A fluorosilicone-modified acrylic resin and its preparation method

Abstract

This invention relates to a fluorosilicone-modified acrylic resin and its preparation method, belonging to the field of polymer materials technology. The resin uses methyl methacrylate, butyl acrylate, and hydroxyethyl methacrylate as basic monomers. Fluorine is introduced through copolymerization with tridecafluorooctyl acrylate. A self-made doped silicone modifier is introduced via blending. The doped silicone modifier is modified by the ring-opening and ring-closing reaction of epichlorohydrin with the secondary amine structure of hexamethylcyclotrisilazane, grafting branched active epoxy groups. Subsequently, n-decylamine is used to open the ring with the grafted epoxy groups, introducing terminal long-chain alkyl modification. This modifier exhibits good compatibility with the acrylic polymer chain and acts as a support in the resin, reducing the shrinkage stress after curing and improving the impact resistance of the cured film. Simultaneously, the reduction in micro-shrinkage results in a film with higher gloss and fullness.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a fluorosilicone modified acrylic resin and its preparation method. Background Technology

[0002] Acrylic resins are copolymers of acrylates, methacrylates, and other olefinic monomers. They possess excellent film-forming properties and good adhesion to most substrates, making them widely used in coatings. However, the large number of hydrophilic ester groups in acrylic resins results in poor coating resistance and stain resistance, significantly limiting their application in coatings. The fluorinated functional groups and silicon-containing structures in organofluorosilicone materials can impart excellent surface properties to the materials. Numerous reports exist on the modification of acrylic resins with organofluorosilicone in the prior art.

[0003] Currently, fluorosilicone-modified acrylic resins are mainly produced through free radical copolymerization, introducing fluorinated monomers and organosilicon monomers into the macromolecular chain via block polymerization. For example, Chinese patent application 202010590355.6 uses vinyltriethoxysilane and dodecafluoroheptyl methacrylate as monomers, and by controlling the dosage and process, obtains a fluorosilicone-modified acrylic resin with good performance. However, a common problem with this type of modified resin is that the fluorine structure, located on the side chain of the macromolecular polymer chain, has a segregation repulsion effect. During the resin curing process, segregation defects are formed around the fluorine structure, resulting in less curing shrinkage compared to the acrylate polymer segment. On the one hand, this generates shrinkage stress within the film layer, leading to a decrease in the film's impact resistance; on the other hand, the uneven shrinkage results in low surface smoothness of the film, macroscopically manifested as a reduction in the film's gloss and fullness. Summary of the Invention

[0004] In order to solve the technical problems mentioned in the background art, the purpose of this invention is to provide a fluorosilicone modified acrylic resin and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A method for preparing a fluorosilicone-modified acrylic resin includes the following steps:

[0007] Step S1: Mix methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and tridecyl fluorooctyl acrylate as mixed monomers, add 1 / 2 amount of azobisisobutyronitrile and xylene, purge with nitrogen, heat the oil bath to 60-70℃, apply mechanical stirring at 50-70 rpm, and stir at a constant temperature for 2-2.5 h to obtain fluorine-modified prepolymer;

[0008] Step S2: Add the premixed silicone modifier, the remaining azobisisobutyronitrile and n-hexane to the fluorinated prepolymer and mix at high speed. Continue heating to 82-88℃, apply mechanical stirring at 100-150 rpm, and stir at a constant temperature for 1.4-1.8 hours. Then cool down to stop the reaction and obtain fluorosilicone modified acrylic resin.

[0009] Furthermore, the molar ratio of methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, tridecafluorooctyl acrylate and the doped silicone modifier is 1:0.3-0.5:0.2-0.3:0.1-0.15:0.08-0.1.

[0010] Furthermore, azobisisobutyronitrile accounts for 0.9-1.1 wt% of the total mixed monomers.

