WO2021097591A1 - 一种氟硅表面活性剂、制备方法及应用 - Google Patents

一种氟硅表面活性剂、制备方法及应用 Download PDF

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WO2021097591A1
WO2021097591A1 PCT/CN2019/119089 CN2019119089W WO2021097591A1 WO 2021097591 A1 WO2021097591 A1 WO 2021097591A1 CN 2019119089 W CN2019119089 W CN 2019119089W WO 2021097591 A1 WO2021097591 A1 WO 2021097591A1
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hydrogen
silicone oil
preparation
containing silicone
alkenyl
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PCT/CN2019/119089
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English (en)
French (fr)
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王新朝
徐大威
孟凡伟
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广州核心新材料科技有限公司
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Priority to PCT/CN2019/119089 priority Critical patent/WO2021097591A1/zh
Priority to US17/777,632 priority patent/US20230064344A1/en
Priority to CN201980048325.8A priority patent/CN113661199B/zh
Publication of WO2021097591A1 publication Critical patent/WO2021097591A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/54—Silicon compounds

Definitions

  • the invention relates to the technical field of organosilicon, in particular to a fluorosilicone surfactant, a preparation method and an application.
  • polyether-modified silicone wetting agents are widely used in water-based coatings, inks, papermaking and leather industries due to their excellent wettability.
  • this type of wetting agent can quickly wet the surface of the substrate to obtain a uniform coating film, and it can also form a good coating when the surface of the substrate has oil stains or even pores. membrane.
  • polyether-modified silicone wetting agents are the most mainstream wetting agents in the coating, ink, paper and leather industries, and they are most widely used.
  • the application of this type of product also brings a headache, that is, too much foam or the foam in the application process is difficult to eliminate.
  • silicone defoamers with strong defoaming ability have to be used to solve the foam problem.
  • it after the addition of defoamer, under the combined action of defoamer and wetting agent, it often causes shrinkage problems on the surface of the coating film. In this way, we have to increase the wetting agent to reduce the surface tension. After the surface tension drops, it will cause the problem of difficulty in defoaming. Repeatedly, the formula is becoming more and more complicated, and there are more and more problems. Not only the cost rises, but the stability of the product is also difficult to guarantee.
  • the purpose of the present invention is to provide a fluorosilicone surfactant with good wettability and low foam, a preparation method and application.
  • a preparation method of fluorosilicone surfactant which is prepared by mixing acetylenic alcohol or its derivatives, allyl polyether and alkenyl fluorine-containing monomer with hydrogen-containing silicone oil for hydrosilylation reaction to make acetylenic alcohol Or its derivatives, allyl polyether and alkenyl fluorine-containing monomers are prepared by grafting hydrogen-containing silicone oil; the molecular structure of the hydrogen-containing silicone oil contains at least three Si-H bonds; the alkenyl group contains fluorine The alkenyl group in the monomer is a vinyl group or a propenyl group.
  • the alkenyl fluorine-containing monomer is a monomer containing an alkenyl group and fluorine.
  • the alkynyl alcohol is a hydrocarbyl alkynyl alcohol.
  • the multiple bond refers to the bond that can undergo a silicon-hydrogen addition reaction with the Si-H bond of hydrogen-containing silicone oil, and can be a carbon-carbon double bond or a carbon-carbon triple bond.
  • acetylene alcohol or its derivatives, allyl polyether and alkenyl fluorine-containing monomers are mixed with hydrogen-containing silicone oil for hydrosilylation reaction.
  • the monomer grafts the acetylenic alcohol or its derivatives, allyl polyether and alkenyl fluorine-containing monomers to the hydrogen-containing silicone oil through at least three Si-H bonds contained in the molecular structure of the hydrogen-containing silicone oil.
  • the new product obtained has good wettability and low foam.
  • a hydrogen-containing silicone oil molecule contains at least three Si-H bonds
  • the reaction can be: at least one Si-H bond in the hydrogen-containing silicone oil molecule and an alkynyl alcohol or its derivative molecule undergo a hydrosilylation reaction ,
  • the acetylenic alcohol or its derivatives are grafted to the hydrogen-containing silicone oil molecule; at least one Si-H bond in the hydrogen-containing silicone oil molecule and an allyl polyether molecule undergo a hydrosilylation reaction to make the allyl polyether Is also grafted to the hydrogen-containing silicone oil molecule;
  • at least one Si-H bond in the hydrogen-containing silicone oil molecule and an alkenyl fluorine-containing monomer undergo a hydrosilylation reaction, so that the alkenyl fluorine-containing monomer is also grafted to the hydrogen-containing silicone oil molecule.
  • Hydrogen silicone oil molecule Hydrogen silicone oil molecule.
  • the preparation method is: prepared by mixing a mixture of acetylenic alcohol or its derivatives, allyl polyether and alkenyl fluorine-containing monomer with hydrogen-containing silicone oil for hydrosilylation reaction; or through alkyne
  • the mixture of alcohol or its derivatives and allyl polyether is mixed with hydrogen-containing silicone oil for hydrosilylation reaction to obtain an intermediate product, which is then prepared by mixing the intermediate product with an alkenyl fluorine-containing monomer for hydrosilylation reaction.
  • the ratio of the amount of multiple bonds to the Si-H bond of hydrogen-containing silicone oil in the acetylenic alcohol or its derivatives, allyl polyether, and alkenyl fluorine-containing monomer is: (0.9-1.1):1 ;
  • the hydrogen content of hydrogen-containing silicone oil is between 0.2-1.5%.
  • the molecular structural formula (first general formula) of the alkynol is:
  • z and g are integers, and 0 ⁇ z ⁇ 4, 0 ⁇ g ⁇ 4;
  • R" is a C 0 -C 12 alkyl group (which can be a straight chain alkyl group or a branched chain alkyl group); 1 R" It is a C 0 -C 12 alkyl group ((may be a straight chain alkyl group and a branched chain alkyl group); R" and 1 R" can be preferably a C 0 -C 6 alkyl group, which can meet the requirements of low foaming and wetting at the same time , The raw materials are more readily available.
