CN108822265B

CN108822265B - Preparation method of organic silicon fluororesin

Info

Publication number: CN108822265B
Application number: CN201810592617.5A
Authority: CN
Inventors: 游胜勇; 李韦伟; 李玲; 董晓娜; 邹吉勇; 谌开红
Original assignee: Institute of Applied Chemistry Jiangxi Academy of Sciences
Current assignee: Institute of Applied Chemistry Jiangxi Academy of Sciences
Priority date: 2018-06-11
Filing date: 2018-06-11
Publication date: 2020-06-09
Anticipated expiration: 2038-06-11
Also published as: CN108822265A

Abstract

A preparation method of an organic silicon fluororesin comprises the steps of adding vinyl silicone resin, a solvent and an initiator into a reaction kettle, uniformly stirring, dropwise adding a mixture of styrene and a fluorine-containing vinyl monomer, after dropwise adding, raising the temperature to 70-75 ℃, reacting for 6-8h, cooling to room temperature, filtering, and distilling under reduced pressure to remove the solvent to obtain the organic silicon fluororesin. The preparation method has the advantages of simple process, mild conditions and high relative molecular weight of the polymer. Through solution polymerization grafting reaction, the prepared material has lower surface energy and improves the elasticity, refractive index and adhesive force of the material on the premise of not changing the excellent performance of the organic silicon resin, can be applied to antifouling paint, waterproof agent and packaging material products, and has wide market prospect.

Description

Preparation method of organic silicon fluororesin

Technical Field

The invention relates to a preparation method of organic silicon fluororesin, and also relates to an application of organic silicon fluororesin, belonging to the technical field of organic silicon application.

Background

The organic silicon resin has a plurality of excellent performances such as high and low temperature resistance, hydrophobicity, air permeability, good flexibility and the like due to the special structure, but the mechanical property is poor and the organic solvent is not resistant; the fluorocarbon resin has excellent performance, the fluorine-containing side group can improve the solvent resistance of the material and improve the surface performance, but the fluorocarbon resin is expensive, and the fluorine-containing silicone resin with more excellent performance can be obtained by utilizing the advantages of the fluorocarbon resin and the fluorine-containing side group. However, in most literature reports, there are two main methods for synthesizing fluorosilicone polymers, one is to graft polysiloxane macromonomer onto fluorocarbon skeleton, and the other is to graft perfluoro side chain onto polysiloxane skeleton, and the polymers obtained by the two methods have relatively low molecular weight and affect the performance of the polymers. Therefore, on the premise of simple operation and low cost, the organic silicon fluororesin with excellent performance is prepared, is applied to the fields of antifouling paint, waterproof material, sealing material and the like, and inevitably has wide market prospect.

Publication No. CN101775095A discloses a functional perfluoro resin and a preparation method thereof; publication No. CN102161723A discloses a high-flexibility quaternary copolymerization fluorine-containing resin, and a preparation method and application thereof. However, no report on the preparation method of the organic silicon fluororesin is found.

Disclosure of Invention

The invention aims to provide an organic silicon fluororesin with aging resistance, solvent resistance, dirt resistance, good stability and excellent waterproof performance, which is applied to the fields of antifouling paint, waterproof material, sealing material and the like.

The preparation method comprises the following steps of adding vinyl silicone resin, a solvent and an initiator into a reaction kettle, uniformly stirring, dropwise adding a mixture of styrene and a fluorine-containing vinyl monomer, after dropwise adding, raising the temperature to 70-75 ℃, reacting for 6-8 hours, cooling to room temperature, filtering, and removing the solvent through reduced pressure distillation to obtain the organic silicone fluororesin.

The vinyl content of the vinyl silicone resin is 2-10%, and the viscosity is 1000-; the vinyl silicone resin is one of methyl vinyl silicone resin and phenyl vinyl silicone resin.

The solvent is one or more of toluene, xylene, ethyl acetate, ethanol, methanol, isopropanol, acetone and tetrahydrofuran.

The initiator is one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.

The fluorine-containing vinyl monomer is one of trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorododecyl methacrylate, trifluoropropene, perfluorostyrene and perfluorobutyl ethylene.

The mass ratio of the vinyl silicone resin to the solvent to the initiator to the styrene to the fluorine-containing vinyl monomer is 1 (1-10): (0.001-0.005): (0.2-1): (0.5 to 20).

The organic silicon fluororesin prepared by the method is suitable for waterproof agents, antifouling paints and packaging materials.

