WO2021109731A1 - Self-emulsifying epoxy resin emulsion, preparation method therefor and application thereof - Google Patents

Abstract

Disclosed are a self-emulsifying epoxy resin emulsion, a preparation method therefor and an application thereof. The raw materials of the emulsion comprise 100-150 parts epoxy resin, 10-20 parts sorbitan polyoxyethylene ether fatty acid ester, 10-20 parts fatty alcohol polyether phosphate, 1-5 parts of an amine accelerator, and 100-10000 parts water. The feeding mass ratios of the epoxy resin to the sorbitan polyoxyethylene ether fatty acid ester and the fatty alcohol polyether phosphate are 1:0.075-0.18 and 1:0.07-0.2, respectively. The preparation thereof comprises: the epoxy resin undergoes a first reaction with the sorbitan polyoxyethylene ether fatty acid ester in the presence of the amine accelerator, then undergoes a second reaction with the fatty alcohol polyether phosphate, and is then mixed with water and is made; and an application thereof in epoxy coatings. In the present invention, a uniform and stable emulsion may be self-emulsified without adding a co-solvent. The emulsion has a long storage period, no VOC emissions, and has excellent film toughness and rust resistance after film formation.

Description

Self-emulsifying epoxy resin emulsion and preparation method and application thereof

This application requires the prior patent application of the State Intellectual Property Office of China with the application number of CN201911212817.4 and the filing date of 2019.12.2 as priority, and the content of the prior patent application text is fully incorporated into this patent application by reference .

Technical field

The invention belongs to the technical field of water-based coatings, and specifically relates to a self-emulsifying epoxy resin emulsion and a preparation method and application thereof.

Background technique

Epoxy resin is widely used in various industries such as construction, woodware, hardware, electronics and electrical appliances because of its good bonding performance, high mechanical strength and low curing shrinkage. Traditional epoxy resin coatings use organic solvents as diluents, causing direct damage to the environment and the physical and mental health of coating workers. As environmental protection requirements are getting higher and higher, traditional epoxy resin coatings can no longer meet, and there is an urgent need to propose sustainable development solutions.

Epoxy emulsion uses water as solvent, which overcomes the VOC problem caused by traditional epoxy coatings due to organic solvents. At the same time, it also maintains the performance of the original coatings, and has excellent economic value and application value. However, most of the epoxy emulsions currently have some problems: (1) Poor storage stability; (2) Higher cured film hardness and poor flexibility, the paint film is easy to crack; (3) The need to add a co-solvent can not achieve completely zero VOC Discharge; (4) Poor anti-corrosion performance and easy rust, which restrict the use of water-based epoxy emulsion.

Summary of the invention

The purpose of the present invention is to overcome the shortcomings of the prior art and provide a new type of self-emulsifying epoxy resin emulsion, which can self-emulsify into a uniform and stable emulsion without adding a co-solvent, with a long storage period, and truly realize Zero VOC emission; At the same time, it has excellent film toughness and anti-rust performance after film formation.

The invention also provides a preparation method of the self-emulsifying epoxy resin emulsion.

The invention also provides an epoxy coating containing the self-emulsifying epoxy resin emulsion.

To solve the above technical problems, the present invention adopts the following technical solutions:

A self-emulsifying epoxy resin emulsion, the raw materials of which include epoxy resin and water, and the raw materials also include sorbitan polyoxyethylene ether fatty acid ester, fatty alcohol polyether phosphate and amine accelerator; in parts by mass In count, among the raw materials, 100-150 parts of epoxy resin, 10-20 parts of sorbitan polyoxyethylene ether fatty acid ester, 10-20 parts of fatty alcohol polyether phosphate, 1-5 parts of amine accelerator Parts and 100-10000 parts of water; wherein the feed mass ratio of the sorbitan polyoxyethylene ether fatty acid ester to the epoxy resin is 0.075-0.180:1, and the fatty alcohol polyether phosphate is The feed mass ratio of the epoxy resin is 0.07-0.20:1.

According to some preferred and specific aspects of the present invention, the polyoxyethylene sorbitan fatty acid ester is selected from one or a combination of Tween 20, Tween 60 and Tween 80.