  • the molecular structural formula (the second general formula) of the alkenyl fluorine-containing monomer is:
  • R is a C 2 -C 12 hydrocarbon group
  • R"' is a vinyl group or a propenyl group
  • e is 0 or 1
  • Rf is a fluorine-substituted alkyl group (fluoroalkyl group), which can be a perfluoroalkyl group or a polyfluoroalkyl group.
  • Alkyl group usually refers to 2 or more
  • the molecular structural formula (third general formula) of the allyl polyether is:
  • x and y are integers, and 0 ⁇ x ⁇ 12; 0 ⁇ y ⁇ 14, when one of x and y is 0, the other is greater than zero;
  • R' is hydrogen, methyl, ethyl or butyl Any of
  • the molecular structural formula (fourth general formula) of the hydrogen-containing silicone oil is:
  • the preparation method is: in the presence of a catalyst and a solvent, slowly mixing a mixture of acetylenic alcohol or its derivatives, allyl polyether and alkenyl fluoromonomers with The hydrogen-containing silicone oil is mixed and reacted for 2-19 hours.
  • the preparation method is: in the presence of a solvent and a catalyst, slowly mixing a mixture of acetylenic alcohol or its derivatives and allyl polyether with hydrogen-containing silicone oil and reacting at a temperature between 75°C and 160°C. 2 -19 hours to obtain the intermediate product, and then slowly mix the intermediate product and the alkenyl fluorine-containing monomer and react for 2-19 hours at between 75°C and 160°C.
  • the slowness mentioned here refers to avoiding the gel phenomenon as much as possible during the reaction.
  • the speed is the speed that does not produce gel and makes the reaction proceed smoothly. For example, when 150 grams of acetylenic alcohol or its derivatives, allyl alcohol are added In the case of a mixture of base polyether and alkenyl fluorine-containing monomer, the addition time can be 2-3 hours.
  • the catalyst is Castor catalyst or chloroplatinic acid; and the solvent is xylene.
  • the present invention also provides a fluorosilicone surfactant, which is prepared by the above-mentioned preparation method.
  • the molecular structural formula (the fifth general formula) of the fluorosilicone surfactant is:
  • x and y are integers, and 0 ⁇ x ⁇ 12; 0 ⁇ y ⁇ 14, when one of x and y is 0, the other is greater than zero;
  • R' is hydrogen, methyl, ethyl or butyl Any of
  • Rf is a fluorine-substituted alkyl group
  • R is a C 2 -C 12 alkyl group
  • e is 0 or 1
  • 1 R′′ is ethyl or propyl, such as: -CH 2 -CH 2 -or
  • B is Both z and g are integers, and 0 ⁇ z ⁇ 4, 0 ⁇ g ⁇ 4; 1 R" and R" are both C 0 -C 12 alkyl groups (which may be linear and branched alkyl groups).
  • the fluorosilicone surfactant prepared by the invention can be well used as a defoaming wetting agent in coating film.
  • the hydrosilylation reaction of acetylenic alcohol or its derivatives, allyl polyether, alkenyl fluorine-containing monomer and hydrogen-containing silicone oil containing at least three Si-H bonds in the molecular structural formula is carried out to obtain a fluorosilicone surface Active agent, the surfactant has good low foaming and wettability, and can well meet the needs of use.
  • fluorine Since fluorine has lower surface tension and chemical stability than silicon, it can provide better wettability and stability.
  • the combination of acetylenic alcohol and its derivatives with allyl polyether can provide good compatibility and low Dynamic surface; various substances grafted to hydrogen-containing silicone oil can achieve good wettability and low foam, at the same time, due to good compatibility, and then the surfactant can be widely used, and the surfactant It also has good hydrolysis resistance.
  • the ingredient formula When used with other ingredients, due to low foaming and good wettability, the ingredient formula is simple, which can well meet the needs of use.
  • a preparation method of fluorosilicone surfactant which is prepared by mixing acetylenic alcohol or its derivatives, allyl polyether and alkenyl fluorine-containing monomer with hydrogen-containing silicone oil for hydrosilylation reaction to make acetylenic alcohol Or its derivatives, allyl polyether and alkenyl fluorine-containing monomers are prepared by grafting hydrogen-containing silicone oil; the molecular structure of the hydrogen-containing silicone oil contains at least three Si-H bonds; the alkenyl group contains fluorine The alkenyl group in the monomer is a vinyl group or a propenyl group.
  • the preparation method of the fluorosilicone surfactant is prepared by mixing a mixture of acetylenic alcohol or its derivatives, allyl polyether and alkenyl fluorine-containing monomer with hydrogen-containing silicone oil for hydrosilylation reaction.
  • the ratio of the amount of multiple bonds in the acetylenic alcohol or its derivatives, allyl polyethers, and alkenyl fluorine-containing monomers to the Si-H bonds in the hydrogen-containing silicone oil is: ( 0.9-1.1): 1.
  • the hydrogen content of the hydrogen-containing silicone oil is between 0.2-1.5%, and the average molecular weight of the hydrogen-containing silicone oil is preferably between 500-3000.
  • the ratio of multiple bonds to the amount of Si-H bonds in the hydrogen-containing silicone oil is: (0.9-1.1):1, which can make the reaction more complete and thorough.
  • the preparation method of the fluorosilicone surfactant is as follows: in the presence of a catalyst and a solvent, slowly adding acetylenic alcohol or its derivatives, allyl polyether and alkenyl fluoride between 75° C. and 160° C.
  • the monomer mixture is mixed with the hydrogen-containing silicone oil and reacted for 2-19 hours, preferably 3-19 hours, most preferably 10-19 hours. 3-19 hours is relatively moderate, the reaction is complete and time saving.
  • the solvent and unreacted monomer can be removed by vacuum.
  • the molecular structure of acetylenic alcohol is the first general formula
  • the molecular structure of alkenyl fluorine-containing monomer is the second general formula
  • the molecular structure of allyl polyether is the third general formula Formula
  • the molecular structure of hydrogen-containing silicone oil is the fourth general formula
  • the molecular structure of the fluorosilicone surfactant is the fifth general formula.
