A vinyl silicone oil, its preparation method and application

Abstract

The present application discloses a vinyl silicone oil, a preparation method thereof and an application thereof, belonging to the technical field of organosilicon industry. The structural formula of the vinyl silicone oil is shown in Formula (1) or Formula (2), #imgabs0#Formula (1), #imgabs1#Formula (2), wherein the structural formula of M is shown in Formula (3), #imgabs2#Formula (3). In Formula (1), Formula (2) and Formula (3), 3 ≤ m ≤ 2000, 1 ≤ n ≤ 600, and m and n are both integers; R1, R2, R3, R4, R5, and R6 can be one or several of methyl, ethyl, vinyl, phenyl, and trifluoropropyl. The vinyl silicone oil has a uniform vinyl distribution, can regulate its degree of polymerization, vinyl content and end groups, and has a wide range of applications.

Description

Technical Field

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

[0002] Silicone rubber has excellent properties such as resistance to high and low temperatures, weather resistance, radiation resistance, etc. Among them, fluorosilicone rubber also has excellent chemical medium resistance. Polyvinyl silicone oil is an important additive for preparing silicone rubber, which can act as a concentrated cross-linking agent in rubber vulcanization, improve the mechanical properties such as tear strength of silicone rubber, and can be applied in both high-temperature vulcanized silicone rubber and room-temperature vulcanized silicone rubber. Traditionally, polyvinyl silicone oil is prepared 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 a equilibration process. However, due to the difference in reaction activity, the vinyl distribution is not uniform. Especially for the preparation of polyvinyl fluorosilicone oil, usually methyltrifluoropropylcyclotrisiloxane (D3 F ), and tetramethyltetravinylcyclotetrasiloxane (D4 Vi ) are used for ring-opening copolymerization. The polymerization rates of the two cyclic monomers are quite different, and there is also a problem of ring degradation of fluorosilicone molecular chains. The vinyl chain segments cannot be evenly distributed by the equilibration method.

[0003] Chinese Patent CN110128657A mentions the preparation of isotactic polyvinyl silicone oil. Polyhydrosiloxane terminated with silicon hydride and alkyl vinyl dialkoxysilane are used to prepare polyvinyl silicone oil in the presence of tris(pentafluorophenyl)boron catalyst, and a uniform vinyl distribution is obtained. However, the silicone oil terminated with silicon hydride in its raw materials has the problem of incomplete end-capping, and the used catalyst tris(pentafluorophenyl)boron is expensive and not suitable for large-scale preparation.

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

[0005] In order to solve the above problems, the present application provides a vinyl silicone oil, a preparation method thereof and an application thereof. The vinyl silicone oil has a uniform vinyl distribution, can regulate its degree of polymerization, vinyl content and end groups, and has a wide range of applications.

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

[0007]

[0008] Formula (1),

[0009]

[0010] Formula (2),

[0011] wherein the structural formula of M is as shown in Formula (3),

[0012]

[0013] Formula (3),

[0014] In Formulas (1), (2), and (3), 3 ≤ m ≤ 2000, 1 ≤ n ≤ 600, and both m and n are integers; R1, R2, R3, R4, R5, and R6 can be one or more of methyl, ethyl, vinyl, phenyl, and trifluoropropyl.

[0015] Preferably, in Formulas (1), (2), and (3), 6 ≤ m ≤ 1000, 1 ≤ n ≤ 200, and both m and n are integers.

[0016] According to another aspect of the present application, there is also provided a method for preparing the above vinyl silicone oil, comprising the following steps:

[0017] (1) Mix the hydroxyl-terminated silicone oil with methylvinyl dichlorosilane and an acid-binding agent, and stir and react under nitrogen protection to obtain reaction solution a;

[0018] (2) Add dimethylvinylchlorosilane to reaction solution a and continue to react to obtain reaction solution b;

[0019] (3) Add an organic solvent to reaction solution b, stir evenly, add an alkali solution, and stir and react until the system is neutral to obtain reaction solution c;

[0020] (4) Add a desiccant to reaction solution c, stir and dry, and filter to obtain reaction solution d;

[0021] (5) Perform vacuum distillation on reaction solution d to recover the solvent and obtain vinyl silicone oil.

[0022] Specifically, the reaction principle is as follows:

[0023]

[0024] Optionally, the structural formula of the hydroxyl-terminated silicone oil is as shown in Formula (4),

[0025]

[0026] Formula (4),

[0027] wherein, 3 ≤ m ≤ 2000, 1 ≤ n ≤ 600, both 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.

[0028] Preferably, 3 ≤ m ≤ 2000, where m is an integer.

[0029] Specifically, by using terminal hydroxyl silicone oil with different numbers of chain links m, the vinyl content of vinyl silicone oil is regulated to obtain vinyl silicone oil with different vinyl contents.

[0030] Preferably, when m = 10 and n = 100, the vinyl content = 10%; when m = 50 and n = 100, the vinyl content = 1.9%; when m = 1000 and n = 100, the vinyl content = 0.1%.

[0031] 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.

[0032] 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 sieve, and anhydrous sodium sulfate.

[0033] Optionally, in step (1), the reaction temperature is 0°C to 90°C, and the reaction time is 0.5 h to 12 h; the molar ratio of methylvinyl dichlorosilane to terminal hydroxyl silicone oil is (1:1) to (1:2); the mass of the acid-binding agent is 1% to 150% of the mass of methylvinyl dichlorosilane.

[0034] Specifically, the present application limits the molar ratio of methylvinyl dichlorosilane to terminal hydroxyl silicone oil to ensure controllable product structure. When the molar ratio of methylvinyl dichlorosilane to terminal hydroxyl silicone oil is higher than 1, methylvinyl dichlorosilane is in excess, and the end group forms Si - Cl capping, resulting in a product with an unexpected structure; when the molar ratio of methylvinyl dichlorosilane to terminal hydroxyl silicone oil is lower than 1 / 2, there is not enough methylvinyl dichlorosilane participating in the reaction, leading to an uncontrollable product structure.

[0035] Specifically, methylvinyl dichlorosilane is used as a chain extender, and the amount of methylvinyl dichlorosilane affects the degree of polymerization n of vinyl silicone oil. By changing the amount of methylvinyl dichlorosilane, vinyl silicone oil with different degrees of polymerization can be obtained.

[0036] Specifically, the mass of the acid-binding agent is 10% to 100% of the mass of methylvinyl dichlorosilane.

[0037] Optionally, 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 hydroxyl-terminated silicone oil.

[0038] Specifically, dimethylvinylchlorosilane is used as a capping agent. When the mass of dimethylvinylchlorosilane is 0, the hydroxyl-terminated vinyl silicone oil shown in formula (1) can be obtained.

[0039] Preferably, the mass of dimethylvinylchlorosilane is 0% to 10% of the mass of the hydroxyl-terminated silicone oil.

[0040] Optionally, in step (3), the stirring reaction time is 0.5 h to 6 h; the mass of the organic solvent is 0% to 1000% of the mass of the hydroxyl-terminated silicone oil; the mass fraction of the alkali solution is 1% to 50%.

[0041] Preferably, the mass of the organic solvent is 0 to 200% of the mass of the hydroxyl-terminated silicone oil, and the mass fraction of the alkali solution is 5% to 25%.

[0042] 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 vacuum distillation is 30 °C to 150 °C, and the time is 1 h to 6 h.

[0043] Preferably, the mass of the desiccant is 20% to 200% of the mass of the alkali solution.

[0044] Specifically, the filtration step in step (4) includes vacuum filtration or pressure filtration.

[0045] Specifically, the solvent recovered in step (5) can be reused.

[0046] 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.

[0047] The beneficial effects of the present application include but are not limited to:

[0048] 1. According to a vinyl silicone oil of the present application, the vinyl distribution of the vinyl silicone oil is uniform, and its degree of polymerization, vinyl content and end groups can be regulated, and the application range is wide.

[0049] 2. A method for preparing vinyl silicone oil according to the present application uses hydroxyl-terminated silicone oil as a raw material and methylvinyl dichlorosilane as a chain extender to prepare vinyl silicone oil with a uniform vinyl distribution through the condensation reaction of Si-OH and Si-Cl; by using hydroxyl-terminated silicone oils with different numbers of chain links m (or viscosities), the vinyl content of the polymer can be adjusted; dimethylvinylchlorosilane is used as a capping agent, and by controlling the addition amount of dimethylvinylchlorosilane, vinyl silicone oil with hydroxyl-terminated or vinyl-terminated can be prepared, thereby obtaining vinyl silicone oils with different vinyl contents, different molecular weights, and different end groups.