According to some preferred and specific aspects of the present invention, the fatty alcohol polyether phosphate is selected from the group consisting of laureth polyoxyethylene ether phosphate, isooctyl alcohol polyoxyethylene ether phosphate, and iso-tridecanol polyoxyethylene ether One or more combinations of phosphate esters.

According to some specific and preferred aspects of the present invention, the fatty alcohol polyether phosphate is selected from the group consisting of polyoxyethylene laureth (AE03) phosphate, polyoxyethylene laureth (AE06) phosphate, polyoxylauryl alcohol Vinyl ether (AE09) phosphate, isooctanol polyoxyethylene ether (n=3) phosphate, isooctanol polyoxyethylene ether (n=6) phosphate, iso-tridecanol polyoxyethylene ether (n= 3) One or more combinations of phosphoric acid ester and isotridecyl alcohol polyoxyethylene ether (n=6) phosphoric acid ester.

According to some preferred aspects of the present invention, the self-emulsifying epoxy resin emulsion is prepared by the following method: in the presence of a protective gas, the epoxy resin is first mixed with the sorbitan polyoxyethylene ether fatty acid ester The first reaction is carried out in the presence of an amine accelerator, and then the second reaction is carried out with the fatty alcohol polyether phosphate, and then mixed with the water.

According to some specific aspects of the present invention, the protective gas may be nitrogen, argon, or the like.

According to some preferred aspects of the present invention, the reaction temperature of the first reaction is 180-190°C.

According to some preferred aspects of the present invention, the reaction temperature of the second reaction is 70-90°C.

According to some specific aspects of the present invention, the epoxy resin is a combination of one or more selected from bisphenol A epoxy resins.

According to some preferred aspects of the present invention, the epoxy resin is composed of at least one selected from the group consisting of bisphenol A epoxy resin E12 and bisphenol A epoxy resin E20, and at least one selected from bisphenol A epoxy resin E44 and At least one type of bisphenol A epoxy resin E51 is constituted.

According to some specific and preferred aspects of the present invention, the amine accelerator is at least one selected from the group consisting of diethanolamine, triethanolamine and N,N-dimethylbenzylamine.

According to some specific aspects of the present invention, the water is deionized water.

Another technical solution provided by the present invention: a preparation method of the self-emulsifying epoxy resin emulsion described above, the preparation method includes the following steps:

(1) Heat the epoxy resin and sorbitan polyoxyethylene ether fatty acid ester to 110-130°C, then remove the moisture in a vacuum, and pass protective gas for protection;

(2) Add the amine accelerator to the mixed solution of the dehydrated epoxy resin and sorbitan polyoxyethylene ether fatty acid ester, and then increase the temperature, and control the temperature to react between 180 and 190°C;

(3) Cool down to 70-90°C, add fatty alcohol polyether phosphate for reaction, then add the reaction product to water under stirring conditions, after all the reaction products are added to water, stir to prepare the self-emulsifying epoxy resin emulsion .

According to some specific aspects of the present invention, in step (1), the protective gas may be nitrogen, argon, or the like.

According to some specific aspects of the present invention, in step (3), the stirring is performed at 40-50°C.

Another technical solution provided by the present invention: a two-component epoxy coating, the two-component epoxy coating includes A component and B component, and the mass ratio of the A component to the B component It is 1:0.95-1.05.

According to some specific and preferred aspects of the present invention, in terms of mass percentage, the A component includes:

30-50% of the self-emulsifying epoxy resin emulsion according to any one of claims 1-8;

Wetting and dispersing agent 0.1-1%;

0.1-1% defoamer;

Leveling agent 0.1-1%;

The balance is water;

In terms of mass percentage, the B component includes:

Water-soluble epoxy curing agent 90-99%;

Neutralizer 1-10%.

According to some specific aspects of the present invention, the wetting and dispersing agent is: dispersing agent SN-5040.

According to some specific aspects of the present invention, the defoamer is: Dow Corning DC-65.

According to some specific aspects of the present invention, the leveling agent is: German KANON CN-301.

According to some specific aspects of the present invention, the water-soluble epoxy curing agent is: Dow D.E.H.805.

According to some specific aspects of the present invention, the neutralizer is triethanolamine, diethanolamine and the like.

According to some specific aspects of the present invention, the water is deionized water.

Due to the implementation of the above technical solutions, the present invention has the following advantages compared with the prior art:

The present invention innovatively uses anhydrous sorbitan polyoxyethylene ether fatty acid ester and fatty alcohol polyether phosphate to modify the epoxy resin, which not only endows the modified epoxy resin without adding a co-solvent The ability to self-emulsify into a uniform and stable emulsion, and the long storage period, truly achieve zero VOC emissions; at the same time, it can also have excellent film toughness and rust resistance after film formation, which makes water-based epoxy resins widely available Application, give full play to the characteristics of epoxy resin and meet the high standards of environmental protection.

Detailed ways

The present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, but the present invention is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and implementation conditions not specified are usually conditions in routine experiments. The raw materials used in the examples are all commercially available industrial products.

In the following examples, unless otherwise specified, all raw materials are basically commercially available or prepared by conventional methods in the art. In the following, bisphenol A epoxy resin E-44 was purchased from Kunshan Nanya, bisphenol A epoxy resin E-51 was purchased from Kunshan Nanya, bisphenol A epoxy resin E12 was purchased from Kunshan Nanya, and Tween 20 was purchased from Zhejiang Real Madrid Chemical, Tween 60 was purchased from Zhejiang Real Madrid Chemical, Tween 80 was purchased from Zhejiang Real Madrid Chemical, Laureth (n=3) phosphate was purchased from Zhejiang Real Madrid, Laureth (AE06) phosphoric acid The ester was purchased from Zhejiang Real Madrid Chemical.

Example 1

This example provides a self-emulsifying epoxy resin emulsion, in parts by mass, its raw materials include 100 parts of bisphenol A epoxy resin E-44, 30 parts of bisphenol A epoxy resin E12, and 10 parts of Tween 20 and 10 Parts of polyoxyethylene laureth (n=3) phosphate, 5 parts of diethanolamine and 300 parts of deionized water.

The preparation method is as follows:

(1) Heat the bisphenol A epoxy resin E-44, bisphenol A epoxy resin E12 and Tween 20 to about 120°C, then remove the moisture in a vacuum, and pass nitrogen for protection;

(2) Add diethanolamine to the dehydrated mixed solution of bisphenol A epoxy resin E-44, bisphenol A epoxy resin E12 and Tween 20, then increase the temperature, and control the temperature to react at about 185°C;

(3) Cool down to about 80°C, add lauryl alcohol polyoxyethylene ether (n=3) phosphate ester to react, then slowly add the reaction product to deionized water under stirring conditions, control the emulsion temperature to about 45°C, wait for the reaction product After all is added to deionized water, the self-emulsifying epoxy resin emulsion is prepared by stirring.

Example 2

This example provides a self-emulsifying epoxy resin emulsion, in parts by mass, its raw materials include 100 parts of bisphenol A epoxy resin E-51, 20 parts of bisphenol A epoxy resin E12, and 10 parts of Tween 80 and 10 Parts of polyoxyethylene laureth (n=3) phosphate, 5 parts of diethanolamine and 400 parts of deionized water.

The preparation method is as follows:

(1) Heat the bisphenol A epoxy resin E-51, bisphenol A epoxy resin E12 and Tween 80 to about 120°C, then remove the moisture in a vacuum, and pass nitrogen for protection;

(2) Add diethanolamine to the dehydrated mixed solution of bisphenol A epoxy resin E-51, bisphenol A epoxy resin E12 and Tween 80, then increase the temperature, and control the temperature to react at about 185°C;

(3) Cool down to about 80°C, add lauryl alcohol polyoxyethylene ether (n=3) phosphate ester to react, then slowly add the reaction product to deionized water under stirring conditions, control the emulsion temperature to about 45°C, wait for the reaction product After all is added to deionized water, the self-emulsifying epoxy resin emulsion is prepared by stirring.

Example 3

This example provides a self-emulsifying epoxy resin emulsion, in parts by mass, its raw materials include 100 parts of bisphenol A epoxy resin E-44, 30 parts of bisphenol A epoxy resin E12, and 10 parts of Tween 60, 15 Parts of polyoxyethylene laureth (AE06) phosphate, 5 parts of diethanolamine and 400 parts of deionized water.

The preparation method is as follows:

(1) Heat the bisphenol A epoxy resin E-44, bisphenol A epoxy resin E12 and Tween 60 to 110-130°C, then remove the moisture in a vacuum, and pass nitrogen for protection;

(2) Add diethanolamine to the dehydrated mixed solution of bisphenol A epoxy resin E-44, bisphenol A epoxy resin E12 and Tween 60, then increase the temperature and control the temperature to react at about 185°C;

(3) Cool down to about 80°C, add lauryl alcohol polyoxyethylene ether (AE06) phosphate to react, then slowly add the reaction product to deionized water under stirring conditions, control the emulsion temperature to about 45°C, and wait until all the reaction products are added After being poured into deionized water, the self-emulsifying epoxy resin emulsion is prepared by stirring.

Comparative example 1

This example provides an epoxy resin emulsion, in parts by mass, its raw materials include 100 parts of bisphenol A epoxy resin E-51, 20 parts of bisphenol A epoxy resin E12, 5 parts of Tween 80, and 5 parts of two parts. 400 parts of ethanolamine and deionized water.

The preparation method is as follows:

(1) Heat the bisphenol A epoxy resin E-51, bisphenol A epoxy resin E12 and Tween 80 to about 120°C, then remove the moisture in a vacuum, and pass nitrogen for protection;

(2) Add diethanolamine to the dehydrated mixed solution of bisphenol A epoxy resin E-51, bisphenol A epoxy resin E12 and Tween 80, then increase the temperature, and control the temperature to react at about 185°C;

(3) Then the reaction product is slowly added to deionized water under stirring conditions, and the temperature of the emulsion is controlled to about 45° C. After all the reaction products are added to the deionized water, the epoxy resin emulsion is prepared by stirring.

Comparative example 2

It is basically the same as Example 2, except that the addition amount of Tween 80 is adjusted to 5 parts.

Performance Testing

The epoxy resin emulsions obtained in the foregoing Examples 1-3 and Comparative Examples 1-2 were respectively subjected to the following performance tests.

(1), emulsion stability test (using static method, visual inspection)

Table 1. Normal temperature test

Examples 7 days 30 days 60 days 90 days 180 days Example 1 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Example 2 Stable no stratification Stable no stratification Stable no stratification Stable No stratification Stable no stratification Example 3 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Comparative example 1 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Slight Stratification Comparative Example 2 Stable and no stratification Stable and no stratification Stable and no stratification Stable and no stratification Stable and no stratification

Table 2. 50℃ high temperature test

Examples 7 days 30 days 60 days 90 days 180 days Example 1 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Example 2 Stable no stratification Stable no stratification Stable no stratification Stable No stratification Stable no stratification Example 3 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Stable no stratification Comparative example 1 Stable no stratification Stable no stratification Stable no stratification Stable no stratification Slight Stratification Comparative Example 2 Stable and no stratification Stable and no stratification Stable and no stratification Stable and no stratification Stable and no stratification

(Two), paint film flexibility test (test standard: GB/T 1731-93)

table 3

Note: The smaller the diameter of the round rod, the better the flexibility without cracks

(3) Anti-rust performance test of emulsion (test standard: GB6458-86)

Table 4

Note: The experimental condition is a neutral salt spray test, using 5% sodium chloride aqueous solution

Application experiment

The application experiment of this example provides a two-component epoxy coating, the two-component epoxy coating includes A component and B component, and the mass ratio of the A component to the B component is 1:1 , See Table 5 below for specific formulation materials and dosages.

table 5

Preparation method: (1) Preparation of component A: weigh each raw material according to the formula, and then mix to make; (2) Preparation of component B: weigh each raw material according to the formula, and then mix to make;

During application, weigh the components A and B according to the amount of the formula. After mixing, they can be coated and sprayed.

