Fluorine and boron-containing hydroxyl-terminated silicone oil and preparation method thereof

Abstract

The invention discloses fluorine and boron-containing hydroxyl-terminated silicone oil and a preparation method thereof, and relates to the technical field of high polymer material preparation, dichlorosilane compounds, (3, 3, 3-trifluoropropyl) dichloromethylsilane and boron-containing acid are used as raw materials, and a series of fluorine and boron-containing hydroxyl-terminated silicone oil is synthesized through a hydrolysis-condensation method. The fluorine and boron-containing hydroxyl-terminated silicone oil has a temperature of 420-440 DEG C at a weight loss of 5% and a glass-transition temperature of-130 to-140 DEG C in an N2 atmosphere, has a wide use temperature range, and can be applied in a plurality of extreme occasions.

Description

Technical Field

[0001] The invention relates to the technical field of polymer material preparation, in particular to a fluorine- and boron-containing terminal hydroxyl silicone oil and a preparation method thereof. Background Art

[0002] Hydroxyl silicone oil is a commonly used organosilicon compound. With its excellent properties, such as high flexibility and easy processing, it can be used to prepare adhesives, casting sealants, surface coatings, composite materials, etc., and is in urgent demand in electronic, electrical, aviation and other products. At present, ordinary methyl silicone oil can only be used in the range of -50℃ to 200℃, which is difficult to meet the performance requirements of silicone oil in special fields.

[0003] Patent CN 118580496A discloses a method for preparing methylphenyl silicone oil, which effectively improves the high and low temperature resistance of silicone oil by introducing phenyl group and utilizing its high steric hindrance, so that the use temperature of phenylmethyl silicone oil is extended to -70℃~250℃. However, the introduction of phenyl group will affect the fluidity of silicone oil to a certain extent, so it is of great significance to design silicone oil with a new structure and further extend its use temperature without sacrificing its fluidity. Summary of the invention

[0004] Based on the above content, the present invention provides a fluorine- and boron-containing terminal hydroxyl silicone oil and a preparation method thereof. The fluorine- and boron-containing terminal hydroxyl silicone oil prepared by the present invention not only greatly broadens the use temperature of silicone oil, but also has certain hydrophobic properties.

[0005] The present invention provides the following scheme:

[0006] A fluorine- and boron-containing terminal hydroxyl silicone oil, the silicone oil structural formula is as follows:

[0007]

[0008] Wherein, R1, R2 and R3 are independently methyl or phenyl;

[0009] x, y, and z all represent mole fractions; x is 0 to 0.5 and is not 0; y is 0.05 to 0.15; and z is 0.02 to 0.1.

[0010] The fluorine- and boron-containing terminal hydroxyl silicone oil has x of 0.2 to 0.5, y of 0.07 to 0.13, and z of 0.02 to 0.05.

[0011] A method for preparing fluorine- and boron-containing terminal hydroxyl silicone oil, the method comprising the following steps:

[0012] Step 1, hydrolyzing a dichlorosilane compound to obtain a Si-containing hydrolyzate;

[0013] Hydrolyzing (3,3,3-trifluoropropyl)dichloromethylsilane to obtain a F-containing hydrolyzate;

[0014] Step 2: subjecting the Si-containing hydrolyzate, the F-containing hydrolyzate and a boron-containing acid to a condensation reaction under the action of a catalyst to obtain the fluorine- and boron-containing terminal hydroxyl silicone oil.

[0015] In the preparation method of the fluorine- and boron-containing terminal hydroxyl silicone oil, the dichlorosilane compound is dimethyldichlorosilane, diphenyldichlorosilane or methylphenyldichlorosilane; the boron-containing acid is methylboric acid or phenylboric acid; and the catalyst is concentrated sulfuric acid or p-toluenesulfonic acid.

[0016] The method for preparing the fluorine- and boron-containing terminal hydroxyl silicone oil comprises the following steps: the molar ratio of the dichlorosilane compound to the (3,3,3-trifluoropropyl)dichloromethylsilane and the boron-containing acid is (0-0.5):(0.05-0.15):(0.02-0.1); and the amount of the catalyst used is 1% to 3% of the total molar amount of the dichlorosilane compound, (3,3,3-trifluoropropyl)dichloromethylsilane and the boron-containing acid.

[0017] In the preparation method of the fluorine- and boron-containing terminal hydroxyl silicone oil, the polycondensation reaction temperature is 50 to 80° C. and the time is 5 to 7 hours.

[0018] The preparation method of the fluorine- and boron-containing terminal hydroxyl silicone oil comprises the following steps: when preparing the Si-containing hydrolyzate, adding a dichlorosilane compound to a mixed solution of deionized water and an organic solvent A for hydrolysis; the molar ratio of the deionized water to the dichlorosilane compound is 5 to 10:1; the amount of the organic solvent A is 56% of the mass of the deionized water; and the organic solvent A is toluene or xylene.

[0019] The preparation method of the fluorine- and boron-containing terminal hydroxyl silicone oil comprises the following steps: when preparing the F-containing hydrolyzate, (3,3,3-trifluoropropyl)dichloromethylsilane is added to a mixed solution of deionized water and an organic solvent A for hydrolysis; the molar ratio of the deionized water to the (3,3,3-trifluoropropyl)dichloromethylsilane is 5 to 10:1; the amount of the organic solvent A is 56% of the mass of the deionized water; and the organic solvent A is toluene or xylene.

[0020] In the preparation method of the fluorine- and boron-containing terminal hydroxyl silicone oil, the solvent used in the polycondensation reaction is one or more of tetrahydrofuran, N,N-dimethylformamide, toluene, 1,4-dioxane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

[0021] Technical effects of the invention:

[0022] 1. The fluorine- and boron-containing terminal hydroxyl silicone oil of the present invention has a large Si-O bond angle and high flexibility; the main chain also contains a small amount of BO bonds, which have high bond energy and are not easy to break; the side chain contains a small amount of CF3 bonds, whose irregularity will inhibit the low-temperature crystallization of the silicone oil to a certain extent, and at the same time improve its hydrophobic performance. Under N2 atmosphere, the temperature of 5% weight loss is 420-440℃, and the glass transition temperature is -130--140℃, which has a wide range of operating temperatures.

[0023] 2. The present invention prepares a fluorine- and boron-containing terminal hydroxyl silicone oil for the first time by hydrolysis and polycondensation. The present invention uses dichlorosilane compounds, (3,3,3-trifluoropropyl)dichloromethylsilane and boron-containing acid as raw materials, and synthesizes a series of fluorine- and boron-containing terminal hydroxyl silicone oils by hydrolysis-condensation. The method of the present invention is simple in process and easy to promote and apply industrially. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0025] Figure 1 The TG and DSC secondary temperature rise curves of the fluorine- and boron-containing terminal hydroxyl silicone oil in Example 1 indicate that the terminal hydroxyl silicone oil containing both BO and -CF3 bonds has a higher thermal decomposition temperature and a lower glass transition temperature.

[0026] Figure 2 This is the infrared spectrum of the fluorine- and boron-containing terminal hydroxyl silicone oil in Example 1.

[0027] Figure 3 This is the NMR boron spectrum of the fluorine- and boron-containing terminal hydroxyl silicone oil in Example 1.

[0028] Figure 4 This is a comparison chart of the water contact angles of the fluorine- and boron-containing terminal hydroxyl silicone oil in Example 1 and the reference sample. DETAILED DESCRIPTION

[0029] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0030] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0031] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0032] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0033] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0034] The first aspect of the present invention provides a fluorine- and boron-containing terminal hydroxyl silicone oil, the structural formula of which is as follows:

[0035]

[0036] Wherein, R1, R2 and R3 are independently methyl or phenyl;

[0037] x, y, and z all represent mole fractions; x is 0 to 0.5 and is not 0; y is 0.05 to 0.15; and z is 0.02 to 0.1.

[0038] In a preferred embodiment of the present invention, x is 0.2 to 0.5; y is 0.07 to 0.13; and z is 0.02 to 0.05.

[0039] In a more preferred embodiment of the present invention, x is from 0.2 to 0.35.

[0040] The terminal hydroxy silicone oil containing fluorine and boron prepared by the present invention has a wide range of use temperature. Since the bond energy of the BO bond (537.6KJ / mol) is much greater than the bond energy of the Si-O bond (460.5KJ / mol), the thermal stability of the main chain of the silicone oil is greatly improved. Under N2 atmosphere, the temperature at which it loses 5% of its weight is 420-440°C; at the same time, the introduction of -CH2CH2CF3 in the side chain destroys the regularity of the silicone oil chain segment and increases the difficulty of the movement of the molecular chain, thereby effectively inhibiting the crystallization of the silicone oil under low temperature conditions, and its glass transition temperature is -130--140°C. In addition, the F atom on the side chain can also make the silicone oil have a lower surface energy, so that it has excellent hydrophobic properties. In summary, the terminal hydroxy silicone oil containing fluorine and boron prepared by the present invention not only has a wide range of use temperature, but also has a certain hydrophobicity, and can be used in many extreme occasions, such as fields that have certain requirements for the high temperature resistance, low temperature resistance and hydrophobic properties of the material.

[0041] The second aspect of the present invention provides a method for preparing the fluorine- and boron-containing terminal hydroxyl silicone oil, comprising the following steps:

[0042] Step 1, hydrolyzing a dichlorosilane compound to obtain a Si-containing hydrolyzate;

[0043] Hydrolyzing (3,3,3-trifluoropropyl)dichloromethylsilane to obtain a F-containing hydrolyzate;

[0044] Step 2, subjecting the Si-containing hydrolyzate, the F-containing hydrolyzate and the boron-containing acid to a condensation reaction under the action of a catalyst to obtain the fluorine- and boron-containing terminal hydroxyl silicone oil. (i.e., the main chain contains a BO bond and the side chain contains -CF3 terminal hydroxyl silicone oil)

[0045] In a preferred embodiment of the present invention, the dichlorosilane compound is dimethyldichlorosilane, diphenyldichlorosilane or methylphenyldichlorosilane; the boron-containing acid is methylboric acid or phenylboric acid; and the catalyst is concentrated sulfuric acid or p-toluenesulfonic acid.

[0046] In a preferred embodiment of the present invention, the molar ratio of the dichlorosilane compound to the (3,3,3-trifluoropropyl)dichloromethylsilane and the boron-containing acid is (0-0.5):(0.05-0.15):(0.02-0.1); the amount of the catalyst used is 1% to 3% of the total molar amount of the dichlorosilane compound, (3,3,3-trifluoropropyl)dichloromethylsilane and the boron-containing acid.

[0047] In a preferred embodiment of the present invention, the temperature of the polycondensation reaction is 50-80° C. and the time is 5-7 hours.

[0048] In a preferred embodiment of the present invention, when preparing the Si-containing hydrolyzate, dichlorosilane compounds are added to a mixed solution of deionized water and organic solvent A for hydrolysis; the molar ratio of the deionized water to the dichlorosilane compounds is 5 to 10:1; the amount of the organic solvent A is 56% of the mass of the deionized water; and the organic solvent A is toluene or xylene.

[0049] In a preferred embodiment of the present invention, when preparing the F-containing hydrolyzate, (3,3,3-trifluoropropyl)dichloromethylsilane is added to a mixed solution of deionized water and organic solvent A for hydrolysis; the molar ratio of the deionized water to the (3,3,3-trifluoropropyl)dichloromethylsilane is 5 to 10:1; the amount of the organic solvent A is 56% of the mass of the deionized water; and the organic solvent A is toluene or xylene.

[0050] When preparing the Si-containing hydrolyzate and the F-containing hydrolyzate, the hydrolysis is performed twice. After the first hydrolysis reaction lasts for a certain period of time, the acid water is removed and the same amount of deionized water is added for secondary hydrolysis. After the same period of time, the acid water is removed again to obtain the corresponding hydrolyzate. When preparing the Si-containing hydrolyzate and the F-containing hydrolyzate, the hydrolysis is performed in an ice water bath or at room temperature; the hydrolysis time is 20 to 60 minutes.

[0051] In a preferred embodiment of the present invention, the solvent used in the polycondensation reaction is one or more of tetrahydrofuran, N,N-dimethylformamide, toluene, 1,4-dioxane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. Specifically, when the boron-containing acid is methylboric acid, the solvent used in the polycondensation reaction is tetrahydrofuran or N,N-dimethylformamide; when the boron-containing acid is phenylboric acid, the solvent used in the polycondensation reaction is one or more of toluene, 1,4-dioxane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

[0052] After the polycondensation reaction is completed, the steps of standing for stratification, removing the acid water and then distilling off the solvent, washing the obtained product and then drying are also included.

[0053] The molar volume ratio of the solvent used in the polycondensation reaction to the boron-containing acid is (0.07-0.1) mol: (25-30) mL.

[0054] The third aspect of the present invention provides a use of the fluorine- and boron-containing terminal hydroxyl silicone oil in the preparation of electronic, electrical or aviation products.

[0055] In practical applications, the fluorine- and boron-containing terminal hydroxyl silicone oil of the present invention can be further cured into silicone rubber, making it an elastomeric material that not only has a wide range of operating temperatures but also has high-quality hydrophobicity.

[0056] The technical solutions described in the present invention, unless otherwise specified, are all conventional solutions in the art, and the reagents or raw materials used, unless otherwise specified, are purchased from commercial channels or have been disclosed.

[0057] The test and analysis methods involved in the present invention are as follows:

[0058] NMR boron spectrum test: Deuterated chloroform is used as solvent and pure quartz NMR tube is used for testing.

[0059] TG test (a conventional test method in the art): under nitrogen atmosphere, the initial equilibrium temperature is 30°C, the temperature is increased to 800°C at a rate of 10°C / min, and the T5 value of the obtained fluorine- and boron-terminated hydroxyl silicone oil is read.

[0060] DSC test (a conventional test method in the art): in a nitrogen atmosphere, the initial equilibrium temperature is 30°C, and the temperature is lowered to -170°C at a rate of 10°C / min and maintained for 5 minutes; then the sample is heated from -170°C to 30°C at a rate of 10°C / min. From the second heating curve, the T of the obtained fluorine- and boron-terminated hydroxyl silicone oil is read. g value.

[0061] Water contact angle test (a conventional test method in the art): Use MC500 angular contact tester to measure the θ value of H2O and the sample, and measure five times to get the average value. The water drop in the water contact angle test is 4 μL.

[0062] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0063] Example 1

[0064] A method for preparing fluorine- and boron-containing terminal hydroxyl silicone oil, comprising the following steps:

[0065] (1) Hydrolysis of dimethyldichlorosilane

[0066] Deionized water (52.20 g) and toluene (29.23 g) were added to a three-necked flask. Under mechanical stirring at 30°C, a certain amount of dimethyldichlorosilane (37.43 g) was added dropwise into the three-necked flask within 15 min. After continuous stirring for 30 min under the same conditions, the lower layer of acid water was separated. Then the same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a Si-containing hydrolyzate.

[0067] (2) Hydrolysis of (3,3,3-trifluoropropyl)dichloromethylsilane

[0068] Deionized water (3.60 g) and toluene (2.01 g) were added to a three-necked flask. Under mechanical stirring at 30°C, a certain amount of (3,3,3-trifluoropropyl)dichloromethylsilane (4.49 g) was added dropwise into the three-necked flask within 15 min. After continuous stirring for 30 min under the same conditions, the lower layer of acid water was separated. The same amount of deionized water was then added for hydrolysis for 30 min, and the acid water was separated to obtain a F-containing hydrolyzate.

[0069] (3) Condensation of Si-containing hydrolyzate, F-containing hydrolyzate and methylboric acid

[0070] Dissolve methylboric acid (4.19 g) in 25 mL tetrahydrofuran and add it to the Si-containing hydrolyzate and the F-containing hydrolyzate. After the three are fully stirred for 10 minutes, add 1.08 g p-toluenesulfonic acid as a catalyst and heat to 50°C for 8 hours. After the reaction is completed, stand and separate the layers, remove the acid water and evaporate the solvent, then wash with deionized water and anhydrous ethanol for 3 times (the amount used is 2 times the volume of the product), and finally dry in vacuum at 90°C for 24 hours to obtain fluorine- and boron-containing terminal hydroxyl silicone oil.