[0050] 3. A method for preparing vinyl silicone oil according to the present application uses methylvinyl dichlorosilane as a chain extender, which can rapidly and efficiently prepare vinyl silicone oil under mild conditions. The preparation method is simple, the reaction is economical and efficient, and it solves the problems of low yield and uneven vinyl distribution in the current preparation of vinyl silicone oil.

[0051] 4. A method for preparing vinyl silicone oil according to the present application completely hydrolyzes and neutralizes the excessive chlorosilane with lye, avoiding the residue of acid or alkali, and improving the thermal stability of the product; by using a desiccant to adsorb or combine with water to remove the moisture in the system, various salts are precipitated and then filtered off, avoiding the problem of generating a large amount of industrial wastewater by vacuum dehydration or multiple water washes, which is economical and environmentally friendly.

[0052] 5. A method for preparing vinyl silicone oil according to the present application has a high product yield, the product is stable and easy to control, and has good quality. The prepared vinyl silicone oil can be widely used in liquid silicone rubber, high-temperature vulcanized silicone rubber, etc. to improve the polymer crosslinking network and mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] 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 to the present application. In the drawings:

[0054] Figure 1 The 1 HNMR spectrum of the vinyl fluorosilicone oil prepared in Example 1.

[0055] Figure 2 The 1 Enlarged view of a partial peak in the HNMR spectrum of the vinyl fluorosilicone oil prepared in Example 1.

[0056] Figure 3 The 1 HNMR spectrum of the vinyl fluorosilicone oil prepared in Example 3.

[0057] Figure 4The local peak magnification diagram in the 1 HNMR spectrum of the vinyl fluorosilicone oil prepared in Example 3.

[0058] Figure 5 The 1 HNMR spectrum of the vinyl fluorosilicone oil prepared in Example 5.

[0059] Figure 6 The 1 local peak magnification diagram in the HNMR spectrum of the vinyl fluorosilicone oil prepared in Example 5.

[0060] Figure 7 The 29 SiNMR spectrum of the vinyl fluorosilicone oil prepared in Example 5.

[0061] Figure 8 The 1 HNMR spectrum of the vinyl fluorosilicone oil prepared in Comparative Example 1.

[0062] Figure 9 The 29 SiNMR spectrum of the vinyl fluorosilicone oil prepared in Comparative Example 1. Specific Embodiments

[0063] The present application will be described in detail below in conjunction with the embodiments, but the present application is not limited to these embodiments.

[0064] Unless otherwise specified, the raw materials in the embodiments and comparative examples of the present application are purchased through commercial channels.

[0065] Unless otherwise specified, the methods used in the embodiments and comparative examples of the present application are conventional methods in the prior art.

[0066] Example 1

[0067] ⑴ Pour 868.9 g of hydroxyl-terminated fluorosilicone oil with a molecular weight of 1870 and a chain segment number m of 9 - 12 into a 3 L four-necked flask, place it in an ice-water bath and stir constantly at a constant temperature. Under nitrogen protection, add 49.1 g of pyridine, stir mechanically for 20 min, add 32.72 g of methylvinyldichlorosilane, and stir and react for 12 h to obtain reaction solution a;

[0068] ⑵ Add 435 g of dimethylethenylchlorosilane to reaction solution a and continue to react for 6 h to obtain reaction solution b;

[0069] ⑶ Add 276 g of a 50% sodium hydroxide aqueous solution to reaction solution b, stir and react for 6 h until the system is neutral to obtain reaction solution c;

[0070] ⑷ Add 1380 g of anhydrous calcium chloride to reaction solution c, stir and dry for 24 h, filter to obtain reaction solution d;

[0071] ⑸ 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.

[0072] The vinyl fluorosilicone oil prepared in this example had a molecular weight of 2000, m = 9 - 12, n = 1, and a yield of 96.8%. From Figure 1 and Figure 2 the 1H NMR spectrum, it can be seen that the silicone oil end groups of the vinyl fluorosilicone oil prepared in Example 1 were vinyl groups, the vinyl groups on the side chains were evenly distributed, and the vinyl peaks were distinct.

[0073] Example 2

[0074] ⑴ 1000 g of a hydroxyl-terminated fluorosilicone oil with a molecular weight of 9478 and a chain link number m = 59 - 62 was poured into a 3 L four-necked flask, placed in an oil bath at 60 °C and stirred constantly. Under nitrogen protection, 1.5 g of potassium carbonate was added, and mechanical stirring was carried out for 20 min. Then 14.85 g of methylvinyl dichlorosilane was added, and the reaction was stirred for 1 h to obtain reaction solution a;

[0075] ⑵ 10 g of dimethylvinylchlorosilane was added to reaction solution a, and the reaction was continued for 4 h to obtain reaction solution b;

[0076] ⑶ 100 g of trifluoroethanol was added to reaction solution b and stirred evenly. Then 1498 g of a 1% sodium carbonate aqueous solution was added, and the reaction was stirred for 6 h until the system was neutral to obtain reaction solution c;

[0077] ⑷ 300 g of anhydrous sodium sulfate was added to reaction solution c, and the mixture was stirred and dried for 24 h, then filtered to obtain reaction solution d;

[0078] ⑸ 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.

[0079] The vinyl fluorosilicone oil prepared in this example had a molecular weight of 761322, m = 59 - 62, n = 80, and a yield of 98.9%. The obtained silicone oil end groups were vinyl groups, and the vinyl groups on the side chains were evenly distributed and the peaks were distinct.

[0080] Example 3

[0081] ⑴ 1000 g of a hydroxyl-terminated fluorosilicone oil with a molecular weight of 154445 and a chain link number m = 889 - 892 was poured into a 3 L four-necked flask, placed in an oil bath at 70 °C and stirred constantly. Under nitrogen protection, 0.61 g of N,N - diisopropylethylamine was added, and mechanical stirring was carried out for 20 min. Then 0.608 g of methylvinyl dichlorosilane was added, and the reaction was stirred for 3 h to obtain reaction solution a;

[0082] ⑵ Dimethylvinylchlorosilane was not added to this reaction solution a to obtain reaction solution b;

[0083] ⑶ Add 2000 g of acetone to the reaction solution b, stir evenly, add 0.54 g of 25% ammonia water by mass, stir and react for 6 h until the system is neutral to obtain the reaction solution c;

[0084] ⑷ Add 1 g of molecular sieve to the reaction solution c, stir and dry for 2 h, filter to obtain the reaction solution d;

[0085] ⑸ Distill the reaction solution d under reduced pressure at room temperature for 1 h to recover the solvent, and then distill it under reduced pressure at 150 °C for 4 h to obtain 992 g of the target vinyl fluorosilicone oil with hydroxyl end groups.

[0086] The vinyl fluorosilicone oil prepared in this example has a molecular weight of 309190, m = 889 - 892, n = 2, and a yield of 99.1%. From Figure 3 and Figure 4 The 1H NMR spectrum shows that the end groups of the obtained silicone oil are hydroxyl groups, the vinyl groups on the side chains are evenly distributed, and the splitting peaks are relatively clear.

[0087] Example 4

[0088] ⑴ Pour 1000 g of hydroxyl-terminated 20% phenyl silicone oil with a molecular weight of 6102 and a chain link number m = 69 - 72 into a 3 L four-necked flask, place it in an oil bath at 50 °C and stir constantly. Under nitrogen protection, add 33 g of triethylamine, stir mechanically for 20 min, add 23 g of methylvinyldichlorosilane, and stir and react for 2 h to obtain the reaction solution a;

[0089] ⑵ Add 39.4 g of dimethylvinylchlorosilane to the reaction solution a and continue to react for 2 h to obtain the reaction solution b;

[0090] ⑶ Add 274 g of 10% sodium bicarbonate aqueous solution to the reaction solution b, stir and react for 1 h until the system is neutral to obtain the reaction solution c;

[0091] ⑷ Add 100 g of molecular sieve to the reaction solution c, stir and dry for 24 h, filter to obtain the reaction solution d;

[0092] ⑸ Distill the reaction solution d under reduced pressure at 150 °C for 4 h to obtain 1020 g of the target vinyl phenyl silicone oil.

