CN107857882B - Fluorosilicone oil and preparation method thereof - Google Patents

Fluorosilicone oil and preparation method thereof Download PDF

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CN107857882B
CN107857882B CN201710998841.XA CN201710998841A CN107857882B CN 107857882 B CN107857882 B CN 107857882B CN 201710998841 A CN201710998841 A CN 201710998841A CN 107857882 B CN107857882 B CN 107857882B
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trifluoropropyl
fluorosilicone oil
tris
catalyst
pentasiloxane
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CN107857882A (en
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胡应乾
耿梦鸾
张方
邬继荣
张国栋
王华兰
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Hangzhou Kejia New Materials Co ltd
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Hangzhou Normal University
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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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • 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
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen

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Abstract

The invention relates to the technical field of organic silicon industry and aims to solve the problemThe invention provides low-viscosity end-functional group fluorosilicone oil with single variety (mainly hydroxyl-terminated low-molecular-weight fluorosilicone oil) and poor quality in the current domestic market, and provides high-purity fluorosilicone oil with low viscosity and high functional group content and a preparation method thereof, wherein the fluorosilicone oil has a structural formula shown as (I), the content of siloxane ring bodies in the obtained product is extremely low or even zero,

Description

Fluorosilicone oil and preparation method thereof
Technical Field
The invention relates to the technical field of organosilicon industry, in particular to novel fluorosilicone oil and a preparation method thereof.
Background
In recent years, introduction of fluorine-containing groups into polysiloxanes has become a new focus of research. The fluorine-containing polymer not only has excellent heat resistance and weather resistance of common siloxane, but also can overcome the defects of poor oil resistance and solvent resistance of polydimethylsiloxane, and a lubricant, a defoaming agent, a release agent, a waterproof and antifouling finishing agent for fabric and leather and the like prepared from the fluorine-containing polymer are widely applied to the industrial fields of airplanes, automobiles, machinery, chemical engineering, light industry, textile and the like. The low-viscosity end functional group fluorosilicone oil not only has the high-low temperature resistance and oil resistance shared by fluorosilicone materials, but also has higher chemical activity due to the existence of a large number of end functional groups, thereby having special application. For example, the product can be used as an intermediate and a molecular weight regulator of fluorosilicone rubber, a copolymer with special performance prepared by copolymerization with other organic matters, or a hydrophobic/oleophobic finishing agent of fabric, a defoaming agent of an organic solvent, a cosmetic additive and the like, and particularly can be used as a structural control agent of thermally vulcanized fluorosilicone rubber, so that the physical adsorption and chemical bonding between white carbon black particles and raw rubber molecules of silicone rubber can be inhibited, the occurrence of structural reaction is prevented, and finally, the white carbon black can be uniformly dispersed in the silicone rubber to achieve the purpose of reinforcement.
However, low viscosity end-functional fluorosilicone oil currently on the domestic marketThe variety is single, the oil is mainly hydroxyl-terminated low-molecular-weight fluorosilicone oil, and the quality is poor: firstly, the molecular weight distribution is in multiple shoulder peak distribution (which shows that the preparation controllability is poor), and secondly, the product has more byproduct methyl trifluoro propyl siloxane tetracyclic body D4F (difficult to remove by distillation due to its boiling point above 280 ℃).
Disclosure of Invention
In order to solve the problems of single variety and poor quality of the low-viscosity end-functional group fluorosilicone oil in the current domestic market, the invention provides the low-viscosity high-functional group-content high-purity fluorosilicone oil and the preparation method thereof, and the content of siloxane ring bodies in the obtained product is extremely low or even zero.
The invention is realized by the following technical scheme:
a fluorosilicone oil has a structural formula shown as (I):
Figure BDA0001442429390000011
wherein, R is H or OH.
When R is H, the fluorosilicone oil is 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane.
The preparation method of the fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane comprises the following steps: 1,1,3, 3-tetramethyldisiloxane (namely hydrogen-containing double-end cap, MM)H) 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane (i.e., D)3F) Mixing the hydrogen-terminated fluorosilicone oil with a catalyst A in a reactor, stirring and reacting for 0.5-6 h at 0-80 ℃, then cooling to room temperature under a stirring state, removing the catalyst, distilling under reduced pressure, and collecting fractions under the condition of 109-110 ℃/800Pa to obtain the hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane.
Wherein the molar ratio of the 1,1,3, 3-tetramethyldisiloxane to the 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane is 1.05-10: 1.
The catalyst A is selected from one of strong acid cation exchange resin, concentrated sulfuric acid, trifluoromethanesulfonic acid or acid clay, and is preferably strong acid cation exchange resin.
The mass ratio of the catalyst A to the 1,3, 5-trimethyl-1, 3, 5-tri (3,3, 3-trifluoropropyl) cyclotrisiloxane is 0.005-0.5: 1, preferably 0.1-0.2: 1.
The reaction temperature is 0-80 ℃, and preferably room temperature-50 ℃.
When R is OH, the fluorosilicone oil is 1, 9-dihydroxy-1, 1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane.
The preparation method of the 1, 9-dihydroxy-1, 1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane comprises the following steps: mixing 1,1,3, 3-tetramethyldisiloxane, 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane and a catalyst A in a reactor, stirring and reacting for 0.5-6 h at 0-80 ℃, then cooling to room temperature under the stirring state, removing the catalyst, carrying out reduced pressure distillation, and collecting fractions under the condition of 109-110 ℃/800Pa to obtain hydrogen-terminated fluorosilicone oil (1, 1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane); and then mixing the obtained hydrogen-terminated fluorosilicone oil with deionized water, a catalyst B and a reaction solvent, stirring and reacting for 1-6 h at the temperature of 0-60 ℃, cooling to room temperature, filtering to remove the catalyst, and removing low-boiling-point substances at the temperature of 110 ℃/600Pa to obtain the hydroxyl-terminated fluorosilicone oil 1, 9-dihydroxy-1, 1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane.
The molar ratio of the 1,1,3, 3-tetramethyldisiloxane to the 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane is 1.05-10: 1.
The catalyst A is selected from one of strong acid cation exchange resin, concentrated sulfuric acid, trifluoromethanesulfonic acid or acid clay, and is preferably strong acid cation exchange resin.
The mass ratio of the catalyst A to the 1,3, 5-trimethyl-1, 3, 5-tri (3,3, 3-trifluoropropyl) cyclotrisiloxane is 0.005-0.5: 1, preferably 0.1-0.2: 1.
The catalyst B is selected from Pd/C, H2PtCl6Preferably Pd/C.
The mass ratio of the catalyst B to the hydrogen-terminated fluorosilicone oil is 0.005-0.2: 1, and preferably 0.01-0.05: 1.
The reaction solvent is selected from one of dichloromethane, chloroform, 1, 4-dioxane and tetrahydrofuran, and is preferably tetrahydrofuran.
The fluorosilicone oil prepared by the method has a definite molecular structure, is a small molecular compound, can be directly used as functional fluorosilicone oil, can also be used as a chain extender for preparing high-viscosity fluorosilicone products, and has the advantages of mild preparation conditions, high efficiency, controllability, low content of siloxane ring by-products and simple and convenient purification.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides fluorosilicone oil which can be directly used as functional fluorosilicone oil and can also be used as a chain extender for preparing high-viscosity fluorosilicone products.
(2) The preparation method of the novel fluorosilicone oil provided by the invention has the advantages of high reaction speed, mild reaction conditions, high product functional group content, simple equipment and process and the like, and particularly has obvious advantages in the aspect of preparing micromolecule hydroxyl silicone oil for a fluorosilicone rubber structure control agent and a fluorosilicone chain extender.
Detailed Description
The technical scheme of the invention is further specifically described by the following examples, and the raw materials used in the examples are all commercially available or prepared by a conventional method.
The embodiments are not intended to limit the scope of the present invention, and many operational combinations are possible, and those skilled in the art can directly derive the embodiments from the following examples and all such modifications are intended to be included within the scope of the present invention.
Example 1
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F，Then placing in an oil bath at 20 ℃, adding 28g of strong acid cation exchange resin, stirring for reaction for 4h, and detecting D by GC3The conversion of F was 92.4%. And cooling to room temperature under stirring, filtering to remove resin, distilling under reduced pressure, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 87.3%. The density at 25 ℃ was 1.11 and the refractive index was 1.373.
Example 2
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at the temperature of 30 ℃, adding 28g of strong-acid cation exchange resin, stirring and reacting for 2 hours, and detecting D by GC3The conversion of F was 93.8%. Cooling to room temperature under stirring, filtering to remove resin, carrying out reduced pressure distillation, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 90.5%.
Example 3
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at 40 ℃, adding 28g of strong-acid cation exchange resin, stirring and reacting for 1h, and detecting D by GC3The F conversion was 91.3%. Cooling to room temperature under stirring, filtering to remove resin, carrying out reduced pressure distillation, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 86.5%.
Example 4
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at 50 ℃, adding 28g of strong-acid cation exchange resin, stirring and reacting for 1h, and detecting D by GC3The F conversion was 92.1%. Cooling to room temperature under stirring, filtering to remove resin, distilling under reduced pressure, and collecting the product at 109-110 ℃/800Pa to obtain colorless transparent hydrogenThe end-capped fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane, yield 87.0%.
Example 5
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing in an oil bath at 60 ℃, adding 28g of strong acid cation exchange resin, stirring for reacting for 45min, and detecting D by GC3The F conversion was 92.6%. Cooling to room temperature under stirring, filtering to remove resin, carrying out reduced pressure distillation, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 85.7%.
Example 6
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at the temperature of 80 ℃, adding 28g of strong-acid cation exchange resin, stirring and reacting for 30min, and detecting D by GC3The conversion of F was 93.1%. And cooling to room temperature under stirring, filtering to remove resin, distilling under reduced pressure, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 86.9%.
Example 7
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at 40 ℃, adding 9.36g of strong-acid cation exchange resin, stirring and reacting for 2 hours, and detecting D by GC3The conversion of F was 90.3%. Cooling to room temperature under stirring, filtering to remove resin, carrying out reduced pressure distillation, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 86.1%.
Example 8
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing in 40 ℃ oil bath, adding 18.7g of strong acid cation exchange resin, stirring for reaction for 75min, and detecting D by GC3The F conversion was 91.2%. And cooling to room temperature under stirring, filtering to remove resin, distilling under reduced pressure, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 87.0%.
Example 9
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing in an oil bath at 30 ℃, adding 57g of strong acid cation exchange resin, stirring for reaction for 45min, and detecting D by GC3The F conversion was 94.0%. Cooling to room temperature under stirring, filtering to remove resin, carrying out reduced pressure distillation, and collecting the product under the condition of 109-110 ℃/800Pa to obtain colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 91.1%.
Example 10
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at 50 ℃, adding 4.68g of concentrated sulfuric acid, stirring the mixture for reaction for 2 hours, and detecting D by GC3The F conversion was 92.1%. And cooling to room temperature under stirring, transferring to a separating funnel, washing to neutrality to remove concentrated sulfuric acid, carrying out reduced pressure distillation, and collecting a product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 88.2%.
Example 11
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at 50 ℃, adding 2g of concentrated sulfuric acid, stirring and reacting for 6 hours, and detecting D by GC3The conversion of F was 93.7%. Cooling to room temperature under stirring, transferring to a separating funnel, washing with water to neutrality to remove concentrated sulfuric acid, distilling under reduced pressure, and collecting the product at 109-110 ℃/800Pa to obtain colorlessThe yield of the transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane is 88.9%.
Example 12
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at 40 ℃, adding 1.2g of trifluoromethanesulfonic acid, stirring and reacting for 6 hours, and detecting D by GC3The F conversion was 92.2%. And cooling to room temperature under stirring, transferring to a separating funnel, washing with water until the catalyst is neutral, removing the catalyst, carrying out reduced pressure distillation, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 88.1%.
Example 13
134g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture into an oil bath at the temperature of 80 ℃, adding 25g of acid clay, stirring and reacting for 45min, and detecting D by GC3The conversion of F was 96.3%. And cooling to room temperature under stirring, filtering to remove acid clay, distilling under reduced pressure, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 92.6%.
Example 14
150g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and spherical condenserHAnd 234g D3F, then placing the mixture into an oil bath at 60 ℃, adding 30g of acid clay, stirring and reacting for 1.5h, and detecting D by GC3The conversion of F was 92.7%. And cooling to room temperature under stirring, filtering to remove acid clay, distilling under reduced pressure, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 88.8%.
Example 15
70.4g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and bulb condenserHAnd 234g D3F, then placing the mixture in an oil bath at 40 ℃, adding 18.7g of strong-acid cation exchange resin, stirring and reacting for 2 hours, and detecting D by GC3The F conversion was 94.3%. And cooling to room temperature under stirring, filtering to remove resin, distilling under reduced pressure, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 90.7%.
Example 16
270g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, and spherical condenserHAnd 234g D3F, then placing the mixture in an oil bath at 40 ℃, adding 11.7g of strong-acid cation exchange resin, stirring and reacting for 2 hours, and detecting D by GC3The conversion of F was 93.5%. And cooling to room temperature under stirring, filtering to remove resin, distilling under reduced pressure, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 89.6%.
Example 17
335g MM was added to a 1L three-necked flask equipped with a mechanical stirrer, thermometer, bulb condenserHAnd 117g D3F, then placing the mixture in an oil bath at 40 ℃, adding 6g of strong-acid cation exchange resin, stirring and reacting for 2 hours, and detecting D by GC3The conversion of F was 95.1%. And cooling to room temperature under stirring, filtering to remove resin, distilling under reduced pressure, and collecting the product under the condition of 109-110 ℃/800Pa to obtain the colorless and transparent hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane with the yield of 91.7%.
Example 18
151g of 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane prepared in example 1, 18g of deionized water, 5g of 10% Pd/C and 150mL of 1, 4-dioxane are added into a 500mL three-necked flask provided with a magnetic stirring, thermometer and spherical condenser, then the mixture is placed in an ice water bath at the temperature of 0 ℃ for stirring reaction for 4 hours, then the catalyst is filtered and removed, and low-boiling-point substances are removed under the condition of 110 ℃/600Pa to obtain colorless and transparent hydroxyl-terminated fluorosilicone oil 1, 9-dihydroxy-1, 1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane, the yield is 85.2%, and the content of Si-OH is 5.22 wt%. The density at 25 ℃ was 1.20 and the refractive index was 1.379.
Example 19
A500 mL three-necked flask equipped with a magnetic stirrer, a thermometer, and a spherical condenser was charged with 151g of 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane prepared in example 2, 45g of deionized water, and 0.01g H2PtCl6Hydrate and 200ml tetrahydrofuran are stirred and reacted for 2h at the temperature of 60 ℃, then the catalyst is removed by filtration, and the colorless and transparent hydroxyl-terminated fluorosilicone oil 1, 9-dihydroxy-1, 1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane is obtained after low-boiling-point substances are removed under the condition of 110 ℃/600Pa, the yield is 80.7 percent, and the content of Si-OH is 5.15 percent by weight.
Example 20
151g of 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane prepared in example 3, 36g of deionized water, 7.5g of 5% Pd/C and 200mL of tetrahydrofuran are added into a 500mL three-necked flask provided with a magnetic stirring, thermometer and spherical condenser, stirred and reacted for 3 hours at room temperature, then the catalyst is filtered and removed, and low-boiling-point substances are removed at the temperature of 110 ℃/600Pa, so that colorless and transparent hydroxyl-terminated fluorosilicone oil 1, 9-dihydroxy-1, 1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane is obtained, the yield is 87.4%, and the Si-OH content is 5.30 wt%.
Example 21
151g of 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane prepared in example 4, 45g of deionized water, 5g of 5% Pd/C and 200mL of chloroform are added into a 500mL three-necked flask provided with a magnetic stirring, thermometer and spherical condenser, stirred and reacted at 30 ℃ for 3 hours, then the catalyst is removed by filtration, and low-boiling-point substances are removed at the temperature of 110 ℃/600Pa, so that colorless and transparent hydroxyl-terminated fluorosilicone oil 1, 9-dihydroxy-1, 1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane is obtained, the yield is 82.3%, and the Si-OH content is 5.26 wt%.

Claims (4)

1. A preparation method of hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tri (3,3, 3-trifluoropropyl) pentasiloxane, it is characterized in that 1,1,3, 3-tetramethyldisiloxane, 1,3, 5-trimethyl-1, 3, 5-tri (3,3, 3-trifluoropropyl) cyclotrisiloxane and catalyst A are mixed in a reactor, stirring at 0-80 ℃ for reaction for 0.5-6 h, cooling to room temperature under a stirring state, removing the catalyst, carrying out reduced pressure distillation, and collecting fractions under the condition of 109-110 ℃ per 800Pa, namely hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane;
the structural formula of the hydrogen-terminated fluorosilicone oil 1,1,3,5,7,9, 9-heptamethyl-3, 5, 7-tris (3,3, 3-trifluoropropyl) pentasiloxane is as follows:
Figure 741085DEST_PATH_IMAGE001
wherein R = H;
wherein the molar ratio of the 1,1,3, 3-tetramethyldisiloxane to the 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane is 1.05-10: 1;
the mass ratio of the catalyst A to the 1,3, 5-trimethyl-1, 3, 5-tri (3,3, 3-trifluoropropyl) cyclotrisiloxane is 0.005-0.5: 1.
2. the method for preparing fluorosilicone oil according to claim 1, wherein the catalyst A is selected from one of strong acid cation exchange resin and concentrated sulfuric acid.
3. The method for preparing fluorosilicone oil according to claim 1 or 2, wherein the catalyst A is selected from a strongly acidic cation exchange resin.
4. The method for preparing fluorosilicone oil according to claim 1 or 2, wherein the mass ratio of the catalyst A, the strong-acid cation exchange resin, and the 1,3, 5-trimethyl-1, 3, 5-tris (3,3, 3-trifluoropropyl) cyclotrisiloxane is 0.1-0.2: 1.
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