阅读说明：本技术 含磺基磷酸根的二乙烯有机硅改性丙烯酸水分散体及其制备方法与应用 (Sulfophosphoric acid radical-containing divinyl organic silicon modified acrylic acid aqueous dispersion and preparation method and application thereof ) 是由 郭逍遥 马晓阳 汤汉良 王辉 赖浩城 郭伟杰 何再学 刘其平 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种含磺基磷酸根的二乙烯有机硅改性丙烯酸水分散体及其制备方法与应用。制备方法包括如下步骤：将丙烯酸、二甲基丙烯酸、丙烯酸异冰片酯、聚乙二醇丙烯酸磺酸盐、聚乙二醇丙烯酸磷酸盐、二乙烯基四甲基二硅氧烷、引发剂和链转移剂混匀,反应,得到预聚体,采用三乙胺中和,脱气,加水乳化,得到水分散体。该水分散体具有优异的贮存稳定性及阳离子稳定,透明度好,粘度低；采用该水分散体得到的涂料VOC含量小于10.0％,符合最严格的环保要求,对环境友好,且具有高硬度、高光泽、极佳的丰满度及美观效果,还具有优良的物理化学性能和良好的储存稳定性,具有较高的推广应用价值。(The invention discloses a divinyl organic silicon modified acrylic acid aqueous dispersion containing sulfo phosphate and a preparation method and application thereof. The preparation method comprises the following steps: uniformly mixing acrylic acid, dimethylacrylic acid, isobornyl acrylate, polyethylene glycol acrylate sulfonate, polyethylene glycol acrylate phosphate, divinyl tetramethyl disiloxane, an initiator and a chain transfer agent, reacting to obtain a prepolymer, neutralizing with triethylamine, degassing, and adding water for emulsification to obtain the aqueous dispersion. The aqueous dispersion has excellent storage stability and cation stability, good transparency and low viscosity; the VOC content of the coating obtained by adopting the aqueous dispersion is less than 10.0 percent, meets the strictest environmental protection requirement, is environment-friendly, has high hardness, high gloss, excellent fullness and beautiful effect, has excellent physical and chemical properties and good storage stability, and has higher popularization and application values.)

1. A preparation method of divinyl organic silicon modified acrylic acid aqueous dispersion containing sulfo phosphate is characterized by comprising the following steps:

(1) synthesis of polyethylene glycol ethyl acrylate: mixing polyethylene glycol, ethyl acrylic acid chloride, a solvent and a catalyst, and reacting to obtain polyethylene glycol ethyl acrylate;

(2) synthesis of polyethylene glycol ethacrylic acid sulfonate: mixing the polyethylene glycol ethyl acrylate and sodium carbonate in the step (1), adding sodium methyl acrylate, mixing again, and reacting to obtain polyethylene glycol ethyl acrylate sulfonate;

(3) synthesis of polyethylene glycol acrylate phosphate: mixing polyethylene glycol phosphate, acrylic acid acyl chloride, a solvent and a catalyst, and reacting to obtain polyethylene glycol acrylic acid phosphate;

(4) preparing a divinyl organic silicon modified acrylate prepolymer containing sulfo phosphate radicals: uniformly mixing acrylic acid, dimethylacrylic acid, isobornyl acrylate, polyethylene glycol ethyl acrylate sulfonate in the step (2), polyethylene glycol acrylic phosphate in the step (3), divinyl tetramethyl disiloxane, an initiator and a chain transfer agent, and reacting to obtain a divinyl organic silicon modified acrylate prepolymer containing sulfo phosphate;

(5) preparation of aqueous dispersion: and (4) carrying out neutralization reaction on the divinyl organic silicon modified acrylate prepolymer containing the sulfo phosphate radical in the step (4) by adopting triethylamine, degassing and emulsifying to obtain the divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate radical.

2. The production method according to claim 1,

the catalyst in the step (1) is p-toluenesulfonic acid;

in the step (1), the solvent is cyclohexane and toluene according to a molar ratio of 3: 1 proportion of mixed solvent;

the polyethylene glycol phosphate in the step (3) is vacuum dehydrated polyethylene glycol phosphate;

the catalyst in the step (3) is styrene phosphoric acid;

the solvent in the step (3) is cyclohexane;

in the step (4), the initiator is at least one of potassium persulfate, sodium persulfate and ammonium persulfate;

in the step (4), the chain transfer agent is at least one of tert-dodecyl mercaptan and n-dodecyl mercaptan.

3. The production method according to claim 1 or 2,

in the step (1), the molar ratio of the polyethylene glycol to the ethyl acrylic acid chloride is 0.5-1: 1-2;

the dosage of the catalyst in the step (1) is 1-5% of the molar weight of the polyethylene glycol;

the dosage of the solvent in the step (1) is 1 to 1.5 times of the molar weight of the polyethylene glycol;

the molar weight relationship among the polyethylene glycol ethyl acrylate, the sodium carbonate and the sodium methallyl sulfonate in the step (2) is 5-6: 0.1-0.5: 2-3;

in the step (3), the molar ratio of the polyethylene glycol phosphate to the acrylic acid chloride is 0.5-1: 1-2;

the dosage of the catalyst in the step (3) is 1-4% of the molar weight of the polyethylene glycol phosphate;

in the step (3), the solvent is cyclohexane, and the dosage of the solvent is 2-3 times of the molar weight of the polyethylene glycol phosphate;

in the step (4), the molar weight ratio of the acrylic acid to the dimethylacrylic acid to the isobornyl acrylate to the polyethylene glycol ethyl acrylate sulfonate to the polyethylene glycol acrylic acid phosphate to the divinyl tetramethyl disiloxane is 16-23: 8-13: 6-10: 5-10: 10-15: 8-12;

the using amount of the initiator in the step (4) accounts for 2-3% of the total mass;

the amount of the chain transfer agent in the step (4) accounts for 3-5% of the total mass;

in the step (5), the dosage of the triethylamine is 0.5-1 time of the molar weight of the prepolymer;

in the step (5), the emulsification is carried out by adopting water, and the using amount of the water is 0.3-0.4 time of the mass of the prepolymer.

4. The production method according to claim 3,

in the step (1), the molar ratio of the polyethylene glycol to the ethyl acrylic acid chloride is 1: 1;

in the step (3), the molar ratio of the polyethylene glycol phosphate to the acrylic acid chloride is 1: 1;

in the step (4), the molar weight ratio of the acrylic acid to the dimethylacrylic acid to the isobornyl acrylate to the polyethylene glycol ethyl acrylate sulfonate to the polyethylene glycol acrylic acid phosphate to the divinyl tetramethyl disiloxane is 18: 12: 8: 6: 12: 10.

5. the production method according to claim 1,

dehydrating the polyethylene glycol in vacuum before the reaction in the step (1);

the reaction in the step (1) is carried out for 6-16h at the temperature of 70-95 ℃;

the mixing time in the step (2) is 1-2 h;

the reaction time in the step (2) is 24-28 h;

the polyethylene glycol phosphate in the step (3) is vacuum dehydrated polyethylene glycol phosphate;

the reaction in the step (3) is carried out for 4-12h at the temperature of 60-90 ℃;

the reaction temperature in the step (4) is 90-95 ℃;

and (4) the reaction in the step (4) is that the uniformly mixed mixture is firstly taken to react according to the mass ratio of 8-15%, and then the rest mixture is uniformly dripped into the mixture for reaction again.

6. The production method according to claim 5,

the reaction in the step (1) is carried out for 8 hours at the temperature of 90 ℃;

the reaction in the step (3) is carried out for 5 hours at the temperature of 80 ℃;

the dripping time is 4-5 h;

the reaction time and the secondary reaction time are adjusted according to the mass ratio of the mixture of the two reactions, and the total time is 5.5 to 6.5 hours.

7. The production method according to claim 1,

the polymerization degree of the polyethylene glycol in the step (1) is 600-1000;

the reaction in the step (1) is carried out under the condition of introducing nitrogen;

removing the solvent before the product obtained by the reaction in the step (1) is subjected to the next reaction;

purifying the polyethylene glycol ethyl acrylate sulfonate in the step (2) and then participating in the next step, wherein the purification method comprises the steps of dissolving the polyethylene glycol ethyl acrylate sulfonate in methanol, extracting the dissolved polyethylene glycol ethyl acrylate sulfonate by using n-hexane, and evaporating ethanol to obtain a purified product;

the reaction in the step (3) is carried out under the condition of introducing nitrogen;

removing the solvent before the product obtained by the reaction in the step (3) is subjected to the next reaction;

and (5) vacuumizing and degassing.

8. An aqueous dispersion of divinyl silicone modified acrylic acid containing a sulphophosphate radical, characterised in that it is obtained by a process according to any one of claims 1 to 7.

9. Use of the sulfophosphate-containing aqueous divinyl silicone modified acrylic dispersion of claim 8 in acrylic automotive coatings.

10. The automobile coating is characterized by comprising the following components in parts by weight: 100 parts of divinyl organic silicon modified acrylic acid aqueous dispersion containing sulfo phosphate, 0.1-1.5 parts of wetting agent, 0.1-0.3 part of defoaming agent, 0.1-0.5 part of flatting agent, 0.2-0.8 part of thickening agent, 15-45 parts of pigment, 0.1-0.2 part of functional auxiliary agent and 5-8 parts of water;

the functional auxiliary agent is at least one of an emulsion ph regulator, a wetting agent and a dispersing agent.

Technical Field

The invention relates to the technical field of organosilicon modified acrylic acid aqueous dispersions, in particular to a divinyl organosilicon modified acrylic acid aqueous dispersion containing sulfo phosphate, a preparation method and application thereof.

Background

With the rapid development of the automobile industry, China has become the largest automobile producing and selling country in the world, has huge automobile reserves, and has become an indispensable part in life. Along with the improvement of the standard of life quality, people pay more and more attention to health and environmental protection. However, in the field of automobile coatings, the acrylic acid aqueous dispersion has the problems of sensitivity to temperature, obvious hot adhesion and cold brittleness, low solid content, high viscosity, much VOC residue and the like.

In recent years, the emergence of environment-friendly low-emission acrylic acid aqueous dispersion opens up a new way for preparing high-performance high-molecular polymers. The acrylic acid water dispersion high hydroxylation, ionization, organic silicon modification and other technologies have the advantages of improving solid content, reducing VOC, improving coating performance and the like. However, the content of polar groups such as carboxyl and hydroxyl in the high-hydroxylated acrylic resin aqueous dispersion is too high, which easily causes the viscosity abnormality of the aqueous dispersion system; the ionized acrylic acid aqueous dispersion is characterized in that salt-containing groups with extremely strong water solubility, such as sulfonate, are directly introduced to a polymer molecular chain, and the strong acid and strong base salt structure of the ionized acrylic acid aqueous dispersion can improve the viscosity of the acrylic acid aqueous dispersion, but the film-forming brittleness of the ionized acrylic acid aqueous dispersion is improved; the organosilicon modification can obviously improve the water resistance, heat resistance and hardness of the resin, but has poor water solubility.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a divinyl organic silicon modified acrylic acid aqueous dispersion containing sulfo phosphate.

The invention also aims to provide a preparation method of the divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate.

The invention also aims to provide application of the divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate.

The purpose of the invention is realized by the following technical scheme: a preparation method of divinyl organic silicon modified acrylic acid aqueous dispersion containing sulfo phosphate comprises the following steps:

(1) synthesis of polyethylene glycol ethyl acrylate (Poly (ethylene glycol) ethyl acrylate, PEGEA): mixing polyethylene glycol (PEG), ethyl acrylic acid chloride, a solvent and a catalyst, and reacting to obtain polyethylene glycol ethyl acrylate;

preferably, the polymerization degree of the polyethylene glycol in the step (1) is 600-1000; more preferably, the degree of polymerization is 1000.

Preferably, the polyethylene glycol is dehydrated under vacuum before the reaction in step (1).

Preferably, the catalyst in step (1) is p-toluenesulfonic acid.

Preferably, the solvent in step (1) is cyclohexane and toluene in a molar ratio of 3: 1 proportion of mixed solvent.

Preferably, the molar ratio of the polyethylene glycol to the ethyl acrylic acid chloride in the step (1) is 0.5-1: 1-2; more preferably, the molar ratio is 1: 1.

preferably, the catalyst is used in step (1) in an amount of 1-5% by mole based on the polyethylene glycol.

Preferably, the solvent used in step (1) is 1 to 1.5 times the molar amount of the polyethylene glycol.

Preferably, the reaction in the step (1) is carried out for 6 to 16 hours at the temperature of between 70 and 95 ℃; more preferably, the reaction is carried out at 90 ℃ for 8 h.

Preferably, the reaction in step (1) is carried out under nitrogen gas.

Preferably, the solvent is removed from the product obtained by the reaction in step (1) before the next reaction.

(2) Synthesis of polyethylene glycol ethacrylic acid sulfonate: mixing the polyethylene glycol ethyl acrylate and sodium carbonate in the step (1), adding sodium methyl acrylate, mixing again, and reacting to obtain polyethylene glycol ethyl acrylate sulfonate;

preferably, the molar weight relationship among the polyethylene glycol ethyl acrylate, the sodium carbonate and the sodium methallyl sulfonate in the step (2) is 5-6: 0.1-0.5: 2-3.

Preferably, the mixing time in step (2) is 1-2 h.

Preferably, the reaction time in step (2) is 24-28 h.

Preferably, the polyethylene glycol ethyl acrylate sulfonate in the step (2) is purified and then participates in the next step, and the purification method comprises the steps of dissolving the polyethylene glycol ethyl acrylate sulfonate in methanol, extracting the dissolved polyethylene glycol ethyl acrylate sulfonate with n-hexane, and evaporating ethanol to obtain a purified product.

(3) Synthesis of polyethylene glycol acrylate phosphate: mixing polyethylene glycol phosphate, acrylic acid acyl chloride, a solvent and a catalyst, and reacting to obtain polyethylene glycol acrylic acid phosphate;

preferably, the polyethylene glycol phosphate in step (3) is a vacuum dehydrated polyethylene glycol phosphate.

Preferably, the catalyst in step (3) is styrene phosphoric acid.

Preferably, the solvent in step (3) is cyclohexane.

Preferably, the molar ratio of the polyethylene glycol phosphate to the acrylic acid chloride in the step (3) is 0.5-1: 1-2; more preferably, the molar ratio is 1: 1.

Preferably, the amount of the catalyst used in step (3) is 1-4% of the molar amount of the polyethylene glycol phosphate.

Preferably, the solvent in step (3) is cyclohexane, and the amount of the cyclohexane is 2 to 3 times of the molar weight of the polyethylene glycol phosphate.

Preferably, the reaction in the step (3) is carried out at the temperature of 60-90 ℃ for 4-12 h; more preferably, the reaction is carried out at 80 ℃ for 5 h.

Preferably, the reaction in step (3) is carried out under nitrogen gas.

Preferably, the solvent is removed from the product obtained by the reaction in step (3) before the next reaction.

(4) Preparing a divinyl organic silicon modified acrylate prepolymer containing sulfo phosphate radicals: uniformly mixing acrylic acid, dimethylacrylic acid, isobornyl acrylate, polyethylene glycol ethyl acrylate sulfonate in the step (2), polyethylene glycol acrylic phosphate in the step (3), divinyl tetramethyl Disiloxane (DVMS), an initiator and a chain transfer agent, and reacting to obtain a divinyl organic silicon modified acrylate prepolymer containing sulfo phosphate;

preferably, the molar weight ratio of the acrylic acid, the dimethylacrylic acid, the isobornyl acrylate, the polyethylene glycol ethyl acrylate sulfonate, the polyethylene glycol acrylic acid phosphate and the divinyl tetramethyl disiloxane in the step (4) is 16-23: 8-13: 6-10: 5-10: 10-15: 8-12; more preferably, the molar ratio is 18: 12: 8: 6: 12: 10.

preferably, the initiator in the step (4) is at least one of potassium persulfate, sodium persulfate and ammonium persulfate.

Preferably, the chain transfer agent in the step (4) is at least one of tert-dodecyl mercaptan and n-dodecyl mercaptan; more preferably, the chain transfer agent is tert-dodecyl mercaptan.

Preferably, the amount of the initiator used in step (4) is 2 to 3% by mass of the total mass.

Preferably, the chain transfer agent is used in the step (4) in an amount of 3 to 5% by mass based on the total mass.

Preferably, the temperature of the reaction in step (4) is 90-95 ℃.

Preferably, the reaction in the step (4) is to take 8-15% of the uniformly mixed mixture by mass ratio for reaction, and then uniformly dropwise add the rest mixture for reaction again.

Preferably, the dropping time is 4-5 h.

Preferably, the time of the reaction and the re-reaction is adjusted according to the mass ratio of the two reaction mixtures, and the total time is 5.5 to 6.5 hours.

(5) Preparation of aqueous dispersion: and (4) carrying out neutralization reaction on the divinyl organic silicon modified acrylate prepolymer containing the sulfo phosphate radical in the step (4) by adopting triethylamine, degassing and emulsifying to obtain the divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate radical.

Preferably, the amount of the triethylamine in the step (5) is 0.5-1 time of the molar amount of the prepolymer.

Preferably, the degassing in step (5) is vacuum degassing.

Preferably, the emulsification in the step (5) is carried out by adopting water, and the using amount of the water is 0.3-0.4 time of the mass of the prepolymer.

The divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate radical is prepared by the preparation method.

The application of the divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate in acrylic resin automobile coatings.

An automobile coating comprises the following components in parts by weight: 100 parts of divinyl organic silicon modified acrylic acid aqueous dispersion containing sulfo phosphate, 0.1-1.5 parts of wetting agent, 0.1-0.3 part of defoaming agent, 0.1-0.5 part of flatting agent, 0.2-0.8 part of thickening agent, 15-45 parts of pigment, 0.1-0.2 part of functional auxiliary agent and 5-8 parts of water.

Preferably, the functional auxiliary agent is at least one of an emulsion ph regulator, a wetting agent and a dispersing agent; more preferably, at least one of AN-100 and AMP-95.

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

the invention starts from an acrylate polymerization structure, introduces polyethylene glycol with high hydroxyl into an acrylic acid aqueous dispersion, introduces sulfo and phosphate groups with hydrophilicity, and simultaneously utilizes bimolecular vinyl siloxane to carry out organic silicon modification to obtain the divinyl organic silicon modified acrylic acid aqueous dispersion containing sulfo phosphate. On one hand, the introduction of the sulfonate and the phosphate ensures that the aqueous dispersion contains stronger hydrophilic anionic groups, so that the solid content of the aqueous dispersion can be greatly improved; meanwhile, the water dispersion also contains an ethoxy nonionic chain segment, so that excellent storage and cation stability can be endowed to the water dispersion; on the other hand, the bimolecular vinyl organic silicon modification greatly improves the transparency of the aqueous dispersion, reduces the viscosity, improves the compactness and the glossiness of the coating, improves the adhesive force and the like. The VOC content of the coating obtained by adopting the aqueous dispersion is less than 10.0 percent, the coating completely meets the strictest environmental protection requirement, is extremely friendly to the environment, has high hardness, high gloss, excellent fullness and beautiful effect, excellent physical and chemical properties and good storage stability, has higher popularization and application values, and has important social significance for the development of novel green and environment-friendly resin automobile coatings.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

EXAMPLE 1 preparation of a Sulfophosphate-containing aqueous divinyl Silicone modified acrylic Dispersion

Step S1: synthesis of polyethylene glycol Ethyl acrylate (PEGEA): taking a mixed solution of cyclohexane and toluene (molar ratio of 3: 1) with the same total molar amount as polyethylene glycol as a reaction solvent, and mixing the polyethylene glycol 1000 subjected to vacuum dehydration and ethyl acrylic acid chloride according to a molar ratio of 1:1, adding a catalyst p-toluenesulfonic acid (3% of the molar weight of polyethylene glycol) into a reaction kettle solvent, introducing nitrogen, reacting at 90 ℃ for 8 hours, removing the reaction solvent to obtain polyethylene glycol ethyl acrylate, wherein the yield reaches 96%;

step S2: synthesis of polyethylene glycol ethacrylic acid sulfonate: adding the polyethylene glycol ethyl acrylate obtained in the step S1 into a reaction kettle, adding sodium carbonate with the molar weight of 10% of the polyethylene glycol ethyl acrylate, mixing for 2 hours at room temperature, adding sodium methallyl sulfonate with the molar weight of 40% of the polyethylene glycol ethyl acrylate, mixing, reacting for 24 hours at room temperature, dissolving a reaction product in methanol, extracting for three times by using n-hexane, washing away unreacted raw materials and other impurities, and evaporating methanol to obtain sodium polyethylene glycol ethyl acrylate;

step S3: synthesis of polyethylene glycol sodium acrylate phosphate: cyclohexane with 2 times of molar weight of polyethylene glycol sodium phosphate is used as a reaction solvent, and the molar ratio of 1: adding 1 of polyethylene glycol sodium phosphate and acrylic acid acyl chloride into a reaction kettle solvent, adding a catalyst styrene phosphoric acid (2% of the molar weight of the polyethylene glycol sodium acrylate phosphate), introducing nitrogen, reacting for 5 hours at 80 ℃, and removing the reaction solvent to obtain polyethylene glycol sodium acrylate phosphate, wherein the yield reaches 95%;

step S4: preparing a divinyl organic silicon modified acrylate prepolymer containing sulfo phosphate radicals: taking the molar ratio as 18: 12: 8: 6: 12: 10 of acrylic acid, dimethyl acrylic acid, isobornyl acrylate, polyethylene glycol ethyl acrylic acid sodium sulfonate, polyethylene glycol acrylic acid sodium phosphate and divinyl tetramethyl Disiloxane (DVMS), adding an initiator potassium persulfate (accounting for 2 percent of the total mass) and a chain transfer agent tert-dodecyl mercaptan (accounting for 3 percent of the total mass), and uniformly mixing to obtain a monomer mixture. Firstly, monomer mixture with the mass ratio of 8% is put into a reaction kettle at one time, the reaction is carried out for 30 minutes at the temperature of 90 ℃, the residual monomer mixture is evenly dripped within 5 hours, the reaction is carried out for 6 hours at the temperature of 90 ℃, and then the conversion rate can reach 99.8%.

Step S5: preparation of aqueous dispersion: and (2) performing neutralization reaction on the divinyl organic silicon modified acrylate prepolymer containing the sulfo phosphate radical obtained in the step (S4) by adopting triethylamine (the molar ratio is 1: 1), vacuumizing and degassing, and adding water (0.3 time of the mass of the prepolymer) for emulsification to obtain the divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate radical, wherein the performances of the divinyl organic silicon modified acrylic acid aqueous dispersion are shown in Table 1.

TABLE 1 examination of the Properties of the aqueous dispersions

The solid content of the water dispersion reaches 47.5 percent, the viscosity is 427 mPa.s, the pencil hardness is 2H, the glossiness reaches 95, and the water dispersion has the advantages of high solid content, stable storage, cation stability, good transparency, low viscosity and the like.

Example 2

EXAMPLE 1 preparation of a Sulfophosphate-containing aqueous divinyl Silicone modified acrylic Dispersion

Step S1: synthesis of polyethylene glycol Ethyl acrylate (PEGEA): taking a mixed solution of cyclohexane and toluene (molar ratio of 3: 1) with the total molar amount being 1.5 times of the molar amount of polyethylene glycol as a reaction solvent, and mixing the polyethylene glycol 600 and the ethyl acrylic acid chloride dehydrated in vacuum according to the molar ratio of 1: 1.5, adding a catalyst p-toluenesulfonic acid (1% of the molar weight of polyethylene glycol) into a reaction kettle solvent, introducing nitrogen, reacting at 70 ℃ for 12 hours, removing the reaction solvent to obtain polyethylene glycol ethyl acrylate, wherein the yield reaches 94%;

step S2: synthesis of polyethylene glycol ethacrylic acid sulfonate: adding the polyethylene glycol ethyl acrylate obtained in the step S1 into a reaction kettle, adding sodium carbonate with the molar weight of 4% of the polyethylene glycol ethyl acrylate, mixing for 1h at room temperature, adding sodium methallyl sulfonate with the molar weight of 50% of the polyethylene glycol ethyl acrylate, mixing, reacting for 26h at room temperature, dissolving a reaction product in methanol, extracting for three times by using n-hexane, washing away unreacted raw materials and other impurities, and evaporating methanol to obtain sodium polyethylene glycol ethyl acrylate;

step S3: synthesis of polyethylene glycol sodium acrylate phosphate: cyclohexane with the molar weight 3 times that of polyethylene glycol sodium phosphate is used as a reaction solvent, and the molar ratio of 1: 2, adding polyethylene glycol sodium phosphate and acrylic acid acyl chloride into a reaction kettle solvent, adding a catalyst styrene phosphoric acid (the molar weight of the polyethylene glycol sodium acrylate phosphate is 3%), introducing nitrogen, reacting for 8 hours at 90 ℃, and removing the reaction solvent to obtain polyethylene glycol sodium acrylate phosphate, wherein the yield reaches 95%;

step S4: preparing a divinyl organic silicon modified acrylate prepolymer containing sulfo phosphate radicals: taking the molar ratio as 20: 9: 8: 8: 10: 10 of acrylic acid, dimethyl acrylic acid, isobornyl acrylate, polyethylene glycol ethyl acrylic acid sodium sulfonate, polyethylene glycol acrylic acid sodium phosphate and divinyl tetramethyl Disiloxane (DVMS), adding an initiator sodium persulfate (accounting for 3 percent of the total mass) and a chain transfer agent tert-dodecyl mercaptan (accounting for 5 percent of the total mass), and uniformly mixing to obtain a monomer mixture. Firstly, a monomer mixture with the mass ratio of 10% is put into a reaction kettle at one time, the reaction is carried out for 30 minutes at the temperature of 92 ℃, the residual monomer mixture is uniformly dripped within 4 hours, the reaction is carried out for 6 hours at the temperature of 92 ℃, and then the conversion rate can reach 99.7%.

Step S5: preparation of aqueous dispersion: and (3) carrying out neutralization reaction on the divinyl organic silicon modified acrylate prepolymer containing the sulfo phosphate radical obtained in the step (S4) by adopting triethylamine (the molar ratio of the prepolymer to the triethylamine is 2: 1), vacuumizing and degassing, and adding water (0.3 time of the mass of the prepolymer) for emulsification to obtain the divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate radical.

The performance of the obtained aqueous dispersion was measured by the same method as in example 1, and the results showed that the aqueous dispersion had a solid content of 47%, a viscosity of 430mPa · s, a pencil hardness of 2H, and a gloss of 95, and had the advantages of high solid content, storage stability, cationic stability, good transparency, low viscosity, and the like.

Example 3

EXAMPLE 1 preparation of a Sulfophosphate-containing aqueous divinyl Silicone modified acrylic Dispersion

Step S1: synthesis of polyethylene glycol Ethyl acrylate (PEGEA): taking a mixed solution of cyclohexane and toluene (molar ratio of 3: 1) with the same total molar amount as polyethylene glycol as a reaction solvent, and mixing the polyethylene glycol 800 and the ethacrylic acid chloride dehydrated in vacuum according to a molar ratio of 0.5: 1, adding a catalyst p-toluenesulfonic acid (5% of the molar weight of polyethylene glycol) into a reaction kettle solvent, introducing nitrogen, reacting at 80 ℃ for 15 hours, removing the reaction solvent to obtain polyethylene glycol ethyl acrylate, wherein the yield reaches 96%;

step S2: synthesis of polyethylene glycol ethacrylic acid sulfonate: adding the polyethylene glycol ethyl acrylate obtained in the step S1 into a reaction kettle, adding sodium carbonate with the molar weight of 5% of the polyethylene glycol ethyl acrylate, mixing for 1.5h at room temperature, adding sodium methallyl sulfonate with the molar weight of 50% of the polyethylene glycol ethyl acrylate, mixing, reacting for 28h at room temperature, dissolving a reaction product in methanol, extracting for three times by using n-hexane, washing away unreacted raw materials and other impurities, and evaporating methanol to obtain polyethylene glycol ethyl acrylate sodium sulfonate;

step S3: synthesis of polyethylene glycol sodium acrylate phosphate: cyclohexane with 2 times of molar weight of polyethylene glycol sodium phosphate is used as a reaction solvent, and the molar ratio of the cyclohexane to the polyethylene glycol sodium phosphate is 2: 3, adding polyethylene glycol sodium phosphate and acrylic acid acyl chloride into a reaction kettle solvent, adding a catalyst styrene phosphoric acid (4% of the molar weight of the polyethylene glycol sodium acrylate phosphate), introducing nitrogen, reacting for 12 hours at 70 ℃, and removing the reaction solvent to obtain polyethylene glycol sodium acrylate phosphate, wherein the yield reaches 95%;

step S4: preparing a divinyl organic silicon modified acrylate prepolymer containing sulfo phosphate radicals: taking the molar ratio of 22: 10: 8: 10: 14: 8, adding initiator ammonium persulfate (accounting for 3 percent of the total mass) and chain transfer agent n-dodecyl mercaptan (accounting for 4 percent of the total mass) and uniformly mixing to obtain a monomer mixture. Firstly, 15 mass percent of monomer mixture is put into a reaction kettle at one time, the reaction is carried out for 30 minutes at 95 ℃, the residual monomer mixture is evenly dripped within 5 hours, the reaction is carried out for 5 hours at 95 ℃, and then the conversion rate can reach 99.6 percent.

Step S5: preparation of aqueous dispersion: and (4) carrying out neutralization reaction on the divinyl organic silicon modified acrylate prepolymer containing the sulfo phosphate radical obtained in the step (S4) by adopting triethylamine (the molar ratio of the prepolymer to the triethylamine is 5: 4), vacuumizing and degassing, and adding water (0.4 time of the mass of the prepolymer) for emulsification to obtain the divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate radical.

The performance of the obtained aqueous dispersion was measured by the same method as in example 1, and the results showed that the aqueous dispersion had a solid content of 46.8%, a viscosity of 425mPa · s, a pencil hardness of 2H, and a gloss of 95, and had the advantages of high solid content, storage stability, cationic stability, good transparency, low viscosity, and the like.

Example 4 preparation of automotive coatings Using sulfophosphate-containing aqueous divinyl Silicone modified acrylic Dispersion

The divinyl organic silicon modified acrylic acid aqueous dispersion containing the sulfo phosphate radical prepared in the embodiment 1 is used as a matrix, and a wetting agent, a defoaming agent, a flatting agent, deionized water, a pigment, a functional cosolvent and a thickening agent are added to obtain the divinyl organic silicon modified acrylic acid aqueous dispersion coating containing the sulfo phosphate radical, wherein the adding amount (in parts by weight) of each component is as follows:

100 parts of divinyl organic silicon modified acrylic acid aqueous dispersion containing sulfo phosphate;

1 part of wetting agent (Surfynol 104E Evonik);

0.2 part of defoaming agent (BYK024 bike company);

0.2 part of leveling agent (BYK346 Pic company);

0.3 part of thickener (Borchi Gel PW-25, Borchers, Germany);

30 parts of pigment (TIONA595 Meilian).

1000.1 parts of functional auxiliary agent AN.

And 6 parts of water.

The automotive coatings obtained in example 4 were tested using the test methods commonly used in the coatings art and the associated performance results obtained for the automotive coatings are shown in table 2.

TABLE 2 automotive coatings Performance test results

According to the test results in table 2, it can be seen that: the Volatile Organic Compound (VOC) content of the automobile coating product is less than 10.0%, the automobile coating completely meets the strictest environmental protection requirement, the automobile coating is extremely friendly to the environment, and the comprehensive performance of a paint film is excellent. The pencil has the hardness of 2H and the glossiness of more than 95, and the product has good comprehensive performance, not only has the advantages of high hardness, high glossiness, excellent fullness and beautiful effect, but also has the advantages of excellent physical and chemical properties, good storage stability and the like.

While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.