[0093] The vinyl phenyl silicone oil prepared in this example has a molecular weight of 241920, m = 69 - 72, n = 40, and a yield of 98.2%. The end groups of the obtained silicone oil are vinyl groups, the vinyl groups on the side chains are evenly distributed, and the vinyl splitting peaks are clear.

[0094] Example 5

[0095] ⑴ Take 1000 g of hydroxyl-terminated fluorosilicone oil with a molecular weight of 6118 and a number of chain segments m = 39 - 42 and pour it into a 3 L four-necked flask. Place it in an oil bath and stir at a constant temperature of 50 °C. Under nitrogen protection, add 33 g of triethylamine and stir mechanically for 20 min. Then add 23 g of methylvinyl dichlorosilane and stir and react for 6 h to obtain reaction solution a;

[0096] ⑵ Add 39.4 g of dimethylvinylchlorosilane to reaction solution a and continue to react for 2 h to obtain reaction solution b;

[0097] ⑶ Add 200 g of dioxane to reaction solution b, stir evenly, add 274 g of 10% sodium bicarbonate aqueous solution, stir and react for 1 h until the system is neutral to obtain reaction solution c;

[0098] ⑷ Add 300 g of anhydrous magnesium sulfate to reaction solution c, stir and dry for 24 h, then filter to obtain reaction solution d;

[0099] ⑸ Distill reaction solution d under reduced pressure at room temperature for 2 h to recover the solvent, and then distill it under reduced pressure at 150 °C for 4 h to obtain 1017 g of the target vinyl fluorosilicone oil.

[0100] The vinyl fluorosilicone oil prepared in this example has a molecular weight of 489500, m = 39 - 42, n = 80, and a yield of 97.8%. From Figure 5 and Figure 6 1 the HNMR spectrum, it can be seen that the obtained silicone oil is terminated with vinyl, and the vinyl side groups are evenly distributed and the vinyl peaks are distinct; from Figure 7 29 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 is evenly distributed in the molecular chain.

[0101] Example 6

[0102] ⑴ Take 1000 g of hydroxyl-terminated dimethyl silicone oil with a molecular weight of 3000 and a number of chain segments m = 39 - 42 and pour it into a 3 L four-necked flask. Place it in an oil bath and stir at a constant temperature of 50 °C. Under nitrogen protection, add 33 g of triethylamine and stir mechanically for 20 min. Then add 47 g of methylvinyl dichlorosilane and stir and react for 10 h to obtain reaction solution a;

[0103] ⑵ Add 39.4 g of dimethylvinylchlorosilane to reaction solution a and continue to react for 2 h to obtain reaction solution b;

[0104] ⑶ Add 1000 g of toluene to reaction solution b, stir evenly, add 560 g of 10% sodium bicarbonate aqueous solution, stir and react for 1 h until the system is neutral to obtain reaction solution c;

[0105] ⑷ Add 560 g of anhydrous magnesium sulfate to the reaction solution c, stir and dry for 24 h, then filter to obtain the reaction solution d;

[0106] ⑸ Distill the reaction solution d under reduced pressure at room temperature for 2 h to recover the solvent, and then distill it under reduced pressure at 150 °C for 4 h to obtain 1025 g of the target vinyl silicone oil.

[0107] The vinyl silicone oil prepared in this example has a molecular weight of 600000, m = 39 - 42, n = 200, a yield of 98.6%, the end groups of the obtained silicone oil are vinyl groups, the vinyl groups on the side chains are evenly distributed, and the vinyl peaks are distinct.

[0108] Example 7

[0109] ⑴ Pour 1000 g of hydroxyl-terminated fluorosilicone oil with a molecular weight of 9478 and the number of chain segments m = 59 - 62 into a 3 L four-necked flask, place it in an oil bath at 60 °C and stir constantly. Under nitrogen protection, add 0.15 g of potassium carbonate, stir mechanically for 20 min, then add 14.85 g of methylvinyl dichlorosilane, and stir and react for 1 h to obtain the reaction solution a;

[0110] ⑵ Add 10 g of dimethylvinylchlorosilane to the reaction solution a and continue to react for 4 h to obtain the reaction solution b;

[0111] ⑶ Add 10000 g of trifluoroethanol to the reaction solution b, stir evenly, then add 1498 g of a 1% sodium carbonate aqueous solution, stir and react for 6 h until the system is neutral to obtain the reaction solution c;

[0112] ⑷ Add 300 g of anhydrous sodium sulfate to the reaction solution c, stir and dry for 24 h, then filter to obtain the reaction solution d;

[0113] ⑸ Distill the reaction solution d under reduced pressure at room temperature for 1 h to recover the solvent, and then distill it under reduced pressure at 150 °C for 4 h to obtain 993 g of the target vinyl fluorosilicone oil.