  • the hydrogen content of the hydrogen-containing silicone oil refers to the mass percentage of hydrogen in the silicon-hydrogen bonds of the hydrogen-containing silicone oil.
  • the molecular weight of allyl polyether is the average molecular weight, because in the third general formula, in addition to the main part, there will be a little impurity (x and y, part of the value is deviated (a few x and y Will fluctuate)), so its molecular weight is the average molecular weight, which can be the molecular weight given by the product supplier when the product is purchased.
  • the molecular weight of hydrogen-containing silicone oil is also an average molecular weight.
  • the chloroplatinic acid solution is a chloroplatinic acid aqueous solution with a chloroplatinic acid content of 8%. 1 R" is a branched or branched alkyl group, and R" is a branched or branched alkyl group.
  • x and y refer to the x and y of the main body.
  • R' is butyl, 0.30mol
  • 425.4 grams of octaethoxydodecynediol that is, in the first general formula, 1 R" is C 5 alkyl, R" is C 5 alkyl , Z and g are both 4; molecular weight is 550; 0.77 mol), 64.8 g of tridecafluorooctyl methacrylate (molecular weight of 432; 0.15 mol) and 0.0705 g of a mixture of chloroplatinic acid solution, gradually add 137.5 g at a uniform rate Hydrogen-containing silicone oil (average molecular weight of 1000, hydrogen content of 0.8%, 0.14 mol) is added dropwise in 8 hours, and the temperature is gradually increased to 150°C and maintained at 150-160°C for 3 hours.
  • 1 R" and R" can both be -CH 2 CH 2 CH 2 CH 2 CH 2 -.
  • the preparation method of the fluorosilicone surfactants described in Examples 1-6 can also be: in the presence of a solvent and a catalyst, at a temperature between 75°C and 160°C, slowly mixing the acetylenic alcohol or its derivatives with allyl polyether The mixture is mixed with hydrogen-containing silicone oil and reacted for 2-19 hours (preferably 3-19 hours) to obtain an intermediate product, and then slowly mix and react the intermediate product and the alkenyl fluoromonomer between 75°C and 160°C. 2 -19 hours (preferably 3-19 hours of reaction).
  • the preparation method can be:
  • R' is butyl, 0.30mol
  • 425.4 grams of octaethoxydodecynediol that is, in the first general formula, 1 R" is C 5 alkyl, R" is C 5 alkyl , Z and g are 4; molecular weight is 550; 0.77mol) and 0.0705g chloroplatinic acid solution mixture, gradually add 137.5 grams of hydrogen-containing silicone oil (average molecular weight 1000, hydrogen content 0.8%, 0.14mol), 8
  • the temperature is gradually increased to 150°C and maintained between 150-160°C for 2-11 hours to obtain an intermediate product; after the temperature is lowered to 105°C, 64.8 grams of methacrylic acid 13 are added dropwise to the intermediate product.
  • Fluorooctyl ester (molecular weight: 432; 0.15 mol), after 8 hours of dripping, gradually increase the temperature to 150 °C, and maintain between 150-160 °C for 2-11 hours;
  • Example 6 the preparation method can be:
  • Step 1) Take 10 containers and add 85 grams of water-based acrylic resin (commodity brand: DS M; model: Neocryl XK14) and 15 grams of deionized water into each container;
  • Step 2) Take 10 samples, 0.3 g each, and add them to each container.
  • Step 3) Mix the materials in the container uniformly and let it stand for 2 hours to test its foam suppression ability, wettability, and appearance leveling.
  • 10 samples are: the samples prepared in Examples 1-6 (sample 1, sample 2, sample 3, sample 4, sample 5, sample 6) and four typical samples on the market. Aerosol products (commodity 1, product 2, product 3, and product 4); the four typical products on the market are all commercially available polyether modified silicones.
  • the liquid in each container is sample 1 (the added sample is sample 1), sample 2 (the added sample is sample 2), sample 3 (the added sample is sample 3), and sample 4 (the added sample is sample 3).
  • the sample is sample 4), sample 5 (the added sample is sample 5), sample 6 (the added sample is sample 6), sample 7 (the added sample is product 1), sample 8 ( The added sample is product 2), sample 9 (the added sample is product 3), and sample 10 (the added sample is product 4).
  • the data in Table 1 shows that the fluorosilicone surfactant prepared by the present invention has low-foaming properties, which is much lower than the foam of products on the market, and the initial height and height after 2 hours are significantly lower than those of commercial wetting agents on the market. This indicates that the product prepared by the present invention has low foaming properties.
  • a ring-type static surface tension meter (model: SFZL-A1, production number: 20170501003) is used to test the surface tension. The smaller the reading, the lower the surface tension. The experimental results are shown in Table 2.
  • Preparation of the squeegee spread each sample on a flat plate, press the sample with a film maker (the film maker is a hollow object with left and right sides and a top surface), and then pull up the mold maker to make the coating
  • the thickness of the film is 100 microns.
  • the various properties of the film in this case, the dry film
  • the process of preparing the dry film is also called the scraping process.
  • the compatibility criterion is that the permeability of the coating film gradually increases from level 1-5, level 5 is the most transparent, and level 1 is the least transparent.
  • the gloss is tested with a specular gloss meter with an incident angle of 60°. The higher the gloss, the better the compatibility of the coating film; the smaller the shrinkage width data, the better the wettability of the coating film.
  • samples 1-10 take 2 parts of each sample and add the defoamer BYK022 respectively, so that the mass parts of the defoamer BYK022 in one sample is 0.2% (the sample is 1# sample), and the other Among the samples, the mass part of YK022 is 0.4% (the sample is 2# sample), and then use 1# sample and 2# sample to prepare scrapers to observe the anti-crater ability of the wetting agent and the shrinkage on the coating film The more the number, the worse the wetting effect of the wetting agent.
