阅读说明：本技术 3,3,3,-三氟丙基甲基硅氧烷聚合物及制备方法 (3,3, 3-trifluoropropylmethylsiloxane polymer and preparation method thereof ) 是由 张迪 黄�俊 尤小姿 杨善志 刘继 于 2020-07-17 设计创作，主要内容包括：本发明提供了一种3,3,3,-三氟丙基甲基硅氧烷聚合物及制备方法,将三(3,3,3-三氟丙基)三甲基环三硅氧烷、封端剂以及固体酸在无水条件下进行调聚反应,得到3,3,3,-三氟丙基甲基硅氧烷聚合物。该方法制备的氟硅油纯度更高,更稳定。(The invention provides a 3,3, 3-trifluoropropyl methyl siloxane polymer and a preparation method thereof, wherein tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane, a capping agent and solid acid are subjected to telomerization under anhydrous conditions to obtain the 3,3, 3-trifluoropropylmethyl siloxane polymer. The fluorosilicone oil prepared by the method has higher purity and is more stable.)

1. A preparation method of a 3,3, 3-trifluoropropylmethylsiloxane polymer is characterized in that tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane, an end-capping agent and a solid acid are subjected to telomerization under the solvent-free condition to obtain the 3,3, 3-trifluoropropylmethylsiloxane polymer.

2. The method of preparing a 3,3,3, -trifluoropropylmethylsiloxane polymer according to claim 1, wherein the method of preparing the solid acid comprises:

sulfonating sulfonic acid and a carbon-based carrier, washing and drying to obtain the solid acid; wherein the molar ratio of the sulfonic acid to the carbon-based carrier is 1: 1 to 1: 2, preferably, the molar ratio is 1: 1.5;

the preparation method of the carbon-based carrier comprises the following steps:

soaking lignin in weak acid, washing and carbonizing to obtain the carbon-based carrier.

3. The method of preparing 3,3,3, -trifluoropropylmethylsiloxane polymer according to claim 2, wherein the sulfonation conditions are stirring at 50-120 ℃ for 1-6 h; preferably, the sulfonation condition is that the mixture is stirred for 2 to 4 hours at a temperature of between 80 and 100 ℃; further preferably, the sulfonation condition is stirring at 85-100 ℃ for 3-4 h.

4. The method for preparing 3,3,3, -trifluoropropylmethylsiloxane polymer according to claim 2, wherein the carbonizing condition is 200-300 ℃ carbonizing for 5-15 h; preferably, the carbonization condition is carbonization at 250-290 ℃ for 8-12 h; more preferably, the carbonization condition is stirring at 280 ℃ for 9-10 h.

5. The method of claim 2, wherein the sulfonic acid is selected from one or more of trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride.

6. The process for the preparation of 3,3,3, -trifluoropropylmethylsiloxane polymer according to claim 1, wherein the telomerization temperature is 60-100 ℃ and the telomerization time is 1-8 h; preferably, the temperature of the telomerization reaction is 70-90 ℃, and the telomerization time is preferably 2-5 h; further preferably, the temperature of the telomerization reaction is 80 ℃, and the telomerization time is preferably 3-4 h.

7. The preparation method of the 3,3, 3-trifluoropropylmethyl siloxane polymer according to 1, characterized in that the mass ratio of the solid acid, the tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane and the end-capping agent is 0.01% -10%: 1: 0.5% -20%, preferably 0.1% -5%: 1: 1% -15%.

8. The method of claim 1, wherein the blocking agent is one or more of vinyl bis-head, methyl bis-head, short chain methyl silicone oil, or short chain vinyl silicone oil.

9. A 3,3,3, -trifluoropropylmethylsiloxane polymer prepared by the process of any of claims 1-8.

10. The 3,3,3, -trifluoropropylmethylsiloxane polymer of claim 9, wherein said 3,3,3, -trifluoropropylmethylsiloxane polymer has the structure:

wherein the polymerization degree n is 5-500, and R is methyl or vinyl.

Technical Field

The invention relates to the field of fluorine-containing silicone oil, in particular to a 3,3, 3-trifluoropropylmethylsiloxane polymer and a preparation method thereof.

Background

In recent years, with the high-end application field, the fluorine-silicon products are receiving more and more attention, and the fluorine-silicon products have both organic silicon and organic siliconThe organic fluorine has the advantages of extremely low surface energy, excellent oil resistance, solvent resistance and the like. Methyl fluorosilicone oil is a kind of main chain with (CH)₃SiCH₂CH₂CF₃O) n, a polymer of methyl terminated trifluoropropylmethylsiloxane as a colorless or light yellow transparent liquid; the vinyl fluorosilicone oil belongs to modified silicone oil. The trifluoropropyl is introduced on the silicon atom, so that the product has the characteristics of oil resistance, solvent resistance, low surface tension and low refractive index, and simultaneously keeps the excellent weather resistance (-60-200 ℃) of the silicone oil, can be used as an intermediate for adjusting molecular weight by fluorine-silicon polymerization, and can be used as a finishing agent for hydrophobic and oleophobic fabrics, a defoaming agent of an organic solvent, a release agent and the like.

The prior patents for preparing the fluorosilicone oil refer to a few, and are mostly high-molecular-weight fluorosilicone polymers. Such as CN201711244138.6, CN201811001694.5, CN201811002417.6 and the like, are all used for preparing fluorine-silicon polymers like methyl raw rubber and 107 rubber. The vinyl fluorosilicone oil prepared by CN201811525672.9 is prepared by reacting vinyl silazane oligomer with hydroxyl fluorosilicone oil, and the viscosity is 1500-100000 mPa.s. CN200910232533.1 is fluorine-containing silicon oil obtained by dechlorinating and cyclizing reaction of fluorine-containing dichlorosilane and dimethyldichlorosilane under the action of metal oxide and finally ring opening. CN201010512137.7 is prepared by amino addition of fluorine-containing alkyl methyl acrylate and amino silicone oil. CN201210077938.4 and CN201210470726.2 are condensed by hydrolyzing trifluoropropylmethyldichlorosilane at low temperature to obtain hydroxyfluorosilicone oil.

Therefore, the fluorosilicone oil siloxane prepared by the conventional hydrolysis method has more cyclic impurities, poor base catalysis end-capping effect and poor reaction controllability, the cost of the non-acid and non-alkali catalysis ring-opening polymerization method is high, a large amount of organic solvent is used, and the acidity of solid acid is limited.

Disclosure of Invention

In order to solve the technical problems, the invention provides the 3,3, 3-trifluoropropylmethyl siloxane polymer and the preparation method thereof, and the prepared fluorosilicone oil has higher purity and is more stable.

In one aspect, a method for preparing a 3,3,3, -trifluoropropylmethylsiloxane polymer is provided, comprising the step of telomerizing tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane, an end-capping agent and a solid acid under a solvent-free condition to obtain the 3,3,3, -trifluoropropylmethylsiloxane polymer.

Further, the preparation method of the solid acid comprises the following steps:

sulfonating sulfonic acid and a carbon-based carrier, washing and drying to obtain solid acid; wherein the molar ratio of the sulfonic acid to the carbon-based carrier is 1: 1 to 1: 2, preferably, the molar ratio is 1: 1.5.

further, the preparation method of the carbon-based carrier comprises the following steps:

soaking lignin in weak acid, washing and carbonizing to obtain the carbon-based carrier.

Further, the sulfonation condition is that the mixture is stirred for 1 to 6 hours at the temperature of between 50 and 120 ℃; preferably, the sulfonation condition is that the mixture is stirred for 2 to 4 hours at a temperature of between 80 and 100 ℃; further preferably, the sulfonation condition is stirring at 90-100 ℃ for 3-4 h.

Further, the carbonization condition is 200-300 ℃ for carbonization for 5-15 h; preferably, the carbonization condition is carbonization at 250-290 ℃ for 8-12 h; further preferably, the sulfonation condition is stirring at 280 ℃ for 9-10 h.

Further, the sulfonic acid is selected from one or more of trifluoromethanesulfonic acid or trifluoromethanesulfonic anhydride.

Further, the temperature of the telomerization reaction is 60-100 ℃, and the telomerization time is 1-8 h; preferably, the temperature of the telomerization reaction is 70-90 ℃, and the telomerization time is preferably 2-5 h; further preferably, the temperature of the telomerization reaction is 80 ℃, and the telomerization time is preferably 3-4 h.

Further, the ratio of the solid acid to tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane is 0.01 to 10 wt%, preferably 0.1 to 5 wt%.

Further, the ratio of the end-capping agent to tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane is 0.5-20 wt%; preferably 1 to 15 wt%.

Further, the end-capping agent is one or more of vinyl double end caps, methyl double end caps, short-chain methyl silicone oil or short-chain vinyl silicone oil.

In another aspect, the present invention provides a 3,3,3, -trifluoropropylmethylsiloxane polymer prepared by any of the methods described above.

Further, the 3,3,3, -trifluoropropylmethylsiloxane polymer has the structure:

wherein the polymerization degree n is 5-500, and R is methyl or vinyl.

The beneficial effect of this patent:

the method for preparing the fluorosilicone oil by solid acid catalysis has the advantages that on one hand, the super-strong acidity (F is strongest in electronegativity, the stronger the electron-withdrawing capability is, and the more electron is lacking in C) is presented, the ring-opening reaction can be catalyzed by the acidity, on the other hand, the reaction is rapidly stopped, the peculiar back-biting phenomenon of the tri (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane (D3F) is reduced, and no solvent is used. The method has the advantages of high catalytic activity, environmental protection, simple process, and high and stable purity of the prepared fluorosilicone oil.

Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.

Drawings

The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the example serve to explain the principles of the invention and not to limit the invention.

FIG. 1 is a flow chart of the preparation process of the present invention.