[0011] The doped silicon modifier is prepared by the following method:

[0012] Step A1: Mix hexamethylcyclotrisilazane and tetrahydrofuran, add a small amount of triethylamine as a catalyst, purge with nitrogen for protection, preheat to 40°C, add epichlorohydrin and mix, then continue heating to 62-68°C, apply mechanical stirring at 300-400 rpm, reflux for 1-1.4 h, then add sodium hydroxide and mix, remove tetrahydrofuran and excess epichlorohydrin by rotary evaporation under reduced pressure, dissolve the rotary evaporation product in acetone, filter and remove acetone by rotary evaporation to obtain the epoxide support;

[0013] Furthermore, the molar ratio of hexamethylcyclotrisilazane, epichlorohydrin, triethylamine, sodium hydroxide, and tetrahydrofuran is 0.1 mol : 0.32-0.35 mol : 5-8 mL : 12-15 g : 80-110 mL. Epichlorohydrin preferentially ring-opens with hexamethylcyclotrisilazane under the catalysis of triethylamine, and then ring-closes under the action of sodium hydroxide, grafting epoxy groups onto the hexamethylcyclotrisilazane molecule for modification. The specific reaction process can be represented as follows:

[0014]

[0015] Step A2: Mix n-decylamine, catalyst TBD and dimethylacetamide, purge with nitrogen for protection, heat to 45-55℃, apply mechanical stirring at 120-180 rpm, add epoxide support slowly and uniformly, control the reaction time to 1.8-2.5 h, add deionized water to wash after reaction, centrifuge to remove aqueous phase, vacuum dry to obtain doped silicon modifier;

[0016] Furthermore, the molar ratio of epoxide support, n-decylamine, catalyst TBD, and dimethylacetamide is 0.1 mol : 0.305-0.31 mol : 0.1-0.15 g : 50-60 mL. The n-decylamine undergoes a ring-opening reaction with the epoxide support, introducing a long-chain alkyl group modification to the outer end of the epoxide support molecule. The specific reaction process can be represented as follows:

[0017]

[0018] The beneficial effects of this invention are:

[0019] This invention uses methyl methacrylate, butyl acrylate, and hydroxyethyl methacrylate as basic monomers, introduces fluorine through copolymerization with tridecylfluorooctyl acrylate, and prepares a self-made doped silicone modifier. Organosilicon is introduced through blending and doping. The doped silicone modifier is modified by a ring-opening and ring-closing reaction of epichlorohydrin with the secondary amine structure of hexamethylcyclotrisilazane, grafting branched active epoxy groups, followed by ring-opening with n-decylamine and the grafted epoxy groups to introduce a long-chain alkyl group. This long-chain alkyl group has good compatibility with the acrylic polymer chain, which is beneficial for uniform polymerization. Dispersed between macromolecular polymer chains, it plays a certain toughening role. The overall molecular structure of the doped silicone modifier is tribranched. After curing, it is not easy to migrate or detach through the intercalation effect, thus having good doping stability. The fluorine structure introduced into the side chain of the block copolymer has a segregation repulsion effect, which makes the doped silicone modifier intercalate between the side chain fluorine structures. Its silicon nitrogen ring structure plays a supporting role, reducing the shrinkage internal stress of the acrylic resin after curing and improving the impact resistance of the cured film. At the same time, the reduction of micro-shrinkage makes the film have higher gloss and fullness. Detailed Implementation

[0020] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] Example 1

[0022] The preparation of fluorosilicone-modified acrylic resin in this embodiment is carried out through the following specific process:

[0023] 1) Preparation of doped silicon modifier

[0024] 1.1. Hexamethylcyclotrisilazane and tetrahydrofuran were added and mixed. A small amount of triethylamine was added as a catalyst and mixed. Nitrogen gas was introduced to replace the air, and the temperature was preheated to 40°C. Epichlorohydrin was then added and mixed. The temperature was then further increased to 68°C, and mechanical stirring was applied at 400 rpm. The mixture was refluxed for 1 hour. After the reaction was completed, sodium hydroxide was added and mixed. The ratio of hexamethylcyclotrisilazane, epichlorohydrin, triethylamine, sodium hydroxide and tetrahydrofuran in the reaction was 0.1 mol: 0.35 mol: 8 mL: 15 g: 110 mL. Then, tetrahydrofuran and excess epichlorohydrin were removed by rotary evaporation under reduced pressure. Acetone was added to the rotary evaporated substrate and stirred to dissolve it. The insoluble matter was removed by filtration, and the acetone was removed by rotary evaporation of the filtrate to obtain the epoxide support.