Performance test of two-component epoxy coating:

Table 6

The above-mentioned embodiments are only to illustrate the technical concept and features of the present invention, and their purpose is to enable those familiar with the technology to understand the content of the present invention and implement them accordingly, and cannot limit the scope of protection of the present invention. The equivalent changes or modifications made by the spirit essence should all be covered within the protection scope of the present invention.

Claims (10)

1. A self-emulsifying epoxy resin emulsion, its raw materials include epoxy resin and water, characterized in that the raw materials also include sorbitan polyoxyethylene ether fatty acid ester, fatty alcohol polyether phosphate and amine accelerator ; In parts by mass, in the raw materials, 100-150 parts of epoxy resin, 10-20 parts of sorbitan polyoxyethylene ether fatty acid ester, 10-20 parts of fatty alcohol polyether phosphate, amine promoting 1-5 parts of agent and 100-10000 parts of water; wherein the feed mass ratio of the sorbitan polyoxyethylene ether fatty acid ester to the epoxy resin is 0.075-0.180:1, and the fatty alcohol polyether The mass ratio of the phosphoric acid ester to the epoxy resin is 0.07-0.20:1.
2. The self-emulsifying epoxy resin emulsion of claim 1, wherein the sorbitan polyoxyethylene ether fatty acid ester is one selected from the group consisting of Tween 20, Tween 60 and Tween 80 or Multiple combinations.
3. The self-emulsifying epoxy resin emulsion according to claim 1, wherein the fatty alcohol polyether phosphate is selected from the group consisting of laureth polyoxyethylene ether phosphate, isooctanol polyoxyethylene ether phosphate and isomer One or more combinations of trideceth phosphate.
4. The self-emulsifying epoxy resin emulsion according to any one of claims 1 to 3, wherein the self-emulsifying epoxy resin emulsion is prepared by the following method: in the presence of a protective gas, the The epoxy resin first reacts with the sorbitan polyoxyethylene ether fatty acid ester in the presence of an amine accelerator, and then performs a second reaction with the fatty alcohol polyether phosphate, and then reacts with the water Mix and make.
5. The self-emulsifying epoxy resin emulsion according to claim 4, wherein the reaction temperature of the first reaction is 180-190°C; and/or the reaction temperature of the second reaction is 70-90°C.
6. The self-emulsifying epoxy resin emulsion of claim 1, wherein the epoxy resin is a combination of one or more selected from bisphenol A epoxy resins.
7. The self-emulsifying epoxy resin emulsion according to claim 6, wherein the epoxy resin is made of at least one selected from the group consisting of bisphenol A epoxy resin E12 and bisphenol A epoxy resin E20. It is composed of at least one of bisphenol A epoxy resin E44 and bisphenol A epoxy resin E51.
8. The self-emulsifying epoxy resin emulsion of claim 1, wherein the amine accelerator is at least one selected from the group consisting of diethanolamine, triethanolamine and N,N-dimethylbenzylamine.
9. A method for preparing a self-emulsifying epoxy resin emulsion according to any one of claims 1-8, wherein the preparation method comprises the following steps:

   (1) Heat the epoxy resin and sorbitan polyoxyethylene ether fatty acid ester to 110-130°C, then remove the moisture in a vacuum, and pass protective gas for protection;

   (2) Add the amine accelerator to the mixed solution of the dehydrated epoxy resin and sorbitan polyoxyethylene ether fatty acid ester, and then increase the temperature, and control the temperature to react between 180 and 190°C;

   (3) Cool down to 70-90°C, add fatty alcohol polyether phosphate for reaction, then add the reaction product into water under stirring conditions, after all the reaction products are added to water, stir to prepare the self-emulsifying epoxy resin emulsion .
10. A two-component epoxy coating, said two-component epoxy coating comprising A component and B component, characterized in that the mass ratio of the A component to the B component is 1:0.95- 1.05;

    Wherein, in terms of mass percentage, the A component includes:

    30-50% of the self-emulsifying epoxy resin emulsion according to any one of claims 1-8;

    Wetting and dispersing agent 0.1-1%;

    0.1-1% defoamer;

    Leveling agent 0.1-1%;

    The balance is water;

    In terms of mass percentage, the B component includes:

    Water-soluble epoxy curing agent 90-99%;

    Neutralizer 1-10%.