Vinyl silicone oil as well as preparation method and application thereof

Abstract

The invention discloses vinyl silicone oil as well as a preparation method and application thereof, and belongs to the technical field of organic silicon industry. The structural formula of the vinyl silicone oil is shown as a formula (1) or a formula (2), # imgabs 0 # formula (1) and # imgabs 1 # formula (2), the structural formula of M is shown as a formula (3), and in the formula (1), the formula (2) and the formula (3), m is larger than or equal to 3 and smaller than or equal to 2000, n is larger than or equal to 1 and smaller than or equal to 600, and m and n are integers; r1, R2, R3, R4, R5 and R6 can be one or more of methyl, ethyl, vinyl, phenyl and trifluoropropyl. The vinyl silicone oil is uniform in vinyl distribution, can regulate and control the polymerization degree, the vinyl content and the end group, and is wide in application range.

Description

Technical Field

[0001] The present application relates to a vinyl silicone oil and a preparation method and application thereof, belonging to the technical field of organic silicone industry. Background Art

[0002] Silicone rubber has excellent properties such as resistance to high and low temperatures, weather resistance, and radiation resistance. Among them, fluorosilicone rubber also has excellent resistance to chemical media. Polyvinyl silicone oil is an important auxiliary agent for the preparation of silicone rubber. It can play the role of a concentrated cross-linking agent in rubber vulcanization, improve the mechanical properties of silicone rubber such as tear strength, and can be used in high-temperature vulcanized silicone rubber and room temperature vulcanized silicone rubber. The preparation of polyvinyl silicone oil is traditionally carried out by ring-opening copolymerization or co-condensation in the presence of acid or alkali. The reaction time is extended to improve the uniformity of vinyl distribution through the equilibration process. However, due to differences in reaction activity, the vinyl distribution is not uniform. In particular, for the preparation of polyvinyl fluorosilicone oil, methyltrifluoropropylcyclotrisiloxane (D3 F ) and tetramethyltetravinylcyclotetrasiloxane (D4 Vi ) The method of ring-opening copolymerization has a large difference in the polymerization rates of the two ring bodies, and there is also the problem of degradation of the fluorosilicone molecular chain into a ring, and the vinyl chain segments cannot be evenly distributed through the balancing method.

[0003] Chinese patent CN110128657A mentions the preparation of isotactic polyvinyl silicone oil, which uses silane-terminated polysiloxane and alkyl vinyl dialkoxysilane in the presence of tri(pentafluorophenyl)boron as a catalyst to prepare polyvinyl silicone oil, thereby obtaining a uniform vinyl distribution. However, the silane-terminated silicone oil in the raw material has the problem of incomplete end-capping, and the catalyst tri(pentafluorophenyl)boron used is expensive and is not suitable for large-scale preparation.

[0004] Therefore, the polyvinyl silicone oil prepared by the above method has problems such as uneven vinyl distribution, high preparation cost, and unsuitability for large-scale preparation, which affects the preparation and application of the product. Summary of the invention

[0005] In order to solve the above problems, the present application provides a vinyl silicone oil and a preparation method and application thereof. The vinyl group of the vinyl silicone oil is evenly distributed, and its polymerization degree, vinyl content and end group can be regulated, and it has a wide range of applications.

[0006] According to one aspect of the present application, a vinyl silicone oil is provided, wherein the structural formula of the vinyl silicone oil is as shown in Formula (1) or Formula (2),

[0007] Formula (1),

[0008] Formula (2), Wherein, the structural formula of M is shown in formula (3),

[0009] Formula (3), In formula (1), formula (2) and formula (3), 3≤m≤2000, 1≤n≤600, m and n are integers; R1, R2, R3, R4, R5 and R6 can be one or more of methyl, ethyl, vinyl, phenyl and trifluoropropyl.

[0010] Preferably, in formula (1), formula (2) and formula (3), 6≤m≤1000, 1≤n≤200, and m and n are both integers.