[0025] 1.2 Take n-decylamine, catalyst TBD, and dimethylacetamide, add them and mix well. Purge with nitrogen for protection, heat to 55℃, and apply mechanical stirring at 180 rpm. Slowly and uniformly add the epoxide support over 30 minutes. After complete addition, continue stirring at a constant temperature. Control the total reaction time to 1.8 hours. The ratio of epoxide support, n-decylamine, catalyst TBD, and dimethylacetamide in the reaction is 0.1 mol: 0.31 mol: 0.15 g: 60 mL. After the reaction is complete, add three times the mass of deionized water to wash the mixture. Centrifuge to remove the aqueous phase, and vacuum dry to obtain the doped silicon modifier.

[0026] 2) Synthetic resins

[0027] 2.1. Take methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and tridecyl fluorooctyl acrylate and mix them evenly to form a mixed monomer. Then take 1.1 wt% of azobisisobutyronitrile as an initiator. First, mix half of the initiator with xylene at 0.6 times the mass of the mixed monomers, purge with nitrogen for protection, heat the oil bath to 70°C, apply mechanical stirring at 70 rpm, and stir at a constant temperature for 2 hours to obtain the fluorinated prepolymer.

[0028] 2.2 Take the prepared silicone modifier and the remaining azobisisobutyronitrile, add an equal mass of n-hexane to premix them, add the mixture to the fluorinated prepolymer, mix at 800 rpm for 10 min, then continue to heat to 88℃, apply mechanical stirring at 150 rpm, and stir at a constant temperature for 1.4 h. In the reaction, the molar ratio of methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, tridefluorooctyl acrylate and silicone modifier is 1:0.5:0.2:0.1:0.1. After the reaction is completed, cool to room temperature to end the reaction, and obtain fluorosilicone modified acrylic resin.

[0029] Example 2

[0030] The preparation of fluorosilicone-modified acrylic resin in this embodiment is carried out through the following specific process:

[0031] 1) Preparation of doped silicon modifier

[0032] 1.1. Hexamethylcyclotrisilazane and tetrahydrofuran were added and mixed. A small amount of triethylamine was added as a catalyst and mixed. Nitrogen gas was introduced to replace the air, and the temperature was preheated to 40°C. Epichlorohydrin was then added and mixed. The temperature was then further increased to 62°C, and mechanical stirring was applied at 300 rpm. The mixture was refluxed for 1.4 h. After the reaction was completed, sodium hydroxide was added and mixed. The ratio of hexamethylcyclotrisilazane, epichlorohydrin, triethylamine, sodium hydroxide and tetrahydrofuran in the reaction was 0.1 mol: 0.32 mol: 5 mL: 12 g: 80 mL. Then, tetrahydrofuran and excess epichlorohydrin were removed by rotary evaporation under reduced pressure. Acetone was added to the rotary evaporated substrate and stirred to dissolve it. The insoluble matter was removed by filtration, and the acetone was removed by rotary evaporation of the filtrate to obtain the epoxide support.

[0033] 1.2 Take n-decylamine, catalyst TBD, and dimethylacetamide, add them and mix well. Purge with nitrogen for protection, heat to 45℃, and apply mechanical stirring at 120 rpm. Slowly and uniformly add the epoxide support over 50 min. After complete addition, continue stirring at a constant temperature. Control the total reaction time to 2.5 h. The ratio of epoxide support, n-decylamine, catalyst TBD, and dimethylacetamide in the reaction is 0.1 mol: 0.305 mol: 0.1 g: 50 mL. After the reaction is complete, add three times the mass of deionized water to wash the mixture. Centrifuge to remove the aqueous phase, and vacuum dry to obtain the doped silicon modifier.

[0034] 2) Synthetic resins

[0035] 2.1. Take methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and tridefluorooctyl acrylate and mix them evenly to form a mixed monomer. Then take 0.9 wt% of azobisisobutyronitrile as an initiator. First, mix half of the initiator with 0.5 times the mass of xylene of the mixed monomer. Purge with nitrogen for protection, heat the oil bath to 60°C, apply mechanical stirring at 50 rpm, and stir at a constant temperature for 2.5 h to obtain the fluorinated prepolymer.

[0036] 2.2 Take the prepared silicone modifier and the remaining azobisisobutyronitrile, add an equal mass of n-hexane to premix them, add the mixture to the fluorinated prepolymer, mix at 800 rpm for 10 min, then continue to heat to 82℃, apply mechanical stirring at 100 rpm, and stir at a constant temperature for 1.8 h. In the reaction, the molar ratio of methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, tridefluorooctyl acrylate and silicone modifier is 1:0.3:0.3:0.15:0.08. After the reaction is completed, cool to room temperature to end the reaction, and obtain fluorosilicone modified acrylic resin.

[0037] Example 3

[0038] The preparation of fluorosilicone-modified acrylic resin in this embodiment is carried out through the following specific process:

[0039] 1) Preparation of doped silicon modifier

[0040] 1.1. Hexamethylcyclotrisilazane and tetrahydrofuran were added and mixed. A small amount of triethylamine was added as a catalyst and mixed. Nitrogen gas was introduced to replace the air, and the temperature was preheated to 40°C. Epichlorohydrin was then added and mixed. The temperature was then further increased to 65°C, and mechanical stirring was applied at 400 rpm. The mixture was refluxed for 1.2 h. After the reaction was completed, sodium hydroxide was added and mixed. The ratio of hexamethylcyclotrisilazane, epichlorohydrin, triethylamine, sodium hydroxide and tetrahydrofuran in the reaction was 0.1 mol: 0.34 mol: 7 mL: 13 g: 100 mL. Then, tetrahydrofuran and excess epichlorohydrin were removed by rotary evaporation under reduced pressure. Acetone was added to the rotary evaporated substrate and stirred to dissolve it. The insoluble matter was removed by filtration, and the acetone was removed by rotary evaporation of the filtrate to obtain the epoxide support.

[0041] 1.2 Take n-decylamine, catalyst TBD, and dimethylacetamide, add them and mix well. Purge with nitrogen for protection, heat to 50℃, and apply mechanical stirring at 180 rpm. Slowly and uniformly add the epoxide support over 40 minutes. After complete addition, continue stirring at a constant temperature. Control the total reaction time to 2.2 hours. The ratio of epoxide support, n-decylamine, catalyst TBD, and dimethylacetamide in the reaction is 0.1 mol: 0.31 mol: 0.12 g: 55 mL. After the reaction is complete, add three times the mass of deionized water to wash the mixture. Centrifuge to remove the aqueous phase, and vacuum dry to obtain the doped silicon modifier.

[0042] 2) Synthetic resins

[0043] 2.1. Take methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and tridefluorooctyl acrylate and mix them evenly to form a mixed monomer. Then take 1 wt% of azobisisobutyronitrile as an initiator. First, mix half of the initiator with xylene at 0.5 times the mass of the mixed monomers. Purge with nitrogen for protection, heat the oil bath to 65°C, apply mechanical stirring at 60 rpm, and stir at a constant temperature for 2.2 h to obtain the fluorinated prepolymer.

[0044] 2.2 Take the prepared silicone modifier and the remaining azobisisobutyronitrile, add an equal mass of n-hexane to premix them, add the mixture to the fluorinated prepolymer, mix at 800 rpm for 10 min, then continue to heat to 85℃, apply mechanical stirring at 120 rpm, and stir at a constant temperature for 1.6 h. In the reaction, the molar ratio of methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, tridecafluorooctyl acrylate and silicone modifier is 1:0.45:0.22:0.13:0.09. After the reaction is completed, cool to room temperature to end the reaction, and obtain fluorosilicone modified acrylic resin.

[0045] Example 4

[0046] The preparation of fluorosilicone-modified acrylic resin in this embodiment is carried out through the following specific process:

[0047] 1) Preparation of doped silicon modifier

[0048] 1.1. Hexamethylcyclotrisilazane and tetrahydrofuran were added and mixed. A small amount of triethylamine was added as a catalyst and mixed. Nitrogen gas was introduced to replace the air, and the temperature was preheated to 40°C. Epichlorohydrin was then added and mixed. The temperature was then further increased to 65°C, and mechanical stirring was applied at 400 rpm. The mixture was refluxed for 1.3 h. After the reaction was completed, sodium hydroxide was added and mixed. The ratio of hexamethylcyclotrisilazane, epichlorohydrin, triethylamine, sodium hydroxide and tetrahydrofuran in the reaction was 0.1 mol: 0.33 mol: 8 mL: 13 g: 110 mL. Then, tetrahydrofuran and excess epichlorohydrin were removed by rotary evaporation under reduced pressure. Acetone was added to the rotary evaporated substrate and stirred to dissolve it. The insoluble matter was removed by filtration, and the acetone was removed by rotary evaporation of the filtrate to obtain the epoxide support.

