阅读说明：本技术 一种无皂合成水性丙烯酸分散体树脂制备方法及配方 (Preparation method and formula of soap-free synthetic aqueous acrylic acid dispersion resin ) 是由 曾杰 于 2020-08-13 设计创作，主要内容包括：本发明公开了涉及高分子材料技术领域的一种无皂合成水性丙烯酸分散体树脂制备方法,该水性树脂具有核中壳三层结构,通过硬核软壳的结构设计,解决了水性户外木器涂料存在的,难以具备木器涂料本身具备的高硬度、初期抗粘连性和打磨性的同时还兼具备户外木器涂料的柔韧性的问题。其技术要点是：制备预乳化液；加入预乳化液；加入引发剂、引发剂(2)和催化剂；加入氧化剂、还原剂、预乳化液(2)、交联剂、杀菌剂和固含量调节剂；过滤。水性树脂的平均粒径达到35纳米以下,高硬度、高抗粘,打磨性能优秀,又兼具低温成膜的特性,在硬度、耐水性、附着力、光泽等方面得到提高,达到硬度、初期抗粘连性、打磨性能和柔韧性较好的优点。(The invention discloses a preparation method of soap-free synthetic aqueous acrylic acid dispersion resin, which relates to the technical field of high polymer materials, wherein the aqueous resin has a core-middle shell three-layer structure, and solves the problem that the aqueous outdoor wood coating is difficult to have high hardness, initial blocking resistance and sanding property and simultaneously has the flexibility of the outdoor wood coating through the structural design of a hard core and a soft shell. The technical key points are as follows: preparing a pre-emulsion; adding the pre-emulsion; adding an initiator, an initiator (2) and a catalyst; adding an oxidant, a reducing agent, a pre-emulsion (2), a cross-linking agent, a bactericide and a solid content regulator; and (5) filtering. The average particle size of the water-based resin reaches below 35 nanometers, and the water-based resin has the advantages of high hardness, high anti-adhesion property and excellent polishing property, has the characteristic of low-temperature film forming, is improved in the aspects of hardness, water resistance, adhesive force, luster and the like, and has the advantages of good hardness, initial anti-adhesion property, polishing property and flexibility.)

1. A method for preparing soap-free synthetic aqueous acrylic dispersion resin is characterized by comprising the following steps:

preparing a pre-emulsion: adding acrylic acid, diacetone acrylamide, butyl acrylate and a chain transfer agent into a monomer tank to prepare a pre-emulsion;

adding a pre-emulsion: adding the prepared 20% pre-emulsion into a reaction kettle, stirring for 5 minutes, adding an initial initiator, heating the reaction kettle to 80 ℃, keeping the temperature for 10 minutes, controlling the temperature of the reaction kettle to be 84-86 ℃, and dropwise adding the rest pre-emulsion for 60 minutes;

adding an initiator, an initiator (2) and a catalyst: adding an initiator, an initiator (2) and a catalyst into a reaction kettle;

adding an oxidant, a reducing agent, a pre-emulsion (2), a cross-linking agent, a bactericide and a solid content regulator: adding an oxidant, a cross-linking agent, a bactericide and a solid content regulator into a reaction kettle;

and (3) filtering: and filtering the water-based resin finished product in the reaction kettle by using a 10um filter element.

2. The method for preparing a soap-free synthetic aqueous acrylic dispersion resin according to claim 1, further comprising the steps of, before the step of adding the initiator, the initiator (2) and the catalyst:

preparing an initiator: deionized water and ammonium persulfate are added into an initiator tank to be mixed and dissolved to prepare the initiator for later use.

3. The method for preparing a soap-free synthetic aqueous acrylic dispersion resin according to claim 1, wherein in the step of adding the initiator, the initiator (2) and the catalyst, the method further comprises the steps of:

and (3) flushing the initiator in the initiator tank by using deionized water, and then uniformly blending the deionized water and tert-butyl hydroperoxide and adding the mixture into the initiator tank to prepare the initiator (2) for later use.

4. The method for preparing a soap-free synthetic aqueous acrylic dispersion resin according to claim 1, further comprising the steps of, before the step of adding the initiator, the initiator (2) and the catalyst:

preparing a catalyst: mixing sodium sulfite and deionized water uniformly, adding the mixture into a catalyst tank, and preparing the catalyst for later use.

5. The method for preparing a soap-free synthetic aqueous acrylic dispersion resin according to claim 1, further comprising the steps of, before the step of adding an oxidizing agent, a reducing agent, a pre-emulsion (2), a crosslinking agent, a bactericide and a solid content regulator:

preparing a reducing agent: and uniformly mixing deionized water, isoascorbic acid and ammonia water, adding the mixture into a reducing agent tank, and preparing the reducing agent for later use.

6. The method for preparing a soap-free synthetic aqueous acrylic dispersion resin according to claim 1, further comprising the steps of, before the step of adding an oxidizing agent, a reducing agent, a pre-emulsion (2), a crosslinking agent, a bactericide and a solid content regulator:

preparation of pre-emulsion (2): and (3) uniformly blending diacetone acrylamide, deionized water, isooctyl acrylate and methyl methacrylate, and adding into a monomer tank to prepare a pre-emulsion (2) for later use.

7. The method for preparing a soap-free synthetic aqueous acrylic dispersion resin according to claim 1, wherein in the step of adding an oxidizing agent, a reducing agent, a pre-emulsion (2), a crosslinking agent, a bactericide and a solid content adjusting agent, the method further comprises the steps of:

adding tert-butyl hydroperoxide and deionized water serving as an oxidant and a diluent oxidant respectively, uniformly blending, adding the mixture into a reaction kettle, stirring for 5 minutes, adding 30% of a reducing agent, stirring the mixture at the highest temperature after the temperature of the reaction kettle rises, stirring for 10 minutes, adding the deionized water serving as cooling water into the reaction kettle, cooling the temperature of the reaction kettle to 55 ℃, adding the pre-emulsion (2), stirring for 15 minutes, uniformly blending the tert-butyl hydroperoxide and the deionized water, adding the rest reducing agent into the reaction kettle, heating the reaction kettle to 80 ℃, preserving the heat for 30 minutes, and cooling to 40 ℃ by using the cooling water.

8. The method for preparing a soap-free synthetic aqueous acrylic dispersion resin according to claim 7, wherein in the step of adding an oxidizing agent, a reducing agent, a pre-emulsion (2), a crosslinking agent, a bactericide and a solid content adjusting agent, the method further comprises the steps of:

after the temperature of the reaction kettle is lower than 40 ℃, adipic dihydrazide and deionized water are respectively used as a cross-linking agent and a diluting cross-linking agent to be added into the reaction kettle, and then the mixture is stirred for 30 minutes.

9. The method for preparing a soap-free synthetic aqueous acrylic dispersion resin according to claim 8, wherein in the step of adding an oxidizing agent, a reducing agent, a pre-emulsion (2), a crosslinking agent, a bactericide and a solid content adjusting agent, the method further comprises the steps of:

adding the bactericide BT20 into a reaction kettle, adding deionized water serving as a solid content regulator into the reaction kettle, and regulating the solid content of the water-based resin in the reaction kettle to 43-45%.

10. The formula of the soap-free synthetic aqueous acrylic dispersion resin is characterized in that: the feed comprises the following raw materials in parts by weight: 18 parts of acrylic acid, 10.29 parts of diacetone acrylamide, 53 parts of butyl acrylate, 78 parts of dimethyl ester, 212 parts of isooctyl acrylate, 78 parts of methyl methacrylate, 0.01 part of catalyst, 0.67 part of reducing agent, 4 parts of cross-linking agent, 2.92 parts of chain transfer agent, 1.31 parts of emulsifier, 5.52 parts of bactericide, 0.27 part of ammonia water, 0.54 part of oxidant, 0.36 part of initiator and 510-540 parts of deionized water.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a preparation method and a formula of soap-free synthetic aqueous acrylic acid dispersoid resin.

Background

In the prior art, the outdoor and semi-outdoor resin for the water-based outdoor wood coating can independently solve the problems of weather resistance, water resistance and flexibility of the water-based outdoor wood coating by adding an auxiliary agent at the later stage of the application formula of the water-based outdoor wood coating. However, the existing aqueous outdoor wood coating is difficult to obtain by simultaneously endowing the aqueous resin with the sanding property, the initial blocking resistance and the good adhesive force of the wood coating.

For example, prior art aqueous outdoor wood coatings improve sandability by adding a sanding aid and initial blocking resistance by adding a wax emulsion or wax powder. The sanding additive and the wax emulsion or the wax powder respectively improve the sanding property and the initial anti-blocking property of the water-based outdoor wood coating, and the addition of the additive in the later period can bring the incidental adverse reaction, such as the defects of strong bubbles, difficult settlement prevention, more expensive price, unstable system, poor inherent adhesive force and the like. The water-based outdoor wood coating in the prior art has the problems of poor hardness, initial blocking resistance, polishing performance and flexibility.

Disclosure of Invention

In order to overcome the above disadvantages of the prior art, the present invention aims to provide a method and a formula for preparing a soap-free synthetic aqueous acrylic dispersion resin, which has the advantages of good hardness, initial blocking resistance, sanding property and flexibility.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a method for preparing soap-free synthetic aqueous acrylic dispersion resin comprises the following steps:

preparing a pre-emulsion: adding acrylic acid, diacetone acrylamide, butyl acrylate and a chain transfer agent into a monomer tank to prepare a pre-emulsion;

adding a pre-emulsion: adding the prepared 20% pre-emulsion into a reaction kettle, stirring for 5 minutes, adding an initial initiator, heating the reaction kettle to 80 ℃, keeping the temperature for 10 minutes, controlling the temperature of the reaction kettle to be 84-86 ℃, and dropwise adding the rest pre-emulsion for 60 minutes;

adding an initiator, an initiator (2) and a catalyst: adding an initiator, an initiator (2) and a catalyst into a reaction kettle;

adding an oxidant, a reducing agent, a pre-emulsion (2), a cross-linking agent, a bactericide and a solid content regulator: adding an oxidant, a cross-linking agent, a bactericide and a solid content regulator into a reaction kettle;

and (3) filtering: and filtering the water-based resin finished product in the reaction kettle by using a 10um filter element.

As a further improvement of the invention: before the step of adding the initiator, the initiator (2) and the catalyst, the method also comprises the following steps:

preparing an initiator: deionized water and ammonium persulfate are added into an initiator tank to be mixed and dissolved to prepare the initiator for later use.

As a further improvement of the invention: in the step of adding the initiator, the initiator (2) and the catalyst, the method further comprises the following steps:

and (3) flushing the initiator in the initiator tank by using deionized water, and then uniformly blending the deionized water and tert-butyl hydroperoxide and adding the mixture into the initiator tank to prepare the initiator (2) for later use.

As a further improvement of the invention: before the step of adding the initiator, the initiator (2) and the catalyst, the method also comprises the following steps:

preparing a catalyst: mixing sodium sulfite and deionized water uniformly, adding the mixture into a catalyst tank, and preparing the catalyst for later use.

As a further improvement of the invention: before the step of adding the oxidant, the reducing agent, the pre-emulsion (2), the cross-linking agent, the bactericide and the solid content regulator, the method also comprises the following steps:

preparing a reducing agent: and uniformly mixing deionized water, isoascorbic acid and ammonia water, adding the mixture into a reducing agent tank, and preparing the reducing agent for later use.