[0011] According to another aspect of the present application, a method for preparing the above-mentioned vinyl silicone oil is also provided, comprising the following steps: (1) Mixing terminal hydroxyl silicone oil, methylvinyldichlorosilane and an acid binding agent, stirring and reacting under nitrogen protection to obtain a reaction solution a; (2) adding dimethylvinyl chlorosilane to the reaction solution a and continuing the reaction to obtain a reaction solution b; (3) Add an organic solvent to the reaction solution b, stir evenly, add an alkali solution, stir and react until the system becomes neutral, and obtain a reaction solution c; (4) Add a desiccant to the reaction solution c, stir to dry, and filter to obtain a reaction solution d; (5) The reaction solution d is subjected to reduced pressure distillation to recover the solvent and obtain vinyl silicone oil.

[0012] Specifically, the reaction principle is as follows:

[0013] Optionally, the structural formula of the hydroxyl-terminated silicone oil is as shown in formula (4),

[0014] Formula (4), Among them, 3≤m≤2000, 1≤n≤600, m and n are integers, and R1, R2, R3, R4, R5, and R6 can be one or more of methyl, ethyl, vinyl, phenyl, and trifluoropropyl.

[0015] Preferably, 3≤m≤2000, where m is an integer.

[0016] Specifically, the vinyl content of the vinyl silicone oil is adjusted by using terminal hydroxyl silicone oils with different chain numbers m, so as to obtain vinyl silicone oils with different vinyl contents.

[0017] Preferably, when m=10 and n=100, the vinyl content is 10%; when m=50 and n=100, the vinyl content is 1.9%; when m=1000 and n=100, the vinyl content is 0.1%.

[0018] Optionally, the acid binding agent is selected from one or more of pyridine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, triethylamine, potassium carbonate, ammonium carbonate, and sodium carbonate.

[0019] Optionally, the organic solvent is selected from one or more of acetone, dichloromethane, dioxane, tetrahydrofuran, petroleum ether, cyclohexane, toluene, and trifluoroethanol; the alkali solution is selected from one or more of ammonia water, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, and sodium bicarbonate aqueous solution; the desiccant is selected from one or more of anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous potassium carbonate, anhydrous magnesium sulfate, anhydrous calcium sulfate, molecular sieves, and anhydrous sodium sulfate.

[0020] Optionally, in step (1), the reaction temperature is 0°C to 90°C, the reaction time is 0.5h to 12h; the molar ratio of the methylvinyldichlorosilane to the terminal hydroxyl silicone oil is (1:1) to (1:2); and the mass of the acid binding agent is 1% to 150% of the mass of the methylvinyldichlorosilane.

[0021] Specifically, the present application defines the molar ratio of methylvinyldichlorosilane to terminal hydroxyl silicone oil to ensure that the product structure is controllable. When the molar ratio of methylvinyldichlorosilane to terminal hydroxyl silicone oil is higher than 1, there is an excess of methylvinyldichlorosilane, the end groups form Si-Cl capping, and the product of the expected structure cannot be obtained; when the molar ratio of methylvinyldichlorosilane to terminal hydroxyl silicone oil is lower than 1 / 2, there is not enough methylvinyldichlorosilane to participate in the reaction, resulting in an uncontrollable product structure.

[0022] Specifically, methylvinyldichlorosilane is used as a chain extender. The amount of methylvinyldichlorosilane used affects the polymerization degree n of the vinyl silicone oil. Vinyl silicone oils with different polymerization degrees can be obtained by changing the amount of methylvinyldichlorosilane used.

[0023] Specifically, the mass of the acid binding agent is 10% to 100% of the mass of methylvinyldichlorosilane.

[0024] Optionally, in step (2), the reaction time is 0 h to 12 h; and the mass of the dimethylvinylchlorosilane is 0% to 50% of the mass of the terminal hydroxyl silicone oil.

[0025] Specifically, dimethylvinylchlorosilane is used as a capping agent. When the mass of dimethylvinylchlorosilane is 0, a hydroxy-terminated vinyl silicone oil as shown in formula (1) can be obtained.

[0026] Preferably, the mass of dimethylvinylchlorosilane is 0% to 10% of the mass of the terminal hydroxyl silicone oil.

[0027] Optionally, in step (3), the stirring reaction time is 0.5h~6h; the mass of the organic solvent is 0%~1000% of the mass of the terminal hydroxyl silicone oil; and the mass fraction of the alkali solution is 1%~50%.