The invention has the beneficial effects that the fluorine-containing substance and the styrene are grafted on the vinyl silicone resin by adopting solution polymerization reaction to prepare the high-performance organic silicon fluororesin; noble metals involved in the hydrosilylation reaction are avoided being used as catalysts, so that the cost is lower; the influence of the emulsifier in the emulsion polymerization on the performance is avoided, and the process is difficult to control. The organic silicon fluororesin prepared by the invention has multiple functions, wherein the fluorine-containing component can ensure that the modified surface has good low surface energy, and the vinyl silicone resin can provide crosslinking active points and elasticity of the product; in addition, the resin polymer has high refractive index, is a colorless transparent solid, does not change the surface color of the material after being used, and has good compatibility with other resins.

The organic silicon fluororesin prepared by the invention has wide application field, and can be prepared into paint to be applied to wood, building exterior walls, fabrics and oceans for preventing fouling; can be prepared into a waterproof agent to be applied to the fields of stone materials, heat-insulating plates and building engineering, and can also be applied to the fields of LEDs and integrated circuits as a packaging material

Detailed Description

Example 1

Adding 100g of methyl vinyl silicone resin with 2% of vinyl content and 8000cs of viscosity, 100g of toluene and 0.1g of azobisisobutyronitrile into a reaction kettle, uniformly stirring, dropwise adding a mixture of 20g of styrene and 50g of trifluoroethyl acrylate, raising the temperature to 70 ℃ after dropwise adding, reacting for 8 hours, cooling to room temperature, filtering, and removing the toluene by reduced pressure distillation to obtain the organic silicon fluororesin.

Example 2

Adding 100g of phenyl vinyl silicone resin with 10% of vinyl content and 1000cs of viscosity, 1000g of acetone and 0.5g of azobisisoheptonitrile into a reaction kettle, uniformly stirring, dropwise adding a mixture of 100g of styrene and 100g of trifluoropropene, raising the temperature to 75 ℃ after dropwise adding, reacting for 6h, cooling to room temperature, filtering, and removing the acetone through reduced pressure distillation to obtain the organic silicon fluororesin.

Example 3

Adding 100g of methyl vinyl silicone resin with 2% of vinyl content and 8000cs of viscosity, 500g of xylene and 0.5g of azobisisobutyronitrile into a reaction kettle, uniformly stirring, dropwise adding a mixture of 50g of styrene and 100g of trifluoroethyl methacrylate, raising the temperature to 70 ℃ after dropwise adding, reacting for 6 hours, cooling to room temperature, filtering, and removing the xylene through reduced pressure distillation to obtain the organic silicon fluororesin.

Example 4

100g of methyl vinyl silicone resin with 5% of vinyl content and 4000cs of viscosity, 800g of ethyl acetate and 0.4g of dimethyl azodiisobutyrate are added into a reaction kettle, after uniform stirring, a mixture of 80g of styrene and 200g of perfluorostyrene is dropwise added, after dropwise addition, the temperature is raised to 75 ℃, reaction is carried out for 8 hours, the temperature is reduced to room temperature, filtration is carried out, and ethyl acetate is removed by reduced pressure distillation, so that the organic silicon fluororesin is obtained.

Table 1 shows the index of the curing and film-forming properties of the silicone fluororesins prepared in examples 1 to 4 of the present invention.

TABLE 1 index of curing film-Forming Properties of Silicone fluororesins prepared in examples 1-4

Claims

1. A method for preparing an organic silicon fluororesin, characterized by comprising the steps of:

adding vinyl silicone resin, a solvent and an initiator into a reaction kettle, stirring uniformly, dropwise adding a mixture of styrene and a fluorine-containing vinyl monomer, after dropwise adding, raising the temperature to 70-75 ℃, reacting for 6-8h, cooling to room temperature, filtering, and distilling under reduced pressure to remove the solvent to obtain the organic silicon fluororesin;

the mass ratio of the vinyl silicone resin to the solvent to the initiator to the styrene to the fluorine-containing vinyl monomer is 1 (1-10): (0.001-0.005): (0.2-1): (0.5 to 20);

2. The method of claim 1, wherein the solvent is a mixture of at least one of toluene, xylene, ethyl acetate, ethanol, methanol, isopropanol, acetone, and tetrahydrofuran.

3. The method of claim 1, wherein the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.

4. The method of claim 1, wherein the fluorine-containing vinyl monomer is one of trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorododecyl methacrylate, trifluoropropene, perfluorostyrene, and perfluorobutyl ethylene.

5. The method for preparing a silicone fluororesin according to claim 1, wherein the silicone fluororesin prepared by the method is suitable for water repellent, antifouling paint and packaging material.