阅读说明：本技术 一种新型环氧基硅油改性丙烯酸酯防涂鸦乳液的制备方法 (Preparation method of novel epoxy silicone oil modified acrylate anti-doodling emulsion ) 是由 季永新 郑绪敏 吕正伟 陈永康 于 2020-04-02 设计创作，主要内容包括：本发明公开了一种新型环氧基硅油改性丙烯酸酯防涂鸦乳液的制备方法,利用酰胺基与环氧基的反应,在乳液聚合时加入丙烯酰胺,在乳液分子链上引入酰胺基,再与端环氧基硅油反应,制备新型环氧基硅油改性丙烯酸酯防涂鸦乳液。本发明公开的新型环氧基硅油改性丙烯酸酯防涂鸦乳液,通过酰胺基与环氧基的开环反应接入硅油,解决了常规方法所造成的有机硅引入量低、挥发性有机物、有机硅单体难聚合等问题,极大提高了乳液的耐水性、柔软性、抗污性能。本发明制得的乳液不仅具有极强的附着力、较好的耐洗刷性与耐乙醇性,而且还具有优异的储存稳定性、耐候性和耐化学品性,可广泛应用于涂料、油墨、粘合剂等领域。(The invention discloses a preparation method of novel epoxy silicone oil modified acrylate doodle-proof emulsion, which utilizes the reaction of amide groups and epoxy groups, adds acrylamide during emulsion polymerization, introduces amide groups on emulsion molecular chains, and then reacts with epoxy-terminated silicone oil to prepare the novel epoxy silicone oil modified acrylate doodle-proof emulsion. According to the novel epoxy silicone oil modified acrylate anti-doodling emulsion disclosed by the invention, silicone oil is introduced through the ring-opening reaction of the amide group and the epoxy group, so that the problems of low organic silicon introduction amount, difficult polymerization of volatile organic compounds and organic silicon monomers and the like caused by a conventional method are solved, and the water resistance, flexibility and anti-fouling performance of the emulsion are greatly improved. The emulsion prepared by the invention not only has strong adhesive force, better washing resistance and ethanol resistance, but also has excellent storage stability, weather resistance and chemical resistance, and can be widely applied to the fields of coatings, printing ink, adhesives and the like.)

1. The invention discloses a preparation method of a novel epoxy silicone oil modified acrylate anti-doodling emulsion, which is characterized by comprising the following steps:

(1) adding 20-24 parts of deionized water and 1.0-1.5 parts of a composite emulsifier into a reaction kettle, stirring for 20-40 minutes at 400-600 rpm, then dropwise adding a mixture of 30-36 parts of methyl methacrylate monomer, 10-16 parts of butyl acrylate monomer, 1.6-2.0 parts of acrylic acid monomer, 15-20 parts of hydroxyethyl methacrylate monomer and 0.6-1.2 parts of acrylamide monomer, dropwise adding for 40-80 minutes, and stirring for 30-60 minutes after dropwise adding to obtain the acrylic ester pre-emulsion.

(2) Adding 6-10 parts of the pre-emulsion in the step (1), 0.8-1.2 parts of an emulsifier, 0.08-0.12 part of an initiator and 50-58 parts of deionized water into a reaction kettle, dropwise adding 74-78 parts of the pre-emulsion and 0.16-0.24 part of the initiator (dissolved in 8-16 parts of deionized water), carrying out polymerization reaction for 2-4 hours at 80-90 ℃, keeping the temperature for 40-80 minutes after dropwise adding, and cooling to normal temperature to obtain the acylamino-containing acrylate emulsion.

(3) Adding 40-50 parts of double-end hydrogen-containing silicone oil, 1.2-1.8 parts of allyl glycidyl ether and 40-50 parts of solvent into a reaction kettle, stirring and heating to 75-95 ℃, adding 0.03-0.05 part of catalyst, reacting for 20-40 minutes, raising the temperature to 100-120 ℃, keeping the temperature for 2-4 hours after the solution is reacted to be clear and transparent, and removing residual low-boiling-point substances through reduced pressure distillation to obtain the epoxy-terminated silicone oil.

(4) And (3) adding 60-80 parts of the acylamino-containing acrylate emulsion in the step (2) into a reaction kettle, dropwise adding 2.4-3.2 parts of epoxy-terminated silicone oil, opening the reaction kettle at 60-80 ℃ for ring opening reaction for 10-18 minutes, and preserving heat for 2-4 hours after dropwise adding to obtain the target emulsion (the parts are in parts by weight).

2. The preparation method of the novel epoxy silicone oil modified acrylate doodle-proof emulsion as claimed in claim 1, characterized in that: the composite emulsifier in the step (1) is a compound mixture of fatty alcohol polyoxyethylene ether disodium sulfosuccinate (A-102) and isomeric tridecanol polyoxyethylene ether (TO-8), and the compound ratio is 5:1, 7:1 and 9: 1.

3. The preparation method of the novel epoxy silicone oil modified acrylate doodle-proof emulsion as claimed in claim 1, characterized in that: the emulsifier in the step (2) is fatty alcohol polyoxyethylene ether sulfosuccinic acid monoester disodium (A-102), and the initiator is potassium persulfate or ammonium persulfate or sodium persulfate.

4. The preparation method of the novel epoxy silicone oil modified acrylate doodle-proof emulsion as claimed in claim 1, characterized in that: the solvent in the step (3) is isopropanol or butanol or dimethyl sulfoxide, and the catalyst is chloroplatinic acid.

5. The preparation method of the novel epoxy silicone oil modified acrylate doodle-proof emulsion as claimed in claim 1, wherein the emulsion has the following structural formula:

Technical Field

The invention relates to a preparation method of a novel epoxy silicone oil modified acrylate anti-doodling emulsion, belonging to the field of fine chemical chemicals.

Background

As is well known, emulsion paint is mostly adopted for wall decoration of modern buildings, but common emulsion paint does not have the anti-doodling function, is easy to be polluted by doodling, is difficult to clean and has high maintenance cost, so that the market has great expectation on professional anti-doodling paint products.

In recent years, with the progress of the preparation technology of the anti-doodling emulsion, the organosilicon modified acrylate anti-doodling emulsion is developed. The organosilicon modified acrylate doodling-proof emulsion not only has excellent film-forming property, but also can improve the water resistance, stain resistance and scrubbing resistance of a coating film, thereby being paid attention to by the industry people. The organosilicon modified acrylate anti-doodling emulsion prepared by the conventional method at home at present is mainly prepared by adding an organosilicon monomer containing unsaturated bonds and an acrylic monomer into a proper auxiliary agent and then carrying out a core-shell coating polymerization process; although the emulsion has the characteristics of high temperature resistance, water resistance, flexibility and the like, the preparation technology is not mature enough, and the problems of difficult polymerization of organic silicon monomers, easy self-crosslinking of silane active groups, low organic silicon introduction amount, pollution of volatile organic compounds and the like exist, so that the quality of the anti-doodling emulsion product is easily adversely affected.

The organic silicon modified acrylate doodling-proof emulsion is prepared by utilizing the reaction of an amido group and an epoxy group, adding acrylamide during emulsion polymerization, introducing the amido group on the molecular chain of the emulsion, and then reacting with epoxy-terminated silicone oil. The preparation method is simple, compared with the conventional preparation method, the preparation method does not need to adopt an organic silicon emulsifier or cosolvent, and has the characteristics of environmental protection in production, easy operation, no volatile organic matter and the like. The emulsion prepared by the method has the characteristics of ethanol resistance, stain resistance, scrubbing resistance and the like, so that the emulsion has a good application prospect.

Disclosure of Invention

The invention aims to provide a preparation method of a novel epoxy silicone oil modified acrylate doodle-proof emulsion, and aims to solve the problems that an organic silicon monomer is difficult to polymerize, a silane active group is easy to generate self-crosslinking, the introduction amount of organic silicon is low, volatile organic compounds are polluted and the like in the preparation of the conventional organic silicon modified acrylate doodle-proof emulsion. The anti-doodling emulsion disclosed by the invention is simple in preparation method, reasonable in process, free of organic silicon emulsifier, free of volatile organic compounds, environment-friendly in production and low in energy consumption.

The purpose of the invention is realized by the following technical scheme:

a preparation method of a novel epoxy silicone oil modified acrylate anti-doodling emulsion comprises the following steps:

(1) adding 20-24 parts of deionized water and 1.0-1.5 parts of a composite emulsifier into a reaction kettle, stirring for 20-40 minutes at 400-600 rpm, then dropwise adding a mixture of 30-36 parts of methyl methacrylate monomer, 10-16 parts of butyl acrylate monomer, 1.6-2.0 parts of acrylic acid monomer, 15-20 parts of hydroxyethyl methacrylate monomer and 0.6-1.2 parts of acrylamide monomer, dropwise adding for 40-80 minutes, and stirring for 30-60 minutes after dropwise adding to obtain the acrylic ester pre-emulsion.

(2) Adding 6-10 parts of the pre-emulsion in the step (1), 0.8-1.2 parts of an emulsifier, 0.08-0.12 part of an initiator and 50-58 parts of deionized water into a reaction kettle, dropwise adding 74-78 parts of the pre-emulsion and 0.16-0.24 part of the initiator (dissolved in 8-16 parts of deionized water), carrying out polymerization reaction for 2-4 hours at 80-90 ℃, keeping the temperature for 40-80 minutes after dropwise adding, cooling to normal temperature, and preparing the amide group-containing acrylate emulsion by a semi-continuous seed emulsion polymerization method.

(3) Adding 40-50 parts of double-end hydrogen-containing silicone oil, 1.2-1.8 parts of allyl glycidyl ether and 40-50 parts of solvent into a reaction kettle, stirring and heating to 75-95 ℃, then adding 0.03-0.05 part of catalyst, reacting for 20-40 minutes, raising the temperature to 100-120 ℃, preserving heat for 2-4 hours after the solution is reacted to be clear and transparent, and carrying out reduced pressure distillation to remove residual low-boiling-point substances, thus obtaining the epoxy-terminated silicone oil.

(4) And (3) adding 60-80 parts of the acylamino-containing acrylate emulsion in the step (2) into a reaction kettle, dropwise adding 2.4-3.2 parts of epoxy-terminated silicone oil, opening the reaction kettle at 60-80 ℃ for ring opening reaction for 10-18 minutes, and preserving heat for 2-4 hours after dropwise adding to obtain the target emulsion (the parts are in parts by weight).

Preferably, the composite emulsifier in the step (1) is a compound mixture of fatty alcohol polyoxyethylene ether disodium sulfosuccinate (A-102) and isomeric tridecanol polyoxyethylene ether (TO-8), and the compound ratio is 5:1, 7:1 and 9: 1.

Preferably, the emulsifier in the step (2) is fatty alcohol polyoxyethylene ether sulfosuccinic acid monoester disodium (A-102), and the initiator is potassium persulfate or ammonium persulfate or sodium persulfate.

The solvent in the step (3) is isopropanol or butanol or dimethyl sulfoxide, and the catalyst is chloroplatinic acid.

Further preferably, the novel epoxy silicone oil modified acrylate anti-doodling emulsion has the following structural formula:

advantageous effects

1) Compared with the conventional organic silicon modified acrylate anti-doodling emulsion, the anti-doodling emulsion has higher silicone oil introduction amount and excellent water resistance and stain resistance.

2) Compared with the conventional organic silicon modified acrylate anti-doodling emulsion, the anti-doodling emulsion disclosed by the invention does not lose activity due to self crosslinking polycondensation of organic silicon.

3) Compared with the conventional organic silicon modified acrylate anti-doodling emulsion, the anti-doodling emulsion disclosed by the invention can avoid the problems of reduced film forming performance, volatile organic compounds and the like caused by using an organic silicon emulsifier or cosolvent.

4) The anti-doodling emulsion has the characteristics of simple preparation method, no need of organic silicon emulsifier, environment-friendly production process, easy operation, no volatile organic matter and the like.

5) Compared with the conventional organic silicon modified acrylate anti-doodling emulsion, the anti-doodling emulsion disclosed by the invention has the advantages of strong adhesive force, good scrubbing resistance and ethanol resistance, excellent storage stability, weather resistance and chemical resistance, and can be widely applied to the fields of coatings, printing ink, adhesives and the like.

Detailed Description

The following description is given in conjunction with the preferred embodiments, which are given for illustration purposes only and do not limit the present invention.

A novel epoxy silicone oil modified acrylate anti-doodling emulsion has the following structural formula: