Solution polymerized styrene-butadiene rubber and preparation method thereof

Abstract

The invention relates to the technical field of synthetic rubber and a preparation method thereof, in particular to solution polymerized styrene-butadiene rubber and a preparation method thereof.The preparation method comprises the steps that a hydrocarbon solvent, styrene and butadiene are added into a reaction container and stirred and mixed; the method comprises the following steps: adding ethyl tetrahydrofurfuryl ether and organic lithium into a reaction container, and carrying out copolymerization reaction on styrene and butadiene in a hydrocarbon solvent to finally prepare the solution polymerized styrene-butadiene rubber. According to the preparation method disclosed by the invention, the polymerization capability of an initiator is effectively enhanced, the content of vinyl in the microstructure of a polymer is controlled, a styrene unit can be uniformly and randomly distributed on a macromolecular chain, and the content of styrene blocks is effectively controlled, so that the Mooney viscosity (ML (1 + 4) 120 DEG C) of the prepared solution polymerized styrene-butadiene rubber is 120-150, the random degree is 100%, and the viscosity of the solution polymerized styrene-butadiene rubber is greatly improved. The content of styrene and vinyl is 30%-50%; the solution polymerized styrene-butadiene rubber is excellent in tensile strength and balanced in wear resistance, rolling resistance and wet skid resistance.

Description

Technical Field

[0001] The invention relates to the technical field of synthetic rubber and a preparation method thereof, in particular to a solution-polymerized styrene-butadiene rubber and a preparation method thereof. Background Art

[0002] In the related art, during the preparation process of solution-polymerized styrene-butadiene rubber, less lithium-based initiator is added, which may lead to non-polymerization, weak reaction and deactivation. Although increasing the amount of ether structure regulator can improve the polymerization activity, improve the reactivity ratio of styrene, and facilitate the formation of a random structure, the increase in the amount of structure regulator will also increase the vinyl content in the product. Therefore, how to overcome the shortcomings of the prior art and set up the preparation process to control the styrene content and vinyl content in styrene-butadiene rubber, ensure the uniform and random distribution of styrene units on the macromolecular chain, and then obtain a random solution-polymerized styrene-butadiene rubber with a high bound benzene content and a high Mooney viscosity is a technical problem that needs to be solved at present. Summary of the invention

[0003] The present invention provides a solution-polymerized styrene-butadiene rubber and a preparation method thereof, which overcomes the above-mentioned shortcomings of the prior art, can effectively enhance the polymerization ability of the initiator, control the microstructure of the polymer to have a medium vinyl content, and can make the styrene units evenly and randomly distributed on the macromolecular chain, effectively realizing the control of the styrene block content.

[0004] One of the technical schemes of the present invention is achieved by the following measures: a method for preparing solution-polymerized styrene-butadiene rubber, which is carried out as follows: a hydrocarbon solvent, styrene and butadiene are added into a reaction container and stirred and mixed; then ethyl tetrahydrofurfuryl ether and organic lithium are added into the reaction container to copolymerize the styrene and the butadiene in the hydrocarbon solvent, wherein the molar ratio of the ethyl tetrahydrofurfuryl ether to the organic lithium is (2 to 8): 1; after reaching a preset reaction time, a terminator is added into the reaction container to terminate the copolymerization reaction to obtain a polymer; and the polymer is dried to obtain the solution-polymerized styrene-butadiene rubber.

[0005] By limiting the molar ratio of the ethyltetrahydrofurfuryl ether to the organic lithium, the addition amount of the lithium-based initiator and the addition amount of the ether structure regulator are both appropriate during the preparation process of the solution-polymerized styrene-butadiene rubber, thereby enhancing the polymerization ability of the initiator and controlling the microstructure of the polymer to have a medium vinyl content, while also making the styrene units uniformly and randomly distributed on the macromolecular chain, thereby effectively realizing the control of the styrene block content.

[0006] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions: The molar ratio of the ethyl tetrahydrofurfuryl ether to the organic lithium is (3 to 6):1.

[0007] The molar ratio of ethyl tetrahydrofurfuryl ether to organic lithium is preferably 3 to 6:1, so that the amount of lithium initiator added and the amount of ether structure regulator added are more appropriate, which can not only enhance the polymerization ability of the initiator and control the microstructure of the polymer to have a medium vinyl content, but also make the styrene units evenly and randomly distributed on the macromolecular chain, effectively realizing the control of the styrene block content.

[0008] Specifically, the molar ratio of ethyltetrahydrofurfuryl ether to organic lithium can be 3:1, the molar ratio of ethyltetrahydrofurfuryl ether to organic lithium can also be 4:1, the molar ratio of ethyltetrahydrofurfuryl ether to organic lithium can also be 5:1, and the molar ratio of ethyltetrahydrofurfuryl ether to organic lithium can also be 6:1.

[0009] The molar ratio of the butadiene to the styrene is (1 to 3):1.

[0010] By limiting the molar ratio of butadiene to styrene, the amounts of butadiene and styrene added during the preparation of solution-polymerized butadiene styrene rubber are appropriate, and a polymer can be obtained smoothly after a copolymerization reaction, and finally the solution-polymerized butadiene styrene rubber is obtained. In addition, the situation of residual raw materials due to incomplete reaction can be avoided, thereby effectively controlling the cost of preparing the solution-polymerized butadiene styrene rubber.

[0011] The reaction temperature of the copolymerization reaction is 70°C to 140°C.

[0012] The temperature conditions of the copolymerization reaction are limited. As for the temperature conditions, since the copolymerization of butadiene and styrene to prepare solution butadiene styrene rubber is an exothermic reaction, the temperature of the reaction system increases as the copolymerization reaction continues. About half an hour after the start of the copolymerization reaction, the temperature of the reaction system can reach 70°C to 140°C depending on the reaction conditions. The temperature of the reaction system is controlled to be stable within the range of 70°C to 140°C, thereby ensuring that butadiene and styrene can be completely copolymerized, and the vinyl content of the final solution butadiene styrene rubber can be adjusted to be 30% to 50%.

[0013] The reaction temperature of the above copolymerization reaction is preferably 80°C to 100°C.

[0014] The above-mentioned ethyl tetrahydrofurfuryl ether contains an alkyl group, and the alkyl group is a C1 to C9 alkyl group.

[0015] The present invention defines the groups contained in ethyl tetrahydrofurfuryl ether. Specifically, ethyl tetrahydrofurfuryl ether includes an alkyl group, and the alkyl group is specifically an alkyl group containing one to nine carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl and nonyl.

[0016] The above hydrocarbon solvent is one or more of C5 to C8 alkanes and C5 to C8 cycloalkanes.

[0017] The hydrocarbon solvent may include alkanes containing five to eight carbons, and the hydrocarbon solvent may also include cycloalkanes containing five to eight carbons. In addition, the hydrocarbon solvent may also be a mixture of C5 to C8 alkanes and C5 to C8 cycloalkanes.

[0018] Hydrocarbon solvents are organic solvents that are inert during the copolymerization of styrene and butadiene. They provide a good reaction environment for the copolymerization of styrene and butadiene. Moreover, since hydrocarbon solvents do not participate in the copolymerization reaction, they can be recycled in actual industrial production processes to reduce production costs.

[0019] In the preferred technical solution of the present invention, cyclopentane can be specifically selected as the hydrocarbon solvent, which has good compatibility with the organic lithium initiator and the ethyltetrahydrofurfuryl ether regulator.

[0020] The present invention does not impose a strict limit on the amount of hydrocarbon solvent added, and can be determined based on the conventional amount of hydrocarbon solvent added in the current preparation process of solution-polymerized styrene-butadiene rubber.

[0021] The above-mentioned organic lithium is one of n-butyl lithium, sec-butyl lithium, pentyl lithium, ethyl lithium, propyl lithium and isopropyl lithium.

[0022] The terminator is one of anhydrous ethanol, fatty acid and trimethylchlorosilane.

[0023] The terminator can successfully terminate the copolymerization reaction to obtain a polymer.

[0024] The above preset reaction time is 1h to 4h.

[0025] By limiting the preset reaction time within the above time range, it can be ensured that the material monomers have sufficient reaction time for copolymerization.

[0026] The step of adding ethyl tetrahydrofurfuryl ether and organic lithium into the reaction container specifically comprises: The ethyl tetrahydrofurfuryl ether is added into the reaction container; then the temperature of the reaction container is controlled to rise, and after the temperature in the reaction container rises to a preset temperature, the organic lithium is added into the reaction container, and the preset temperature is determined according to the initiation temperature of the organic lithium.

[0027] Before the step of controlling the temperature of the reaction container, the mixture of the ethyl tetrahydrofurfuryl ether, the hydrocarbon solvent, the styrene and the butadiene is stirred for 10 to 12 minutes.

[0028] The copolymerization reaction adopts a continuous method, the reaction vessel comprises a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle, and the step of adding a hydrocarbon solvent, styrene and butadiene into the reaction vessel and stirring and mixing specifically comprises: Adding the hydrocarbon solvent, the styrene and the butadiene into the first polymerization kettle, and stirring and mixing them; The step of adding ethyl tetrahydrofurfuryl ether and organic lithium into a reaction container to copolymerize the styrene and the butadiene in a hydrocarbon solvent specifically comprises: adding the ethyl tetrahydrofurfuryl ether and the organic lithium into the first polymerization reactor, so that the styrene and the butadiene undergo a first stage copolymerization reaction in the hydrocarbon solvent to obtain a first conversion product; The first conversion product is transported to the second polymerization kettle, and the first conversion product completes a second stage copolymerization reaction in the second polymerization kettle to obtain a second conversion product; The second converted product is transported to the third polymerization kettle, and the second converted product completes the third stage copolymerization reaction in the third polymerization kettle to obtain the third converted product; The third conversion product is transported to the fourth polymerization kettle, and the third conversion product completes the fourth stage copolymerization reaction in the fourth polymerization kettle.

[0029] Before adding the hydrocarbon solvent, styrene and butadiene into the reaction container, an inert gas is introduced into the reaction container.

[0030] The step of drying the polymer specifically comprises: transferring the polymer into a vacuum drying oven and drying it at a temperature of 60° C. to 70° C. for 12 to 13 hours.

[0031] The method for preparing the solution-polymerized styrene-butadiene rubber of the present invention selects ethyl tetrahydrofurfuryl ether as a structural regulator, selects organic lithium as an initiator, and limits the specific molar ratio of organic lithium to ethyl tetrahydrofurfuryl ether, thereby controlling the vinyl content in the solution-polymerized styrene-butadiene rubber and controlling the production cost. The solution-polymerized styrene-butadiene rubber finally prepared by the method for preparing the solution-polymerized styrene-butadiene rubber of the present invention has a Mooney viscosity (ML (1+4) 120°C) of 120 to 150, a bound benzene content of 30% to 40%, a vinyl content of 30% to 50%, and excellent tensile strength of the solution-polymerized styrene-butadiene rubber, and balanced wear resistance, rolling resistance and anti-slip properties.

[0032] The second technical solution of the present invention is achieved by the following measures: a solution polymerized styrene butadiene rubber prepared according to the preparation method of solution polymerized styrene butadiene rubber described in one of the technical solutions.

[0033] The following is a further optimization and / or improvement of the second technical solution of the above invention: The randomness of the solution-polymerized styrene-butadiene rubber is 100%, the styrene content is 30% to 50%, and the vinyl content is 30% to 50%.

[0034] The method for preparing the solution-polymerized styrene-butadiene rubber of the present invention selects ethyl tetrahydrofurfuryl ether as a structural regulator, selects organic lithium as an initiator, and limits the specific molar ratio of organic lithium to ethyl tetrahydrofurfuryl ether, thereby controlling the vinyl content in the solution-polymerized styrene-butadiene rubber and controlling the production cost; the Mooney viscosity (ML (1+4) 120°C) of the solution-polymerized styrene-butadiene rubber prepared by the present invention is between 120 and 150, the randomness is 100%, the styrene content is between 30% and 50%, and the vinyl content is between 30% and 50%; the solution-polymerized styrene-butadiene rubber has excellent tensile strength, and balanced wear resistance, rolling resistance and anti-slip performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 One of the schematic flow diagrams of a method for preparing a solution-polymerized styrene-butadiene rubber provided by the present invention; Figure 2 The second schematic flow diagram of a method for preparing a solution-polymerized styrene-butadiene rubber provided by the present invention; Figure 3 The third schematic diagram of the process of preparing a solution-polymerized styrene-butadiene rubber provided by the present invention; Figure 4 A fourth schematic flow diagram of a method for preparing a solution-polymerized styrene-butadiene rubber provided by the present invention; Figure 5 A fifth flow chart of a method for preparing a solution-polymerized styrene-butadiene rubber provided by the present invention; Figure 6 The 1H-NMR spectrum of the random high bound benzene content and high Mooney viscosity solution polymerized styrene-butadiene rubber of the present invention. DETAILED DESCRIPTION

[0036] The present invention is not limited by the following embodiments, and specific implementation methods can be determined according to the technical scheme of the present invention and actual conditions. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all known and commonly used chemical reagents and chemicals in the prior art; the percentages in the present invention are all mass percentages unless otherwise specified.

[0037] Reference Figure 1 As shown, the present invention provides a method for preparing a solution-polymerized styrene-butadiene rubber, the method comprising the following steps: S102: adding a hydrocarbon solvent, styrene and butadiene into a reaction container, and stirring and mixing; S104: adding ethyl tetrahydrofurfuryl ether and organic lithium into a reaction container to copolymerize styrene and butadiene in a hydrocarbon solvent; S106: After a preset reaction time, adding a terminator into the reaction container to terminate the copolymerization reaction to obtain a polymer; S108: Drying the polymer to obtain solution polymerized styrene-butadiene rubber.

[0038] The copolymerization reaction is carried out by a continuous process or a batch process.

[0039] Reference Figure 2 As shown, the present invention provides a method for preparing a solution-polymerized styrene-butadiene rubber, the method comprising the following steps: S202: adding a hydrocarbon solvent, styrene and butadiene into a reaction container, and stirring and mixing; S204: adding ethyl tetrahydrofurfuryl ether into a reaction container; S206: Controlling the temperature of the reaction container to rise, and after the temperature in the reaction container rises to a preset temperature, adding organic lithium into the reaction container to copolymerize styrene and butadiene in a hydrocarbon solvent; S208: After a preset reaction time, adding a terminator into the reaction container to terminate the copolymerization reaction to obtain a polymer; S210: Drying the polymer to obtain solution polymerized styrene-butadiene rubber.

[0040] In the preparation method, in the step of adding ethyl tetrahydrofurfuryl ether and organic lithium into a reaction container, ethyl tetrahydrofurfuryl ether is first added into the reaction container, and then the temperature of the reaction container is controlled to rise. After the temperature of the reaction container rises to a preset temperature, the organic lithium is added into the reaction container, thereby ensuring that the organic lithium can smoothly achieve initiation.

[0041] Specifically, the preset temperature is determined according to the initiation temperature of the organic lithium. For example, when the initiation temperature of the organic lithium is 40°C, the preset temperature is also 40°C. That is, the relationship between the preset temperature and the initiation temperature of the organic lithium is: the value of the preset temperature is equal to the value of the initiation temperature of the organic lithium.

[0042] Reference Figure 3 As shown, the present invention provides a method for preparing a solution-polymerized styrene-butadiene rubber, the method comprising the following steps: S302: adding a hydrocarbon solvent, styrene and butadiene into a reaction container, and stirring and mixing; S304: adding ethyl tetrahydrofurfuryl ether into a reaction container; S306: stirring a mixture of ethyl tetrahydrofurfuryl ether, a hydrocarbon solvent, styrene and butadiene for a preset time; S308: Controlling the temperature of the reaction container to rise, and after the temperature in the reaction container rises to a preset temperature, adding organic lithium into the reaction container to make styrene and butadiene copolymerize in a hydrocarbon solvent; S310: After a preset reaction time, adding a terminator into the reaction container to terminate the copolymerization reaction to obtain a polymer; S312: Drying the polymer to obtain solution polymerized styrene-butadiene rubber.

[0043] In the preparation method, after adding ethyl tetrahydrofurfuryl ether to the reaction container and before controlling the temperature of the reaction container to rise, the preparation method of solution-polymerized styrene-butadiene rubber proposed in the present invention further includes the step of stirring a mixture of ethyl tetrahydrofurfuryl ether with a hydrocarbon solvent, styrene and butadiene for a preset time. By setting the above preparation steps, ethyl tetrahydrofurfuryl ether can be mixed into the above three substances to play a role in structural regulation.

[0044] Specifically, the preset time is 10 minutes to 12 minutes. During the actual preparation, the stirring and mixing can be carried out for 10 minutes, 11 minutes, or 12 minutes. The limitation of the preset time can ensure that ethyl tetrahydrofurfuryl ether can be fully mixed into the above three substances.

[0045] Reference Figure 4 As shown, the present invention provides a method for preparing a solution-polymerized styrene-butadiene rubber, the method comprising the following steps: S402: adding a hydrocarbon solvent, styrene and butadiene into a first polymerization kettle, and stirring and mixing them; S404: adding ethyl tetrahydrofurfuryl ether and organic lithium into a first polymerization reactor to carry out a first stage copolymerization reaction of styrene and butadiene in a hydrocarbon solvent to obtain a first conversion product; S406: transporting the first conversion product to the second polymerization kettle, and completing the second stage copolymerization reaction of the first conversion product in the second polymerization kettle to obtain the second conversion product; S408: transporting the second conversion product to a third polymerization kettle, and completing a third stage copolymerization reaction of the second conversion product in the third polymerization kettle to obtain a third conversion product; S410: transporting the third conversion product to a fourth polymerization kettle, and completing a fourth stage copolymerization reaction of the third conversion product in the fourth polymerization kettle; S412: After a preset reaction time, adding a terminator into the fourth polymerization kettle to terminate the copolymerization reaction to obtain a polymer; S414: Drying the polymer to obtain solution polymerized styrene-butadiene rubber.

[0046] In the preparation method, the present invention specifically adopts a polymerization kettle as a reaction vessel, and the polymerization method adopts a continuous method. During the preparation, multiple polymerization kettles can be used, specifically including a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle.

[0047] In the preparation process, first, the first polymerization kettle is continuously fed, specifically, a hydrocarbon solvent, styrene, and butadiene are added into the first polymerization kettle and stirred and mixed.

[0048] Afterwards, ethyl tetrahydrofurfuryl ether and organic lithium are introduced into the first polymerization kettle, so that the styrene and butadiene in the first polymerization kettle undergo a first stage copolymerization reaction. Specifically, the first stage copolymerization reaction is a reaction process in which the conversion rate of the original material reaches a first preset conversion rate, and the first converted product with the conversion rate of the original material being the first preset conversion rate is obtained.

[0049] After obtaining the first conversion product, the first conversion product is transported to the second polymerization kettle, and the first conversion product completes the second stage copolymerization reaction process in the second polymerization kettle. Specifically, the second stage copolymerization reaction is a process for further converting the unconverted material in the first conversion product, that is, a process for increasing the conversion rate of the original material from the first preset conversion rate to the second preset conversion rate, and obtaining the second conversion product whose original material conversion rate reaches the second preset conversion rate.

[0050] After obtaining the second conversion product, the second conversion product is transported to the third polymerization kettle, and the second conversion product completes the third stage copolymerization reaction process in the third polymerization kettle. Specifically, the third stage copolymerization reaction is a process for further converting the original material that has not been converted in the second conversion product, that is, a reaction process for increasing the conversion rate of the original material from the second preset conversion rate to the third preset conversion rate, and finally obtaining the third conversion product whose conversion rate of the original material reaches the third preset conversion rate.

[0051] After obtaining the third conversion product, the third conversion product is transported to the fourth polymerization kettle, and the third conversion product completes the fourth stage copolymerization reaction process in the fourth polymerization kettle. Specifically, the fourth stage copolymerization reaction is a process for further converting the original material that has not been converted in the third conversion product, that is, a reaction process for increasing the conversion rate of the original material from the third preset conversion rate to 100%. When the sum of the reaction times of the copolymerization reaction in the first to fourth polymerization kettles reaches the preset reaction time, a terminator is added to the fourth polymerization kettle to terminate the copolymerization reaction, and finally a polymer with a conversion rate of 100% of the original material is obtained.

[0052] Through the above-mentioned preparation process setting, the continuous preparation of solution-polymerized styrene-butadiene rubber can be achieved to meet the needs of industrial production.

