Synthesis method of chlorinated hydrogen-containing silicone oil grafted silanol

Abstract

The invention belongs to the field of polymer chemistry, and particularly relates to a synthetic method of chlorinated hydrogen-containing silicone oil grafted silanol. The preparation method comprises the following steps: firstly, adding hydrogen-containing silicone oil, methylsilanetriol and a chlorine-containing solvent into a three-neck flask according to a certain proportion, stirring, and after fully stirring, carrying out a hydrogen-containing silicone oil grafted silanol reaction; and secondly, increasing the temperature, dropwise adding a chlorine-containing solvent solution containing an initiator, introducing chlorine to perform chlorination reaction, continuing the reaction for a period of time after stopping introducing chlorine, stopping heating, adding epoxy resin to continue stirring, removing residual chlorine by using dry nitrogen, washing a final product by using an absolute ethyl alcohol solution after finishing introducing the chlorine, and drying to obtain the epoxy resin. And heating and distilling to remove the chlorine-containing solvent, absolute ethyl alcohol and redundant silanol so as to remove impurities, thereby obtaining the purified chlorinated hydrogen-containing silicone oil grafted silanol. The process method can be widely applied to the fields of coatings, adhesives, printing ink, finishing agents and the like, and the adhesive force, ultraviolet irradiation resistance and weather resistance of the product to a base material are improved.

Description

Technical Field

[0001] The invention belongs to the field of polymer chemistry, and in particular relates to a method for synthesizing chlorinated hydrogen-containing silicone oil grafted with silanol. Background Art

[0002] Hydrogenated silicone oil, also known as polymethylhydrogensiloxane, is a silicone oil containing active silicon-hydrogen bonds. Because of its large number of methyl groups in its structure, it has particularly excellent hydrophobicity and is widely used as a surface treatment agent for glass, metal, fiber and powder. In recent years, it has also been widely used as a surface water repellent for concrete materials. As people have higher and higher requirements for the surface performance and appearance of some concrete materials, in order to improve the competitiveness of hydrogenated silicone oil in the concrete market, it is necessary to chemically modify hydrogenated silicone oil. The surface of concrete materials contains a large number of hydroxyl groups, and hydrogenated silicone oil has poor adhesion to the surface of concrete materials. Therefore, through the grafting reaction of silanol and hydrogenated silicone oil, the silicone oil is connected with some hydroxyl groups, and then hydrogen bonds are formed with the hydroxyl groups on the surface of concrete materials and finally condensation reactions are carried out, so that the adhesion of the material to the concrete is improved, and the durability of the surface water repellent on the concrete surface is improved. In order to improve the adhesion and weather resistance of modified silicone oil to other materials, chlorination reaction can be used to achieve the modified silicone oil into a more stable substance, which is more suitable as a concrete surface water repellent. Summary of the invention

[0003] The purpose of the present invention is to provide a method for synthesizing chlorinated hydrogenated silicone oil grafted with silanol, which has the advantages of simple method, low cost and high product grafting rate, in order to solve the problems existing in the prior art.

[0004] To achieve the above object, the technical solution adopted by the present invention is: First, hydrogenated silicone oil, methyl silanol and chlorinated solvent are put into a three-necked flask, stirred, and the reaction temperature is controlled at 50-70°C. After sufficient stirring, the hydrogenated silicone oil grafted silanol reaction is carried out for 4-6 hours; secondly, the temperature is increased to 100-120°C, and then a chlorinated solvent solution containing an initiator is dripped into it, and chlorine gas is introduced for chlorination reaction for 2-4 hours. After stopping the chlorine gas, the reaction is continued for a period of 1-2 hours, and the heating is stopped. The epoxy resin is added and stirred for 0.5 hours, and the residual chlorine is driven away with dry nitrogen. After the ventilation is completed, the final product is washed with anhydrous ethanol solution, and then the temperature is increased to 180°C, and the chlorinated solvent, anhydrous ethanol and excess silanol are distilled to remove impurities, so as to obtain purified chlorinated hydrogenated silicone oil grafted silanol.

[0005] In the above-mentioned method for synthesizing chlorinated hydrogenated silicone oil grafted with silanol, preferably, the hydrogenated silicone oil is a high hydrogenated silicone oil.

[0006] In the above-mentioned method for synthesizing chlorinated hydrogen-containing silicone oil grafted silanol, preferably, the methyl silanol is methyl silanol triol.

[0007] In the above synthesis method of grafting silanol with hydrogen chloride-containing silicone oil, preferably, the weight parts of each substance added are as follows: 100 parts of hydrogen chloride-containing silicone oil, 5 - 20 parts of methyl silanol, and 500 parts of chlorine-containing solvent.

[0008] In the above synthesis method of grafting silanol with hydrogen chloride-containing silicone oil, preferably, the chlorine-containing solvent is 1,1,2,2 - tetrachloroethane.

[0009] In the above synthesis method of grafting silanol with hydrogen chloride-containing silicone oil, preferably, the initiator can be benzoyl peroxide.

[0010] In the above synthesis method of grafting silanol with hydrogen chloride-containing silicone oil, preferably, the addition amount of the initiator benzoyl peroxide is 0.01 - 0.1% of the total mass of the solution.

[0011] In the above synthesis method of grafting silanol with hydrogen chloride-containing silicone oil, preferably, the time for introducing dry nitrogen is 0.5 - 1 h.

[0012] In the above synthesis method of grafting silanol with hydrogen chloride-containing silicone oil, preferably, the mass of the epoxy resin is 1 - 3% of the mass of the solution.

[0013] In summary, compared with the prior art, the present invention has the following advantages: (1) The present invention uses 1,1,2,2 - tetrachloroethane as the reaction solvent, which is green and environmentally friendly. The use of the solvent is not restricted by environmental protection conventions, is relatively stable during the reaction process, and has a very broad market application prospect and more profound significance; (2) The two-step preparation method provided by the present invention is all carried out in one reaction vessel, the process steps are simple, saving raw material costs and time costs, and is economical and efficient; (3) In the preparation method provided by the present invention, the modified silicone oil is further chlorinated, which can improve the stability of the modified silicone oil product, has better protection for various substrates when used as a surface treatment agent, and has more excellent environmental and weather resistance.

[0014] (4) The epoxy resin is added in the preparation method provided by the present invention, which ensures the acidic substances remaining after the chlorination reaction of the final product, and ensures that the pH value of the product after washing and distillation is neutral and the quality is stable. Specific Embodiments

[0015] The present invention will be further described below in conjunction with specific embodiments.

[0016] I. Preparation Examples Example 1

[0017] First, weigh 100 g of hydrogen-containing silicone oil, 10 g of methylsilanetriol, and 300 g of tetrachloroethane and add them to a 500 mL three-necked flask. Slowly heat up to 50 °C, and under the conditions of condensation reflux and uniform stirring, stir thoroughly for 4 h to allow the hydrogen-containing silicone oil to react with methylsilanetriol. After the first-step reaction is completed, slowly heat up to 115 °C, then add dropwise 5 g of a tetrachloroethane solution containing 0.1 g of benzoyl peroxide, and continuously introduce chlorine gas at 115 °C for 2 h for chlorination reaction. After stopping the introduction of chlorine gas, keep stirring at this temperature for 1.5 h, stop heating, then add 15 g of epoxy resin and continue stirring for 0.5 h. Use dry nitrogen to drive away the residual chlorine gas. After the ventilation is completed, wash the final product with an anhydrous ethanol solution, then heat up to 180 °C, and distill off the chlorine-containing solvent, anhydrous ethanol, and excess silanol to remove all impurities, thus obtaining purified chlorinated hydrogen-containing silicone oil grafted with silanol. The grafting rate of methylsilanetriol in the product is 4.8%, and the chlorine content is 23.18%. Example 2

[0018] First, weigh 100 g of hydrogen-containing silicone oil, 15 g of methylsilanetriol, and 300 g of tetrachloroethane and add them to a 500 mL three-necked flask. Slowly heat up to 60 °C, and under the conditions of condensation reflux and uniform stirring, stir thoroughly for 4.5 h to allow the hydrogen-containing silicone oil to react with methylsilanetriol. After the first-step reaction is completed, slowly heat up to 110 °C, then add dropwise 5 g of a tetrachloroethane solution containing 0.1 g of benzoyl peroxide, and continuously introduce chlorine gas at 110 °C for 2.5 h for chlorination reaction. After stopping the introduction of chlorine gas, keep stirring at this temperature for 1.5 h, stop heating, then add 20 g of epoxy resin and continue stirring for 0.5 h. Use dry nitrogen to drive away the residual chlorine gas. After the ventilation is completed, wash the final product with an anhydrous ethanol solution, then heat up to 180 °C, and distill off the chlorine-containing solvent, anhydrous ethanol, and excess silanol to remove all impurities, thus obtaining purified chlorinated hydrogen-containing silicone oil grafted with silanol. The grafting rate of methylsilanetriol in the product is 6.4%, and the chlorine content is 24.36%. Example 3