As a further improvement of the invention: before the step of adding the oxidant, the reducing agent, the pre-emulsion (2), the cross-linking agent, the bactericide and the solid content regulator, the method also comprises the following steps:

preparation of pre-emulsion (2): and (3) uniformly blending diacetone acrylamide, deionized water, isooctyl acrylate and methyl methacrylate, and adding into a monomer tank to prepare a pre-emulsion (2) for later use.

As a further improvement of the invention: in the step of adding the oxidizing agent, the reducing agent, the pre-emulsion (2), the cross-linking agent, the bactericide and the solid content regulator, the method further comprises the following steps:

adding tert-butyl hydroperoxide and deionized water serving as an oxidant and a diluent oxidant respectively, uniformly blending, adding the mixture into a reaction kettle, stirring for 5 minutes, adding 30% of a reducing agent, stirring the mixture at the highest temperature after the temperature of the reaction kettle rises, stirring for 10 minutes, adding the deionized water serving as cooling water into the reaction kettle, cooling the temperature of the reaction kettle to 55 ℃, adding the pre-emulsion (2), stirring for 15 minutes, uniformly blending the tert-butyl hydroperoxide and the deionized water, adding the rest reducing agent into the reaction kettle, heating the reaction kettle to 80 ℃, preserving the heat for 30 minutes, and cooling to 40 ℃ by using the cooling water.

As a further improvement of the invention: in the step of adding the oxidizing agent, the reducing agent, the pre-emulsion (2), the cross-linking agent, the bactericide and the solid content regulator, the method further comprises the following steps:

after the temperature of the reaction kettle is lower than 40 ℃, adipic dihydrazide and deionized water are respectively used as a cross-linking agent and a diluting cross-linking agent to be added into the reaction kettle, and then the mixture is stirred for 30 minutes.

As a further improvement of the invention: in the step of adding the oxidizing agent, the reducing agent, the pre-emulsion (2), the cross-linking agent, the bactericide and the solid content regulator, the method further comprises the following steps:

adding the bactericide BT20 into a reaction kettle, adding deionized water serving as a solid content regulator into the reaction kettle, and regulating the solid content of the water-based resin in the reaction kettle to 43-45%.

The formula of the soap-free synthetic aqueous acrylic dispersion resin comprises the following raw materials in parts by weight: 18 parts of acrylic acid, 10.29 parts of diacetone acrylamide, 53 parts of butyl acrylate, 78 parts of dimethyl ester, 212 parts of isooctyl acrylate, 78 parts of methyl methacrylate, 0.01 part of catalyst, 0.67 part of reducing agent, 4 parts of cross-linking agent, 2.92 parts of chain transfer agent, 1.31 parts of emulsifier, 5.52 parts of bactericide, 0.27 part of ammonia water, 0.54 part of oxidant, 0.36 part of initiator and 510-540 parts of deionized water.

Compared with the prior art, the invention has the beneficial effects that:

the high hardness, high anti-adhesion and excellent polishing performance are provided, and the low-temperature film forming property is provided, so that the hardness, water resistance, adhesive force, gloss and the like are improved, and the advantages of good hardness, initial anti-adhesion, polishing performance and flexibility are achieved.

The paint film has excellent clear property, has excellent emulsion fine particle size, has the average particle size of the water-based resin below 35 nanometers, and can be applied to high-transparency transparent varnish and finishing varnish of colored paint.

The paint has excellent adhesion to various base materials, has excellent permeability, comprises galvanized iron plates, galvanized pipes, glass, porcelain, melamine plates, PVC and the like, has excellent adhesion, and is suitable for PVC window frame varnish and paint.

Drawings

FIG. 1 is a schematic representation of a sample of a varnish after use of a soap-free synthetic aqueous acrylic dispersion resin in an example of the present application for outdoor wood testing;

FIG. 2 is a schematic representation of a sample of white paint after use of a soap-free synthetic aqueous acrylic dispersion resin in an example of the present application for outdoor wood testing.

Detailed Description

The invention will now be further described with reference to the accompanying description and examples: