阅读说明：本技术 一种氟硅树脂及其制备方法 (fluorine-silicon resin and preparation method thereof ) 是由 白为为 于 2019-10-29 设计创作，主要内容包括：本发明提供了一种氟硅树脂,由以下质量分数的原料制备得到：乙基丁基全氟醚100～200份、有机醇200～600份、有机氯硅烷80～200份、催化剂10～30份、正硅酸乙酯100～300份、三烃基一氯硅烷30～100份。利用以上原料制备的氟硅树脂苯基共轭的平面结构以及碳氟键键能大,与现有有机硅材料相比耐热性能优越。本发明还提供了一种氟硅树脂的制备方法,利用市售的乙基丁基全氟醚、正硅酸乙酯、三烃基一氯硅烷等制备出一系列的氟硅树脂,合成方法科学合理,从而提供了一条合成一系列氟硅树脂的通用方法。该方法原料易得,适用范围广,产率高,工业化生产操作简单可行。(The invention provides kinds of fluorosilicone resins, which are prepared from the following raw materials, by mass, 100-200 parts of ethylbutyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of a catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane.)

kinds of fluorosilicone resin is characterized by being prepared from the following raw materials, by mass, 100-200 parts of ethylbutyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of a catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane.

2. The fluorosilicone resin of claim 1, wherein the organic alcohol is dodecyl mercaptan.

3, preparation method of fluorosilicone resin, characterized by comprising the following steps:

, weighing 100-200 parts of butyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane according to mass fractions.

Secondly, adding 100-200 parts of ethyl butyl perfluoroether and 200-600 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 20-30 ℃ for 1-2 hours to obtain a prepolymer 1;

step three, adding 80-200 parts of organic chlorosilane into the prepolymer 1 obtained in the step two, uniformly stirring at the temperature of 20-30 ℃, adding 10-30 parts of catalyst, continuously stirring and heating to 70-90 ℃, and reacting for 15-18 hours to obtain a prepolymer 2;

fourthly, at the temperature of 70-80 ℃, 100-300 parts of tetraethoxysilane is dripped into the prepolymer 2 obtained in the third step, and after the dripping is finished, the temperature is preserved for polycondensation for 40-60 minutes to obtain a prepolymer 3;

and fifthly, dripping 30-100 parts of trihydrocarbyl chlorosilane into the prepolymer 3 obtained in the fourth step, and after finishing dripping, keeping the temperature to perform polycondensation reaction for 90-120 minutes to obtain the target product, namely the fluorosilicone resin.

4. The method for preparing kinds of fluorosilicone resins, according to claim 3, wherein the stirring speed in the third step is 200-500 r/min.

5. The method for preparing kinds of fluorosilicone resins, as claimed in claim 3, wherein the time for dropping tetraethoxysilane in the fourth step is 30-40 minutes.

6. The method for preparing kinds of fluorosilicone resins, as claimed in claim 3, wherein the time for dropping chlorosilane in the fifth step is 40-50 minutes.

Technical Field

The invention belongs to the technical field of high polymer materials, and relates to kinds of fluorosilicone resin and a preparation method of kinds of fluorosilicone resin.

Background

The silicon resin is generally hydrolyzed by various mixtures of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane or methylphenyldichlorosilane in the presence of an organic solvent such as toluene at a lower temperature to obtain an acidic hydrolysate, the acidic hydrolysate is washed with water to remove acid and neutral primary condensation polymers, and is thermally oxidized in air or subjected to -step condensation polymerization in the presence of a catalyst to finally form a highly crosslinked three-dimensional network structure.

MQ resin is of most -generic silicon resin, other groups are introduced into the MQ silicon resin to expand the application, but after other structures are introduced into the MQ silicon resin, the structures are not favorable for the heat-resistant performance of the silicon resin due to the reactivity of the structures under conditions, and even if the silicon resin with a phenyl M structure is introduced, the silicon resin can be heated at 250 ℃ for 24 hours to generate mass loss of 8 percent, so that the application of the silicon resin as a composite material component under the temperature condition of higher than 250 ℃ is limited.

Disclosure of Invention

The invention aims to provide kinds of fluorosilicone resin, which solves the problem that the heat resistance of the silicone resin is insufficient in the prior art.

