阅读说明：本技术 一种酯环环氧丙烯酸酯杂化硅树脂、制备方法及应用 (Ester ring epoxy acrylate hybrid silicone resin, preparation method and application ) 是由 李小杰 吕朝龙 顾正明 徐健 刘晓亚 于 2021-10-15 设计创作，主要内容包括：本发明提供一种酯环环氧丙烯酸酯杂化硅树脂、制备方法及应用,属于聚合物涂层材料领域,所述酯环环氧丙烯酸酯杂化硅树脂的制备方法包括：将环氧环己烷基硅氧烷、丙烯酸、催化剂I、阻聚剂和溶剂I加到反应容器中,升温搅拌反应后,正己烷洗涤,减压蒸馏得到含丙烯酰氧基的硅氧烷；将含丙烯酰氧基的硅氧烷、二官能度硅氧烷、三官能度硅氧烷、四官能度硅氧烷、溶剂II和阻聚剂混合,滴加催化剂II和去离子水的混合物,升温搅拌反应2～8小时,加入六甲基二硅氧烷,继续升温搅拌反应2～5小时；然后静置分层,将油层水洗至中性,减压蒸馏除去小分子物质,得到产物。将其应用在塑胶基材上,提高其使用寿命,较高的水接触角,较好的防污性能。(The invention provides ester ring epoxy acrylate hybrid silicone resin, a preparation method and application, belonging to the field of polymer coating materials, wherein the preparation method of the ester ring epoxy acrylate hybrid silicone resin comprises the following steps: adding epoxy cyclohexyl siloxane, acrylic acid, a catalyst I, a polymerization inhibitor and a solvent I into a reaction container, heating, stirring, reacting, washing with n-hexane, and distilling under reduced pressure to obtain siloxane containing acryloyloxy; mixing siloxane containing acryloyloxy, difunctional siloxane, trifunctional siloxane, tetrafunctional siloxane, a solvent II and a polymerization inhibitor, dropwise adding a mixture of a catalyst II and deionized water, heating, stirring and reacting for 2-8 hours, adding hexamethyldisiloxane, and continuing heating, stirring and reacting for 2-5 hours; and then standing for layering, washing an oil layer to be neutral, and distilling under reduced pressure to remove small molecular substances to obtain a product. The anti-fouling coating is applied to a plastic substrate, so that the service life of the anti-fouling coating is prolonged, the water contact angle is high, and the anti-fouling performance is good.)

1. The preparation method of the ester ring epoxy acrylate hybrid silicone resin is characterized by comprising the following steps:

(1) adding epoxy cyclohexyl siloxane, acrylic acid, a catalyst I, a polymerization inhibitor and a solvent I into a reaction container, heating to 80-90 ℃, stirring for reaction for 5-7 hours, washing with n-hexane, and distilling under reduced pressure to obtain siloxane containing acryloyloxy;

(2) mixing siloxane containing acryloyloxy, difunctional siloxane, trifunctional siloxane, tetrafunctional siloxane, a solvent II and a polymerization inhibitor, heating to 30-50 ℃, dropwise adding a mixture of a catalyst II and deionized water, completing dropwise adding within 0.5-1 hour, heating to 50-70 ℃, stirring for reacting for 2-8 hours, adding hexamethyldisiloxane, heating to 70-80 ℃, and stirring for reacting for 2-5 hours; then standing for layering, washing an oil layer to be neutral, and finally distilling under reduced pressure to remove small molecular substances to obtain ester epoxy acrylate hybrid silicone resin;

wherein, the catalyst I is one or more of N, N-dimethylbenzylamine, N-diethylbenzylamine, triethylamine, triethanolamine, trimethyl benzyl ammonium chloride, triphenyl antimony, triphenylphosphine, chromium acetylacetonate and tetraethylammonium bromide; the solvent I is one or more of methyl ethyl ketone, ethyl acetate, acetone, toluene, xylene and tetrahydrofuran; the catalyst II is one or more of glacial acetic acid, formic acid, hydrochloric acid, oxalic acid and sulfuric acid; the solvent II is one or more of methanol, ethanol, isopropanol, ethyl formate, ethyl acetate, toluene, xylene and tetrahydrofuran.

2. The method for preparing ester ring epoxy acrylate hybrid silicone resin according to claim 1, wherein the acryloxy group-containing siloxane has the following structure:

wherein R is₁is-CH₃or-CH₂CH₃。

3. The method for preparing ester ring epoxy acrylate hybrid silicone resin according to claim 1, wherein the difunctional siloxane has the following structure:

the trifunctional siloxane has the following structure:

the tetrafunctional siloxane has the following structure:

wherein R is₁is-CH₃or-CH₂CH₃，R₂is-CH₃or-CH₂CH₃，R₃is-CH₃、-CH₂CH₃or-CH₂CH₂CH₃。

4. The preparation method of the ester epoxy acrylate hybrid silicone resin as claimed in claim 1, wherein the molar ratio of the acrylic acid to the epoxycyclohexylalkyl siloxane in step (1) is 1: 1-1.3; the dosage of the catalyst I is 0.1 to 3 percent of the total mass of the epoxycyclohexylalkyl siloxane and the acrylic acid; the dosage of the polymerization inhibitor is 0.1 to 5 percent of the total mass of the epoxycyclohexylalkyl siloxane and the acrylic acid.

5. The method for preparing ester ring epoxy acrylate hybrid silicone resin according to claim 1, wherein the epoxycyclohexane siloxane in step (1) is one or more of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane.

6. The preparation method of the ester epoxy acrylate hybrid silicone resin as claimed in claim 1, wherein the molar ratio of the acryloxy group-containing siloxane, the difunctional siloxane, the trifunctional siloxane, the tetrafunctional siloxane and the hexamethyldisiloxane in step (2) is 1: 0.2-0.8: 1-5: 0.1-0.5: 0.1-0.8; the dosage of the polymerization inhibitor is 0.1 to 5 percent of the total mass of the siloxane containing acryloxy, the difunctional siloxane, the trifunctional siloxane, the tetrafunctional siloxane and the hexamethyldisiloxane; the molar amount of the deionized water is 3-9 times of the total molar number of the siloxane containing the acryloxy group, the difunctional siloxane, the trifunctional siloxane and the tetrafunctional siloxane; the dosage of the catalyst II is 0.1-5% of the mass of the deionized water.

7. An ester ring epoxy acrylate hybrid silicone resin prepared by the preparation method of any one of claims 1 to 6, wherein the ester ring epoxy acrylate hybrid silicone resin has the following structure:

wherein R is₂is-CH₃or-CH₂CH₃，R₃is-CH₃、-CH₂CH₃or-CH₂CH₂CH₃。

8. The use of the ester ring epoxy acrylate hybrid silicone resin as claimed in claim 7, wherein the ester ring epoxy acrylate hybrid silicone resin is mixed with a multifunctional acrylate resin and a photoinitiator, and then a film is coated on a plastic substrate, and then the film is cured by ultraviolet irradiation to form a film;

wherein the dosage of the ester ring epoxy acrylate hybrid silicone resin is 5-20% of the mass of the multifunctional acrylate resin; the dosage of the photoinitiator is 1 to 5 percent of the total mass of the multifunctional acrylate resin and the ester ring epoxy acrylate hybrid silicon resin.

9. The use of the ester ring epoxy acrylate hybrid silicone resin according to claim 8, wherein the multifunctional acrylate resin is selected from one or more of urethane acrylate resin, epoxy acrylate resin and polyester acrylate resin.

10. The use of the ester ring epoxy acrylate hybrid silicone resin according to claim 8, wherein the photoinitiator is selected from one or more of diethyl 2, 4, 6-trimethylbenzoylphosphonate, 2-phenyl-2, 2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, α -diethoxyacetophenone, 1-hydroxy-cyclohexylbenzophenone, and 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide.

Technical Field

The invention relates to the field of polymer coating materials, in particular to ester ring epoxy acrylate hybrid silicone resin, a preparation method and application.

Background

The organic silicon resin has many excellent physical and chemical properties, such as high hardness, high and low temperature resistance, oxidation resistance, weather resistance and the like, and has wide application in the fields of electronic devices, buildings, aviation, aerospace, medical materials and the like. Although silicone resins have superior properties compared to polyurethane resins, epoxy resins, and acrylate resins, their individual use is often limited by the high cost. Ultraviolet (UV) curable coatings are receiving more and more attention due to their unique advantages of room temperature curing, wide applicability, low energy consumption, high efficiency, environmental protection, etc., and are particularly suitable for surface treatment of heat-sensitive substrates such as plastics. However, the existing ultraviolet curing coating generally has insufficient scratch resistance.

