CN111848958A - Hydroxy fluorosilicone oil and preparation method thereof - Google Patents

Hydroxy fluorosilicone oil and preparation method thereof Download PDF

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CN111848958A
CN111848958A CN202010689423.4A CN202010689423A CN111848958A CN 111848958 A CN111848958 A CN 111848958A CN 202010689423 A CN202010689423 A CN 202010689423A CN 111848958 A CN111848958 A CN 111848958A
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catalyst
temperature
fluorosilicone oil
carbon
mass ratio
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CN111848958B (en
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张育林
尤小姿
乔文强
刘继
王植源
杨善志
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Dalian University of Technology
Zhejiang Xinan Chemical Industrial Group Co Ltd
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Zhejiang Xinan Chemical Industrial Group Co Ltd
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/22Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • CCHEMISTRY; METALLURGY
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/06Preparatory processes
    • C08G77/08Preparatory processes characterised by the catalysts used
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/14Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups

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Abstract

The invention relates to the field of fluorosilicone oil, and more specifically relates to hydroxyl fluorosilicone oil and a preparation method thereof, wherein the method comprises the following steps: performing ring-opening polymerization reaction on trifluoropropyl methyl cyclotrisiloxane, water and a catalyst to obtain the hydroxyl fluorosilicone oil; wherein the carbon-based solid acid catalyst is prepared from anhydrous glucose and p-toluenesulfonic acid. The preparation process is simple and easy to operate, the catalyst is easy to remove, the repeated utilization rate is high, the process steps are simple, and the obtained hydroxyl fluorosilicone oil is stable in viscosity.

Description

Hydroxy fluorosilicone oil and preparation method thereof
Technical Field
The invention relates to the field of fluorosilicone oil, and particularly relates to hydroxyl fluorosilicone oil and a preparation method thereof.
Background
A hydroxyl terminated polymethyl (3, 3, 3-trifluoropropyl) siloxane fluid, commonly referred to as hydroxyfluorosilicone oil. The hydroxyl fluorosilicone oil is colorless or faint yellow oily liquid, not only has the properties of high and low temperature resistance and fuel oil resistance of common fluorosilicone polymers, but also has great chemical activity due to the existence of a large number of silicon hydroxyl groups, so that the application of the hydroxyl fluorosilicone oil is wider. For example, the modified polyether polyurethane can be used as an intermediate of a high molecular weight fluorosilicone polymer, can be used as a processing aid of heat vulcanized silicone rubber and room temperature vulcanized silicone rubber, can also be used as a defoaming agent of an organic solvent, an additive in cosmetics and the like, and in addition, the modified polyether polyurethane is modified by taking hydroxyl fluorosilicone oil as a raw material to obtain the polyfluorosiloxane-polyurethane block copolymer, so that the modified polyether polyurethane block copolymer has a good development prospect.
At present, the preparation method of the hydroxyl fluorosilicone oil mainly comprises a hydrolytic condensation preparation method and a ring-opening polymerization preparation method. The organofluorine industry, 1994 No. 4, pages 21-23, discloses a method for directly hydrolyzing trifluoropropylmethyldichlorosilane, which has the problems of wide molecular weight distribution, unstable hydroxyl group, easy condensation, more wastewater and low yield although the process is simple and the raw materials are easily available.
In summary, in order to solve the problems that the system viscosity is difficult to control, the repeated stability of the reaction process is poor, and the product treatment process steps are troublesome in the existing preparation process of the hydroxyl fluorosilicone oil, the invention provides a preparation method of the hydroxyl fluorosilicone oil, which has the advantages of simple and easy operation of the preparation process, easy removal of the catalyst, high repeated utilization rate, simple process steps, and stable viscosity of the obtained hydroxyl fluorosilicone oil.
Disclosure of Invention
In order to solve the technical problems, the invention provides hydroxyl fluorosilicone oil and a preparation method thereof,
in one aspect, a method for preparing hydroxyfluorosilicone oil is provided, which comprises the following steps: performing ring-opening polymerization reaction on trifluoropropyl methyl cyclotrisiloxane, water and a carbon-based solid catalyst to obtain the hydroxyl fluorosilicone oil; wherein the carbon-based solid catalyst is prepared from anhydrous glucose and p-toluenesulfonic acid.
Further, the mass ratio of the anhydrous glucose to the p-toluenesulfonic acid is 1-5: 1; preferably, the mass ratio is 1-3: 1; further preferably, the mass ratio is 2: 1.
further, the carbonization temperature is 100-300 ℃; preferably, the carbonization temperature is 150-250 ℃; further preferably, the carbonization temperature is 220 ℃.
Further, the carbonization time is 5-15 h; preferably, the carbonization time is 8-12 h; further preferably, the carbonization time is 9 h.
Further, the mass ratio of the trifluoropropylmethylcyclotrisiloxane to the water to the catalyst is 100: (1-10): (0.5 to 5); preferably, the mass ratio is 100: (3-6): (1-4); further preferably, the mass ratio is 100: (4-5): (2-3).
Further, the temperature of the polymerization reaction is 60-150 ℃; preferably, the temperature is 80-120 ℃; further preferably, the temperature is 90-100 ℃.
Further, the time of the polymerization reaction is 12-36 h; preferably, the time is 15-30 h; further preferably, the time is 20-25 h.
Further, the ring-opening polymerization reaction also comprises reduced pressure dehydration, wherein the dehydration temperature is less than or equal to 60 ℃, and the dehydration pressure is less than-0.085 Mpa.
In another aspect, a hydroxyfluorosilicone oil prepared according to the above method is also provided.
Further, the viscosity of the hydroxyl fluorosilicone oil is 40-400 Mpa.S; preferably, the viscosity is 100-; more preferably, the viscosity is 200-.
The hydroxyl fluorosilicone oil, the preparation method and the preparation method thereof have the following advantages:
1. the reaction controllability is strong, the process steps are simple, and the production cost can be reduced;
2. the solid acid has wide raw material source, simple preparation condition and convenient operation;
3. the hydroxyl fluorosilicone oil prepared by the method has stable viscosity and higher yield.
4. The catalyst is easy to remove in the preparation process of the method and has high repeated utilization rate.
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 preparation of hydroxyfluorosilicone oil according to an 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 process for preparing hydroxy fluorosilicone oil of the present invention, which comprises: performing ring-opening polymerization reaction on trifluoropropyl methyl cyclotrisiloxane, water and a carbon-based solid catalyst to obtain the hydroxyl fluorosilicone oil; wherein the carbon-based solid catalyst is prepared from anhydrous glucose and p-toluenesulfonic acid.
The catalyst is easy to remove in the preparation process of the catalyst, the catalyst can be removed only by filtering, the viscosity of the product is easy to control, the operation process is simple, the product can be obtained only by mixing various products and reacting according to a certain proportion and temperature, and the yield of the fluorosilicone oil prepared by the method reaches over 90 percent.
Further, the carbon-based solid acid catalyst is prepared from anhydrous glucose and p-toluenesulfonic acid, and comprises the following components: mixing the anhydrous glucose with p-toluenesulfonic acid, carbonizing and filtering; wherein the mass ratio of the anhydrous glucose to the p-toluenesulfonic acid is 1-5: 1 preferably, the mass ratio is 1-3: 1; further preferably, the mass ratio is 2: 1.
if the acid is excessive, the excessive p-toluenesulfonic acid can block formed pore channels, so that the adsorption and diffusion of reactants on the inner surface of the catalyst are influenced, namely the activity is reduced; on the contrary, the anhydrous glucose is too much, a part of the pore channels do not have sulfonic acid groups, and the activity is also reduced. Therefore, the selection of proper ratio of anhydrous glucose and p-toluenesulfonic acid has great influence on the activity of the catalyst.
Further, the carbonization temperature is 100-300 ℃; preferably, the carbonization temperature is 150-250 ℃; further preferably, the carbonization temperature is 220 ℃.
Because a multi-stage frame porous structure is formed after carbonization, the aperture is reduced when the temperature is over 300 ℃, particularly 220 ℃, so that reactant molecules are prevented from being immersed into the inner surface of the catalyst, and the activity of the catalyst is influenced; when the carbonization temperature is lower than 100 ℃, the full carbonization cannot be realized, and the porous structure of the catalyst is influenced.
Further, the carbonization time is 5-15 h; preferably, the carbonization time is 8-12 h; further preferably, the carbonization time is 9 h.
The carbonization time is less than 5h, the specific surface area and the pore diameter are too small, the carbonization time is too long, and the specific surface area and the pore diameter are too small when the carbonization time is more than 15 h; the carbonization time is 9h, and the specific surface area is maximum.
Further, the trifluoropropylmethylcyclotrisiloxane (D)3F) The mass ratio of water to the catalyst is 100: 1-10: 0.5 to 5; preferably, the mass ratio is 100: 3-6: 1-4; further preferably, the mass ratio is 100: 4-5: 2 to 3. Wherein D is3F can be represented by the formula (CH)3SiCH2CH2CF3O)3And (4) showing.
When the water consumption is excessive, the generated fluorosilicone oil chain link is short and has too low viscosity, and when the water consumption is excessive, the fluorosilicone oil chain link is long and has too high viscosity; when the amount of the catalyst used is too small, the reaction is not complete, and when the amount of the catalyst used is too large, waste is caused.
Further, the temperature of the polymerization reaction is 60-150 ℃; preferably, the temperature is 80-120 ℃; further preferably, the temperature is 90-100 ℃.
When the temperature is lower than 60 ℃, reactants hardly react, and when the temperature reaches 150 ℃, the viscosity tends to be stable, and the energy is wasted due to overhigh temperature.
Further, the polymerization reaction time is 12-36 h; preferably, the time is 15-30 h; further preferably, the time is 20-25 h.
The reaction time is too short and incomplete, and when the reaction time is 12-36h, the fluorosilicone oil with the required viscosity can be obtained, and the viscosity of the fluorosilicone oil tends to be stable.
Further, the ring-opening polymerization reaction also comprises reduced pressure dehydration, wherein the dehydration temperature is less than or equal to 60 ℃, and the dehydration pressure is less than-0.085 Mpa.
The invention also provides the hydroxy fluorosilicone oil prepared by the method.
Further, the viscosity of the hydroxyl fluorosilicone oil is 40-400 Mpa.S; preferably, the viscosity is 100-; more preferably, the viscosity is 200-.
The general formula of the hydroxyl fluorosilicone oil is shown in the specification
Figure BDA0002588757920000051
Wherein: n is a polymerization degree and is a positive integer of 3 or more.
The fluorosilicone oil obtained by the method has the advantages of easy regulation and control of viscosity, capability of reaching the required target viscosity and high repeated preparation rate.
The specific embodiment of the preparation method of the catalyst is as follows, the structure of the catalyst is an amorphous condensed ring aromatic network structure, sulfonic acid groups are connected to the surface of a carbon carrier through covalent bonds, and the catalytic function is derived from the sulfonic acid groups combined on the surface of the carbon carrier.
Example 1
Preparing a carbon-based solid acid catalyst using anhydrous glucose and p-toluenesulfonic acid as raw materials, in a mass ratio of m (anhydrous glucose)/m (p-toluenesulfonic acid) 2: weighing raw materials, dissolving the raw materials in distilled water, rotationally evaporating to remove water to obtain viscous liquid, putting the viscous liquid into a muffle furnace, heating to 220 ℃, dehydrating and carbonizing for 9 hours, putting the obtained black solid into a mortar for grinding, and sieving by a 80-mesh sieve to obtain the carbon-based solid acid catalyst. The catalyst has high reuse rate and can be reused for 5 times.
Example 2
Preparing a carbon-based solid acid catalyst using anhydrous glucose and p-toluenesulfonic acid as raw materials, in a mass ratio of m (anhydrous glucose)/m (p-toluenesulfonic acid) 5: weighing raw materials, dissolving the raw materials in distilled water, rotationally evaporating to remove water to obtain viscous liquid, putting the viscous liquid into a muffle furnace, heating to 100 ℃, dehydrating and carbonizing for 15 hours, putting the obtained black solid into a mortar for grinding, and sieving by a 80-mesh sieve to obtain the carbon-based solid acid catalyst. The catalyst has high reuse rate and can be reused for 6 times.
Example 3
Preparing a carbon-based solid acid catalyst using anhydrous glucose and p-toluenesulfonic acid as raw materials, in a mass ratio of m (anhydrous glucose)/m (p-toluenesulfonic acid) 1: weighing raw materials, dissolving the raw materials in distilled water, rotationally evaporating to remove water to obtain viscous liquid, putting the viscous liquid into a muffle furnace, heating to 300 ℃, dehydrating and carbonizing for 5 hours, putting the obtained black solid into a mortar for grinding, and sieving by a 80-mesh sieve to obtain the carbon-based solid acid catalyst. The catalyst has high reuse rate and can be reused for 5 times.
Example 4
Preparing a carbon-based solid acid catalyst using anhydrous glucose and p-toluenesulfonic acid as raw materials, in a mass ratio of m (anhydrous glucose)/m (p-toluenesulfonic acid) 3: 1, weighing raw materials, dissolving the raw materials in distilled water, rotationally evaporating the solution to remove water to obtain viscous liquid, putting the viscous liquid into a muffle furnace, heating the viscous liquid to 150 ℃, dehydrating and carbonizing the viscous liquid for 12 hours, putting the obtained black solid into a mortar for grinding, and sieving the black solid with a 80-mesh sieve to obtain the carbon-based solid acid catalyst. The catalyst has high reuse rate and can be reused for 6 times.
Example 5
Preparing a carbon-based solid acid catalyst using anhydrous glucose and p-toluenesulfonic acid as raw materials, and reacting the carbon-based solid acid catalyst in a mass ratio of m (anhydrous glucose)/m (p-toluenesulfonic acid) 4: weighing raw materials, dissolving the raw materials in distilled water, rotationally evaporating to remove water to obtain viscous liquid, putting the viscous liquid into a muffle furnace, heating to 250 ℃, dehydrating and carbonizing for 8 hours, putting the obtained black solid into a mortar for grinding, and sieving by a 80-mesh sieve to obtain the carbon-based solid acid catalyst. The catalyst has high reuse rate and can be reused for 6 times.
The preparation method for preparing the hydroxyl fluorosilicone oil by adopting the catalyst comprises the following steps:
example 6
100g D was put into a three-necked flask equipped with a thermometer, a condenser and a stirrer3F. 1g of water and 0.5g of carbon-based solid acid catalyst, stirring and reacting for 36h at 60 ℃, stopping the reaction, carrying out suction filtration on the product, removing the carbon-based solid acid catalyst, carrying out reduced pressure distillation on the obtained filtrate for 4h at 60 ℃ and under the condition that the dehydration pressure is less than-0.085 MPa, removing water to obtain colorless and transparent hydroxy fluorosilicone oil, and cooling to obtain the product with the viscosity of 250 Mpa.S at 25 ℃. Wherein the catalyst was the catalyst of example 1. The yield of the hydroxyl fluorosilicone oil reaches 98 percent.
Example 7
100g D was put into a three-necked flask equipped with a thermometer, a condenser and a stirrer3F. Stirring 10g water and 5g carbon-based solid acid catalyst at 150 deg.C for 12 hr, stopping reaction, vacuum filtering, removing carbon-based solid acid catalyst, vacuum distilling the filtrate at 50 deg.C under dehydration pressure of less than-0.065 MPa for 4 hr, removing water to obtain colorless transparent hydroxy fluorosilicone oil, cooling, measuring temperature to 25 deg.CThe lower viscosity was 400MPa S. Wherein the catalyst was the catalyst of example 2. The yield of the hydroxyl fluorosilicone oil reaches 95 percent.
Example 8
100g D was put into a three-necked flask equipped with a thermometer, a condenser and a stirrer3F. 3g of water and 1g of carbon-based solid acid catalyst, stirring and reacting for 30h at 80 ℃, stopping the reaction, performing suction filtration on the product, removing the carbon-based solid acid catalyst, distilling the obtained filtrate under reduced pressure for 5h at 45 ℃ and under the dehydration pressure of less than-0.075 MPa, removing water to obtain colorless and transparent hydroxy fluorosilicone oil, and cooling to obtain the catalyst with the viscosity of 100 Mpa.S at 25 ℃. The yield of the hydroxyl fluorosilicone oil reaches 96 percent.
Example 9
100g D was put into a three-necked flask equipped with a thermometer, a condenser and a stirrer 3F. 4g of water and 2g of carbon-based solid acid catalyst are stirred and reacted for 15h at the temperature of 120 ℃, the reaction is stopped, the product is filtered, the carbon-based solid acid catalyst is removed, the obtained filtrate is subjected to reduced pressure distillation for 6h under the conditions that the temperature is 40 ℃ and the dehydration pressure is less than-0.060 MPa, the moisture is removed, colorless and transparent hydroxy fluorosilicone oil is obtained, and the viscosity is 300Mpa S at the temperature of 25 ℃ after cooling. The yield of the hydroxyl fluorosilicone oil reaches 95 percent.
Example 10
100g D was put into a three-necked flask equipped with a thermometer, a condenser and a stirrer3F. 5g of water and 3g of carbon-based solid acid catalyst, stirring and reacting for 20h at 100 ℃, stopping the reaction, performing suction filtration on the product, removing the carbon-based solid acid catalyst, distilling the obtained filtrate under reduced pressure for 7h at 30 ℃ and under the dehydration pressure of less than-0.040 MPa, removing water to obtain colorless and transparent hydroxy fluorosilicone oil, and cooling to obtain the catalyst with the viscosity of 200Mpa S at 25 ℃. The yield of the hydroxyl fluorosilicone oil reaches 92 percent.
Comparative example 1:
mass ratio m (anhydrous glucose)/m (p-toluenesulfonic acid) 6: 1, the raw materials are weighed, the carbonization temperature is 80 ℃, the carbonization time is 20h, and other steps and parameters are the same as those of the example 1. The catalyst has low reuse rate, and the catalytic activity is obviously reduced after 2 times of use.
Comparative example 2
The trifluoropropylmethylcyclotrisiloxane (D)3F) The mass ratio of water to the catalyst is 100: 20: 0.1; the polymerization temperature was 50 ℃ and the polymerization time was 40h, wherein the catalyst prepared in example 1 was selected as the catalyst. The other steps and parameters were the same as in example 6.
Comparative example 3
Catalyst the catalyst obtained in comparative example 1 was used, and the other steps and parameters were the same as in example 6.
Comparative example 4
The catalyst used a heteropoly acid and the other steps and parameters were the same as in example 6.
Comparative example 5
The catalyst used was a carbon-based solid acid catalyst, but the starting materials for the preparation of the catalyst were fructose, water and sulfuric acid, and the other steps and parameters were the same as in example 6.
The yields and viscosities of hydroxyfluorosilicone oils prepared in comparative examples 2 to 5 and example 6 were compared and are shown in table 1.
TABLE 1 comparison of Hydroxysilicon oils prepared by different methods
Example 6 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Yield of 98% 82% 80% 81% 78%
Viscosity (Mpa S) 250 32 800 1000 5000
The hydroxyl fluorosilicone oil prepared by the preparation parameters and the catalyst of the method has high yield and stable and moderate viscosity, and can be obtained by the method shown in the table 1.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The preparation method of the hydroxyl fluorosilicone oil is characterized in that trifluoropropyl methylcyclotrisiloxane, water and a carbon-based solid catalyst are subjected to ring-opening polymerization reaction to obtain the hydroxyl fluorosilicone oil; wherein the carbon-based solid acid catalyst is prepared from anhydrous glucose and p-toluenesulfonic acid.
2. The method for preparing hydroxyfluorosilicone oil according to claim 1, wherein the carbon-based solid acid catalyst prepared from anhydrous glucose and p-toluenesulfonic acid comprises: mixing the anhydrous glucose with p-toluenesulfonic acid, carbonizing and filtering; wherein the content of the first and second substances,
the mass ratio of the anhydrous glucose to the p-toluenesulfonic acid is 1-5: 1; preferably, the mass ratio is 1-3: 1; further preferably, the mass ratio is 2: 1.
3. the method for preparing hydroxyfluorosilicone oil as claimed in claim 2, wherein the carbonization temperature is 100-300 ℃; preferably, the carbonization temperature is 150-250 ℃; further preferably, the carbonization temperature is 220 ℃.
4. The method for preparing hydroxyfluorosilicone oil according to claim 2, wherein the carbonization time is 5-15 h; preferably, the carbonization time is 8-12 h; further preferably, the carbonization time is 9 h.
5. The method for preparing hydroxyfluorosilicone oil according to claim 1, wherein the mass ratio of trifluoropropylmethylcyclotrisiloxane to water to carbon-based solid catalyst is 100: (1-10): (0.5 to 5); preferably, the mass ratio is 100: (3-6): (1-4); further preferably, the mass ratio is 100: (4-5): (2-3).
6. The method for preparing hydroxyfluorosilicone oil according to claim 1, wherein the temperature of the polymerization reaction is 60-150 ℃; preferably, the temperature is 80-120 ℃; further preferably, the temperature is 90-100 ℃.
7. The method for preparing hydroxyfluorosilicone oil according to claim 1, wherein the polymerization reaction time is 12-36 h; preferably, the time is 15-30 h; further preferably, the time is 20-25 h.
8. The method for preparing hydroxyfluorosilicone oil according to claim 1, further comprising dehydration under reduced pressure after the ring-opening polymerization reaction, wherein the dehydration temperature is less than or equal to 60 ℃ and the dehydration pressure is less than-0.085 Mpa.
9. A hydroxyfluorosilicone oil prepared by the preparation method according to any one of claims 1 to 8.
10. The hydroxyfluorosilicone oil of claim 9, wherein the viscosity of the hydroxyfluorosilicone oil is 40-400Mpa · S; preferably, the viscosity is 100-; more preferably, the viscosity is 200-.
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CN102977373A (en) * 2012-11-19 2013-03-20 福建省邵武市永晶化工有限公司 Preparation method of hydroxyfluorosilicone oil
US20200140617A1 (en) * 2015-01-28 2020-05-07 Dow Silicones Corporation Elastomeric compositions and their applications
CN111286030A (en) * 2020-03-23 2020-06-16 新纳奇材料科技江苏有限公司 Preparation method of vinyl phenyl silicone oil

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CN102408567A (en) * 2011-11-11 2012-04-11 杭州师范大学 Preparation method for hydroxyl silicone oil
CN102977373A (en) * 2012-11-19 2013-03-20 福建省邵武市永晶化工有限公司 Preparation method of hydroxyfluorosilicone oil
US20200140617A1 (en) * 2015-01-28 2020-05-07 Dow Silicones Corporation Elastomeric compositions and their applications
CN111286030A (en) * 2020-03-23 2020-06-16 新纳奇材料科技江苏有限公司 Preparation method of vinyl phenyl silicone oil

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