[0053] Reference Figure 5 As shown, the present invention provides a method for preparing a solution-polymerized styrene-butadiene rubber, the method comprising the following steps: S502: introducing an inert gas into the reaction container; S504: adding a hydrocarbon solvent, styrene and butadiene into a reaction container and stirring and mixing; S506: adding ethyl tetrahydrofurfuryl ether and organic lithium into a reaction container to copolymerize styrene and butadiene in a hydrocarbon solvent; S508: After a preset reaction time, adding a terminator into the reaction container to terminate the copolymerization reaction to obtain a polymer; S510: Drying the polymer to obtain solution polymerized styrene-butadiene rubber.

[0054] In the preparation method, the preparation method also includes a process of introducing an inert gas into the reaction container. Specifically, before adding hydrocarbon solvents, styrene and butadiene into the reaction container and stirring and mixing, an inert gas is introduced into the reaction container, thereby exhausting the air in the reaction container to avoid interference with the subsequent preparation process.

[0055] Specifically, the inert gas includes any one of helium, neon, argon, krypton, xenon and radon.

[0056] Furthermore, nitrogen can be introduced into the reaction vessel instead of the above-mentioned inert gas. Nitrogen is a very chemically inert gas and can also play the role produced by the introduction of the above-mentioned inert gas. Nitrogen is more common in industrial production, so it can reduce the operational difficulty of the preparation method of the solution-polymerized styrene-butadiene rubber proposed in the present invention.

[0057] The present invention will be further described below in conjunction with embodiments: Example 1 Ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 2:1.

[0058] During the preparation, the batch method is adopted, that is, a single first polymerization kettle is used for preparation, and cyclopentane is selected as the hydrocarbon solvent. Specifically, 2000g cyclopentane, 200g styrene, and 300g butadiene are added to the 5L first polymerization kettle in sequence, and stirred and mixed after addition, and then the prepared ethyl tetrahydrofurfuryl ether regulator is added. After mixing and stirring for 10 minutes, the temperature of the polymerization kettle is raised to 40°C, and then 1.2*10 -3 mol of n-butyl lithium. After 0.5h, the temperature of the polymerization kettle rises to the highest point of 74°C. After the reaction continues for 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0059] Example 2 Under the conditions of a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 3:1.

[0060] During the preparation, a single polymerization kettle was used for the preparation, that is, the first polymerization kettle was used for the preparation, and cyclopentane was selected as the hydrocarbon solvent. 2000g cyclopentane, 200g styrene, and 300g butadiene were added to the 5L first polymerization kettle in sequence and stirred evenly, and then the prepared ethyl tetrahydrofurfuryl ether regulator was added. After stirring for 10 minutes, the temperature of the polymerization kettle was controlled to rise to 40°C, and then 1.2*10 -3 mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 100°C, and after the reaction continues for 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0061] Example 3 In a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 3.5:1.

[0062] During the preparation, a single polymerization kettle was used for the preparation, that is, the first polymerization kettle was used for the preparation, and cyclopentane was selected as the hydrocarbon solvent. Specifically, 2000 g of cyclopentane, 200 g of styrene, and 300 g of butadiene were added to the 5 L first polymerization kettle in sequence, and then the prepared ethyl tetrahydrofurfuryl ether regulator was added. After stirring for 10 minutes, the temperature of the polymerization kettle was controlled to rise to 40°C, and 1.2*10 -3 mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 95°C, and after continuing the reaction for another 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0063] Example 4 In a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 4:1.

[0064] During the preparation, a single polymerization kettle is used for preparation, that is, the first polymerization kettle is used for preparation, and cyclopentane is selected as the hydrocarbon solvent. Specifically, 2000g of cyclopentane, 200g of styrene, and 300g of butadiene are sequentially added into the 5L first polymerization kettle, and mixed and stirred evenly. Then, the prepared ethyl tetrahydrofurfuryl ether regulator is added. After stirring for 10 minutes, the temperature of the polymerization kettle is raised to 40°C. 1.2*10 -3 mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 98°C, and after the reaction continues for 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0065] Example 5 Under the conditions of a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 4.5:1.

[0066] During the preparation, a single polymerization kettle was used for the preparation, that is, the first polymerization kettle was used for the preparation, and cyclopentane was selected as the hydrocarbon solvent. Specifically, 2000 g of cyclopentane, 200 g of styrene, and 300 g of butadiene were added to the 5L first polymerization kettle in sequence and stirred evenly, and then the prepared ethyl tetrahydrofurfuryl ether regulator was added. After stirring for 10 minutes, the temperature of the polymerization kettle was controlled to rise to 40°C, and then 1.2*10 -3 mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 85°C, and after continuing the reaction for 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0067] Example 6 Under the conditions of a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 5:1.

[0068] During the preparation, a single polymerization kettle was used for the preparation, that is, the first polymerization kettle was used for the preparation, and cyclopentane was selected as the hydrocarbon solvent. Specifically, 2000 g of cyclopentane, 200 g of styrene, and 300 g of butadiene were added to the 5L first polymerization kettle in sequence and stirred evenly, and then the prepared ethyl tetrahydrofurfuryl ether regulator was added. After stirring for 10 minutes, the temperature of the polymerization kettle was controlled to rise to 40°C, and then 1.2*10 -3 mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 94°C, and after continuing the reaction for another 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0069] Example 7 Under the conditions of a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 5.5:1.

[0070] During the preparation, a single polymerization kettle was used for the preparation, that is, the first polymerization kettle was used for the preparation, and cyclopentane was selected as the hydrocarbon solvent. Specifically, 2000 g of cyclopentane, 200 g of styrene, and 300 g of butadiene were added to the 5L first polymerization kettle in sequence and stirred evenly, and then the prepared ethyl tetrahydrofurfuryl ether regulator was added. After stirring for 10 minutes, the temperature of the polymerization kettle was controlled to rise to 40°C, and then 1.2*10 -3 mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 88°C, and after the reaction continues for 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0071] Example 8 Under the conditions of a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 6:1.

[0072] During the preparation, a single polymerization kettle was used for the preparation, that is, the first polymerization kettle was used for the preparation, and cyclopentane was selected as the hydrocarbon solvent. Specifically, 2000 g of cyclopentane, 200 g of styrene, and 300 g of butadiene were added to the 5L first polymerization kettle in sequence and stirred evenly, and then the prepared ethyl tetrahydrofurfuryl ether regulator was added. After stirring for 10 minutes, the temperature of the polymerization kettle was controlled to rise to 40°C, and then 1.2*10 -3 mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 81°C, and after continuing the reaction for another 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0073] Example 9 Under the conditions of a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 7:1.

[0074] During the preparation, a single polymerization kettle was used for the preparation, that is, the first polymerization kettle was used for the preparation, and cyclopentane was selected as the hydrocarbon solvent. Specifically, 2000 g of cyclopentane, 200 g of styrene, and 300 g of butadiene were added to the 5L first polymerization kettle in sequence and stirred evenly, and then the prepared ethyl tetrahydrofurfuryl ether regulator was added. After stirring for 10 minutes, the temperature of the polymerization kettle was controlled to rise to 40°C, and then 1.2*10 -3mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 112°C, and after continuing the reaction for 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0075] Example 10 Under the conditions of a batch polymerization system, ethyl tetrahydrofurfuryl ether is used as a regulator, n-butyl lithium is used as an initiator, and the molar ratio of ethyl tetrahydrofurfuryl ether to the initiator is 8:1.

[0076] During the preparation, a single polymerization kettle was used for preparation, that is, the first polymerization kettle was used for preparation, and cyclopentane was selected as the hydrocarbon solvent. Specifically, 2000 g of cyclopentane, 200 g of styrene, and 300 g of butadiene were added to the 5L first polymerization kettle in sequence and stirred evenly, and then the prepared ethyl tetrahydrofurfuryl ether regulator was added. After stirring for 10 minutes, the temperature of the polymerization kettle was controlled to rise to 40°C, and then 1.2*10 -3 mol of n-butyl lithium, after 0.5h, the temperature of the polymerization kettle rises to the highest point of 131°C, and after continuing the reaction for another 1.5h, anhydrous ethanol is introduced into the first polymerization kettle to terminate the copolymerization reaction and obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12h to obtain a solution-polymerized styrene-butadiene rubber.

[0077] Embodiment 11 In a continuous polymerization system, the preparation is carried out using a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle.

[0078] During the preparation process, first, the first polymerization kettle is fed. Specifically, the hydrocarbon solvent is selected as cyclopentane solvent, and cyclopentane solvent, styrene, and butadiene are added to the first polymerization kettle, wherein the rate of adding cyclopentane solvent is 66kg / h, the rate of adding styrene is 4kg / h, and the rate of adding butadiene is 6kg / h.

[0079] Ethyl tetrahydrofurfuryl ether was used as a regulator, and the molar ratio of the amount of ethyl tetrahydrofurfuryl ether introduced into the first polymerization kettle to the amount of n-butyl lithium introduced was 3.5:1, and the amount of n-butyl lithium was 2.6*10 -2 mol.

[0080] Ethyl tetrahydrofurfuryl ether and organic lithium are introduced into a first polymerization kettle, and styrene and butadiene in the first polymerization kettle are subjected to a first stage copolymerization reaction. Specifically, the first stage copolymerization reaction is a reaction process in which the conversion rate of the original material reaches 80%. The residence time of the above materials in the first polymerization kettle is controlled to be 60 minutes, and the temperature of the first polymerization kettle is controlled to be 70° C., to obtain a first converted product with a conversion rate of the original material of 80%.

[0081] After obtaining the first conversion product, the first conversion product is transported to the second polymerization kettle, and the second stage copolymerization reaction process is completed in the second polymerization kettle. Specifically, the second stage copolymerization reaction is a process for further converting the unconverted material in the first conversion product, that is, a process for increasing the conversion rate of the original material from 80% to 90%. The first conversion product is controlled to stay in the second polymerization kettle for 60 minutes, and the unconverted original material in the first conversion product is further converted to obtain a second conversion product with an original material conversion rate of 90%.

[0082] After obtaining the second conversion product, the second conversion product is transported to the third polymerization kettle, and the third stage copolymerization reaction process is completed in the third polymerization kettle. Specifically, the third stage copolymerization reaction is a process for further converting the original material that has not been converted in the second conversion product, that is, a reaction process for increasing the conversion rate of the original material from 90% to 95%. The above-mentioned second conversion product is controlled to stay in the third polymerization kettle for 60 minutes, and the original material that has not been converted in the second conversion product is further converted to obtain a third conversion product with an original material conversion rate of 95%.

[0083] After obtaining the third conversion product, the third conversion product is conveyed to the fourth polymerization kettle, and the fourth stage copolymerization reaction process is completed in the fourth polymerization kettle. Specifically, the fourth stage copolymerization reaction is a process for further converting the original material that has not been converted in the third conversion product, that is, a reaction process for increasing the conversion rate of the original material from 95% to 100%. The third conversion product is controlled to stay in the fourth polymerization kettle for 60 minutes, the original material that has not been converted in the third conversion product is further converted, and fatty acid is introduced into the fourth polymerization kettle to terminate the copolymerization reaction to obtain a polymer, and the obtained polymer is dried in a vacuum drying oven at 60°C for 12 hours to obtain solution-polymerized styrene-butadiene rubber.

[0084] Example 12 In a continuous polymerization system, the preparation is carried out using a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle.

[0085] During the preparation process, first, the first polymerization kettle is fed. Specifically, the hydrocarbon solvent is selected as cyclopentane solvent, and cyclopentane solvent, styrene, and butadiene are added to the first polymerization kettle, wherein the rate of adding cyclopentane solvent is 66kg / h, the rate of adding styrene is 4kg / h, and the rate of adding butadiene is 6kg / h.

[0086] Ethyl tetrahydrofurfuryl ether was used as a regulator, and the molar ratio of ethyl tetrahydrofurfuryl ether introduced into the first polymerization kettle to n-butyl lithium was 5:1, and n-butyl lithium was 2.6*10 -2 mol.

[0087] Ethyl tetrahydrofurfuryl ether and organic lithium are introduced into a first polymerization kettle, and styrene and butadiene in the first polymerization kettle are subjected to a first stage copolymerization reaction. Specifically, the first stage copolymerization reaction is a reaction process in which the conversion rate of the original material reaches 83%. The residence time of the above materials in the first polymerization kettle is controlled to be 60 minutes, and the temperature of the first polymerization kettle is controlled to be 80° C., to obtain a first converted product with a conversion rate of the original material of 83%.

[0088] After obtaining the first conversion product, the first conversion product is transported to the second polymerization kettle, and the second stage copolymerization reaction process is completed in the second polymerization kettle. Specifically, the second stage copolymerization reaction is a process for further converting the unconverted material in the first conversion product, that is, a process for increasing the conversion rate of the original material from 83% to 92%. The first conversion product is controlled to stay in the second polymerization kettle for 60 minutes, and the unconverted original material in the first conversion product is further converted to obtain a second conversion product with an original material conversion rate of 92%.

[0089] After obtaining the second conversion product, the second conversion product is transported to the third polymerization kettle, and the third stage copolymerization reaction process is completed in the third polymerization kettle. Specifically, the third stage copolymerization reaction is a process for further converting the original material that has not been converted in the second conversion product, that is, a reaction process for increasing the conversion rate of the original material from 92% to 97%. The above-mentioned second conversion product is controlled to stay in the third polymerization kettle for 60 minutes, and the original material that has not been converted in the second conversion product is further converted to obtain a third conversion product with an original material conversion rate of 97%.

[0090] After obtaining the third conversion product, the third conversion product is conveyed to the fourth polymerization kettle, and the fourth stage copolymerization reaction process is completed in the fourth polymerization kettle. Specifically, the fourth stage copolymerization reaction is a process for further converting the original material that has not been converted in the third conversion product, that is, a reaction process for increasing the conversion rate of the original material from 97% to 100%. The above-mentioned third conversion product is controlled to stay in the fourth polymerization kettle for 60 minutes, and the original material that has not been converted in the third conversion product is further converted. Fatty acid is introduced into the fourth polymerization kettle to terminate the copolymerization reaction to obtain a polymer, and the obtained polymer is dried in a vacuum drying oven at 60°C for 12 hours to obtain solution-polymerized styrene-butadiene rubber.

[0091] Example 13 In a continuous polymerization system, the preparation is carried out using a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle.

[0092] During the preparation process, first, the first polymerization kettle is fed. Specifically, the hydrocarbon solvent is selected as cyclopentane solvent, and cyclopentane solvent, styrene, and butadiene are added to the first polymerization kettle, wherein the rate of adding cyclopentane solvent is 66kg / h, the rate of adding styrene is 4kg / h, and the rate of adding butadiene is 6kg / h.

[0093] Ethyl tetrahydrofurfuryl ether was used as a regulator, and the molar ratio of ethyl tetrahydrofurfuryl ether introduced into the first polymerization kettle to propyl lithium was 6:1, and propyl lithium was 2.6*10 -2 mol.

[0094] Ethyl tetrahydrofurfuryl ether and organic lithium are introduced into a first polymerization kettle, and styrene and butadiene in the first polymerization kettle are subjected to a first stage copolymerization reaction. Specifically, the first stage copolymerization reaction is a reaction process in which the conversion rate of the original material reaches 85%. The residence time of the above materials in the first polymerization kettle is controlled to be 60 minutes, and the temperature of the first polymerization kettle is controlled to be 90° C., to obtain a first converted product with a conversion rate of the original material of 85%.

[0095] After obtaining the first conversion product, the first conversion product is transported to the second polymerization kettle, and the second stage copolymerization reaction process is completed in the second polymerization kettle. Specifically, the second stage copolymerization reaction is a process for further converting the unconverted material in the first conversion product, that is, a process for increasing the conversion rate of the original material from 85% to 94%. The first conversion product is controlled to stay in the second polymerization kettle for 60 minutes, and the unconverted original material in the first conversion product is further converted to obtain a second conversion product with an original material conversion rate of 94%.

[0096] After obtaining the second conversion product, the second conversion product is transported to the third polymerization kettle, and the third stage copolymerization reaction process is completed in the third polymerization kettle. Specifically, the third stage copolymerization reaction is a process for further converting the original material that has not been converted in the second conversion product, that is, a reaction process for increasing the conversion rate of the original material from 94% to 98%. The above-mentioned second conversion product is controlled to stay in the third polymerization kettle for 60 minutes, and the original material that has not been converted in the second conversion product is further converted to obtain a third conversion product with an original material conversion rate of 98%.

[0097] After obtaining the third conversion product, the third conversion product is conveyed to the fourth polymerization kettle, and the fourth stage copolymerization reaction process is completed in the fourth polymerization kettle. Specifically, the fourth stage copolymerization reaction is a process for further converting the original material that has not been converted in the third conversion product, that is, a reaction process for increasing the conversion rate of the original material from 98% to 100%. The third conversion product is controlled to stay in the fourth polymerization kettle for 60 minutes, the original material that has not been converted in the third conversion product is further converted, and fatty acid is introduced into the fourth polymerization kettle to terminate the copolymerization reaction to obtain a polymer, and the obtained polymer is dried in a vacuum drying oven at 60°C for 12 hours to obtain solution-polymerized styrene-butadiene rubber.

[0098] Embodiment 14 In a continuous polymerization system, the preparation is carried out using a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle.

[0099] During the preparation process, first, the first polymerization kettle is fed. Specifically, the hydrocarbon solvent is selected as cyclopentane solvent, and cyclopentane solvent, styrene, and butadiene are added to the first polymerization kettle, wherein the rate of adding cyclopentane solvent is 66kg / h, the rate of adding styrene is 4kg / h, and the rate of adding butadiene is 6kg / h.

[0100] Ethyl tetrahydrofurfuryl ether was used as a regulator, and the molar ratio of ethyl tetrahydrofurfuryl ether introduced into the first polymerization kettle to ethyl lithium was 7:1, and ethyl lithium was 2.6*10 -2 mol.

[0101] Ethyl tetrahydrofurfuryl ether and organic lithium are introduced into a first polymerization kettle, and styrene and butadiene in the first polymerization kettle are subjected to a first stage copolymerization reaction. Specifically, the first stage copolymerization reaction is a reaction process in which the conversion rate of the original material reaches 60%. The residence time of the above materials in the first polymerization kettle is controlled to be 60 minutes, and the temperature of the first polymerization kettle is controlled to be 100° C., to obtain a first converted product with a conversion rate of the original material of 90%.

[0102] After obtaining the first conversion product, the first conversion product is transported to the second polymerization kettle, and the second stage copolymerization reaction process is completed in the second polymerization kettle. Specifically, the second stage copolymerization reaction is a process for further converting the unconverted material in the first conversion product, that is, a process for increasing the conversion rate of the original material from 90% to 95%. The first conversion product is controlled to stay in the second polymerization kettle for 60 minutes, and the unconverted original material in the first conversion product is further converted to obtain a second conversion product with an original material conversion rate of 95%.

[0103] After obtaining the second conversion product, the second conversion product is transported to the third polymerization kettle, and the third stage copolymerization reaction process is completed in the third polymerization kettle. Specifically, the third stage copolymerization reaction is a process for further converting the original material that has not been converted in the second conversion product, that is, a reaction process for increasing the conversion rate of the original material from 95% to 99%. The above-mentioned second conversion product is controlled to stay in the third polymerization kettle for 60 minutes, and the original material that has not been converted in the second conversion product is further converted to obtain a third conversion product with an original material conversion rate of 99%.

[0104] After obtaining the third conversion product, the third conversion product is conveyed to a fourth polymerization kettle, and a fourth stage copolymerization reaction process is completed in the fourth polymerization kettle. Specifically, the fourth stage copolymerization reaction is a process for further converting the original material that has not been converted in the third conversion product, that is, a reaction process for increasing the conversion rate of the original material from 99% to 100%. The third conversion product is controlled to stay in the fourth polymerization kettle for 60 minutes, and the original material that has not been converted in the third conversion product is further converted. Fatty acid is introduced into the fourth polymerization kettle to terminate the copolymerization reaction to obtain a polymer, and the obtained polymer is dried in a vacuum drying oven at 60°C for 12 hours to obtain a solution-polymerized styrene-butadiene rubber.

[0105] Embodiment 15 In a continuous polymerization system, the preparation is carried out using a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle.

[0106] During the preparation process, first, the first polymerization kettle is fed. Specifically, the hydrocarbon solvent is selected as cyclopentane solvent, and cyclopentane solvent, styrene, and butadiene are added to the first polymerization kettle, wherein the rate of adding cyclopentane solvent is 66kg / h, the rate of adding styrene is 4kg / h, and the rate of adding butadiene is 6kg / h.

[0107] Ethyl tetrahydrofurfuryl ether was used as a regulator, and the molar ratio of ethyl tetrahydrofurfuryl ether introduced into the first polymerization kettle to amyl lithium was 3:1, and amyl lithium was 2.6*10 -2 mol.

[0108] Ethyl tetrahydrofurfuryl ether and organic lithium are introduced into a first polymerization kettle, and styrene and butadiene in the first polymerization kettle are subjected to a first stage copolymerization reaction. Specifically, the first stage copolymerization reaction is a reaction process in which the conversion rate of the original material reaches 82%. The residence time of the above materials in the first polymerization kettle is controlled to be 60 minutes, and the temperature of the first polymerization kettle is controlled to be 90° C., to obtain a first converted product with a conversion rate of the original material of 82%.

[0109] After obtaining the first conversion product, the first conversion product is transported to the second polymerization kettle, and the second stage copolymerization reaction process is completed in the second polymerization kettle. Specifically, the second stage copolymerization reaction is a process for further converting the unconverted material in the first conversion product, that is, a process for increasing the conversion rate of the original material from 82% to 88%. The first conversion product is controlled to stay in the second polymerization kettle for 60 minutes, and the unconverted original material in the first conversion product is further converted to obtain a second conversion product with an original material conversion rate of 88%.

[0110] After obtaining the second conversion product, the second conversion product is transported to the third polymerization kettle, and the third stage copolymerization reaction process is completed in the third polymerization kettle. Specifically, the third stage copolymerization reaction is a process for further converting the original material that has not been converted in the second conversion product, that is, a reaction process for increasing the conversion rate of the original material from 88% to 94%. The above-mentioned second conversion product is controlled to stay in the third polymerization kettle for 60 minutes, and the original material that has not been converted in the second conversion product is further converted to obtain a third conversion product with an original material conversion rate of 94%.

[0111] After obtaining the third conversion product, the third conversion product is conveyed to a fourth polymerization kettle, and a fourth stage copolymerization reaction process is completed in the fourth polymerization kettle. Specifically, the fourth stage copolymerization reaction is a process for further converting the original material that has not been converted in the third conversion product, that is, a reaction process for increasing the conversion rate of the original material from 94% to 100%. The third conversion product is controlled to stay in the fourth polymerization kettle for 60 minutes, and the original material that has not been converted in the third conversion product is further converted. Fatty acid is introduced into the fourth polymerization kettle to terminate the copolymerization reaction to obtain a polymer, and the obtained polymer is dried in a vacuum drying oven at 60°C for 12 hours to obtain solution-polymerized styrene-butadiene rubber.

[0112] Example 16 In a continuous polymerization system, the preparation is carried out using a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle.

[0113] During the preparation process, first, the first polymerization kettle is fed. Specifically, the hydrocarbon solvent is selected as cyclopentane solvent, and cyclopentane solvent, styrene, and butadiene are added to the first polymerization kettle, wherein the rate of adding cyclopentane solvent is 66kg / h, the rate of adding styrene is 4kg / h, and the rate of adding butadiene is 6kg / h.

[0114] Ethyl tetrahydrofurfuryl ether was used as a regulator, and the molar ratio of ethyl tetrahydrofurfuryl ether introduced into the first polymerization kettle to sec-butyl lithium was 4:1, and sec-butyl lithium was 2.6*10 -2 mol.

[0115] Ethyl tetrahydrofurfuryl ether and organic lithium are introduced into a first polymerization kettle, and styrene and butadiene in the first polymerization kettle are subjected to a first stage copolymerization reaction. Specifically, the first stage copolymerization reaction is a reaction process in which the conversion rate of the original material reaches 83%. The residence time of the above materials in the first polymerization kettle is controlled to be 60 minutes, and the temperature of the first polymerization kettle is controlled to be 80° C., to obtain a first converted product with a conversion rate of the original material of 83%.

[0116] After obtaining the first conversion product, the first conversion product is transported to the second polymerization kettle, and the second stage copolymerization reaction process is completed in the second polymerization kettle. Specifically, the second stage copolymerization reaction is a process for further converting the unconverted material in the first conversion product, that is, a process for increasing the conversion rate of the original material from 83% to 88%. The first conversion product is controlled to stay in the second polymerization kettle for 60 minutes, and the unconverted original material in the first conversion product is further converted to obtain a second conversion product with an original material conversion rate of 88%.

[0117] After obtaining the second conversion product, the second conversion product is transported to the third polymerization kettle, and the third stage copolymerization reaction process is completed in the third polymerization kettle. Specifically, the third stage copolymerization reaction is a process for further converting the original material that has not been converted in the second conversion product, that is, a reaction process for increasing the conversion rate of the original material from 88% to 95%. The above-mentioned second conversion product is controlled to stay in the third polymerization kettle for 60 minutes, and the original material that has not been converted in the second conversion product is further converted to obtain a third conversion product with an original material conversion rate of 95%.

[0118] After obtaining the third conversion product, the third conversion product is conveyed to the fourth polymerization kettle, and the fourth stage copolymerization reaction process is completed in the fourth polymerization kettle. Specifically, the fourth stage copolymerization reaction is a process for further converting the original material that has not been converted in the third conversion product, that is, a reaction process for increasing the conversion rate of the original material from 95% to 100%. The third conversion product is controlled to stay in the fourth polymerization kettle for 60 minutes, the original material that has not been converted in the third conversion product is further converted, and fatty acid is introduced into the fourth polymerization kettle to terminate the copolymerization reaction to obtain a polymer. The obtained polymer is dried in a vacuum drying oven at 60°C for 12 hours to obtain a finished product of solution-polymerized styrene-butadiene rubber.

[0119] The solution polymerized styrene butadiene rubber prepared in Examples 1 to 16 was characterized using nuclear magnetic resonance technology to obtain the microstructure and randomness of the solution polymerized styrene butadiene rubber, as shown in Table 1 below.

[0120] It can be seen from Table 1 that under the same reaction time, the final reaction temperature of Examples 1 to 16 is within the design range. When the molar ratio of ethyltetrahydrofurfuryl ether to the initiator is (2 to 8):1, the random type high bound benzene content and high Mooney viscosity solution polymerized styrene-butadiene rubber can be obtained by coagulation and drying after the polymerization is completed, and the samples are randomly distributed. This shows that the random type high bound benzene content solution polymerized styrene-butadiene rubber can be produced by the present invention.

[0121] The solution polymerized styrene butadiene rubber prepared in Examples 3, 4, 11 and 16 and the existing commercially available product HP755R solution polymerized styrene butadiene rubber (provided by JSR Corporation) were selected to test the vulcanization properties of the mixed rubber, and the test data were shown in Table 2 below.

[0122] The solution polymerized butadiene styrene rubber prepared in Examples 3, 4, 11 and 16 and the existing commercially available product HP755R solution polymerized butadiene styrene rubber were selected for physical and mechanical property tests and dynamic thermodynamic property tests of the vulcanized rubber. The obtained dynamic thermodynamic properties are shown in Tables 3 and 4, respectively.

[0123] From the comparative analysis of the data in Table 2, Table 3 and Table 4, it can be seen that the rubber prepared by the preparation method of solution-polymerized styrene butadiene rubber proposed in the present invention has excellent tensile strength, balanced wear resistance, rolling resistance and anti-skid performance, compared with the rubber products prepared by the existing preparation technology, and can replace the existing solution-polymerized styrene butadiene rubber products.

[0124] The solution polymerized butadiene styrene rubber prepared in Example 16 was selected for testing and characterization. The 1H-NMR spectrum of the solution polymerized butadiene styrene rubber prepared in Example 16 is shown in FIG. Figure 6 .Depend on Figure 6 It can be seen that in the solution-polymerized styrene-butadiene rubber prepared in the present invention, the styrene units are uniformly and randomly distributed on the macromolecular chain.

[0125] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or reduced according to actual needs to meet the requirements of different situations.

Claims

1. A method for preparing a solution-polymerized styrene-butadiene rubber, characterized in that: The method is carried out as follows: a hydrocarbon solvent, styrene and butadiene are added into a reaction container and stirred to mix; then ethyl tetrahydrofurfuryl ether and organic lithium are added into the reaction container to copolymerize the styrene and the butadiene in the hydrocarbon solvent, wherein the molar ratio of the ethyl tetrahydrofurfuryl ether to the organic lithium is (2 to 8): 1; after reaching a preset reaction time, a terminator is added into the reaction container to terminate the copolymerization reaction to obtain a polymer; and the polymer is dried to obtain the solution polymerized styrene-butadiene rubber.

2. The method for preparing solution-polymerized styrene-butadiene rubber according to claim 1, wherein: The molar ratio of the ethyltetrahydrofurfuryl ether to the organic lithium is (3 to 6):

1.

3. The method for preparing solution-polymerized styrene-butadiene rubber according to claim 1 or 2, characterized in that: The molar ratio of the butadiene to the styrene is (1 to 3):

1.

4. The method for preparing the solution-polymerized styrene-butadiene rubber according to claim 3, characterized in that: The ethyl tetrahydrofurfuryl ether contains an alkyl group, and the alkyl group is a C1 to C9 alkyl group.

5. The method for preparing solution-polymerized styrene-butadiene rubber according to any one of claims 1 to 4, characterized in that: The organic lithium is one of n-butyl lithium, sec-butyl lithium, pentyl lithium, ethyl lithium, propyl lithium and isopropyl lithium.

6. The method for preparing solution-polymerized styrene-butadiene rubber according to any one of claims 1 to 5, characterized in that: The preset reaction time is 1 hour to 4 hours.

7. The method for preparing solution-polymerized styrene-butadiene rubber according to any one of claims 1 to 6, characterized in that: The reaction temperature of the copolymerization reaction is 70°C to 140°C.

8. The method for preparing solution-polymerized styrene-butadiene rubber according to claim 7, characterized in that: The reaction temperature of the copolymerization reaction is 80°C to 100°C.

9. The method for preparing the solution-polymerized styrene-butadiene rubber according to claim 1, 2, 4 or 8, characterized in that: The step of adding ethyl tetrahydrofurfuryl ether and organic lithium into the reaction container specifically comprises: The ethyl tetrahydrofurfuryl ether is added into the reaction container; then the temperature of the reaction container is controlled to rise, and after the temperature in the reaction container rises to a preset temperature, the organic lithium is added into the reaction container, and the preset temperature is determined according to the initiation temperature of the organic lithium.

10. The method for preparing the solution-polymerized styrene-butadiene rubber according to claim 1, 2, 4 or 8, characterized in that Before the step of controlling the temperature of the reaction container to rise, the mixture of the ethyltetrahydrofurfuryl ether, the hydrocarbon solvent, the styrene and the butadiene is stirred for 10 to 12 minutes.

11. The method for preparing a solution-polymerized styrene-butadiene rubber according to any one of claims 1 to 10, characterized in that The copolymerization reaction adopts a continuous method, the reaction vessel includes a first polymerization kettle, a second polymerization kettle, a third polymerization kettle and a fourth polymerization kettle, and the step of adding a hydrocarbon solvent, styrene and butadiene into the reaction vessel and stirring and mixing specifically includes: Adding the hydrocarbon solvent, the styrene and the butadiene into the first polymerization kettle, and stirring and mixing them; The step of adding ethyl tetrahydrofurfuryl ether and organic lithium into a reaction container to copolymerize the styrene and the butadiene in a hydrocarbon solvent specifically comprises: adding the ethyl tetrahydrofurfuryl ether and the organic lithium into the first polymerization reactor, so that the styrene and the butadiene undergo a first stage copolymerization reaction in the hydrocarbon solvent to obtain a first conversion product; The first conversion product is transported to the second polymerization kettle, and the first conversion product completes a second stage copolymerization reaction in the second polymerization kettle to obtain a second conversion product; The second converted product is transported to the third polymerization kettle, and the second converted product completes the third stage copolymerization reaction in the third polymerization kettle to obtain the third converted product; The third conversion product is transported to the fourth polymerization kettle, and the third conversion product completes the fourth stage copolymerization reaction in the fourth polymerization kettle.

12. The method for preparing solution-polymerized styrene-butadiene rubber according to any one of claims 1 to 11, characterized in that: Before adding the hydrocarbon solvent, styrene and butadiene into the reaction container, an inert gas is introduced into the reaction container.

13. The method for preparing solution-polymerized styrene-butadiene rubber according to any one of claims 1 to 12, characterized in that: The step of drying the polymer specifically includes: transferring the polymer to a vacuum drying oven for drying.

14. The method for preparing solution-polymerized styrene-butadiene rubber according to claim 13, characterized in that: The drying temperature is 60°C to 70°C.

15. The method for preparing solution-polymerized styrene-butadiene rubber according to claim 14, characterized in that: The drying time is 12h to 13h.

16. The method for preparing solution-polymerized styrene-butadiene rubber according to any one of claims 1 to 15, characterized in that: The terminator is one of anhydrous ethanol, fatty acid and trimethylchlorosilane.

17. The method for preparing solution-polymerized styrene-butadiene rubber according to any one of claims 1 to 15, characterized in that: The hydrocarbon solvent is one or more of C5 to C8 alkanes or C5 to C8 cycloalkanes.

18. The method for preparing solution-polymerized styrene-butadiene rubber according to claims 1 to 15, characterized in that: The hydrocarbon solvent is a mixture of C5 to C8 alkanes and C5 to C8 cycloalkanes.

19. A solution polymerized styrene butadiene rubber prepared according to the method for preparing solution polymerized styrene butadiene rubber according to any one of claims 1 to 18.

20. The solution polymerized styrene-butadiene rubber according to claim 19, characterized in that The randomness of the solution-polymerized styrene-butadiene rubber is 100%, the styrene content is 30% to 50%, and the vinyl content is 30% to 50%.

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