[0019] First, weigh 100 g of hydrogen-containing silicone oil, 20 g of methylsilanetriol, and 300 g of tetrachloroethane and add them to a 500 mL three-necked flask. Slowly heat the mixture to 65 °C and stir it vigorously for 5 h under the conditions of condensation reflux and uniform stirring until the hydrogen-containing silicone oil reacts with methylsilanetriol. After the first-step reaction is completed, slowly heat the mixture to 110 °C, then dropwise add 5 g of a tetrachloroethane solution containing 0.1 g of benzoyl peroxide, and continuously introduce chlorine gas at 110 °C for 3 h for chlorination reaction. After stopping the introduction of chlorine gas, keep stirring at this temperature for 1.5 h, stop heating, then add 20 g of epoxy resin and continue stirring for 0.5 h. Use dry nitrogen to expel the residual chlorine gas. After the ventilation is completed, wash the final product with an anhydrous ethanol solution, then heat it to 180 °C to distill off the chlorine-containing solvent, anhydrous ethanol, and excess silanol to remove all impurities, thus obtaining purified hydrogen-containing chlorinated silicone oil grafted with silanol. The grafting rate of methylsilanetriol in the product is 7.5%, and the chlorine content is 26.78%.

[0020] Finally, it should be noted that the above embodiments are only preferred embodiments of the present invention rather than limitations. It should be pointed out that those of ordinary skill in the art should understand that without departing from the technical principle and scope of the present invention, several improvements and modifications can be made to the technical solution of the present invention, and these improvements and modifications should all be covered within the scope of the claims of the present invention.

Claims

1. A method for synthesizing chlorinated hydrogenated silicone oil grafted with silanol, characterized in that: The method comprises the following steps: First, hydrogen-containing silicone oil, methyl silanol, and chlorine-containing solvent are put into a three-necked flask, stirred, and the reaction temperature is controlled at 50-70°C. After sufficient stirring, the hydrogen-containing silicone oil grafting silanol reaction is carried out for 4-6 hours; Secondly, the temperature is raised to 100-120°C, and a chlorine-containing solvent solution containing an initiator is dripped in, and chlorine gas is introduced for chlorination reaction for 2-4 hours. After the chlorine gas is stopped, the reaction is continued for a period of 1-2 hours, and the heating is stopped. The epoxy resin is added and stirred for 0.5 hours, and the residual chlorine is driven away with dry nitrogen. After the ventilation is completed, the final product is washed with anhydrous ethanol solution, and then the temperature is raised to 180°C, and the chlorine-containing solvent, anhydrous ethanol and excess silanol are distilled to remove impurities, thereby obtaining purified chlorinated hydrogen silicone oil grafted silanol.

2. The method for synthesizing chlorinated hydrogenated silicone oil grafted silanol according to claim 1, characterized in that: The hydrogen-containing silicone oil is a high-hydrogen-containing silicone oil.

3. The method for synthesizing chlorinated hydrogenated silicone oil grafted silanol according to claim 1, characterized in that: The methylsilanol is methylsilanol.

4. The method for synthesizing chlorinated hydrogenated silicone oil grafted silanol according to claim 1, characterized in that: The weight proportions of the added substances are: 100 parts of hydrogenated silicone oil, 5-20 parts of methylsilanol, and 500 parts of chlorinated solvent.

5. The method for synthesizing chlorinated hydrogenated silicone oil grafted silanol according to claim 1, characterized in that: The chlorine-containing solvent is 1,1,2,2-tetrachloroethane.

6. The method for synthesizing chlorinated hydrogenated silicone oil grafted silanol according to claim 1, characterized in that: The initiator is dibenzoyl peroxide.

7. The method for synthesizing chlorinated hydrogenated silicone oil grafted silanol according to claim 1, characterized in that: The added amount of the initiator dibenzoyl peroxide is 0.01-0.1% of the total mass of the solution.

8. The method for synthesizing chlorinated hydrogenated silicone oil grafted silanol according to claim 1, characterized in that: The time for introducing dry nitrogen is 0.5-1h.

9. The method for synthesizing chlorinated hydrogenated silicone oil grafted silanol according to claim 1, characterized in that: The mass of the epoxy resin is 1-3% of the mass of the solution.