[0028] Preferably, the mass of the organic solvent is 0-200% of the mass of the terminal hydroxyl silicone oil, and the mass fraction of the alkali solution is 5%-25%.

[0029] Optionally, in step (4), the stirring and drying time is 1 h to 24 h; the mass of the desiccant is 20% to 500% of the mass of the alkali solution; in step (5), the temperature of the reduced pressure distillation is 30° C. to 150° C., and the time is 1 h to 6 h.

[0030] Preferably, the mass of the desiccant is 20% to 200% of the mass of the alkali solution.

[0031] Specifically, the filtration step in step (4) includes reduced pressure filtration or pressurized filtration.

[0032] Specifically, the solvent recovered in step (5) can be reused.

[0033] According to another aspect of the present application, there is also provided the use of the above-mentioned vinyl silicone oil or the vinyl silicone oil prepared by the above-mentioned preparation method in the preparation of silicone rubber.

[0034] The beneficial effects of this application include but are not limited to: 1. According to the present application, a vinyl silicone oil has a uniform vinyl distribution, and its polymerization degree, vinyl content and terminal group can be regulated, and has a wide range of applications.

[0035] 2. According to a method for preparing vinyl silicone oil of the present application, hydroxy-terminated silicone oil is used as a raw material, methylvinyldichlorosilane is used as a chain extender, and a vinyl silicone oil with a uniform vinyl distribution is prepared through a condensation reaction of Si-OH and Si-Cl; the vinyl content of the polymer is adjusted by using hydroxy-terminated silicone oils with different chain numbers m (or viscosities); dimethylvinylchlorosilane is used as a capping agent, and by controlling the amount of dimethylvinylchlorosilane added, a hydroxy-terminated or vinyl-terminated vinyl silicone oil can be prepared, thereby preparing vinyl silicone oils with different vinyl contents, different molecular weights, and different end groups.

[0036] 3. According to a method for preparing vinyl silicone oil of the present application, methylvinyldichlorosilane is used as a chain extender, and vinyl silicone oil can be prepared quickly and efficiently under mild conditions. The preparation method is simple, the reaction is economical and efficient, and the current problems of low yield and uneven distribution of vinyl in the preparation of vinyl silicone oil are solved.

[0037] 4. According to the preparation method of vinyl silicone oil of the present application, the excess chlorosilane is completely hydrolyzed and neutralized by alkaline solution, thereby avoiding acid or alkali residue and improving the thermal stability of the product; the desiccant is used to adsorb or bind water to remove the moisture in the system, so that various salts are precipitated and then filtered out, thereby avoiding the problem of generating a large amount of industrial wastewater by decompression dehydration or multiple water washings, which is economical and environmentally friendly.

[0038] 5. According to the preparation method of a vinyl silicone oil of the present application, the product yield is high, the product is stable and easy to control, and the quality is good. The prepared vinyl silicone oil can be widely used in liquid silicone rubber, high temperature vulcanized silicone rubber, etc. to improve the polymer cross-linking network and improve the mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings: Figure 1 The vinyl fluorosilicone oil prepared in Example 1 1 HNMR spectrum.

[0040] Figure 2 The vinyl fluorosilicone oil prepared in Example 1 1 A magnified view of a local peak in the HNMR spectrum.

[0041] Figure 3 The vinyl fluorosilicone oil prepared in Example 3 1 HNMR spectrum.

[0042] Figure 4 The vinyl fluorosilicone oil prepared in Example 3 1 A magnified view of a local peak in the HNMR spectrum.

[0043] Figure 5 The vinyl fluorosilicone oil prepared in Example 5 1 HNMR spectrum.

[0044] Figure 6 The vinyl fluorosilicone oil prepared in Example 5 1 A magnified view of a local peak in the HNMR spectrum.

[0045] Figure 7The vinyl fluorosilicone oil prepared in Example 5 29 SiNMR spectrum.

[0046] Figure 8 The vinyl fluorosilicone oil prepared in Comparative Example 1 1 HNMR spectrum.

[0047] Fig. 9 The vinyl fluorosilicone oil prepared in Comparative Example 1 29 SiNMR spectrum. DETAILED DESCRIPTION

[0048] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0049] Unless otherwise specified, the raw materials in the examples and comparative examples of the present application were purchased through commercial channels.

[0050] Unless otherwise specified, the methods used in the examples and comparative examples of the present application are conventional methods in the prior art.

[0051] Example 1 (1) Pour 868.9 g of terminal hydroxyl fluorosilicone oil with a molecular weight of 1870 and a chain number m of 9 to 12 into a 3L four-necked flask, place it in an ice-water bath and stir at constant temperature, add 49.1 g of pyridine under nitrogen protection, stir mechanically for 20 min, add 32.72 g of methylvinyldichlorosilane, stir and react for 12 h to obtain reaction solution a; (2) Add 435 g of dimethylvinylsilyl chloride to the reaction solution a and continue the reaction for 6 h to obtain a reaction solution b; ⑶ Add 276 g of 50% sodium hydroxide aqueous solution to the reaction solution b, and stir the reaction for 6 h until the system becomes neutral to obtain a reaction solution c; (4) Add 1380 g of anhydrous calcium chloride to the reaction solution c, stir and dry for 24 h, and filter to obtain a reaction solution d; (5) The reaction solution d was distilled under reduced pressure at 150°C for 6 h to obtain 916.7 g of the target vinyl fluorosilicone oil.

[0052] The vinyl fluorosilicone oil prepared in this embodiment has a molecular weight of 2000, m=9-12, n=1, and a yield of 96.8%. Figure 1 and Figure 2 The hydrogen nuclear magnetic spectrum shows that the silicone oil terminal group of the vinyl fluorosilicone oil prepared in Example 1 is vinyl, the side chain vinyl is evenly distributed, and the vinyl peak is clear.

[0053] Example 2 ⑴ Take 1000g of terminal hydroxyl fluorosilicone oil with a molecular weight of 9478 and a chain number m=59~62, pour it into a 3L four-necked flask, put it into an oil bath pot and stir it at a constant temperature of 60℃, add 1.5g of potassium carbonate under nitrogen protection, stir mechanically for 20min, add 14.85g of methylvinyldichlorosilane, stir and react for 1h to obtain reaction solution a; (2) Add 10 g of dimethylvinyl chlorosilane to the reaction solution a and continue the reaction for 4 h to obtain a reaction solution b; ⑶ Add 100 g of trifluoroethanol to the reaction solution b, stir evenly, add 1498 g of a 1% sodium carbonate aqueous solution, stir and react for 6 h until the system becomes neutral, to obtain a reaction solution c; (4) Add 300 g of anhydrous sodium sulfate to the reaction solution c, stir and dry for 24 h, and filter to obtain a reaction solution d; (5) The reaction solution d was distilled under reduced pressure at room temperature for 1 h to recover the solvent, and then distilled under reduced pressure at 150°C for 4 h to obtain 993 g of the target vinyl fluorosilicone oil.

[0054] The molecular weight of the vinyl fluorosilicone oil prepared in this example is 761322, m=59-62, n=80, and the yield is 98.9%. The terminal group of the obtained silicone oil is vinyl, and the side chain vinyl is evenly distributed with clear peaks.

[0055] Example 3 ⑴ Pour 1000g of terminal hydroxyl fluorosilicone oil with a molecular weight of 154445 and a chain number m=889~892 into a 3L four-necked flask, put it into an oil bath and stir at 70°C, add 0.61g N,N-diisopropylethylamine under nitrogen protection, stir mechanically for 20min, add 0.608g methylvinyldichlorosilane, stir and react for 3h to obtain reaction solution a; (2) No more dimethylvinyl chlorosilane is added to the reaction solution a to obtain reaction solution b; ⑶ Add 2000 g of acetone to the reaction solution b, stir evenly, add 0.54 g of 25% ammonia water, stir and react for 6 h until the system is neutral, to obtain reaction solution c; (4) Add 1 g of molecular sieve to the reaction solution c, stir and dry for 2 h, and filter to obtain the reaction solution d; (5) The reaction solution d was distilled under reduced pressure at room temperature for 1 h to recover the solvent, and then distilled under reduced pressure at 150° C. for 4 h to obtain 992 g of the target hydroxyl-terminated vinyl fluorosilicone oil.

[0056] The vinyl fluorosilicone oil prepared in this embodiment has a molecular weight of 309190, m=889-892, n=2, and a yield of 99.1%. Figure 3 and Figure 4 The hydrogen nuclear magnetic spectrum shows that the terminal group of the obtained silicone oil is hydroxyl, the side chain vinyl is evenly distributed, and the peaks are clear.

[0057] Example 4 ⑴ Pour 1000g of 20% phenyl silicone oil with terminal hydroxyl group and molecular weight of 6102 and chain number m=69~72 into a 3L four-necked flask, put it into an oil bath pot and stir at 50℃, add 33g of triethylamine under nitrogen protection, stir mechanically for 20min, add 23g of methylvinyldichlorosilane, stir and react for 2h to obtain reaction solution a; (2) Add 39.4 g of dimethylvinyl chlorosilane to the reaction solution a and continue the reaction for 2 h to obtain a reaction solution b; ⑶ Add 274 g of 10% sodium bicarbonate aqueous solution to the reaction solution b, and stir to react for 1 h until the system becomes neutral to obtain a reaction solution c; (4) Add 100 g of molecular sieves to the reaction solution c, stir and dry for 24 h, and filter to obtain the reaction solution d; (5) The reaction solution d was distilled under reduced pressure at 150°C for 4 h to obtain 1020 g of the target vinylphenyl silicone oil.

[0058] The molecular weight of the vinylphenyl silicone oil prepared in this example is 241920, m=69-72, n=40, and the yield is 98.2%. The terminal group of the obtained silicone oil is vinyl, the side chain vinyl is evenly distributed, and the vinyl peak is clear.

[0059] Example 5 ⑴ Pour 1000g of terminal hydroxyl fluorosilicone oil with a molecular weight of 6118 and a chain number m=39~42 into a 3L four-necked flask, put it into an oil bath and stir at a constant temperature of 50°C, add 33g of triethylamine under nitrogen protection, stir mechanically for 20min, add 23g of methylvinyldichlorosilane, stir and react for 6h to obtain reaction solution a; (2) Add 39.4 g of dimethylvinyl chlorosilane to the reaction solution a and continue the reaction for 2 h to obtain a reaction solution b; ⑶ Add 200 g of dioxane to the reaction solution b, stir evenly, add 274 g of a 10% sodium bicarbonate aqueous solution, stir and react for 1 h until the system becomes neutral, to obtain a reaction solution c; (4) Add 300 g of anhydrous magnesium sulfate to the reaction solution c, stir and dry for 24 h, and filter to obtain a reaction solution d; (5) The reaction solution d was distilled under reduced pressure at room temperature for 2 h, the solvent was recovered, and then distilled under reduced pressure at 150°C for 4 h to obtain 1017 g of the target vinyl fluorosilicone oil.

[0060] The vinyl fluorosilicone oil prepared in this embodiment has a molecular weight of 489500, m=39-42, n=80, and a yield of 97.8%. Figure 5 and Figure 6 1The HNMR spectrum shows that the obtained silicone oil is vinyl-terminated, and the side vinyl groups are evenly distributed with clear vinyl peaks. Figure 7 29 From the SiNMR spectrum, it can be seen that the obtained silicone oil has a characteristic peak of terminal vinyl silicon at δ=-2.10 and a characteristic peak of independent side vinyl silicon at δ=-33.71, indicating that the vinyl group is evenly distributed in the molecular chain.

[0061] Example 6 ⑴ Pour 1000g of terminal hydroxy dimethyl silicone oil with a molecular weight of 3000 and a chain number m=39~42 into a 3L four-necked flask, put it into an oil bath pot and stir at a constant temperature of 50℃, add 33g of triethylamine under nitrogen protection, stir mechanically for 20min, add 47g of methylvinyldichlorosilane, stir and react for 10h to obtain reaction solution a; (2) Add 39.4 g of dimethylvinyl chlorosilane to the reaction solution a and continue the reaction for 2 h to obtain a reaction solution b; ⑶ Add 1000 g of toluene to the reaction solution b, stir evenly, add 560 g of a 10% sodium bicarbonate aqueous solution, stir and react for 1 h until the system becomes neutral, to obtain a reaction solution c; (4) Add 560 g of anhydrous magnesium sulfate to the reaction solution c, stir and dry for 24 h, and filter to obtain a reaction solution d; (5) The reaction solution d was distilled under reduced pressure at room temperature for 2 h, the solvent was recovered, and then distilled under reduced pressure at 150°C for 4 h to obtain 1025 g of the target vinyl silicone oil.

[0062] The molecular weight of the vinyl silicone oil prepared in this example is 600000, m=39-42, n=200, and the yield is 98.6%. The terminal group of the obtained silicone oil is vinyl, the side chain vinyl is evenly distributed, and the vinyl peak is clear.

[0063] Example 7 ⑴ Pour 1000g of terminal hydroxyl fluorosilicone oil with a molecular weight of 9478 and a chain number m=59~62 into a 3L four-necked flask, place it in an oil bath and stir at a constant temperature of 60°C, add 0.15g of potassium carbonate under nitrogen protection, stir mechanically for 20min, add 14.85g of methylvinyldichlorosilane, stir and react for 1h to obtain reaction solution a; (2) Add 10 g of dimethylvinyl chlorosilane to the reaction solution a and continue the reaction for 4 h to obtain a reaction solution b; ⑶ Add 10000 g of trifluoroethanol to the reaction solution b, stir evenly, add 1498 g of 1% sodium carbonate aqueous solution, stir and react for 6 h until the system is neutral, to obtain reaction solution c; (4) Add 300 g of anhydrous sodium sulfate to the reaction solution c, stir and dry for 24 h, and filter to obtain a reaction solution d; (5) The reaction solution d was distilled under reduced pressure at room temperature for 1 h to recover the solvent, and then distilled under reduced pressure at 150°C for 4 h to obtain 993 g of the target vinyl fluorosilicone oil.

[0064] The molecular weight of the vinyl fluorosilicone oil prepared in this example is 759900, m=59-62, n=80, and the yield is 98.9%. The terminal group of the obtained silicone oil is vinyl, and the side chain vinyl is evenly distributed with clear peaks.

[0065] Comparative Example 1 ⑴ Pour 400g of trifluoropropyl cyclotrisiloxane, 519g of tetramethyltetravinylcyclotetrasiloxane, 181g of octamethylcyclotetrasiloxane and 8g of tetramethyldivinyldisiloxane into a 3L four-necked flask, add 0.1g of tetramethylammonium hydroxide, put into an oil bath and stir at a constant temperature of 50°C, dehydrate under reduced pressure for 1h; then heat to 100°C under nitrogen protection, stir and react for 3h; then raise the temperature to 150°C for 1h to break the catalyst, then heat to 180°C and reduce pressure for 5h to remove low boiling points to obtain 956g of vinyl fluorosilicone oil.

[0066] In this comparative example 1, a vinyl fluorosilicone oil was prepared by a conventional method in the art with a yield of 86.3%. Figure 8 and Fig. 9 As shown, 1 HNMR and 29 SiNMR characterization revealed that the silicone oil has a complex structure and contains multiple adjacent CH3-Si-CH=CH2 chains. This is because methyltrifluoropropylcyclotrisiloxane (D3 F ) has a significant difference in ring-opening activity with the methyl ring body. The Si-O bond connected to the trifluoropropyl group is more likely to break, resulting in the breaking, rearrangement and ring formation of the fluorosilicon chain segments, which increases the ring body content in the polymer and reduces the yield. At the same time, the vinyl chain segments are not effectively rearranged and are evenly distributed in the polymer chain.

[0067] The vinyl silicone oil prepared in Examples 1 to 7 of the present application has a uniform distribution of side vinyl groups and clear peaks. The structural formula of the terminal hydroxyl silicone oil used in the preparation process is shown in Formula (4):

[0068] Formula (4), Among them, 3≤m≤2000, 1≤n≤600, m and n are integers, R1, R2, R3, R4, R5, and R6 can be one or more of methyl, ethyl, vinyl, phenyl, and trifluoropropyl, all of which can realize the present application. Since the above-mentioned groups involve many types of raw materials, the present application will no longer list them one by one. On the basis of clarifying the technical concept of the present application, those skilled in the art can infer that the above-mentioned terminal hydroxyl silicone oils can realize the present application and achieve the above-mentioned effects.

[0069] The above is only the embodiment of the present application, and the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application can have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.

Claims

1. A vinyl silicone oil, characterized in that: The structural formula of the vinyl silicone oil is shown in formula (1) or formula (2), Formula (1), Formula (2), Wherein, the structural formula of M is shown in formula (3), Formula (3), In formula (1), formula (2) and formula (3), 3≤m≤2000, 1≤n≤600, m and n are integers; R1, R2, R3, R4, R5 and R6 can be one or more of methyl, ethyl, vinyl, phenyl and trifluoropropyl.

2. The method for preparing a vinyl silicone oil according to claim 1, characterized in that: The following steps are involved: (1) Mixing terminal hydroxyl silicone oil, methylvinyldichlorosilane and an acid binding agent, stirring and reacting under nitrogen protection to obtain a reaction solution a; (2) adding dimethylvinyl chlorosilane to the reaction solution a and continuing the reaction to obtain a reaction solution b; (3) Add an organic solvent to the reaction solution b, stir evenly, add an alkali solution, stir and react until the system becomes neutral, and obtain a reaction solution c; (4) Add a desiccant to the reaction solution c, stir to dry, and filter to obtain a reaction solution d; (5) The reaction solution d is subjected to reduced pressure distillation to recover the solvent and obtain vinyl silicone oil.

3. The method for preparing vinyl silicone oil according to claim 2, characterized in that: The structural formula of the hydroxyl-terminated silicone oil is shown in formula (4), Formula (4), Among them, 3≤m≤2000, 1≤n≤600, m and n are integers, and R1, R2, R3, R4, R5, and R6 can be one or more of methyl, ethyl, vinyl, phenyl, and trifluoropropyl.

4. The method for preparing a vinyl silicone oil according to claim 2, characterized in that: The acid binding agent is selected from one or more of pyridine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, triethylamine, potassium carbonate, ammonium carbonate and sodium carbonate.

5. The method for preparing a vinyl silicone oil according to claim 2, characterized in that: The organic solvent is selected from one or more of acetone, dichloromethane, dioxane, tetrahydrofuran, petroleum ether, cyclohexane, toluene, and trifluoroethanol; the alkali solution is selected from one or more of ammonia water, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, and sodium bicarbonate aqueous solution; the desiccant is selected from one or more of anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous potassium carbonate, anhydrous magnesium sulfate, anhydrous calcium sulfate, molecular sieves, and anhydrous sodium sulfate.

6. The method for preparing vinyl silicone oil according to claim 2, characterized in that: In step (1), the reaction temperature is 0°C to 90°C, and the reaction time is 0.5h to 12h; the molar ratio of the methylvinyldichlorosilane to the terminal hydroxyl silicone oil is (1:1) to (1:2); and the mass of the acid binding agent is 1% to 150% of the mass of the methylvinyldichlorosilane.

7. The method for preparing vinyl silicone oil according to claim 2, characterized in that: In step (2), the reaction time is 0 h to 12 h; the mass of the dimethylvinylchlorosilane is 0% to 50% of the mass of the terminal hydroxyl silicone oil.

8. The method for preparing vinyl silicone oil according to claim 2, characterized in that: In step (3), the stirring reaction time is 0.5h~6h; the mass of the organic solvent is 0%~1000% of the mass of the terminal hydroxyl silicone oil; and the mass fraction of the alkali solution is 1%~50%.

9. The method for preparing vinyl silicone oil according to claim 2, characterized in that: In step (4), the stirring and drying time is 1 h to 24 h; the mass of the desiccant is 20% to 500% of the mass of the alkali solution; in step (5), the temperature of the reduced pressure distillation is 30° C. to 150° C., and the time is 1 h to 6 h.

10. Use of the vinyl silicone oil according to claim 1 or the vinyl silicone oil prepared by the preparation method according to any one of claims 2 to 9 in the preparation of silicone rubber.

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