[0071] The structure of the fluorine- and boron-containing terminal hydroxyl silicone oil prepared in this embodiment is as follows:

[0072]

[0073] Where: x=0.29, y=0.07, z=0.02.

[0074] Figure 1 The TG and DSC secondary temperature rise curves of the fluorine- and boron-containing terminal hydroxyl silicone oil in Example 1 indicate that the terminal hydroxyl silicone oil containing both BO and -CF3 bonds has a higher thermal decomposition temperature and a lower glass transition temperature. In addition, the water contact angle test shows that the hydroxyl silicone oil has good hydrophobicity (such as Figure 4 As shown, Figure 4 Here, methylsilicone oil represents terminal hydroxyl silicone oil, B methylsilicone oil represents terminal hydroxyl silicone oil containing boron, and BF methylsilicone oil (Instance 1) represents the terminal hydroxyl silicone oil containing fluorine and boron prepared in Example 1).

[0075] The infrared spectrum and nuclear magnetic hydrogen spectrum are to further verify the consistency of the synthesized product and the expected assumption. For example, for the fluorine- and boron-containing terminal hydroxyl silicone oil prepared in Example 1, in the infrared spectrum ( Figure 2 ), 3701cm -1 The absorption peak of -OH is at 1370cm -1 and 1210cm -1The absorption peaks appearing at are the stretching vibration absorption peak of -CH2- in -CH2CH2CF3 and the stretching vibration absorption peak of CF, which confirms that the F element has been successfully introduced into the side chain of the silicone oil. However, the absorption peak of the BO bond (1410) coincides with the bending vibration peak of the Si-C bond (1407), so whether the B atom has been successfully introduced into the main chain of the silicone oil still needs to be verified. 11 B-NMR characterization confirmed. 11 B NMR spectrum ( Figure 3 ) It can be found that the broad peak with a chemical shift of δ3.84ppm is the absorption peak of B, which confirms that the BO bond has been successfully introduced into the main chain of the silicone oil. Therefore, the above characterization results confirm that the terminal hydroxyl silicone oil containing both fluorine and boron has been successfully prepared.

[0076] Example 2

[0077] A method for preparing fluorine- and boron-containing terminal hydroxyl silicone oil, comprising the following steps:

[0078] (1) Hydrolysis of dimethyldichlorosilane

[0079] Deionized water (46.80 g) and toluene (26.21 g) were added to a three-necked flask. Under mechanical stirring at 30°C, a certain amount of dimethyldichlorosilane (33.56 g) was added dropwise into the three-necked flask within 15 min. After continuous stirring for 30 min under the same conditions, the lower layer of acid water was separated. Then the same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a Si-containing hydrolyzate.

[0080] (2) Hydrolysis of (3,3,3-trifluoropropyl)dichloromethylsilane

[0081] Deionized water (5.40 g) and toluene (3.02 g) were added to a three-necked flask. Under mechanical stirring at 30°C, a certain amount of (3,3,3-trifluoropropyl)dichloromethylsilane (6.33 g) was added dropwise to the three-necked flask within 15 min. After continuous stirring for 30 min under the same conditions, the lower layer of acid water was separated. The same amount of deionized water was then added for hydrolysis for 30 min, and the acid water was separated to obtain a F-containing hydrolyzate.

[0082] (3) Condensation of Si-containing hydrolyzate, F-containing hydrolyzate and methylboric acid

[0083] Dissolve methylboric acid (5.39 g) in 25 mL tetrahydrofuran and add it to the Si-containing hydrolyzate and the F-containing hydrolyzate. After the three are fully stirred for 10 minutes, add 1.08 g p-toluenesulfonic acid as a catalyst and heat to 50°C for 8 hours. After the reaction is completed, stand and separate the layers, remove the acid water and evaporate the solvent, then wash with deionized water and anhydrous ethanol three times (the amount used is twice the volume of the product), and finally dry in vacuum at 90°C for 24 hours to obtain fluorine- and boron-containing terminal hydroxyl silicone oil.

[0084] The structure of the fluorine- and boron-containing terminal hydroxyl silicone oil prepared in this embodiment is as follows:

[0085]

[0086] Where: x=0.26, y=0.09, z=0.03.

[0087] The fluorine- and boron-containing hydroxy-terminated silicone oil prepared in this example has a weight loss temperature of 5% of 423° C. and a glass transition temperature of -132° C.

[0088] Example 3

[0089] A method for preparing fluorine- and boron-containing terminal hydroxyl silicone oil, comprising the following steps:

[0090] (1) Hydrolysis of dimethyldichlorosilane

[0091] Deionized water (41.40 g) and toluene (23.18 g) were added to a three-necked flask. Under mechanical stirring at 30°C, a certain amount of dimethyldichlorosilane (29.68 g) was added dropwise into the three-necked flask within 15 min. After continuous stirring for 30 min under the same conditions, the lower layer of acid water was separated. Then the same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a Si-containing hydrolyzate.

[0092] (2) Hydrolysis of (3,3,3-trifluoropropyl)dichloromethylsilane

[0093] Deionized water (7.20 g) and toluene (4.03 g) were added to a three-necked flask. Under mechanical stirring at 30°C, a certain amount of (3,3,3-trifluoropropyl)dichloromethylsilane (8.44 g) was added dropwise into the three-necked flask within 15 min. After continuous stirring for 30 min under the same conditions, the lower layer of acid water was separated. Then the same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a F-containing hydrolyzate.

[0094] (3) Condensation of Si-containing hydrolyzate, F-containing hydrolyzate and methylboric acid

[0095] Dissolve methylboric acid (6.58 g) in 25 mL tetrahydrofuran and add it to the Si-containing hydrolyzate and the F-containing hydrolyzate. After the three are fully stirred for 10 minutes, add 1.08 g p-toluenesulfonic acid as a catalyst and heat to 50°C for 8 hours. After the reaction is completed, stand and separate the layers, remove the acid water and evaporate the solvent, then wash with deionized water and anhydrous ethanol three times (the amount used is twice the volume of the product), and finally dry in vacuum at 90°C for 24 hours to obtain fluorine- and boron-containing terminal hydroxyl silicone oil.

[0096] The structure of the fluorine- and boron-containing terminal hydroxyl silicone oil prepared in this embodiment is as follows:

[0097]

[0098] Where: x=0.23, y=0.11, z=0.04.

[0099] The fluorine- and boron-containing hydroxy-terminated silicone oil prepared in this example has a weight loss temperature of 5% of 426° C. and a glass transition temperature of -133° C.

[0100] Example 4

[0101] A method for preparing fluorine- and boron-containing terminal hydroxyl silicone oil, comprising the following steps:

[0102] (1) Hydrolysis of dimethyldichlorosilane

[0103] Deionized water (52.38 g) and toluene (29.33 g) were added to a three-necked flask and mechanically stirred under ice bath conditions. A certain amount of dimethyldichlorosilane (37.56 g) was added dropwise into the three-necked flask within 15 min. Stirring was continued under the same conditions for 30 min, and the lower layer of acid water was separated. The same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a Si-containing hydrolyzate.

[0104] (2) Hydrolysis of (3,3,3-trifluoropropyl)dichloromethylsilane

[0105] Deionized water (11.24 g) and toluene (6.29 g) were added to a three-necked flask and mechanically stirred under ice bath conditions. A certain amount of (3,3,3-trifluoropropyl)dichloromethylsilane (4.49 g) was added dropwise to the three-necked flask within 15 min. Stirring was continued under the same conditions for 30 min, and the lower layer of acid water was separated. The same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a F-containing hydrolyzate.

[0106] (3) Condensation of Si-containing hydrolyzate, F-containing hydrolyzate and phenylboric acid

[0107] Dissolve phenylboric acid (8.54 g) in 25 mL 1,4-dioxane and add it to the Si-containing hydrolyzate and the F-containing hydrolyzate. After the three are fully stirred for 10 minutes, add 0.56 g concentrated sulfuric acid as a catalyst and heat to 50°C for 8 hours. After the reaction is completed, stand and separate the layers, remove the acid water and evaporate the solvent, then wash with deionized water and anhydrous ethanol three times (the amount used is twice the volume of the product), and finally dry in vacuum at 90°C for 24 hours to obtain fluorine- and boron-containing terminal hydroxyl silicone oil.

[0108] The structure of the fluorine- and boron-containing terminal hydroxyl silicone oil prepared in this embodiment is as follows:

[0109]

[0110] Where: x=0.29, y=0.07, z=0.02.

[0111] The fluorine- and boron-containing hydroxy-terminated silicone oil prepared in this example has a weight loss temperature of 5% of 427° C. and a glass transition temperature of -135° C.

[0112] Example 5

[0113] A method for preparing fluorine- and boron-containing terminal hydroxyl silicone oil, comprising the following steps:

[0114] (1) Hydrolysis of diphenyldichlorosilane

[0115] Deionized water (52.38 g) and toluene (29.33 g) were added to a three-necked flask and mechanically stirred under ice bath conditions. A certain amount of diphenyldichlorosilane (73.68 g) was added dropwise to the three-necked flask within 15 min. Stirring was continued under the same conditions for 30 min, and the lower layer of acid water was separated. The same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a Si-containing hydrolyzate.

[0116] (2) Hydrolysis of (3,3,3-trifluoropropyl)dichloromethylsilane

[0117] Deionized water (11.24 g) and toluene (6.29 g) were added to a three-necked flask and mechanically stirred under ice bath conditions. A certain amount of (3,3,3-trifluoropropyl)dichloromethylsilane (4.49 g) was added dropwise to the three-necked flask within 15 min. Stirring was continued under the same conditions for 30 min, and the lower layer of acid water was separated. The same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a F-containing hydrolyzate.

[0118] (3) Condensation of Si-containing hydrolyzate, F-containing hydrolyzate and phenylboric acid

[0119] Dissolve phenylboric acid (8.54 g) in 25 mL of diethylene glycol dimethyl ether, and add it to the Si-containing hydrolyzate and the F-containing hydrolyzate. After the three are fully stirred for 10 minutes, add 1.08 g of p-toluenesulfonic acid as a catalyst, and heat to 50°C for 8 hours. After the reaction is completed, stand and separate the layers, separate the acid water, and evaporate the solvent. Then wash with deionized water and anhydrous ethanol three times (the amount used is twice the volume of the product), and finally dry it at 90°C in vacuum for 24 hours to obtain fluorine- and boron-containing terminal hydroxyl silicone oil.

[0120] The structure of the prepared fluorine- and boron-containing terminal hydroxyl silicone oil is as follows:

[0121]

[0122] Where: x=0.29, y=0.07, z=0.02.

[0123] The fluorine- and boron-containing hydroxy-terminated silicone oil prepared in this example has a weight loss temperature of 5% of 440°C and a glass transition temperature of -139°C.

[0124] Example 6

[0125] A method for preparing fluorine- and boron-containing terminal hydroxyl silicone oil, comprising the following steps:

[0126] (1) Hydrolysis of diphenyldichlorosilane

[0127] Deionized water (52.38 g) and toluene (29.33 g) were added to a three-necked flask and mechanically stirred under ice bath conditions. A certain amount of diphenyldichlorosilane (73.68 g) was added dropwise to the three-necked flask within 15 min. Stirring was continued under the same conditions for 30 min, and the lower layer of acid water was separated. The same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a Si-containing hydrolyzate.

[0128] (2) Hydrolysis of (3,3,3-trifluoropropyl)dichloromethylsilane

[0129] Deionized water (11.24 g) and toluene (6.29 g) were added to a three-necked flask and mechanically stirred under ice bath conditions. A certain amount of (3,3,3-trifluoropropyl)dichloromethylsilane (4.49 g) was added dropwise to the three-necked flask within 15 min. Stirring was continued under the same conditions for 30 min, and the lower layer of acid water was separated. The same amount of deionized water was added for hydrolysis for 30 min, and the acid water was separated to obtain a F-containing hydrolyzate.

[0130] (3) Condensation of Si-containing hydrolyzate, F-containing hydrolyzate and methylboric acid

[0131] Dissolve methylboric acid (8.54 g) in 25 mL N, N-dimethylformamide, and add it to the Si-containing hydrolyzate and the F-containing hydrolyzate. After the three are fully stirred for 10 minutes, add 1.08 g p-toluenesulfonic acid as a catalyst, and heat to 50°C for 8 hours. After the reaction is completed, stand and separate the layers, separate the acid water, and evaporate the solvent, then wash with deionized water and anhydrous ethanol three times (the amount used is twice the volume of the product), and finally dry it at 90°C in vacuum for 24 hours to obtain fluorine- and boron-containing terminal hydroxyl silicone oil.

[0132] The structure of the prepared fluorine- and boron-containing terminal hydroxyl silicone oil is as follows:

[0133]

[0134] Where: x=0.29, y=0.07, z=0.02.

[0135] The fluorine- and boron-containing hydroxy-terminated silicone oil prepared in this example has a weight loss temperature of 5% of 434° C. and a glass transition temperature of -137° C.

[0136] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A fluorine- and boron-containing hydroxyl-terminated silicone oil, characterized in that: The silicone oil structural formula is as follows: Wherein, R1, R2 and R3 are independently methyl or phenyl; x, y, and z all represent mole fractions; x is 0 to 0.5 and is not 0; y is 0.05 to 0.15; and z is 0.02 to 0.

1.

2. The fluorine- and boron-containing hydroxyl-terminated silicone oil according to claim 1, characterized in that: x is 0.2~0.5; y is 0.07~0.13; z is 0.02~0.

05.

3. A method for preparing a fluorine- and boron-containing hydroxyl-terminated silicone oil, characterized in that: The method comprises the following steps: Step 1, hydrolyzing a dichlorosilane compound to obtain a Si-containing hydrolyzate; Hydrolyzing (3,3,3-trifluoropropyl)dichloromethylsilane to obtain a F-containing hydrolyzate; Step 2: subjecting the Si-containing hydrolyzate, the F-containing hydrolyzate and a boron-containing acid to a condensation reaction under the action of a catalyst to obtain the fluorine- and boron-containing terminal hydroxyl silicone oil.

4. The method for preparing the fluorine- and boron-containing terminal hydroxyl silicone oil according to claim 3, characterized in that: The dichlorosilane compound is dimethyldichlorosilane, diphenyldichlorosilane or methylphenyldichlorosilane; the boron-containing acid is methylboric acid or phenylboric acid; and the catalyst is concentrated sulfuric acid or p-toluenesulfonic acid.

5. The method for preparing the fluorine- and boron-containing terminal hydroxyl silicone oil according to claim 3, characterized in that: The molar ratio of the dichlorosilane compound to the (3,3,3-trifluoropropyl)dichloromethylsilane and the boron-containing acid is (0-0.5):(0.05-0.15):(0.02-0.1); the amount of the catalyst used is 1% to 3% of the total molar amount of the dichlorosilane compound, (3,3,3-trifluoropropyl)dichloromethylsilane and the boron-containing acid.

6. The method for preparing the fluorine- and boron-containing hydroxyl-terminated silicone oil according to claim 3, characterized in that: The temperature of the polycondensation reaction is 50-80° C. and the time is 5-7 hours.

7. The method for preparing the fluorine- and boron-containing hydroxyl-terminated silicone oil according to claim 3, characterized in that: When preparing the Si-containing hydrolyzate, dichlorosilane compounds are added to a mixed solution of deionized water and organic solvent A for hydrolysis; the molar ratio of the deionized water to the dichlorosilane compounds is 5-10:1; the amount of the organic solvent A is 56% of the mass of the deionized water; and the organic solvent A is toluene or xylene.

8. The method for preparing fluorine- and boron-containing terminal hydroxyl silicone oil according to claim 3, characterized in that: When preparing the F-containing hydrolyzate, (3,3,3-trifluoropropyl)dichloromethylsilane is added to a mixed solution of deionized water and an organic solvent A for hydrolysis; the molar ratio of the deionized water to the (3,3,3-trifluoropropyl)dichloromethylsilane is 5-10:1; the amount of the organic solvent A is 56% of the mass of the deionized water; and the organic solvent A is toluene or xylene.

9. The method for preparing fluorine- and boron-containing hydroxyl-terminated silicone oil according to claim 3, characterized in that: The solvent used in the polycondensation reaction is one or more of tetrahydrofuran, N,N-dimethylformamide, toluene, 1,4-dioxane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

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