[0049] 1.2 Take n-decylamine, catalyst TBD, and dimethylacetamide, add them and mix well. Purge with nitrogen for protection, heat to 52℃, and apply mechanical stirring at 180 rpm. Slowly and uniformly add the epoxide support over 40 minutes. After complete addition, continue stirring at a constant temperature. Control the total reaction time to 2.3 hours. The ratio of epoxide support, n-decylamine, catalyst TBD, and dimethylacetamide in the reaction is 0.1 mol: 0.305 mol: 0.13 g: 60 mL. After the reaction is complete, add three times the mass of deionized water to wash the mixture. Centrifuge to remove the aqueous phase, and vacuum dry to obtain the doped silicon modifier.

[0050] 2) Synthetic resins

[0051] 2.1. Take methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and tridefluorooctyl acrylate and mix them evenly to form a mixed monomer. Then take 1 wt% of azobisisobutyronitrile as an initiator. First, mix half of the initiator with xylene at 0.6 times the mass of the mixed monomers, purge with nitrogen for protection, heat the oil bath to 68°C, apply mechanical stirring at 70 rpm, and stir at a constant temperature for 2.2 h to obtain the fluorinated prepolymer.

[0052] 2.2 Take the prepared silicone modifier and the remaining azobisisobutyronitrile, add an equal mass of n-hexane to premix them, add the mixture to the fluorinated prepolymer, mix at 800 rpm for 10 min, then continue to heat to 85℃, apply mechanical stirring at 120 rpm, and stir at a constant temperature for 1.5 h. In the reaction, the molar ratio of methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, tridefluorooctyl acrylate and silicone modifier is 1:0.4:0.28:0.13:0.1. After the reaction is completed, cool to room temperature to end the reaction, and obtain fluorosilicone modified acrylic resin.

[0053] Comparative Example

[0054] This comparative example uses an existing copolymerization modification method to prepare fluorosilicone-modified acrylic resin. The specific implementation method is as follows:

[0055] Similar to Example 3, methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, and tridecafluorooctyl acrylate were mixed in the same molar ratio, and 12 wt% of the total mass of the four were added as the polymerization substrate, along with 1 wt% of the polymerization substrate and azobisisobutyronitrile as the catalyst, and xylene as the solvent at 0.7 times the mass of the polymerization substrate. A one-pot synthesis method was used, with a polymerization temperature of 80°C and a polymerization time of 3.5 h to obtain fluorosilicone modified acrylic resin.

[0056] The acrylic resin prepared above was adjusted to a solid content of 45±1% with thinner and used as a coating. A thin tinplate sheet was subjected to cross-polishing with 1000-grit metallographic sandpaper, then wiped clean with acetone, dried, and the coating was applied to the surface. The sheet was then baked at 60℃ for 5 hours to cure, with the dry film thickness controlled to approximately 0.2 mm. The resulting sample was subjected to relevant performance tests, as detailed below:

[0057] Contact angle test: The test was conducted using a contact angle measuring instrument and the seated drop method. The test environment was: temperature 23±2℃, relative humidity 50±5%, and water droplet size approximately 2μL.

[0058] Adhesion test: Performed in accordance with GB / T 1720-2020 standard;

[0059] Coating hardness: Refer to GB 6739-2006 standard;

[0060] Coating impact strength: Complies with GB / T 1732-2020 standard;

[0061] Coating gloss: Complies with GB / T 9754-2007 standard;

[0062] The specific test data is shown in Table 1:

[0063] Table 1

[0064]

[0065] As shown in Table 1, the contact angles of the coatings in both the examples and the comparative examples are approximately 90°. Compared to acrylic coatings, both exhibit certain hydrophobic and antifouling effects due to the introduction of fluorine structures, and their adhesion reaches level 0, meeting the requirements for general coating use. However, the impact strength of the examples did not show any visible damage within the 50cm test rail range, while the comparative example only showed an impact strength of 40cm. The hardness of the coatings in the examples is B, while the hardness of the coatings in the comparative examples is HB. It can be seen that the coatings in the examples have better impact toughness and meet the service conditions of most coatings. Finally, the gloss levels of the examples at 60° are all above 100°, indicating a higher gloss fullness compared to the comparative examples.

[0066] To verify the coating's resistance, the prepared samples were subjected to water resistance, salt resistance, and acid and alkali resistance tests, as detailed below:

[0067] Water resistance test: Performed in accordance with GB / T5209-1985 standard, temperature 25℃, test cycle 200h;

[0068] Salt resistance test: Performed in accordance with GB / T1765-1979 standard, temperature 25℃, 5% NaCl, test cycle 48h;

[0069] Acid resistance test: Performed in accordance with GB / T1763-1979 standard, temperature 25℃, 5%H2SO4, test cycle 24h;

[0070] Alkali resistance test: Performed in accordance with GB / T1763-1979 standard, temperature 25℃, 5% NaOH, test cycle 24h;

[0071] The specific test data is shown in Table 2:

[0072] Table 2

[0073]

[0074] As shown in Table 2, the coatings of both the examples and the comparative examples exhibited good tolerance during the test period, meeting the requirements for general coating use.

[0075] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0076] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing a fluorosilicone-modified acrylic resin, characterized in that, Includes the following steps: Step S1: Mix methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and tridecyl fluorooctyl acrylate as mixed monomers, add 1 / 2 amount of azobisisobutyronitrile and xylene, purge with nitrogen, heat in an oil bath to 60-70℃, stir at a constant temperature for 2-2.5h to obtain fluorine-modified prepolymer. Step S2: Add the premixed silicone modifier, the remaining azobisisobutyronitrile and n-hexane to the fluorine-modified prepolymer and mix. Continue to heat to 82-88℃ and stir at a constant temperature for 1.4-1.8h. Cool down to end the reaction and obtain fluorosilicone-modified acrylic resin. The doped silicon modifier is prepared by the following method: Step A1: Mix hexamethylcyclotrisilazane and tetrahydrofuran, add triethylamine and mix, purge with nitrogen for protection, preheat to 40°C, add epichlorohydrin and mix, then continue heating to 62-68°C, stir and reflux for 1-1.4 h, then add sodium hydroxide and mix, remove tetrahydrofuran and excess epichlorohydrin by rotary evaporation under reduced pressure, dissolve the rotary evaporation product with acetone, filter and remove acetone by rotary evaporation to obtain the epoxide support; Step A2: Mix n-decylamine, catalyst TBD and dimethylacetamide, purge with nitrogen for protection, heat to 45-55℃, stir and slowly add epoxide support at a uniform rate, control the addition reaction time to 1.8-2.5h, add deionized water to wash after the reaction is complete, centrifuge to remove the aqueous phase, vacuum dry to obtain the doped silicon modifier. The ratio of hexamethylcyclotrisilazane, epichlorohydrin, triethylamine, sodium hydroxide, and tetrahydrofuran is 0.1 mol: 0.32-0.35 mol: 5-8 mL: 12-15 g: 80-110 mL; The ratio of epoxidized support, n-decylamine, catalyst TBD and dimethylacetamide is 0.1 mol: 0.305-0.31 mol: 0.1-0.15 g: 50-60 mL.

2. The method for preparing a fluorosilicone-modified acrylic resin according to claim 1, characterized in that, The molar ratio of methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, tridefluorooctyl acrylate and the doped silicone modifier is 1:0.3-0.5:0.2-0.3:0.1-0.15:0.08-0.

1.

3. The method for preparing a fluorosilicone-modified acrylic resin according to claim 1, characterized in that, Azobisisobutyronitrile (AIBN) accounts for 0.9-1.1 wt% of the total mixed monomers.

4. A fluorosilicone-modified acrylic resin, characterized in that, It is prepared by the method described in any one of claims 1-3.

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