  • Table 4 The experimental results are shown in Table 4.
  • Sample 1 Sample 2 Sample 3
  • Sample 4 Sample 5
  • Sample 6 Sample 7
  • Sample 8 Sample 9
  • Sample 10 1#sample 0 0 0 0 0 0 2 1 2 3 2#sample 2 0 2 0 0 1 7 6 3 5
  • the anti-cratering ability of the products made in Examples 1-6 of the present invention is significantly better than the anti-cratering ability of the wetting agents on the market.
  • the product has very good wettability, which is significantly better than the products on the market.
  • it still has good anti-cratering ability, that is, it has good wettability, and then has strong anti-destructive ability, and can well resist the interference of other ingredients.
  • C 0 means that it does not contain a carbon group.
  • the allyl polyether in the present invention can be purchased from Nantong Chenrun Chemical Co., Ltd. or Hangzhou Danwei Technology Co., Ltd., or from other companies.

Abstract

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。

Description

一种氟硅表面活性剂、制备方法及应用 技术领域
本发明涉及有机硅技术领域，具体地说是一种氟硅表面活性剂、制备方法及应用。
背景技术
目前在水性体系涂料、油墨、造纸以及皮革等行业中，聚醚改性有机硅润湿剂由于其优异的润湿性而得到广泛的应用。相比较聚醚类(不含有机硅)表面活性剂，这类润湿剂能够快速润湿基材表面，得到均匀的涂膜，并且当基材表面有油污甚至孔隙时也能形成良好的涂膜。
目前市场上聚醚改性有机硅类润湿剂为涂料、油墨、造纸以及皮革等行业中最主流的润湿剂产品，应用最为广泛。但是这类产品应用的同时带来了一个头痛的问题，那就是泡沫太多或者应用过程中的泡沫难以消除。为了消除泡沫，不得不使用具有强烈消泡能力的有机硅消泡剂去解决泡沫问题。但是，加入消泡剂后，在消泡剂和润湿剂的共同作用下，经常会使涂膜表面产生缩孔问题。这样不得不再去增加润湿剂来降低表面张力，表面张力降下来后又会产生难以消泡的问题。周而复始，配方越做越复杂，问题也越来越多，不光是成本上升，产品的稳定性也会难以保证。
发明内容
针对上述存在的问题，本发明的目的在于提供了一种润湿性好且低泡的氟硅表面活性剂、制备方法和应用。
本发明为实现上述目的，采取以下技术方案予以实现：
一种氟硅表面活性剂的制备方法，其制备方法为：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使炔醇或其衍生物、烯丙基聚醚和烯基含氟单体接枝至含氢硅油制备而成；所述含氢硅油分子结构式中含有至少三个Si-H键；所述烯基含氟单体中的烯基为乙烯基或丙烯基。烯基含氟单体为含有烯基和氟的单体。炔醇为烃基炔醇。其中，多重键指的是能够与含氢硅油Si-H键进行硅氢加成反应的键，可以是碳碳双键或碳碳三键。
即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使炔醇或其衍生物、烯丙基聚醚和烯基含氟单体通过与含氢硅油分子结构式中含有的至少三个Si-H键使炔醇或其衍生物、烯丙基聚醚和烯基含氟单体接枝至含氢硅油中。
经过硅氢加成反应，得到的新的产物具有很好的润湿性且低泡。
由于一个含氢硅油分子中含有至少三个Si-H键，在反应中，可以是：该含氢硅油分子中至少一个Si-H键与一个炔醇或其衍生物分子通过硅氢加成反应，使炔醇或其衍生物接枝至该含氢硅油分子；该含氢硅油分子中至少一个Si-H键与一个烯丙基聚醚分子通过硅氢加成反应，使烯丙基聚醚也接枝至该含氢硅油分子；该含氢硅油分子中至少一个Si-H键与一个烯基含氟单体通过硅氢加成反应，使烯基含氟单体也接枝至该含氢硅油分子。
作为进一步的改进，其制备方法为：通过炔醇或其衍生物、烯丙基聚醚和烯基含氟单体的混合物与含氢硅油混合进行硅氢加成反应制备而成；或通过炔醇或其衍生物、烯丙基聚醚的混合物与含氢硅油混合进行硅氢加成反应得到中间产物，再通过该中间产物与烯基含氟单体混合进行硅氢加成反应制备而成；所述炔醇或其衍生物、烯丙基聚醚、烯基含氟单体三者中多重键与含氢硅油Si-H键的物质的量之比为：(0.9-1.1):1；含氢硅油的含氢量在0.2-1.5％之间。
作为进一步的改进，所述炔醇的分子结构式(第一通式)为：
Figure PCTCN2019119089-appb-000001
其中，z和g均为整数，且0≤z≤4,0≤g≤4；R”为C 0-C 12的烷基(可以是直链烷基和支链烷基)； 1R”为C 0-C 12的烷基((可以是直链烷基和支链烷基)；R”和 1R”可以优选C 0-C 6的烷基，在满足低泡和润湿的同时，原料更易得。
所述烯基含氟单体分子结构式(第二通式)为：
Figure PCTCN2019119089-appb-000002
其中，R为C 2-C 12的烃基；R″′为乙烯基或丙烯基；e为0或者1；Rf为氟取代的烷基(氟烷基)，可以是全氟烷基和多氟烷基(多指的是2个以上)；
所述烯丙基聚醚的分子结构式(第三通式)为：
Figure PCTCN2019119089-appb-000003
其中，x，y均为整数，且0≤x≤12；0≤y≤14，x和y中一个为0时，另外一个大于零；R’为氢基、甲基、乙基或丁基中的任意一种；
所述含氢硅油分子结构式(第四通式)为：
Figure PCTCN2019119089-appb-000004
其中，1)a≥0，b+c+d≥3,a、b、c、d为整数且b、c、d为正整数。
作为进一步的改进，其制备方法为：在催化剂和溶剂存在下，在75℃-160℃之间，缓慢将炔醇或其衍生物、烯丙基聚醚和烯基含氟单体的混合物与含氢硅油混合并反应2-19小时。
作为进一步的改进，其制备方法为：在溶剂和催化剂存在下，在75℃-160℃之间，缓慢将炔醇或其衍生物和烯丙基聚醚的混合物与含氢硅油混合并反应2-19小时，得到中间产物，再在75℃-160℃之间，缓慢将中间产物和烯基含氟单体混合并反应2-19小时即可。
此处说的缓慢，是在反应过程中尽量避免凝胶现象的产生，其速度为不产生凝胶，使得反应顺利进行的速度，例如：当要加入150克炔醇或其衍生物、烯丙基聚醚和烯基含氟单体的混合物时，加入时间可以是2-3小时。
作为进一步的改进，所述催化剂为卡斯特催化剂或者氯铂酸；所述溶剂为二甲苯。
本发明还提供了一种氟硅表面活性剂，其由上述所述的制备方法制备而成。
作为进一步的改进，所述氟硅表面活性剂的分子结构式(第五通式)为：
Figure PCTCN2019119089-appb-000005
其中，1)a≥0，b+c+d≥3,a、b、c、d为整数且b、c、d为正整数；
2)x，y均为整数，且0≤x≤12；0≤y≤14，x和y中一个为0时，另外一个大于零；R’为氢基、甲基、乙基或丁基中的任意一种；
3)A为
Figure PCTCN2019119089-appb-000006
其中，Rf为氟取代的烷基；R为C 2-C 12的烷基；e为0或1； 1R″′为乙基或丙基,如：-CH 2-CH 2-或
Figure PCTCN2019119089-appb-000007
B为
Figure PCTCN2019119089-appb-000008
z和g均为整数，且0≤z≤4,0≤g≤4； 1R”和R”均为C 0-C 12的烷基(可以是直链烷基和支链烷基)。
本发明制备的氟硅表面活性剂能很好的作为在消泡润湿剂在涂膜中应用。
与现有技术相比，本发明的有益效果如下：
本发明通过将炔醇或其衍生物、烯丙基聚醚、烯基含氟单体与分子结构式中含有至少三个Si-H键的含氢硅油进行硅氢加成反应，得到氟硅表面活性剂，该表面活性剂具有很好的低泡和润湿性，能很好的满足使用的需要。
由于氟比硅具有更低的表面张力和化学稳定性，进而能提供更好的润湿性和稳定性，炔醇以及其衍生物与烯丙基聚醚配合能提供良好的相容性和低的动态表面；各种物质接枝至含氢硅油可以实现润湿性好的同时还具有低泡，同时，由于相容性好，进而该表面活性剂能够得到广泛的应用，同时该表面活性剂还具有很好的耐水解性能。
在与其他成分一起使用时，由于低泡和润湿性好，进而成分配方简单，能够很好的满足使用的需要。
具体实施方式
以下结合具体实施例来对本发明作进一步的说明。
需要说明的是，本发明提供的技术方案中所采用的原料，除特殊说明外，均通过常规手段制备或通过商业渠道购买。
一种氟硅表面活性剂的制备方法，其制备方法为：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使炔醇或其衍生物、烯丙基聚醚和烯基含氟单体接枝至含氢硅油制备而成；所述含氢硅油分子结构式中含有至少三个Si-H键；所述烯基含氟单体中的烯基为乙烯基或丙烯基。
优选地，所述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 基含氟单体的混合物与含氢硅油混合进行硅氢加成反应制备而成；或通过炔醇或其衍生物和烯丙基聚醚的混合物与含氢硅油混合进行硅氢加成反应得到中间产物，再通过该中间产物与烯基含氟单体混合进行硅氢加成反应制备而成；所述炔醇或其衍生物、烯丙基聚醚、烯基含氟单体三者中多重键与含氢硅油中Si-H键的物质的量之比为：(0.9-1.1):1,所述含氢硅油的含氢量在0.2-1.5％之间，含氢硅油平均分子量优选在500-3000之间。多重键与含氢硅油中Si-H键的物质的量之比为：(0.9-1.1):1，这样能够使得反应更加完全和彻底。
优选地，所述氟硅表面活性剂的制备方法为：在催化剂和溶剂存在下，在75℃-160℃之间，缓慢将炔醇或其衍生物、烯丙基聚醚和烯基含氟单体的混合物与含氢硅油混合并反应2-19小时，优选反应3-19小时，最优选反应10-19小时。3-19小时比较适中，反应完全且节省时间。
当然，反应完成后，可以抽真空去除溶剂和未反应的单体。
实施例1-6中，如无特别说明，则炔醇的分子结构式为第一通式；烯基含氟单体分子结构式为第二通式；烯丙基聚醚的分子结构式为第三通式；含氢硅油分子结构式为第四通式；氟硅表面活性剂的分子结构式为第五通式。
实施例1-6中,含氢硅油的含氢量指的是含氢硅油的硅氢键中的氢占含氢硅油的质量百分含量。
实施例1-6中，烯丙基聚醚的分子量为平均分子量，由于第三通式中除了主体部分以外，会有少许杂质(x和y中，部分取值有偏差(极少数x和y会上下浮动))，故其分子量为平均分子量，可以为购买产品时，产品供应商给出的分子量。含氢硅油的分子量也为平均分子量。氯铂酸溶液为氯铂酸含量为8％的氯铂酸水溶液。 1R”为支链或支链烷基,R”为支链或支链烷基。
