of the water-based epoxy resin comprises the following steps:

the first step is as follows: 50g of epoxy resin YDF165 and the epoxy resin emulsifier described in example 3 are mixed and stirred uniformly by a sand-grinding stirring disperser to obtain a substance A;

the second step is that: and (3) dropwise adding 65 g of deionized water into the waterborne epoxy resin within 20min, stirring while dropwise adding, and continuously stirring for 40-60min after dropwise adding is finished to obtain the milky waterborne epoxy resin.

Through the test: the water-based epoxy emulsion prepared in the example 6 is matched with a Hansen water-based curing agent 6870 to prepare varnish, and the surface of a water-based epoxy varnish film is transparent and smooth; the pencil hardness is 5H, and the coating adhesion is 0 grade; soaking in 3.5% saline water for 48 hr without whitening, foaming, dropping, and discoloration; the electrochemical alternating current impedance value of the membrane soaked in 3.5% saline water for 48 hours reaches 4.318 multiplied by 10⁸Ω。

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art; the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.