阅读说明：本技术 水性有机硅改性阳离子丙烯酸树脂及合成方法 (Water-based organic silicon modified cationic acrylic resin and synthetic method thereof ) 是由 郝隆 朱勇 于 2020-07-08 设计创作，主要内容包括：本发明公开了一种水性有机硅改性阳离子丙烯酸树脂及合成方法,其原料包括单体、功能性单体、溶剂、酸、链转移剂和引发剂；按重量份计：其中单体包括甲基丙烯酸甲酯100-400份、丙烯酸丁酯5-50份和苯乙烯20-200份；功能性单体包括乙烯基三乙氧基硅烷10-100份、甲基丙烯酸二甲胺基乙酯20-200份和丙烯酸羟乙酯30-250份；溶剂包括丙二醇甲醚100-400份、无水乙醇50-400份和N,N-二甲基甲酰胺20-200份；酸为乳酸5-60份；链转移剂为甲基苯乙烯线性二聚体1-50份；引发剂为偶氮二异丁腈1-50份。本发明解决了传统水性木器漆在硬度、透明度耐溶剂等性能不理想、成本高等根本问题,可完全替代油性PU木器漆,在注重环保的大形势下,能够为环境美化产生极大的优势,同时又不损失性能。(The invention discloses a water-based organic silicon modified cationic acrylic resin and a synthesis method thereof, wherein the raw materials comprise a monomer, a functional monomer, a solvent, an acid, a chain transfer agent and an initiator; the weight portion of the material is as follows: wherein the monomer comprises 100-400 parts of methyl methacrylate, 5-50 parts of butyl acrylate and 20-200 parts of styrene; the functional monomer comprises 10-100 parts of vinyl triethoxysilane, 20-200 parts of dimethylaminoethyl methacrylate and 30-250 parts of hydroxyethyl acrylate; the solvent comprises 400 parts of propylene glycol methyl ether 100-400 parts, 50-400 parts of absolute ethyl alcohol and 20-200 parts of N, N-dimethylformamide; the acid is 5-60 parts of lactic acid; the chain transfer agent is 1-50 parts of methyl styrene linear dimer; the initiator is 1-50 parts of azobisisobutyronitrile. The invention solves the fundamental problems of non-ideal performances of hardness, transparency, solvent resistance and the like, high cost and the like of the traditional water-based wood paint, can completely replace the oily PU wood paint, can generate great advantages for beautifying the environment under the large situation of focusing on environmental protection, and simultaneously does not lose the performance.)

1. The water-based organic silicon modified cationic acrylic resin is characterized in that raw materials comprise a monomer, a functional monomer, a solvent, an acid, a chain transfer agent and an initiator; the weight portion of the material is as follows:

wherein the monomer comprises 100-400 parts of methyl methacrylate, 5-50 parts of butyl acrylate and 20-200 parts of styrene;

the functional monomer comprises 10-100 parts of vinyl triethoxysilane, 20-200 parts of dimethylaminoethyl methacrylate and 30-250 parts of hydroxyethyl acrylate;

the solvent comprises 400 parts of propylene glycol methyl ether 100-400 parts, 50-400 parts of absolute ethyl alcohol and 20-200 parts of N, N-dimethylformamide;

the acid is 5-60 parts of lactic acid;

the chain transfer agent is 1-50 parts of methyl styrene linear dimer;

the initiator is 1-50 parts of azobisisobutyronitrile.

2. The aqueous silicone-modified cationic acrylic resin of claim 1, characterized in that: the functional monomer also comprises 10-100 parts of vinyl trimethoxy silane, 30-250 parts of hydroxyethyl methacrylate and 20-200 parts of dimethylaminopropyl methacrylate; wherein the vinyltrimethoxysilane is used for completely or partially replacing the vinyltriethoxysilane, the hydroxyethyl methacrylate is used for partially or completely replacing the hydroxyethyl acrylate, and the dimethylaminopropyl methacrylate is used for partially or completely replacing the dimethylaminoethyl methacrylate.

3. The aqueous silicone-modified cationic acrylic resin of claim 1, characterized in that: 5-60 parts of lactic acid is replaced by 5-50 parts of acetic acid.

4. The aqueous silicone-modified cationic acrylic resin of claim 1, characterized in that: 1-50 parts of the chain transfer agent methyl styrene linear dimer are replaced by 1-50 parts of n-dodecyl mercaptan.

5. The method for synthesizing the water-based organic silicon modified cationic acrylic resin as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:

1) uniformly mixing propylene glycol methyl ether and absolute ethyl alcohol serving as solvents, and heating to 85-95 ℃;

2) uniformly mixing a monomer, a functional monomer, a chain transfer agent, a solvent N, N-dimethylformamide and an initiator to obtain a mixed solution;

3) adding the mixed solution obtained in the step 2) into the solvent obtained in the step 1);

4) step 3), after the dropwise addition is finished, controlling the temperature to be 85-95 ℃ and preserving the heat for 1-2 h; then cooling to below 50 ℃;

5) adding acid into the feed liquid obtained in the step 4), and stirring for more than 30min to obtain the water-based organic silicon modified cationic acrylic resin.

6. The method of claim 5, wherein: and 3) adopting a dripping mode during the addition in the step 3), and stirring while dripping, wherein the addition is finished within 3-6 hours.

7. The method of claim 5, wherein: and 4) cooling by adopting a cooling water medium during cooling in the step 4).

8. An aqueous paint prepared by using the aqueous organosilicon modified cationic acrylic resin according to any one of claims 1 to 4.

9. Use of the aqueous paint of claim 8 in aqueous wood or plastic paints.

Technical Field

The invention relates to furniture decoration and fitment, in particular to a water-based organic silicon modified cationic acrylic resin and a synthesis method thereof.

Background

Since 2015, some regulations and policies are formulated in succession in China, the environmental protection law is formally implemented from 1 month and 1 day 2015, the punishment of the new environmental protection law on enterprises is greatly strengthened, and in order to promote energy conservation and environmental protection, consumption taxes are imposed on batteries and coatings from 2 months and 1 day 2015 after approval of state hospitals. The most severe environmental protection law in history is established, and the collection of coating consumption tax causes severe challenges to the traditional paint industry.

In 6 months of 2015, 3 standards of waterborne industrial coating products, namely waterborne polyurethane coating HG/T4761-2014, waterborne epoxy resin anticorrosive coating HG/T4759-2014 and waterborne acrylic resin coating HG/T4758-2014, which are set by the national technical committee for coating and pigment standardization, are officially implemented from 1 day of 6 months. In 7 months in 2015, solvent-based paint is prohibited from sale in Shenzhen market from 7 months. In 2015, month 7, the "coating for inner walls of children's playgrounds" standard in Guangdong began to be established. The latest revision, called "air pollution control law" with the most severe history, will be performed from 2016, 1/1. The Volatile Organic Compound (VOCS) is brought into the supervision range for the first time, and the opportunity is brought to the popularization of the environmental protection technology while the 'spell of tightening' is brought to enterprises.

The existing waterborne wood lacquer on the market mainly takes anionic emulsion resin as a main material, has the defects of poor sealing property, low hardness, slow drying, low fullness, low solid content, poor permeability and poor temperature resistance, is mainly used for coating children furniture, and cannot meet the hardness and the tolerance required by office furniture.

Disclosure of Invention

In order to solve the technical problems, the invention provides a water-based organic silicon modified cationic acrylic resin and a synthesis method thereof, which solve the defects of insufficient hardness, fullness, transparency and resistance of the existing water-based resin in the preparation of high-grade water-based wood paint.

The technical scheme adopted by the invention is that the raw materials of the water-based organic silicon modified cationic acrylic resin comprise a monomer, a functional monomer, a solvent, an acid, a chain transfer agent and an initiator; the weight portion of the material is as follows:

wherein the monomer comprises 100-400 parts of methyl methacrylate, 5-50 parts of butyl acrylate and 20-200 parts of styrene;

the functional monomer comprises 10-100 parts of vinyl triethoxysilane, 20-200 parts of dimethylaminoethyl methacrylate and 30-250 parts of hydroxyethyl acrylate;

the solvent comprises 400 parts of propylene glycol methyl ether 100-400 parts, 50-400 parts of absolute ethyl alcohol and 20-200 parts of N, N-dimethylformamide;

the acid is 5-60 parts of lactic acid;

the chain transfer agent is 1-50 parts of methyl styrene linear dimer;

the initiator is 1-50 parts of azobisisobutyronitrile.

According to the formula, a solution polymerization technology is utilized, methyl methacrylate, butyl acrylate and styrene are utilized for polymerization under the initiation of an initiator azobisisobutyronitrile, functional monomers of vinyl triethoxysilane, dimethylaminoethyl methacrylate and hydroxyethyl acrylate are introduced at the same time, vinyl in the vinyl triethoxysilane can also participate in double bond reaction, silicon materials are introduced into the whole water-based resin, and lactic acid is used for neutralization, so that the water-based organic silicon modified cationic acrylic resin with high solid content, good transparency and good water solubility is obtained.

The functional monomer of dimethylaminoethyl methacrylate contains acrylic double bond functional groups, and the acrylic double bond can carry out free radical polymerization with other double bonds. The functional monomer dimethylaminoethyl methacrylate contains amino functional groups, and the amino and acid neutralization can provide water solubility, so that the synthesized resin can be dissolved in water.

Further, the functional monomer also comprises 10-100 parts of vinyl trimethoxy silane, 30-250 parts of hydroxyethyl methacrylate and 20-200 parts of dimethylaminopropyl methacrylate; wherein the vinyltrimethoxysilane is used for completely or partially replacing the vinyltriethoxysilane, the hydroxyethyl methacrylate is used for partially or completely replacing the hydroxyethyl acrylate, and the dimethylaminopropyl methacrylate is used for partially or completely replacing the dimethylaminoethyl methacrylate. The vinyl trimethoxy silane functional monomer is added to introduce silicon materials into the resin, and the resin with the introduced silicon materials has higher hardness and resistance. The hydroxyethyl methacrylate is added to introduce hydroxyl functional groups into the resin, thereby improving the solvent resistance and the gloss of the resin. Dimethylamino propyl methacrylate is added to introduce amine functional groups into the resin, and the neutralization of the amine and acid can provide water solubility and provide a water-soluble material.

Further, 5-60 parts of lactic acid is replaced by 5-50 parts of acetic acid. The purpose of adding acetic acid or lactic acid is to perform neutralization reaction with amino functional groups in the methacrylic acid dimethylamino propyl ester or methacrylic acid dimethylamino ethyl ester, and the synthesized resin has water solubility.

Further, 1-50 parts of the chain transfer agent methyl styrene linear dimer is replaced by 1-50 parts of n-dodecyl mercaptan. The chain transfer agent is added to control the molecular weight of the synthesized resin, and the molecular weight distribution of the synthesized waterborne resin can be more concentrated and the performance is more excellent after the chain transfer agent is added.

The invention also relates to a synthetic method of the waterborne organic silicon modified cationic acrylic resin, which comprises the following steps:

1) uniformly mixing propylene glycol methyl ether and absolute ethyl alcohol serving as solvents, and heating to 85-95 ℃;

2) uniformly mixing a monomer, a functional monomer, a chain transfer agent, a solvent N, N-dimethylformamide and an initiator to obtain a mixed solution;

3) adding the mixed solution obtained in the step 2) into the solvent obtained in the step 1);

4) step 3), after the dropwise addition is finished, controlling the temperature to be 85-95 ℃ and preserving the heat for 1-2 h; then cooling to below 50 ℃;

5) adding acid into the feed liquid obtained in the step 4), and stirring for more than 30min to obtain the water-based organic silicon modified cationic acrylic resin.

Further, in the step 3), a dropwise adding mode is adopted during the adding, and the stirring is carried out while dropwise adding, and the adding is controlled to be finished within 3-6 hours. The purpose of dropwise adding in the step 3) is to control the reaction degree, the reaction process can be controlled by adopting the dropwise adding, the dropwise added monomer can fully react, and the molecular weight distribution of the synthesized waterborne resin is narrower by adopting the dropwise adding mode. The explosive polymerization cannot be generated due to excessive addition at one time, so that the safety and reliability of the dropwise addition production mode are ensured.

Further, cooling by adopting a cooling water medium during cooling in the step 4).

The invention also relates to a water paint prepared from the water-based organic silicon modified cationic acrylic resin.

The invention also relates to application of the water-based paint in water-based wood paint or water-based plastic paint.

The invention has the beneficial effects that:

1. the water-based organic silicon modified acrylic resin synthesized by the method can be self-dried to form a film at normal temperature. The water-based resin is used for manufacturing water-based two-component bright paint, and the touch drying time is about 1 hour at normal temperature. The water-based resin used by the original water-based two-component glossy clear finish is high-hydroxyl resin, and the normal-temperature finger-touch drying time of the water-based two-component glossy finish prepared by the water-based resin is more than 4 hours.

2. The synthesized water-based organic silicon modified acrylic resin has the characteristic of high solid content, adopts a solution polymerization technology, introduces dimethylamino ethyl methacrylate hydrophilic monomers in the synthesis process, and neutralizes by adding acetic acid or lactic acid. Meanwhile, a chain transfer agent is added into the formula, so that the molecular weight of the synthesized waterborne resin can be controlled, the molecular weight distribution of the synthesized waterborne resin is narrow, the waterborne resin with high solid content and low viscosity, which is good in water solubility, is obtained, and the solid content reaches 60%. The water-based wood lacquer made of the water-based resin with high solid content has higher solid content, so that the water-based wood lacquer has high construction solid content and good fullness.

3. The synthesized aqueous organic silicon modified acrylic resin has excellent transparency, the aqueous resin adopts a solution polymerization technology, and the synthesized aqueous resin is transparent resin, so that the problem of poor transparency of emulsion resin is solved. The existing emulsion type transparency is similar to milk and is in a semitransparent state or even opaque.

4. The waterborne organic silicon modified acrylic resin is used for preparing waterborne wood paint, and then the waterborne inorganic polysiloxane resin (such as a product in patent application 2017105337250) of the Hubei Jiadefu paint GmbH is matched to be used as a curing agent to prepare the bi-component waterborne wood paint which has excellent hardness and tolerance and can be widely used for preparing top coat for high-grade office furniture. Hardness is more than 3H, water resistance is more than 144 hours, alcohol resistance is more than 24 hours, and acetone wiping resistance is more than 100 times.

5. The traditional resin and paint production line can be used without more investment.

In conclusion, the invention solves the fundamental problems of non-ideal performances of hardness, transparency, solvent resistance and the like, high cost and the like of the traditional water-based wood paint, can completely replace the oil-based PU wood paint, can generate great advantages for beautifying the environment under the large situation of focusing on environmental protection, and simultaneously does not lose the performances.

Detailed Description

The invention will be further elucidated with reference to the following examples.