In the related technology, methacryloxypropyltrimethoxysilane (KH-570) is usually added in the process of synthesizing the silicon resin, methacryloxy capable of being subjected to ultraviolet curing is introduced, and then the silicon resin is compounded with polyfunctional acrylate resin, and a small amount of silicon resin is added to obtain the ultraviolet curing resin with excellent performance.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides ester epoxy acrylate hybrid silicone resin, a preparation method and application thereof.

As a first aspect of the invention, a preparation method of ester ring epoxy acrylate hybrid silicone resin is provided, wherein the preparation method is simple and easy to control, and comprises the following steps:

(1) adding epoxy cyclohexyl siloxane, acrylic acid, a catalyst I, a polymerization inhibitor and a solvent I into a reaction container, heating to 80-90 ℃, stirring for reaction for 5-7 hours, washing with n-hexane, and distilling under reduced pressure to obtain siloxane containing acryloyloxy;

(2) mixing siloxane containing acryloyloxy, difunctional siloxane, trifunctional siloxane, tetrafunctional siloxane, a solvent II and a polymerization inhibitor, heating to 30-50 ℃, dropwise adding a mixture of a catalyst II and deionized water, completing dropwise adding within 0.5-1 hour, heating to 50-70 ℃, stirring for reacting for 2-8 hours, adding hexamethyldisiloxane, heating to 70-80 ℃, and stirring for reacting for 2-5 hours; and then standing for layering, washing an oil layer to be neutral, and finally distilling under reduced pressure to remove small molecular substances to obtain the ester epoxy acrylate hybrid silicone resin.

Wherein, the catalyst I is one or more of N, N-dimethylbenzylamine, N-diethylbenzylamine, triethylamine, triethanolamine, trimethyl benzyl ammonium chloride, triphenyl antimony, triphenylphosphine, chromium acetylacetonate and tetraethylammonium bromide; the polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, hydroquinone methyl ether, p-hydroxyanisole and 2-tert-butylhydroquinone; the solvent I is one or more of methyl ethyl ketone, ethyl acetate, acetone, toluene, xylene and tetrahydrofuran; the catalyst II is one or more of glacial acetic acid, formic acid, hydrochloric acid, oxalic acid and sulfuric acid; the solvent II is one or more of methanol, ethanol, isopropanol, ethyl formate, ethyl acetate, toluene, xylene and tetrahydrofuran.

Preferably, the acryloxy group-containing siloxane has the following structure:

wherein R is₁is-CH₃or-CH₂CH₃；

Preferably, the difunctional siloxane has the following structure:

wherein R is₁is-CH₃or-CH₂CH₃，R₂is-CH₃or-CH₂CH₃；

The trifunctional siloxane has the following structure:

wherein R is₁is-CH₃or-CH₂CH₃，R₃is-CH₃、-CH₂CH₃or-CH₂CH₂CH₃；

The tetrafunctional siloxane has the following structure:

wherein R is₁is-CH₃or-CH₂CH₃。

Preferably, the molar ratio of the acrylic acid to the epoxycyclohexylalkylsiloxane in the step (1) is 1: 1-1.3; the dosage of the catalyst I is 0.1-3% of the total mass of the epoxy cyclohexyl siloxane and the acrylic acid; the dosage of the polymerization inhibitor is 0.1-5% of the total mass of the epoxy cyclohexyl siloxane and the acrylic acid.

Preferably, the epoxycyclohexylsiloxane in step (1) is one or more of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane.

Preferably, the molar amount of the deionized water used in the step (2) is 3-9 times of the total molar number of the acryloxy group-containing siloxane, the difunctional siloxane, the trifunctional siloxane and the tetrafunctional siloxane;

in the step (2), the consumption of the polymerization inhibitor is 0.1-5% of the total mass of the siloxane containing the acryloxy group, the difunctional siloxane, the trifunctional siloxane, the tetrafunctional siloxane and the hexamethyldisiloxane;

the amount of the catalyst II used in the step (2) is 0.1-5% of the mass of the water;

the molar ratio of the siloxane containing the acryloxy group, the difunctional siloxane, the trifunctional siloxane, the tetrafunctional siloxane and the hexamethyldisiloxane in the step (2) is 1: 0.2-0.8: 1-5: 0.1-0.5: 0.1-0.8.

The second aspect of the invention provides an ester ring epoxy acrylate hybrid silicone resin, which is prepared by the method and has the following structure:

wherein R is₂is-CH₃or-CH₂CH₃，R₃is-CH₃、-CH₂CH₃or-CH₂CH₂CH₃。

As a third aspect of the present invention, an application of the ester ring epoxy acrylate hybrid silicone resin is provided, wherein the ester ring epoxy acrylate hybrid silicone resin, the multifunctional acrylate resin and the photoinitiator are mixed, and then a film is coated on the plastic base material, and then the film is cured to form a film by ultraviolet irradiation;

wherein the photoinitiator is selected from one or more of 2, 4, 6-trimethyl benzoyl diethyl phosphonate, 2-phenyl-2, 2-dimethylamino-1- (4-morpholinyl phenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, alpha-diethoxy acetophenone, 1-hydroxy-cyclohexyl benzophenone and 2, 4, 6-trimethyl benzoyl diphenyl phosphine oxide;

the dosage of the photoinitiator is 1 to 5 percent of the total mass of the multifunctional acrylate resin and the ester ring epoxy acrylate hybrid silicon resin.

The multifunctional acrylate resin is selected from one or more of polyurethane acrylate resin, modified polyurethane acrylate resin, epoxy acrylate resin and polyester acrylate resin;

the plastic base material is selected from one or more of a PC plate, a PMMA plate, a PP plate, a PE plate and a PVC plate.

Furthermore, the dosage of the ester ring epoxy acrylate hybrid silicone resin is 5-20% of the mass of the multifunctional acrylate resin.

Has the advantages that:

according to the invention, acrylic acid and epoxy cyclohexane silane are subjected to ring-opening esterification reaction under the action of a catalyst to prepare siloxane containing acryloxy, and then, bifunctional siloxane, trifunctional siloxane, tetrafunctional silane and hexamethyldisiloxane are subjected to hydrolytic condensation to synthesize the ester epoxy acrylate hybrid silicon resin. The acryloxy in the synthesized ester ring epoxy acrylate hybrid silicon resin can provide high photocuring speed, high double bond conversion rate and high coating crosslinking density and hardness; meanwhile, the cyclohexyl and the hydroxyl in the structure can also improve the polarity of the silicon resin, and after being compounded with the multifunctional acrylate resin, the silicon resin does not have phase separation and has good compatibility; the prepared coating is applied to the plastic base material, still has high light transmittance and good adhesive force, the pencil hardness can reach 9H, the wear resistance of the coating is obviously improved, and the service life of the plastic base material with lower hardness is further prolonged; and has a certain antifouling property due to a higher water contact angle.

Drawings

FIG. 1 is a nuclear magnetic spectrum of acryloxy group-containing siloxane obtained in example 1 of the present invention;

FIG. 2 is a nuclear magnetic spectrum of an ester ring epoxy acrylate hybrid silicone resin obtained in example 1 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to specific embodiments, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the 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.

The application of the ester ring epoxy acrylate hybrid silicone resin in the coating is tested and evaluated according to the basic performance of the coating in the following table 1:

TABLE 1 coating Performance test method

The raw materials and sources used in examples 1 to 6 and comparative examples 1 to 2 of the present invention are shown in Table 2:

TABLE 2 raw materials and sources for examples and comparative examples

The acryloxy group-containing siloxanes (a1 to a2) according to examples 1 to 6 of the present invention all have the following structures:

wherein R is₁is-CH₃or-CH₂CH₃。

The ester ring epoxy acrylate hybrid silicone resins (B1-B6) prepared in embodiments 1-6 of the invention all have the following structures:

wherein R is₂is-CH₃or-CH₂CH₃，R₃is-CH₃、-CH₂CH₃or-CH₂CH₂CH₃。

Example 1

(1) Preparation of acryloxy group-containing siloxanes

24.6g (0.1mol) of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 7.2g (0.1mol) of acrylic acid, 0.16g of trimethylbenzylammonium chloride, 0.16g of hydroquinone and 10g of methyl ethyl ketone were charged into a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and the mixture was stirred in an oil bath at 80 ℃ for 6 hours, then washed three times with n-hexane and distilled under reduced pressure to give a siloxane (A1) containing acryloyloxy groups.

(2) Preparation of ester ring epoxy acrylate hybrid silicone resin

Into a 100mL four-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer were charged 31.8g (0.1mol) of acryloxy group-containing siloxane (A1), 4.8g (0.04mol) of dimethyldimethoxysilane, 30.1g (0.2mol) of ethyltrimethoxysilane, 4.2g (0.02mol) of tetraethyl silicate, 10g of isopropanol and 0.9g of hydroquinone, and the mixture was stirred uniformly and warmed to 50 ℃. A small amount of a mixture of 0.19g of concentrated hydrochloric acid and 19.44g (1.08mol) of distilled water was added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ and the reaction stirred for 6 hours. Then, 1.62g (0.01mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to carry out the reaction for 3 hours with stirring under constant temperature. Then standing for layering, washing the oil layer to be neutral by water, then washing the oil layer by deionized water, and then distilling under reduced pressure at 50 ℃/130mmHg to remove the solvent and low-boiling-point residues in the organic phase to obtain the ester epoxy acrylate hybrid silicone resin (B1).

(3) Curing of ester ring epoxy acrylate hybrid silicone resins

Mixing 100 parts by mass of urethane acrylate resin, 5 parts by mass of ester ring epoxy acrylate hybrid silicone resin (B1) and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, coating a film on a PMMA plate, and then irradiating by ultraviolet light to cure the mixture to form a film.

Example 2:

(1) preparation of acryloxy group-containing siloxanes

A four-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 34.6g (0.12mol), 7.2g (0.1mol) of acrylic acid, 0.38g of triphenylphosphine, 0.38g of p-benzoquinone and 12g of xylene, reacted in an oil bath at 85 ℃ under stirring for 6.5 hours, then washed three times with n-hexane, and distilled under reduced pressure to give acryloxy group-containing siloxane (A2).

(2) Preparation of ester ring epoxy acrylate hybrid silicone resin

Into a 100mL four-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer were charged 36.0g (0.1mol) of acryloxy group-containing siloxane (A2), 8.9g (0.06mol) of diethyldimethoxysilane, 39.2g (0.22mol) of methyltriethoxysilane, 6.3g (0.03mol) of tetraethyl silicate, 12g of ethyl acetate and 0.8g of p-benzoquinone, and the mixture was stirred uniformly and warmed to 45 ℃. A mixture of 0.18g of concentrated sulfuric acid and 21.6g (1.2mol) of distilled water in a small amount was added dropwise to the flask over 1 hour. The temperature of the reaction mixture was then raised to 55 ℃ and the reaction was stirred for 7 hours. Thereafter, 4.87g (0.03mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 75 ℃ to conduct a reaction for 4 hours while stirring with constant temperature. Then standing for layering, washing the oil layer to be neutral by water, then washing the oil layer by deionized water, and then distilling under reduced pressure at 50 ℃/130mmHg to remove the solvent and low-boiling-point residues in the organic phase to obtain the ester epoxy acrylate hybrid silicone resin (B2).

(3) Curing of ester ring epoxy acrylate hybrid silicone resins

Mixing 100 parts by mass of epoxy acrylate resin, 7 parts by mass of ester ring epoxy acrylate hybrid silicone resin (B2) and 4 parts by mass of photoinitiator alpha, alpha-diethoxyacetophenone, coating a film on a PVC plate, and then irradiating by ultraviolet light to cure the film to form a film.

Example 3

(1) Preparation of acryloxy group-containing siloxanes

The procedure of example 1 was used to prepare an acryloxy group-containing siloxane (A1).

(2) Preparation of ester ring epoxy acrylate hybrid silicone resin

Into a 100mL four-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer were charged 31.8g (0.1mol) of acryloxy group-containing siloxane (A1), 8.8g (0.05mol) of diethyldiethoxysilane, 30.9g (0.15mol) of propyltriethoxysilane, 4.6g (0.03mol) of tetramethyl silicate, 11g of xylene and 0.6g of p-hydroxyanisole, and the mixture was stirred uniformly and warmed to 40 ℃. A mixture of a small amount of glacial acetic acid 0.18g and distilled water 17.82g (0.99mol) was added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ and the reaction stirred for 8 hours. Then, 6.50g (0.04mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to carry out the reaction for 5 hours with stirring under constant temperature. Then standing for layering, washing the oil layer to be neutral by water, then washing the oil layer by deionized water, and then distilling under reduced pressure at 50 ℃/130mmHg to remove the solvent and low-boiling-point residues in the organic phase to obtain the ester epoxy acrylate hybrid silicone resin (B3).

(3) Curing of ester ring epoxy acrylate hybrid silicone resins

Mixing 100 parts by mass of polyester acrylate resin, 8 parts by mass of ester ring epoxy acrylate hybrid silicone resin (B3) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone, coating a film on a PC board, and then irradiating the PC board with ultraviolet light to cure the PC board into a film.

Example 4

(1) Preparation of acryloxy group-containing siloxanes

The procedure of example 2 was used to prepare an acryloxy group-containing siloxane (A2).

(2) Preparation of ester ring epoxy acrylate hybrid silicone resin

Into a 100mL four-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer were charged 36.0g (0.1mol) of acryloxy group-containing siloxane (A2), 7.4g (0.05mol) of dimethyldiethoxysilane, 34.6g (0.18mol) of ethyltriethoxysilane, 3.1g (0.02mol) of tetramethyl silicate, 10g of toluene and 0.8g of hydroquinone, and the mixture was stirred uniformly and warmed to 50 ℃. A mixture of a small amount of glacial acetic acid 0.17g and distilled water 18.9g (1.05mol) was added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 65 ℃ and the reaction was stirred for 7 hours. Then, 3.3g (0.02mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to carry out the reaction for 4 hours with stirring under constant temperature. Then standing for layering, washing the oil layer to be neutral by water, then washing the oil layer by deionized water, and then distilling under reduced pressure at 50 ℃/130mmHg to remove the solvent and low-boiling-point residues in the organic phase to obtain the ester epoxy acrylate hybrid silicone resin (B4).

(3) Curing of ester ring epoxy acrylate hybrid silicone resins

Mixing 100 parts by mass of polyester acrylate resin, 15 parts by mass of ester ring epoxy acrylate hybrid silicone resin (B3) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone, coating a film on a PVC plate, and then irradiating the PVC plate with ultraviolet light to cure the PVC plate into a film.

Example 5

(1) Preparation of acryloxy group-containing polyester acrylate siloxanes

The procedure of example 1 was used to prepare an acryloxy group-containing siloxane (A1).

(2) Preparation of ester ring epoxy acrylate hybrid silicone resin

Into a 100mL four-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer were charged 31.8g (0.1mol) of acryloxy group-containing siloxane (A1), 8.4g (0.07mol) of dimethyldimethoxysilane, 31.2g (0.19mol) of propyltrimethoxysilane, 6.3g (0.03mol) of tetraethyl silicate, 15g of methyl ethyl ketone and 0.9g of hydroquinone, and the mixture was stirred uniformly and warmed to 45 ℃. A small amount of a mixture of concentrated hydrochloric acid 0.21g and distilled water 21.06g (1.17mol) was added dropwise to the flask over 0.5 h. The temperature of the reaction mixture was then raised to 60 ℃ and the reaction stirred for 8 hours. Then, 8.1g (0.05mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to carry out the reaction for 5 hours with stirring under constant temperature. Then standing for layering, washing the oil layer to be neutral by water, then washing the oil layer by deionized water, and then distilling under reduced pressure at 50 ℃/130mmHg to remove the solvent and low-boiling-point residues in the organic phase to obtain the ester epoxy acrylate hybrid silicone resin (B5).

(3) Curing of ester ring epoxy acrylate hybrid silicone resins

Mixing 100 parts by mass of urethane acrylate resin, 16 parts by mass of ester ring epoxy acrylate hybrid silicone resin (B5) and 3 parts by mass of photoinitiator alpha, alpha-diethoxyacetophenone, coating a film on a PE plate, and then irradiating by ultraviolet light to cure the film to form a film.

Example 6

(1) Preparation of acryloxy group-containing siloxanes

The procedure of example 2 was used to prepare an acryloxy group-containing siloxane (A2).

(2) Preparation of ester ring epoxy acrylate hybrid silicone resin

Into a 100mL four-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer were charged 36.0g (0.1mol) of acryloxy group-containing siloxane (A2), 8.9g (0.06mol) of dimethyldiethoxysilane, 28.6g (0.21mol) of methyltrimethoxysilane, 3.1g (0.02mol) of tetramethyl silicate, 12g of toluene and 0.8g of p-hydroxyanisole, and the mixture was stirred uniformly and warmed to 50 ℃. A mixture of a small amount of glacial acetic acid 0.19g and distilled water 21.06g (1.17mol) was added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 70 ℃ and the reaction was stirred for 5 hours. Thereafter, 4.87g (0.03mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 80 ℃ to conduct a reaction for 2 hours while stirring with heat. Then standing for layering, washing the oil layer to be neutral by water, then washing the oil layer by deionized water, and then distilling under reduced pressure at 50 ℃/130mmHg to remove the solvent and low-boiling-point residues in the organic phase to obtain the ester epoxy acrylate hybrid silicone resin (B6).

(3) Curing of ester ring epoxy acrylate hybrid silicone resins

Mixing 100 parts by mass of epoxy acrylate resin, 20 parts by mass of ester ring epoxy acrylate hybrid silicone resin (B6) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone, coating a PVC plate, and then irradiating by ultraviolet light to cure and form a film.

Comparative example 1

(1) Preparation of KH570 modified silicone resin

Into a 100mL four-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer were charged KH57024.8g (0.1mol), dimethyldimethoxysilane 4.8g (0.04mol), ethyltrimethoxysilane 30.1g (0.2mol), tetraethyl silicate 4.2g (0.02mol), isopropanol 10g and hydroquinone 0.9g, and the mixture was stirred uniformly and warmed to 50 ℃. A small amount of a mixture of 0.19g of concentrated hydrochloric acid and 19.44g (1.08mol) of distilled water was added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ for 6 hours. Thereafter, 1.62g (0.01mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 3 hours while maintaining the temperature. Then washed with deionized water, followed by distillation under reduced pressure at 50 ℃/130mmHg to remove the solvent and low-boiling residues from the organic phase, to give a KH 570-modified silicone resin (B7).

(2) Curing of KH570 modified Silicone

100 parts by mass of epoxy acrylate resin, 10 parts by mass of KH 570-modified silicone resin (B7) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexylbenzophenone were mixed, and then a film was formed on a PC board, followed by ultraviolet irradiation to cure the mixture to form a film.

Comparative example 2:

(1) preparation of KH570 modified silicone resin

Into a 100mL four-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer were charged KH57024.8g (0.1mol), diethyldimethoxysilane 8.9g (0.06mol), methyltriethoxysilane 39.2g (0.22mol), tetraethyl silicate 6.3g (0.03mol), ethyl acetate 12g and p-benzoquinone 0.8g, and the mixture was stirred uniformly and warmed to 45 ℃. A mixture of 0.18g of concentrated sulfuric acid and 21.6g (1.2mol) of distilled water in a small amount was added dropwise to the flask over 1 hour. The temperature of the reaction mixture was then raised to 55 ℃ for 7 hours. Thereafter, 4.87g (0.03mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 75 ℃ to conduct the reaction for 4 hours while maintaining the temperature. Then washed with deionized water, followed by distillation under reduced pressure at 50 ℃/130mmHg to remove the solvent and low-boiling residues from the organic phase, to give a KH 570-modified silicone resin (B8).

(2) Curing of KH570 modified Silicone

100 parts by mass of urethane acrylate resin, 7 parts by mass of KH570 modified silicone resin (B8) and 4 parts by mass of photoinitiator alpha, alpha-diethoxyacetophenone are mixed, and then a film is coated on a PVC plate, and then ultraviolet irradiation is performed to cure the mixture to form a film.

Comparative example 3:

(1) curing of urethane acrylate resins

Mixing 100 parts by mass of urethane acrylate resin and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, coating a film on a PMMA plate, irradiating by ultraviolet light, and curing to form a film.

Comparative example 4:

(1) curing of epoxy acrylate resins

Mixing 100 parts by mass of epoxy acrylate resin and 4 parts by mass of photoinitiator alpha, alpha-diethoxyacetophenone, coating a film on a PVC plate, and then irradiating by ultraviolet light to cure and form a film.

Comparative example 5:

(1) curing of polyester acrylate resins

100 parts by mass of polyester acrylate resin and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone are mixed, and then a film is coated on a PC plate, and then ultraviolet irradiation is carried out to cure the mixture to form a film.

With reference to the test methods and test standards of table 1, the following technical performance tests were performed on the paint films of the above examples 1 to 6 and comparative examples 1 to 5, and the results of the performance tests are as follows: the test results are shown in table 3:

table 3 coating performance test results

As can be seen from Table 3, compared with the paint film performances of the comparative examples 1 to 5, the paint films prepared in the examples 1 to 6 of the invention have better comprehensive performance, and have certain antifouling performance due to better hydrophobicity; in addition, the adhesive force is good, the pencil hardness is high, and particularly the wear resistance is good; the transmittance is high, and the attractiveness of the base material is not influenced; the conversion rate of the multifunctional acrylate resin is not influenced.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.