Another objective of the present invention is to provide a preparation method of fluorosilicone resins, which solves the problem of poor heat resistance of fluorosilicone resins prepared by the prior art.

The technical scheme adopted by the invention is that,

kinds of fluorosilicone resin is prepared from the following raw materials, by mass, 100-200 parts of ethylbutyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organochlorosilane, 10-30 parts of a catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane.

Yet another feature of the present invention is that,

the organic alcohol is dodecyl mercaptan.

preparation method of fluorosilicone resin, comprising the following steps:

, weighing 100-200 parts of butyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane according to mass fractions.

Secondly, adding 100-200 parts of ethyl butyl perfluoroether and 200-600 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 20-30 ℃ for 1-2 hours to obtain a prepolymer 1;

adding 80-200 parts of organic chlorosilane into the prepolymer 1 obtained in the second step, uniformly stirring at the temperature of 20-30 ℃, adding 10-30 parts of catalyst, continuously stirring and heating to 70-90 ℃, and reacting for 15-18 hours to obtain a prepolymer 2;

fourthly, at the temperature of 70-80 ℃, 100-300 parts of tetraethoxysilane is dripped into the prepolymer 2 obtained in the third step, and after the dripping is finished, the temperature is preserved for polycondensation for 40-60 minutes to obtain a prepolymer 3;

and fifthly, dripping 30-100 parts of trihydrocarbyl chlorosilane into the prepolymer 3 obtained in the fourth step, and after finishing dripping, keeping the temperature to perform polycondensation reaction for 90-120 minutes to obtain the target product, namely the fluorosilicone resin.

The stirring speed in the third step is 200-500 r/min.

And in the fourth step, the time for dripping the tetraethoxysilane is 30-40 minutes.

And in the fifth step, the time for dripping the alkyl chlorosilane is 40-50 minutes.

The invention has the beneficial effects that the phenyl conjugated plane structure and the fluorocarbon bond energy of the fluorosilicone resin disclosed by the invention are large, so organic silicon materials with excellent heat resistance are provided, the commercially available ethyl butyl perfluoroether, ethyl orthosilicate, trialkyl chlorosilane and the like are utilized to prepare series fluorosilicone resins, and the synthetic method is scientific and reasonable, so that general methods for synthesizing series fluorosilicone resins are provided.

Detailed Description

The present invention will be described in detail with reference to the following embodiments.

The invention provides kinds of fluorosilicone resin, which is prepared from the following raw materials, by mass, 100-200 parts of ethylbutyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of a catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane.

The invention also provides a preparation method of fluorosilicone resins, which is characterized by comprising the following steps:

, weighing 100-200 parts of butyl perfluoroether, 200-600 parts of organic alcohol, 80-200 parts of organic chlorosilane, 10-30 parts of catalyst, 100-300 parts of ethyl orthosilicate and 30-100 parts of trihydrocarbyl chlorosilane according to mass fractions.

Secondly, adding 100-200 parts of ethyl butyl perfluoroether and 200-600 parts of organic alcohol into a reactor, uniformly stirring, and stirring at the temperature of 20-30 ℃ for 1-2 hours to obtain a prepolymer 1;

adding 80-200 parts of organic chlorosilane into the prepolymer 1 obtained in the second step, uniformly stirring at the temperature of 20-30 ℃ at the speed of 200-500 r/min, adding 10-30 parts of catalyst, continuously stirring and heating to 70-90 ℃, and reacting for 15-18 hours to obtain a prepolymer 2;

fourthly, at the temperature of 70-80 ℃, 100-300 parts of tetraethoxysilane is dripped into the prepolymer 2 obtained in the third step, the dropwise addition is carried out for 30-40 minutes, and the temperature is kept for polycondensation for 40-60 minutes after the dropwise addition is finished, so that a prepolymer 3 is obtained;

and fifthly, dripping 30-100 parts of trihydrocarbyl chlorosilane into the prepolymer 3 obtained in the fourth step for 40-50 minutes, and preserving heat after finishing dripping to perform polycondensation reaction for 90-120 minutes to obtain the target product, namely the fluorosilicone resin.