FIG. 2 is a hydrogen nuclear magnetic spectrum of the vinylfluorosilicone oil according to an embodiment of the present invention.

FIG. 3 is an infrared spectrum of a vinylfluorosilicone oil according to another embodiment of the present invention.

FIG. 4 is a hydrogen nuclear magnetic spectrum of methyl fluorosilicone oil in another embodiment of the present invention.

FIG. 5 is an infrared spectrum of methyl fluorosilicone oil in accordance with another embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.

FIG. 1 is a flow chart of a process for preparing a 3,3, 3-trifluoropropylmethylsiloxane polymer of the present invention. As shown in FIG. 1, tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane, an end-capping agent and a solid acid were telomerized in the absence of a solvent to give a 3,3,3, -trifluoropropylmethylsiloxane polymer.

Specifically, the solvent refers to an inorganic or organic solvent, including but not limited to water, acetone, ethanol, tetrahydrofuran, and the like, which mainly functions to swell the solid acid.

The preparation process of the invention adopts solid acid for catalysis, and not only can catalyze tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane (D)₃F) The ring-opening reaction can be rapidly stopped, the peculiar back-biting phenomenon of the tri (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane can be reduced, no solvent is used in the whole reaction process, no corresponding waste liquid, waste gas and the like are generated, and the method is very environment-friendly. Moreover, the safety performance is better when the scale-up production is carried out. The yield of the fluorosilicone oil prepared by the method reaches more than 94 percent.

In another embodiment of the present invention, the solid acid is a carbon-based solid acid.

The carbon-based solid acid is adopted for catalysis, so that the catalyst has stronger activity and acidity, and a solvent is not required.

In another embodiment of the present invention, the method for preparing the solid acid comprises: sulfonating sulfonic acid and a carbon-based carrier, washing and drying to obtain the solid acid.

The sulfonic acid is solidified, so that the sulfonic acid is easy to neutralize, and if the sulfonic acid is not subjected to solid acid treatment, the sulfonic acid is difficult to neutralize and the neutralization time is long; secondly, the long-term neutralization process can aggravate the back-biting reaction, i.e. the reaction can not be stopped in time.

In another embodiment of the present invention, a method for preparing the carbon-based support includes: soaking lignin in weak acid, washing and carbonizing to obtain the carbon-based carrier.

The lignin may be provided by pulp, plant rhizomes, etc., preferably pulp; the weak acid includes acetic acid, carbonic acid, etc., preferably acetic acid. The pulp contains CaCO₃Effectively remove CaCO through the soaking treatment of acetic acid solution₃。

In another embodiment of the invention, the sulfonation condition is stirring for 1-6h at 50-120 ℃; preferably, the sulfonation condition is that the mixture is stirred for 2 to 4 hours at a temperature of between 80 and 100 ℃; further preferably, the sulfonation condition is stirring at 90-100 ℃ for 3-4 h. By adopting the sulfonation parameters, the sulfonation effect is good, and the energy is saved.

In another embodiment of the invention, the carbonization condition is 200-300 ℃ carbonization for 5-15 h; preferably, the carbonization condition is carbonization at 250-290 ℃ for 8-12 h; further preferably, the sulfonation condition is stirring at 280 ℃ for 9-10 h. By adopting the carbonization parameters, the carbonization effect is good, and the formed solid acid has stronger acidity.

In another embodiment of the present invention, the sulfonic acid is selected from one or more of trifluoromethanesulfonic acid or trifluoromethanesulfonic anhydride. The trifluoromethanesulfonic acid or trifluoromethanesulfonic anhydride is selected to exhibit a super strong acidity. Since F has the strongest electronegativity, the electron-withdrawing ability is also the strongest, and C has more electron deficiency, so the acidity is stronger than that of the common acid.

In another embodiment of the invention, the temperature of the telomerization reaction is 60-100 ℃, and the telomerization time is 1-8 h; preferably, the temperature of the telomerization reaction is 70-90 ℃, and the telomerization time is preferably 2-5 h; further preferably, the temperature of the telomerization reaction is 80 ℃, and the telomerization time is preferably 3-4 h. The telomerization parameter is a better parameter for preparing the 3,3, 3-trifluoropropylmethylsiloxane polymer, the reaction temperature is too low, the reaction is incomplete, the reaction temperature is too high, the activity of the catalyst is influenced, and the yield is lower.

In another embodiment of the invention, the mass ratio of the solid acid, the tris (3,3, 3-trifluoropropyl) trimethylcyclotrisiloxane and the end-capping agent is 0.01-10%: 1: 0.5-20%, preferably 0.1-5%: 1: 1-15%. By adopting the reactants with the proportion, the reaction is more sufficient and complete, excessive reactant residues are avoided, and the back biting phenomenon is avoided.

In another embodiment of the present invention, the blocking agent is one or more of a vinyl double end cap, a methyl double end cap, a short chain methyl silicone oil, or a short chain vinyl silicone oil.

The specific examples of the preparation of the solid acid catalyst in the present invention are as follows: