阅读说明：本技术 一种氟硅表面活性剂、制备方法及应用 (Fluorosilicone surfactant, preparation method and application ) 是由 王新朝 徐大威 孟凡伟 于 2019-11-18 设计创作，主要内容包括：本发明涉及有机硅技术领域,具体的说是一种氟硅表面活性剂、制备方法及应用。该氟硅表面活性剂的制备方法为通过炔醇或其衍生物、烯丙基聚醚和烯基含氟单体与含氢硅油混合进行硅氢加成反应制备而成；所述含氢硅油分子结构式中含有至少三个Si-H键。本发明制备的氟硅表面活性剂具有很好的润湿性,同时还具有低泡的特点。(The invention relates to the technical field of organic silicon, in particular to a fluorine-silicon surfactant, a preparation method and application. The preparation method of the fluorosilicone surfactant is that the fluorosilicone surfactant is prepared by mixing alkynol or derivatives thereof, allyl polyether, alkenyl fluorine-containing monomer and hydrogen-containing silicone oil for hydrosilylation reaction; the molecular structural formula of the hydrogen-containing silicone oil contains at least three Si-H bonds. The fluorosilicone surfactant prepared by the method has good wettability and low foam.)

A preparation method of a fluorine-silicon surfactant is characterized by comprising the following steps: mixing alkynol or derivatives thereof, allyl polyether, alkenyl fluorine-containing monomer and hydrogen-containing silicone oil to perform hydrosilylation reaction, and grafting the alkynol or derivatives thereof, the allyl polyether and the alkenyl fluorine-containing monomer to the hydrogen-containing silicone oil to prepare the modified polyether polyol; the molecular structural formula of the hydrogen-containing silicone oil contains at least three Si-H bonds; the alkenyl in the alkenyl fluorine-containing monomer is vinyl or propenyl.

The method for preparing a fluorosilicone surfactant according to claim 1, comprising: the compound is prepared by mixing a mixture of alkynol or derivatives thereof, allyl polyether and alkenyl fluorine-containing monomer with hydrogen-containing silicone oil for hydrosilylation reaction; or the intermediate product is prepared by mixing the intermediate product and the alkenyl fluorine-containing monomer to carry out hydrosilylation reaction; the ratio of the multiple bonds in the alkynol or the derivative thereof, the allyl polyether and the alkenyl fluorine-containing monomer to the Si-H bonds in the hydrogen-containing silicone oil is as follows: (0.9-1.1):1.

The method for preparing a fluorosilicone surfactant according to claim 1, wherein the hydrogen content of the hydrogen-containing silicone oil is between 0.2% and 1.5%; the average molecular weight is between 500 and 3000.

The method for preparing a fluorosilicone surfactant according to claim 1,

the molecular structural formula of the alkynol is as follows:

wherein z and g are integers, z is more than or equal to 0 and less than or equal to 4, and g is more than or equal to 0 and less than or equal to 4; r' is C₀-C ₁₂Alkyl groups of (a);₁r' is C₀-C ₁₂Alkyl group of (1).

The molecular structural formula of the alkenyl fluorine-containing monomer is as follows:

wherein R is C₂-C ₁₂Alkyl groups of (a); r' is vinyl or propenyl; e is 0 or 1; rf is a fluorine substituted alkyl group;

the molecular structural formula of the allyl polyether is as follows:

wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 12; y is more than or equal to 0 and less than or equal to 14, and when one of x and y is 0, the other is more than zero; r' is any one of hydrogen radical, methyl, ethyl or butyl;

the molecular structural formula of the hydrogen-containing silicone oil is as follows:

wherein, 1) a is more than or equal to 0, b + c + d is more than or equal to 3, a, b, c and d are integers, and b, c and d are positive integers.

The method for preparing a fluorosilicone surfactant according to claim 1, comprising: slowly mixing the mixture of alkynol or derivative thereof, allyl polyether and alkenyl fluorine-containing monomer with hydrogen-containing silicone oil at 75-160 ℃ in the presence of catalyst and solvent, and reacting for 2-19 hours.

The method for preparing a fluorosilicone surfactant according to claim 1, comprising: in the presence of solvent and catalyst, the mixture of alkynol or its derivative and allyl polyether is slowly mixed with hydrogen-containing silicone oil at 75-160 deg.C and reacted for 2-19 hr to obtain intermediate product, and the intermediate product and alkenyl fluorine-containing monomer are slowly mixed at 75-160 deg.C and reacted for 2-19 hr.

The method for preparing a fluorosilicone surfactant according to claim 5 or 6, wherein the catalyst is a Karster catalyst or chloroplatinic acid; the solvent is xylene.

A fluorosilicone surfactant, characterized in that it is prepared by the preparation method according to any one of claims 1 to 7.

The fluorosilicone surfactant of claim 8, wherein the molecular structural formula of the fluorosilicone surfactant is:

wherein, 1) a is more than or equal to 0, b + c + d is more than or equal to 3, a, b, c and d are integers, and b, c and d are positive integers;

2) x and y are integers, and x is more than or equal to 0 and less than or equal to 12; y is more than or equal to 0 and less than or equal to 14, and when one of x and y is 0, the other is more than zero; r' is any one of hydrogen radical, methyl, ethyl or butyl;

3) a isWherein, Rf is a fluorine-substituted alkyl group; r is C₂-C ₁₂Alkyl groups of (a); e is 0 or 1;₁r' isEthyl or propyl;

b isz and g are integers, z is more than or equal to 0 and less than or equal to 4, and g is more than or equal to 0 and less than or equal to 4;₁r 'and R' are both C₀-C ₁₂Alkyl groups of (a);

the use of a fluorosilicone surfactant according to claim 8, wherein the fluorosilicone surfactant is used as a defoaming wetting agent in a coating film.