本发明第三通式中x和y指的是主体部分的x和y。
实施例1
1)将200克二甲苯加入四口烧瓶中，140℃回流2小时除水；
2)将四口烧瓶内的温度降为75℃，向四口烧瓶中加入220克(0.11mol)含氢硅油(含氢量为0.2％、平均分子量为2000)，再逐步向四口烧瓶内滴加130克(0.20mol)烯丙基聚醚(即第三通式中，x为0；y约为14，R’为甲基，平均分子量为650，也叫烯丙基聚乙二醇单甲醚)、40.2克炔醇(第一通式中，z为2，g为2， 1R”为C 4的烷基,R”为C 4的烷基，也称为四乙氧基癸炔二醇，分子量为346,0.12mol)、23.6克丙烯酸六氟丁酯(分子量为236,0.10mol)和0.0414g氯铂酸溶液的混合物，均匀滴加12小 时完毕后，逐渐升温到100℃，并维持90-110℃之间3小时； 1R”和R”可以均是-CH 2-CH 2-CH 2-CH 2-。
3)然后升温至120℃保持4小时后，再抽真空1小时(真空度-0.09以上，抽真空时温度为100-120℃)去除溶剂和未反应的单体。制得试样1。
其中，丙烯酸六氟丁酯分子结构式为：
Figure PCTCN2019119089-appb-000009
实施例2
1)将200克二甲苯加入四口烧瓶，140℃回流2小时除水；
2)将四口烧瓶内的温度降为95℃，向四口烧瓶中加入110克烯丙基聚乙二醇聚丙二醇单丁醚(即第三通式中：x约为12；y约为9；R’为丁基；平均分子量为1100,0.10mol)、28.4克己炔二醇(即第一通式中z和g均为0， 1R”为-CH 2-CH 2-,R”为-CH 2-CH 2-,分子量114,0.25mol)、30克丙烯酸八氟戊酯(分子量286,0.10mol)和0.0139g卡斯特催化剂的混合物,滴加110克含氢硅油(含氢量0.4％、平均分子量为1500，0.07mol)的再逐步向四口烧瓶内滴加，匀速滴加，8小时滴加完，并逐渐升温到100℃，并维持90-110℃之间3小时；
3)然后升温至130℃保持4小时后，再抽真空1小时(真空度-0.09以上；抽真空时温度为100-130℃)去除溶剂和未反应的单体。制得试样2。
其中，丙烯酸八氟戊酯分子结构式为：
Figure PCTCN2019119089-appb-000010
实施例3
1)将200克二甲苯加入四口烧瓶，140℃回流2小时除水；
2)将四口烧瓶内的温度降为85℃，向四口烧瓶中加入100克含氢硅油(含氢量0.6％、平均分子量为3000；0.03mol)，再逐步向四口烧瓶内滴加170克烯丙基聚醚(第二通式中x约为8；y约为8；R’为氢，分子量为850；0.20mol)、78.6克四乙氧基丁炔二醇(即第一通式中， 1R”为-CH 2-,R”为-CH 2-，z和g均为2；分子量262；0.30mol)、43.2克甲基丙烯酸十三氟辛酯(分子量为432，0.10mol)和0.0784g氯铂酸溶液的 混合物，匀速12小时滴加完，并逐渐升温到145℃，并维持140-150℃之间3小时。甲基丙烯酸十三氟辛酯分子结构式为：
Figure PCTCN2019119089-appb-000011
3)然后再在140-150℃之间抽真空1小时(真空度为-0.09以上，抽真空时温度为110-150℃)去除溶剂和未反应的单体，制得试样3。
实施例4
1)将200克二甲苯加入四口烧瓶，140℃回流2小时除水；
2)将四口烧瓶内的温度降为105℃，向四口烧瓶中加入105克烯丙基聚乙二醇丁醚(平均分子量为350，第三通式中x为0，y约为5或6，R’为丁基,0.30mol)、425.4克八乙氧基十二炔二醇(即第一通式中， 1R”为C 5的烷基,R”为C 5的烷基，z和g均为4；分子量为550；0.77mol)、64.8克甲基丙烯酸十三氟辛酯(分子量为432；0.15mol)和0.0705g氯铂酸溶液的混合物，逐渐匀速滴加137.5克含氢硅油(平均分子量1000，含氢量0.8％,0.14mol)，8小时滴加完毕，并逐渐升温到150℃，并维持150-160℃之间3小时。 1R”和R”可以均为-CH 2CH 2CH 2CH 2CH 2-。
3)然后维持150-160℃之间，抽真空30分钟(真空度为-0.09以上，抽真空时温度为120-160℃)去除溶剂和未反应的单体，制得试样4。
实施例5
1)将200克二甲苯加入四口烧瓶中，140℃回流2小时除水；
2)将四口烧瓶内的温度降为115℃，向四口烧瓶中加入100.0克含氢硅油(含氢量为1.0％、分子量为500，0.20mol)，再逐步向四口烧瓶内滴加75.0克烯丙基聚丙二醇单甲醚(分子量约为750，即第三通式中x约为12，y为0，R’为甲基；0.10mol)，161.6克二乙氧基己炔二醇(即第一通式中， 1R”为-CH 2-CH 2-,R”为-CH 2-CH 2-，z和g均为1；分子量202；0.80mol)，30.8克丙烯酸三氟乙酯(分子量154；0.20mol)和0.0367g氯铂酸溶液的混合物，匀速6小时滴加完，并逐渐升温到130℃，并维持120-140℃之间3小时；丙烯酸三氟乙酯的分子结构式为：
Figure PCTCN2019119089-appb-000012
3)然后维持120-140℃之间，抽真空1小时(真空度为-0.09以上；抽真空时温度为110-140℃)去除溶剂和未反应的单体，制得试样5。
实施例6
1)将200克二甲苯加入四口烧瓶，140℃回流2小时除水；
2)将四口烧瓶内的温度降为75℃，向四口烧瓶中加入80克含氢硅油(含氢量1.5％、平均分子量750；0.11mol)，再逐步向四口烧瓶内滴加120克烯丙基聚乙二醇单丁醚(平均分子量为400，即第三通式中y为6或7，R’为丁基；0.30mol)、120克二乙氧基丙炔二醇(即第一通式中， 1R”为-CH 2-,R”为不取或R”为-CH 2-, 1R”为不取，z和g均为1；分子量为160,0.75mol)、60.6克十三氟-1-辛烯(分子量为346；0.18mol)和0.0381g卡斯特催化剂的混合物，匀速6小时滴加完，并逐渐升温到100℃，并维持90-110℃之间6小时；其中，十三氟-1-辛烯CAS号为：25291-17-2，分子式为CF 3(CF 2) 5CH＝CH 2。