[0114] The vinyl fluorosilicone oil prepared in this example has a molecular weight of 759900, m = 59 - 62, n = 80, a yield of 98.9%, the end groups of the obtained silicone oil are vinyl groups, the vinyl groups on the side chains are evenly distributed and the peaks are distinct.

[0115] Comparative Example 1

[0116] ⑴ Pour 400 g of trifluoropropylcyclotrisiloxane, 519 g of tetramethyltetravinylcyclotetrasiloxane, 181 g of octamethylcyclotetrasiloxane, and 8 g of tetramethyldivinyldisiloxane into a 3 L four-necked flask. Add 0.1 g of tetramethylammonium hydroxide, place it in an oil bath at 50 °C and stir constantly. Dehydrate under reduced pressure for 1 h. Then, under nitrogen protection, raise the temperature to 100 °C and stir for 3 h. Then raise the temperature to 150 °C and react for 1 h to break the catalyst. Subsequently, raise the temperature to 180 °C and reduce the pressure for 5 h to remove low boilers, obtaining 956 g of vinyl fluorosilicone oil.

[0117] In Comparative Example 1, a vinyl fluorosilicone oil was prepared by a conventional method in the art, with a yield of 86.3%. As Figure 8 and Figure 9 shown, through 1 HNMR and 29 SiNMR characterization, we found that the structure of this silicone oil is complex and contains a structure with multiple adjacent CH3-Si-CH=CH2 linkages. This is because the ring-opening activities of methyltrifluoropropylcyclotrisiloxane (D3 F ) and methylcyclosiloxane are quite different. The Si-O bond connected to the trifluoropropyl group is more likely to break, resulting in the breakage, rearrangement, and cyclization of fluorosilicon linkages, increasing the content of cyclic siloxanes in the polymer. While the yield decreases, the vinyl linkages are not effectively rearranged and evenly distributed in the polymer chain.

[0118] In Examples 1 to 7 of the present application, the side vinyl groups of the prepared vinyl silicone oil are evenly distributed and the peaks are distinct. The structural formula of the hydroxyl-terminated silicone oil used in the preparation process is as shown in Formula (4).

[0119]

[0120] Formula (4)

[0121] Among them, 3 ≤ m ≤ 2000, 1 ≤ n ≤ 600, and m and n are both integers. R1, R2, R3, R4, R5, and R6 can be one or several of methyl, ethyl, vinyl, phenyl, and trifluoropropyl, all of which can implement the present application. Since there are many types of raw materials involved in the above groups, they are not listed one by one in the present application. Those skilled in the art can infer that the above hydroxyl-terminated silicone oils can all implement the present application and achieve the above effects on the basis of clarifying the technical concept of the present application.

[0122] The above is only the embodiments of the present application. 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 modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application shall be included within 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, 2≤n≤600, m and n are integers; R1, R2, R3, R4, R5 and R6 are selected from one or more of methyl, ethyl, 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, methyl vinyl dichlorosilane and an acid binding agent, stirring and reacting under nitrogen protection to obtain a reaction solution a, wherein the molar ratio of the methyl vinyl dichlorosilane to the terminal hydroxyl silicone oil is (1:1) to (1:2); (2) adding dimethylvinylchlorosilane to the reaction solution a, wherein the mass of the dimethylvinylchlorosilane is 0% to 50% of the mass of the terminal hydroxyl silicone oil, 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 hydroxy-terminated silicone oil is shown in formula (4), Formula (4), Wherein, 3≤m≤2000, m is an integer, and R1, R2, R3, R4, R5, and R6 are selected from one or more of methyl, ethyl, 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 mass of the acid binding agent is 1% to 150% of the mass of 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.

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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