3)然后维持温度在120-140℃之间，抽真空1小时(真空度-0.09以上；抽真空时温度为110-140℃)去除溶剂和未反应的单体，制得试样6。
实施例1-6所述氟硅表面活性剂的制备方法也可以为：在溶剂和催化剂存在下，在75℃-160℃之间，缓慢将炔醇或其衍生物和烯丙基聚醚的混合物与含氢硅油混合并反应2-19小时(优选反应3-19小时)，得到中间产物，再在75℃-160℃之间，缓慢将中间产物和烯基含氟单体混合并反应2-19小时(优选反应3-19小时)即可。
例如实施例4中，其制备方法可以为：
1)将200克二甲苯加入四口烧瓶，140℃回流2小时除水；
2)将四口烧瓶内的温度降为105℃，向四口烧瓶中加入105克烯丙基聚乙二醇丁醚(平均分子量为350，第三通式中x为0，y约为5或6，R’为丁基,0.30mol)、425.4克八乙氧基十二炔二醇(即第一通式中， 1R”为C 5的烷基,R”为C 5的烷基，z和g均为4；分子量为550；0.77mol)和0.0705g氯铂酸溶液的混合物，逐渐匀速滴加137.5克含氢硅油(平均分子量1000，含氢量0.8％,0.14mol)，8小时滴加完毕，并逐渐升温到150℃，并维持150-160℃之间2-11小时，得到中间产物；再降温至105℃后，向该中间产物中滴加64.8克甲基丙烯酸十三氟辛酯(分子量为432；0.15mol)，8小时滴加完毕，并逐渐升温到150℃，并维持150-160℃之间2-11小时；
3)然后维持150-160℃之间，抽真空30分钟(真空度-0.09以上，抽真空时温度为120-160℃)去除溶剂和未反应的单体，制得试样4。
又例如实施例6中，其制备方法可以为：
1)将200克二甲苯加入四口烧瓶，140℃回流2小时除水；
2)将四口烧瓶内的温度降为75℃，向四口烧瓶中加入80克含氢硅油(含氢量1.5％、平均分子量750；0.11mol)，再逐步向四口烧瓶内滴加120克烯丙基聚乙二醇单丁醚(平均分子量为400，即第三通式中y约为6和7，R’为丁基；0.30mol)、120克二乙氧基丙炔二醇(即第一通式中， 1R”为-CH 2-,R”为不取或R”为-CH 2-, 1R”为不取，z和g均为1；分子量为160,0.75mol)和0.0381g卡斯特催化剂的混合物，匀速6小时滴加完，并逐渐升温到100℃，并维持90-110℃之间6小时，得到中间产物；降温至75℃，逐步向四口烧瓶内滴加60.6克十三氟-1-辛烯(分子量为346；0.18mol)，匀速6小时滴加完，并逐渐升温到100℃，并维持90-110℃之间6小时；
3)然后维持温度在120-140℃之间，抽真空1小时(真空度为-0.09以上；抽真空时温度为110-140℃)去除溶剂和未反应的单体，制得试样6。
结果测试：
对比试验
步骤1)：取10个容器，在每个容器中加入85克水性丙烯酸树脂(商品品牌为：DS M；型号为：Neocryl XK14)和15克去离子水；
步骤2)：取试样10份，每份0.3克，分别加入到每个容器中。
步骤3)：将容器内的物质混合均匀并静置2小时后测试其抑泡能力，润湿性，外观流平性。
其中，10份试样分别为：实施例1-6制备的样品(试样1、试样2、试样3、试样4、试样5、试样6)与市场上的四个典型润湿剂产品(商品1、商品2、商品3和商品4)；市场上的四个典型产品均为市售的聚醚改性有机硅。
各个容器内的液体分别为样品1(加入的试样为试样1)、样品2(加入的试样为试样2)、样品3(加入的试样为试样3)、样品4(加入的试样为试样4)、样品5(加入的试样为试样5)、样品6(加入的试样为试样6)、样品7(加入的试样为商品1)、样品8(加入的试样为商品2)、样品9(加入的试样为商品3)和样品10(加入的试样为商品4)。
消泡能力测试：
将装入容器内的样品1-10在震荡机震荡10分钟，然后分别倒入10个带有刻度的瓶子(瓶子为圆柱形；体积为100mL,高度为6cm)中，记下初始泡沐高度，再依次记录2小时以及24小时的泡沫高度。实验结果见表1。
表1
Figure PCTCN2019119089-appb-000013
表1的数据说明，本发明制备的氟硅表面活性剂具有低泡的性能，其比市场上产品的泡沫低很多,初始高度和2小时后的高度都明显低于市面上的润湿剂商品，说明本发明制备的产品具有低泡的性能。
静态表面张力的测试：
采用环式静态表面张力仪(型号为：SFZL-A1,生产编号为：20170501003)测试表面张力，读数越小表面张力越低。实验结果见表2。
表2
Figure PCTCN2019119089-appb-000014
表1的数据说明，本发明制备的氟硅表面活性剂表面张力很低，润湿性很好，能满足市场的需求。大部分样品表面张力还低于市面上售卖的产品，进而能够更好的满足需求。
漆膜相容性、光泽度、漆膜状态(缩边)
1、刮板的的制备：将各个样品涂于平板上，用制膜器(制膜器为具有左右两侧面和顶面且中空的物体)按压样品，然后将制模器拉起，使得涂膜(漆膜)的厚度为100微米，待涂膜干燥后，测定涂膜(此时为干膜)的各种性质，该制备干膜的过程也叫刮板的过程。
观察干膜的状态，判断相容性，然后测光泽度。实验结果见表3。其中，相容性判定标准为涂膜的通透度从1-5级逐渐增加，5级为最透，1级为最不透。光泽度采用60°入射角的镜面光泽度仪测试，光泽度越高，说明涂膜相容性越好；缩边宽度数据越小，说明涂膜润湿性越好。
表3
Figure PCTCN2019119089-appb-000015
从表3可以看出，本发明样品的相容性和润湿性均很好。
2、样品1-10中，每个样品取2份，分别加入消泡剂BYK022，使得一份样品中的消泡剂BYK022的质量份数为0.2％(该样品为1#样品)，另一份样品中，YK022的质量份数为0.4％(该样品为2#样品)，然后分别用1#样品和2#样品制备刮板，观察润湿剂的抗缩孔能力，涂膜上缩孔的个数越多，说明润湿剂的润湿效果越差。实验结果见表4。
表4
样品 样品1 样品2 样品3 样品4 样品5 样品6 样品7 样品8 样品9 样品10
1#样品 0 0 0 0 0 0 2 1 2 3
2#样品 2 0 2 0 0 1 7 6 3 5
从表4可以看出，加入消泡剂后，本发明实施例1-6做出的产品的抗缩孔能力明显好于市面上润湿剂的抗缩孔能力,说明实施例1-6做出的产品润湿性很好，明显好于市场上的产品。在有消泡剂的情况下，依然具有很好的抗缩孔能力，即具有很好地润湿性，进而抗破坏能力强，能很好的抵御其他成分的干扰。
需要说明的是，本发明中C 0的意思为，不含碳基的意思。
本发明中烯丙基聚醚可以购买自南通晨润化工有限公司或杭州丹维科技有限公司，也可以购买自其它公司。
以上对本发明实施例所提供的技术方案进行了详细介绍，本文中应用了具体个例对本发明实施例的原理以及实施方式进行了阐述，以上实施例的说明只适用于帮助理解本发明实施例的原理；同时，对于本领域的一般技术人员，依据本发明实施例，在具体实施方式以及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。

Claims (10)

  1. 一种氟硅表面活性剂的制备方法，其特征在于，其制备方法为：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使炔醇或其衍生物、烯丙基聚醚和烯基含氟单体接枝至含氢硅油制备而成；所述含氢硅油分子结构式中含有至少三个Si-H键；所述烯基含氟单体中的烯基为乙烯基或丙烯基。
  2. 如权利要求1所述的氟硅表面活性剂的制备方法，其特征在于，其制备方法为：通过炔醇或其衍生物、烯丙基聚醚和烯基含氟单体的混合物与含氢硅油混合进行硅氢加成反应制备而成；或通过炔醇或其衍生物和烯丙基聚醚的混合物与含氢硅油混合进行硅氢加成反应得到中间产物，再通过该中间产物与烯基含氟单体混合进行硅氢加成反应制备而成；所述炔醇或其衍生物、烯丙基聚醚、烯基含氟单体三者中多重键与含氢硅油中Si-H键的物质的量之比为：(0.9-1.1):1。
  3. 如权利要求1所述的氟硅表面活性剂的制备方法，其特征在于，所述含氢硅油的含氢量在0.2-1.5％之间；平均分子量在500-3000之间。
  4. 如权利要求1所述的氟硅表面活性剂的制备方法，其特征在于，
    所述炔醇的分子结构式为：
    Figure PCTCN2019119089-appb-100001
    其中，z和g均为整数，且0≤z≤4,0≤g≤4；R”为C 0-C 12的烷基； 1R”为C 0-C 12的烷基。
    所述烯基含氟单体分子结构式为：
    Figure PCTCN2019119089-appb-100002
    其中，R为C 2-C 12的烷基；R″′为乙烯基或丙烯基；e为0或者1；Rf为氟取代的烷基；
    所述烯丙基聚醚的分子结构式为：
    Figure PCTCN2019119089-appb-100003
    其中，x，y均为整数，且0≤x≤12；0≤y≤14，x和y中一个为0时，另外一个大于零；R’为氢基、甲基、乙基或丁基中的任意一种；
    所述含氢硅油分子结构式为：
    Figure PCTCN2019119089-appb-100004
    其中，1)a≥0，b+c+d≥3,a、b、c、d为整数且b、c、d为正整数。
  5. 如权利要求1所述的氟硅表面活性剂的制备方法，其特征在于，其制备方法为：在催化剂和溶剂存在下，在75℃-160℃之间，缓慢将炔醇或其衍生物、烯丙基聚醚和烯基含氟单体的混合物与含氢硅油混合并反应2-19小时。
  6. 如权利要求1所述的氟硅表面活性剂的制备方法，其特征在于，其制备方法为：在溶剂和催化剂存在下，在75℃-160℃之间，缓慢将炔醇或其衍生物和烯丙基聚醚的混合物与含氢硅油混合并反应2-19小时，得到中间产物，再在75℃-160℃之间，缓慢将中间产物和烯基含氟单体混合并反应2-19小时即可。
  7. 如权利要求5或6所述的氟硅表面活性剂的制备方法，其特征在于，所述催化剂为卡斯特催化剂或者氯铂酸；所述溶剂为二甲苯。
  8. 一种氟硅表面活性剂，其特征在于，其由权利要求1-7任意一项所述的制备方法制备而成。
  9. 如权利要求8所述的氟硅表面活性剂，其特征在于，所述氟硅表面活性剂的分子结构式为：
    Figure PCTCN2019119089-appb-100005
    其中，1)a≥0，b+c+d≥3,a、b、c、d为整数且b、c、d为正整数；
    2)x，y均为整数，且0≤x≤12；0≤y≤14，x和y中一个为0时，另外一个大于零；R’为氢基、甲基、乙基或丁基中的任意一种；
    3)A为
    Figure PCTCN2019119089-appb-100006
    其中，Rf为氟取代的烷基；R为C 2-C 12的烷基；e为0或1； 1R″′为乙基或丙基；
    B为
    Figure PCTCN2019119089-appb-100007
    z和g均为整数，且0≤z≤4,0≤g≤4； 1R”和R”均为C 0-C 12的烷基；
  10. 如权利要求8所述氟硅表面活性剂的应用，其特征在于，所述氟硅表面活性剂作为消泡润湿剂在涂膜中的应用。
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