CN111072710A

CN111072710A - Thiosulfonate-terminated mercaptosilane coupling agent and synthesis method and application thereof

Info

Publication number: CN111072710A
Application number: CN201911305605.0A
Authority: CN
Inventors: 贾维杰; 王滨; 宋禹奠; 赵文荣
Original assignee: Eve Rubber Institute Co ltd
Current assignee: Eve Rubber Institute Co ltd
Priority date: 2019-12-18
Filing date: 2019-12-18
Publication date: 2020-04-28

Abstract

The invention belongs to a silane coupling agent, and particularly relates to a thiosulfonate-terminated mercapto silane coupling agent, and a synthesis method and application thereof. The thiosulfonate-terminated mercaptosilane coupling agent has a structure shown in a formula (I). The thiosulfonate-terminated mercaptosilane coupling agent shown in the formula (I) can enhance the interaction between a polymer and a filler and reduce the adhesiveThe hysteresis loss of the material is reduced, the heat generation is reduced, the Payne effect of the sizing material is reduced, and the dispersibility of the white carbon black is improved, so that the oil consumption and the emission of carbon dioxide in the running process of the tire are reduced, and the wear resistance of the tire is enhanced.

Description

Thiosulfonate-terminated mercaptosilane coupling agent and synthesis method and application thereof

Technical Field

The invention relates to a silane coupling agent, in particular to a thiosulfonate-terminated mercapto silane coupling agent, a synthesis method and application thereof.

Background

White carbon black is an inorganic filler, which is the most important inorganic reinforcing filler following carbon black because of its excellent reinforcing property, and exhibits strong polarity and high surface energy because its surface is covered with a large amount of silicon hydroxyl groups. The rubber molecules are nonpolar as alkyl chains, and when the two are blended, phase interface separation is easy to generate due to thermodynamic incompatibility.

The silane coupling agent is a silane containing two groups with different chemical properties simultaneously, including an organic functional group and a hydrolyzable silicon functional group, and the general formula of the silane coupling agent can be expressed as Y-R-SiX₃. Because the silane coupling agent molecules simultaneously have two functional groups which are organophilic and organophilic, the silane coupling agent can play a role of a molecular bridge, connect rubber molecules and white carbon black on an interface, increase the compatibility of the rubber molecules and the white carbon black, improve the dispersibility of the white carbon black, enhance the interaction of the white carbon black and the rubber, and achieve the purposes of improving the processability, the physical property and the dynamic property of the rubber. Silane coupling agents have been developed to date in the middle of the last century and are quite diverse, with hundreds of known structures. Silane coupling agents of novel structure have also been developed and reported as in recent years, such as the oligomer-type silane coupling agent Rheinfiat 1715 from Rheinchemie Rheinau, Germany; an oligomer silane coupling agent developed by Nippon shoku rubber company, having an average molecular weight of about 800; the subject group of the university of south China's Jade & Min professor grafts the silicon functional group and other functional groups of the rubber auxiliary agent segment together, and synthesizes the multifunctional silane coupling agent; several macromolecular silane coupling agents are combined on the subject of the Zhuqing increase professor of Shandong university in China and are used for improving the interaction between the silicon rubber and the white carbon black. Although development and research of novel silane coupling agents have been ongoing, only over twenty types of silane coupling agents are currently distributed in the market from the viewpoint of significance to actual industrial production, and the types of silane coupling agents that can be applied to different industrial fields are rare.

Sulfur-containing silane coupling agents are the most important class in the tire rubber industry, and can be roughly classified into three classes, namely mercaptoalkoxysilane coupling agents; one is bis (polysulfur-chain silane coupling agents) such as Si69, Si 75; still another class is thiocarboxylate-based silane coupling agents (also known as hindered mercaptosilane coupling agents NXT). The mercapto alkoxy silane coupling agent is easy to generate scorch in the processing process due to the high reactivity of the end mercapto group, so that the higher viscosity is caused, the processing and the forming are not favorable, and the application of the silane coupling agent is limited due to the unpleasant smell of the mercapto alkoxy silane coupling agent; due to higher atom economy, proper mixing temperature and final rubber viscosity of the bis (polysulfide chain silane coupling agent), the bis (polysulfide chain silane coupling agent) is the most widely used silane coupling agent at present, for example, Si69 exclusively takes the role of chelating head in the silane coupling agent for tires for a long time, the bis (polysulfide chain silane coupling agent) has multiple functions of a coupling agent, a vulcanizing agent, a lubricant, an anti-vulcanization reversion agent and the like, a longer and softer vulcanization crosslinking bond can improve the dynamic mechanical property of tire rubber, but Si69 easily causes rubber scorching in use; thiocarboxylate silane coupling agents were first discovered in the 21 st century, hydrogen on original mercapto group was replaced by carbonyl, reduced the reactivity of mercapto group, the mercapto group that is blocked is in the sub-active state, the group of blocking mercapto group can be taken off while sulfurizing, thus show the characteristic (US20040210001) that mercapto group participates in the rubber vulcanization, such as NXT can reach better effects compared with Si69 and Si75, such as reducing the sizing material viscosity, reduce the number of mixing stages, lower costs, improve the processing property of sizing material, improve the filler dispersion, improve the dynamic mechanical properties of sizing material, it is the better silane coupling agent for tire at present.

The thiocarboxylate silane coupling agent NXT can be regarded as that carbonyl carries out end capping treatment on the mercapto silane coupling agent at the end position, the silicon functional group of the coupling agent reacts with white carbon black in the mixing process to change the surface polarity of the white carbon black, the driving force of the agglomeration of the filler white carbon black is reduced, the filler-filler interaction is reduced, the filler agglomeration is inhibited, and the dispersibility of the filler is improved. However, since the conventional coupling agent does not exhibit an advantage in enhancing the interaction force between the filler and the polymer, for example, the C — S bond energy of a common alkyl group-linked C — S bond is about 305KJ/mol, and the C — S bond energy of (C ═ O) -S in NXT is about 320.1KJ/mol, the C — S bond is not easily opened under kneading conditions, so that such a silane coupling agent does not easily interact with the polymer, and the interaction force between the polymer and the filler is relatively weak. Therefore, in order to better enhance the interaction force between the polymer and the filler and simultaneously have no obvious damage to the processing performance of the rubber material, finally improve the dispersibility of the white carbon black in the rubber material, achieve the purposes of reducing the hysteresis loss of rubber and reducing the heat generation and energy loss in the running process of a tire, conceptionally design a plurality of high-activity end-capping functional groups, and graft the end-capping functional groups and the mercaptosilane coupling agent together to synthesize the novel silane coupling agent so as to improve the interaction force between the polymer and the filler, and the method has important significance.

Disclosure of Invention

In order to solve the technical problem that the silane coupling agent in the prior art cannot well improve the interaction between a polymer and a filler, the invention provides a thiosulfonate terminated mercaptosilane coupling agent.

In order to solve the technical problems, the invention adopts the following technical scheme:

a thiosulfonate-terminated mercaptosilane coupling agent has a structure shown in formula (I):

wherein, R is¹Is selected from C₁-C₁₈An alkyl, aryl or cycloalkyl group of (a); the R is²Is C_1-C₁₈An alkyl, aryl, cycloalkyl, alkenyl or alkynyl group of (a); the R is³、R⁴、R⁵At least one is a hydrolyzable chlorine, bromine, alkoxy or ester group, the others are selected from hydrogen, alkyl, aryl or cycloalkyl.

Preferably, the coupling agent may be selected from

Silane coupling agents having only one sulfur atom are capable of breaking only the C-S bond to generate a sulfur radical in order to enhance the polymer-filler interaction, such as the most commonly used (C ═ O) -S in NXT where the C-S bond energy is about 320.1KJ/mol, so that the C-S bond is difficult to open under compounding conditions, and thus the silane coupling agent does not readily interact with the polymer, and the interaction force between the polymer and the filler is relatively weak. The inventor intends to design a coupling agent capable of enhancing polymer-filler interaction under mixing conditions in the development process, and finally screens out a coupling agent with S-S bonds by synthesizing and screening a plurality of compounds, but not all coupling agents containing S-S bonds can promote polymer-filler interaction well, and finally, the inventor surprisingly discovers that a characteristic structure (O ═ S ═ O) -S-S exists in a silane coupling agent, wherein sulfonyl (O ═ S ═ O) is a strong electron group, S-S bonds can be polarized better, so that S-S bonds can be broken more easily, more active sulfur radicals can exist under mixing conditions, the sulfur radicals can form chemical bonds with polymers during mixing, polar hydrolysis ends of the coupling agent form chemical bonds with fillers, thereby enhancing the interaction between the polymer and the filler, promoting the dispersion of the filler, inhibiting the agglomeration of the filler, reducing the hysteresis loss of the rubber material, and reducing the energy loss generated by the continuous breaking and reconstruction of the network structure of the filler, thereby reducing the energy loss of the tire in the running process.

The invention also aims to provide a synthesis method of the thiosulfonate end-capped mercaptosilane coupling agent shown in the formula (I), wherein the thiosulfonate end-capped mercaptosilane coupling agent can be prepared by reacting a thiosulfonate compound with a sulfenyl chloride compound corresponding to mercaptoalkylsilane.

Preferably, the molar ratio of the thiosulfonate compound to the sulfenyl chloride compound corresponding to mercaptoalkylsilane is 1: 1.0-1.2.

Preferably, the reaction time is 8-12h, and the reaction is carried out at room temperature.

The invention provides a synthesis method of a thiosulfonate-terminated mercaptosilane coupling agent shown in formula (I), which comprises the steps of dissolving a thiosulfonate compound in an organic solvent in an inert gas atmosphere to prepare a reaction solution with the concentration of 0.4-0.8mol/L, dropwise adding a sulfenyl chloride compound corresponding to mercaptoalkylsilane into the reaction solution, reacting at room temperature, wherein the rotating speed of magnetons is 500-800r/min, and the reaction time is 8-12 h.

Preferably, after the reaction is finished, removing the solvent of the reaction system, and then carrying out column chromatography separation by using 400-mesh silica gel powder, wherein the eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 80:1-10:1, thereby finally obtaining the compound thiosulfonate end-capped mercaptosilane coupling agent.

Finally, the invention also provides the application of the thiosulfonate-terminated mercaptosilane coupling agent shown in the formula (I) in rubber mixing or vulcanization, so as to improve the interaction force between rubber and a filler and reduce hysteresis loss.

Further, the thiosulfonate-terminated mercaptosilane coupling agent is applied to raw rubber isoprene rubber or butadiene styrene/butadiene rubber, and is mixed by a conventional mixing method, and vulcanized rubber is obtained.

The invention provides a thiosulfonate-terminated mercaptosilane coupling agent shown in formula (I), which can enhance the interaction between a polymer and a filler, reduce the hysteresis loss of a rubber material, reduce heat generation, reduce the Payne effect of the rubber material, and improve the dispersibility of white carbon black, thereby reducing the oil consumption and the emission of carbon dioxide in the running process of a tire and enhancing the wear resistance of the tire. The invention adopts nucleophilic substitution reaction of thiosulfonate on sulfenyl chloride to realize the synthesis of the novel thiosulfonate-terminated mercaptosilane coupling agent for the first time.

Detailed Description

The invention discloses a thiosulfonate-terminated mercaptosilane coupling agent, a synthesis method and application thereof, and can be realized by appropriately improving process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.

The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.

Example 1

Under the atmosphere of inert gas and nitrogen, 11.32g (0.05mol) of potassium paratoluenesulfonate is dissolved in 100mL of dichloromethane in a 250mL Schlenk bottle to prepare a suspension with the concentration of 0.5mol/L, then the solution is placed in an ice water bath (0 ℃), 16.38g (0.06mol) of triethoxysilylpropyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1:1.2, the rotation speed of magnetons is 600r/min, the reaction time is 10h, and the reaction progress is tracked by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then carrying out column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 50:1-10:1, so as to obtain 14g of the compound. The coupling agent is characterized by a thiosulfonate terminated mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high-resolution mass spectrum, and the data are as follows:¹H NMR(600MHz,CDCl₃)δ7.80(d,J＝8.2Hz,2H),7.32(d,J＝8.0Hz,2H),3.80(q,J＝7.0Hz,6H),3.14(t,J＝7.3Hz,2H),2.44(s,3H),1.86-1.75(m,2H),1.20(t,J＝7.0Hz,9H),0.72-0.62(m,2H).¹³C NMR(150MHz,CDCl₃) δ 145.22,142.84,130.35,128.51,58.58,39.00,22.83,21.75,18.40,10.02.ESI-MS:447.0760, calculated as (M + Na): 447.0766, respectively; the reaction formula of the above reaction is shown below:

the compound thiosulfonate end-capped mercaptosilane coupling agent prepared by the synthetic method, bis- (gamma-propyltriethoxysilane) (Si69) tetrasulfide and 3-thiocaprylate-1-propyltriethoxysilane (NXT) are applied to raw rubber isoprene rubber to be mixed and vulcanized by a conventional mixing method and a formula (table 1), and the corresponding rubber material is subjected to performance detection, wherein the detection result is shown in table 2.

The common mixing process is carried out by three sections, wherein one section is to keep the temperature of the raw rubber isoprene rubber, the white carbon black and the silane coupling agent at 150 ℃ for 2 min; in the second stage, stearic acid, zinc oxide, protective wax and an anti-aging agent are added into the first-stage rubber compound to carry out mixing reaction, and the mixture is heated to 150 ℃; mixing the accelerant, the sulfur and the second-stage rubber compound to obtain final rubber compound in the third stage;

vulcanizing the final rubber on a flat vulcanizing machine, wherein the vulcanization temperature is 150 ℃, and the vulcanization time of a tensile and tearing test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness and compression heat generation test specimens was (tc90+10) min.

Table 1: IR mixing formula detail

Wherein, the structures of Si69 and NXT in Table 1 are as follows:

TABLE 2 elastomeric compound/vulcanizate Properties measurements

Injecting: the Si69 stock data were all set to 100, and the other stock data were percentages of their true data to the Si69 true data.

the tan delta value can be used for representing the hysteresis loss of the rubber compound, the smaller the tan delta value is, the lower the hysteresis loss is, and the data in the table 2 show that the thiosulfonate-terminated mercaptosilane coupling agent obtained in the embodiment can improve the hysteresis loss of the isoprene rubber compound.

ΔG'_{(0.1％-25％)}The value represents the Payne effect of the sizing material, and further reflects the dispersibility of the white carbon black in the sizing material, delta G'_{(0.1％-25％)}The smaller the value is, the smaller the Payne effect is, and the better the dispersibility of the white carbon black is; data in Table 2 show that from Δ G'_{(0.1％-25％)}The value data show that the thiosulfonate terminated mercaptosilane coupling agent obtained in the embodiment can reduce Payne effect of the sizing material and improve the dispersibility of white carbon black in the sizing material.

300 stretch/100 stretch, the bound gum content can characterize the polymer-filler interaction to a certain extent, generally speaking, the greater the 300 stretch/100 stretch, the higher the bound gum content, the stronger the polymer-filler interaction; the data in table 2 show that the thiosulfonate-terminated mercaptosilane coupling agent obtained in this example can enhance the polymer-filler interaction and, to a certain extent, the abrasion resistance of the tire.

The thiosulfonate-terminated mercaptosilane coupling agent obtained in the example, bis- (gamma-propyltriethoxysilane) tetrasulfide (Si69) and 3-thiooctanoate-1-propyltriethoxysilane (NXT) were applied to raw styrene-butadiene/butadiene rubber to be mixed and vulcanized by a conventional mixing method and a formula (table 3), and the corresponding rubber compound was subjected to performance testing, with the test results shown in table 4.

The mixing process is carried out in three stages, and in the first stage, raw rubber butylbenzene/butadiene rubber, white carbon black, a silane coupling agent, stearic acid, zinc oxide, protective wax and an anti-aging agent are subjected to heat preservation for 2min at the temperature of 150 ℃; in the second stage, the first-stage rubber compound is thermally treated to 150 ℃; mixing the accelerant, the sulfur and the second-stage rubber compound to obtain final rubber compound in the third stage;

vulcanizing the final rubber on a flat vulcanizing machine, wherein the vulcanization temperature is 165 ℃, and the vulcanization time of a tensile and tearing test sample is (tc90+5) min; the vulcanization time of the elasticity, hardness and compression heat generation test specimens was (tc90+10) min.

TABLE 3 SBR/BR compounding recipe

TABLE 4 elastomeric compound/vulcanizate Properties measurements

The data in Table 4 show that tan delta values can be used to characterize the hysteresis loss of the compound, with lower tan delta values giving lower hysteresis losses. Thus, the tan delta data in Table 4 shows that the coupling agent obtained in example 1 can improve the hysteresis loss of butylbenzene/butadiene rubber.

ΔG'_{(0.1％-25％)}The value represents the Payne effect of the sizing material, and further reflects the dispersibility of the white carbon black in the sizing material, delta G'_{(0.1％-25％)}The smaller the value, the smaller the Payne effect, the better the white carbon black dispersibility, from G'_{(0.1％-25％)}The value data show that the thiosulfonate terminated mercaptosilane coupling agent obtained in the embodiment can reduce Payne effect of the sizing material and improve the dispersibility of white carbon black in the sizing material.

The 300/100 elongation, bound gel content in the data of Table 4, characterizes the interaction of polymer and filler to some extent, in general, the greater the 300/100 elongation, the higher the bound gel content, and the stronger the interaction of polymer and filler; therefore, the two data show that the thiosulfonate terminated mercaptosilane coupling agent obtained by the implementation can better enhance the interaction between the polymer and the filler and enhance the wear resistance of the tire to a certain extent.

Example 2

Under the atmosphere of inert gas argon, 11.32g (0.05mol) of potassium paratoluenesulfonate is dissolved in 125mL of tetrahydrofuran in a 250mL Schlenk bottle to prepare a suspension with the concentration of 0.4mol/L, then the solution is placed in an ice water bath (0 ℃), 13.65g (0.055mol) of triethoxysilylpropyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1:1.1, the rotation speed of magnetons is 800r/min, the reaction time is 12h, and the reaction progress is tracked through TLC detection. After the reaction is finished, the chlorination is removed by filtrationRemoving the solvent by using a rotary evaporator, and then carrying out column chromatography separation by using 400-mesh silica gel powder, wherein the eluent system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 50:1-10:1, so as to obtain 13g of the compound. The coupling agent is characterized by a thiosulfonate terminated mercaptosilane coupling agent through a nuclear magnetic resonance spectrum and a high-resolution mass spectrum, and the data are as follows:¹H NMR(600MHz,CDCl₃)δ7.80(d,J＝8.2Hz,2H),7.32(d,J＝8.0Hz,2H),3.80(q,J＝7.0Hz,6H),3.14(t,J＝7.3Hz,2H),2.44(s,3H),1.86-1.75(m,2H),1.20(t,J＝7.0Hz,9H),0.72-0.62(m,2H).¹³C NMR(150MHz,CDCl₃) δ 145.22,142.84,130.35,128.51,58.58,39.00,22.83,21.75,18.40,10.02.ESI-MS:447.0760, calculated as (M + Na): 447.0766, respectively; the reaction formula of the above reaction is shown below:

example 3

Under the atmosphere of inert gas and nitrogen, 5.66g (0.025mol) of potassium paratoluenesulfonate is dissolved in 40mL of toluene in a 100mL Schlenk bottle to prepare a suspension with the concentration of 0.625mol/L, then the solution is placed in an ice water bath (0 ℃), 7.51g (0.0275mol) of triethoxysilylpropyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1:1.1, the rotation speed of magnetons is 500r/min, the reaction time is 8h, and the reaction progress is tracked through TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 50:1-10:1, so that 5.5g of the compound is obtained. The compound is characterized by a nuclear magnetic resonance spectrum and a high-resolution mass spectrum, and the data are as follows:¹H NMR(600MHz,CDCl₃)δ7.80(d,J＝8.2Hz,2H),7.32(d,J＝8.0Hz,2H),3.80(q,J＝7.0Hz,6H),3.14(t,J＝7.3Hz,2H),2.44(s,3H),1.86-1.75(m,2H),1.20(t,J＝7.0Hz,9H),0.72-0.62(m,2H).¹³C NMR(150MHz,CDCl₃) δ 145.22,142.84,130.35,128.51,58.58,39.00,22.83,21.75,18.40,10.02.ESI-MS:447.0760, calculated as (M + Na): 447.0766, respectively; the reaction formula of the above reaction is as followsThe following:

example 4

Under the atmosphere of inert gas nitrogen, 5.66g (0.025mol) of potassium paratoluenesulfonate is dissolved in 31mL of carbon tetrachloride in a 100mL Schlenk bottle to prepare a suspension with the concentration of 0.8mol/L, then the solution is placed in an ice water bath (0 ℃), 6.83g (0.025mol) of triethoxysilylpropyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1:1, the rotation speed of magnetons is 700r/min, the reaction time is 10h, and the reaction progress is tracked by TLC detection. After the reaction is finished, filtering to remove potassium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 50:1-10:1, so as to obtain 5g of the compound. The compound is characterized by a nuclear magnetic resonance spectrum and a high-resolution mass spectrum, and the characterization data is as follows:¹H NMR(600MHz,CDCl₃)δ7.80(d,J＝8.2Hz,2H),7.32(d,J＝8.0Hz,2H),3.80(q,J＝7.0Hz,6H),3.14(t,J＝7.3Hz,2H),2.44(s,3H),1.86-1.75(m,2H),1.20(t,J＝7.0Hz,9H),0.72-0.62(m,2H).¹³C NMR(150MHz,CDCl₃) δ 145.22,142.84,130.35,128.51,58.58,39.00,22.83,21.75,18.40,10.02.ESI-MS:447.0760, calculated as (M + Na): 447.0766, respectively; the reaction formula of the above reaction is shown below:

example 5

Under the atmosphere of inert gas and nitrogen, 3.70g (0.025mol) of sodium ethanethiosulfonate is dissolved in 50mL of dichloromethane in a 100mL Schlenk bottle to prepare a suspension with the concentration of 0.5mol/L, then the solution is placed in an ice water bath (0 ℃), 8.20g (0.03mol) of triethoxysilylpropyl sulfenyl chloride is dripped into the solution system, the solution is placed at room temperature after the dripping, the molar ratio is 1.2:1, the magneton rotating speed is 600r/min, the reaction time is 10h, and the reaction progress is tracked by TLC detection. After the reaction is finishedThen filtering to remove sodium chloride, removing the solvent by using a rotary evaporator, and then performing column chromatography separation by using 400-mesh silica gel powder, wherein an eluant system is petroleum ether and ethyl acetate, and the gradient elution polarity selection range is 80:1-10:1, so as to obtain 5.5g of the compound. The compound is characterized by a nuclear magnetic resonance spectrum and a high-resolution mass spectrum, and the characterization data is as follows:¹H NMR(600MHz,CDCl₃)δ3.78(q,J＝7.0Hz,6H),3.36(q,J＝7.3Hz,2H),3.01(t,J＝7.3Hz,2H),1.78-1.70(m,2H),1.46(t,J＝7.3Hz,3H),1.18(t,J＝7.0Hz,9H),0.66-0.57(m,2H).¹³C NMR(150MHz,CDCl₃) δ 58.54,55.83,38.90,22.76,18.38,9.98,8.57.ESI-MS:385.0622, calculated as (M + Na): 385.0609, respectively; the reaction formula of the above reaction is shown below:

the compound obtained by the embodiment can enhance the interaction between the polymer and the filler, reduce the hysteresis loss of the rubber material, reduce heat generation, reduce the Payne effect of the rubber material, and improve the dispersibility of the white carbon black, so that the oil consumption and the carbon dioxide emission of the tire in the running process are reduced, the wear resistance of the tire is enhanced, and the effect data are not repeated herein.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A thiosulfonate-terminated mercaptosilane coupling agent has a structure shown in formula (I):

wherein, R is¹Is selected from C₁-C₁₈An alkyl, aryl or cycloalkyl group of (a); the R is²Is C_1-C₁₈Alkyl, aryl, cycloalkyl,Alkenyl or alkynyl; the R is³、R⁴、R⁵At least one is a hydrolyzable chlorine, bromine, alkoxy or ester group, the others are selected from hydrogen, alkyl, aryl or cycloalkyl.

2. The thiosulfonate-terminated mercaptosilane coupling agent of claim 1 selected from the group consisting of

3. The method for synthesizing the thiosulfonate-terminated mercaptosilane coupling agent according to claim 1 or 2, wherein the thiosulfonate-terminated mercaptosilane coupling agent is obtained by reacting a thiosulfonate-based compound with a sulfenyl chloride compound corresponding to mercaptoalkylsilane.

4. The method of claim 3, wherein the molar ratio of said thiosulfonate compound to the corresponding sulfenyl chloride compound of mercaptoalkylsilane is from 1:1.0 to 1.2.

5. The synthesis method according to claim 3, wherein the reaction is carried out at room temperature for 8-12 h.

6. The method as claimed in claim 3, wherein the reaction is carried out by dissolving thiosulfonate compound in organic solvent under inert gas atmosphere to obtain reaction solution with concentration of 0.4-0.8mol/L, adding mercaptoalkylsilane corresponding sulfenyl chloride compound dropwise into the reaction solution, reacting at room temperature with magneton rotation speed of 500-800r/min and reaction time of 8-12 h.

7. The synthesis method of claim 3 or 6, wherein after the reaction is finished, the solvent of the reaction system is removed, and then column chromatography separation is carried out by using 400-mesh silica gel powder, the eluant system is petroleum ether and ethyl acetate, the gradient elution polarity selection range is 80:1-10:1, and finally the compound thiosulfonate terminated mercaptosilane coupling agent is obtained.

8. Use of the thiosulfonate-terminated mercaptosilane coupling agent of claim 1 in rubber compounding or vulcanization to increase the interaction force between rubber and filler to reduce hysteresis loss.

9. The use of claim 8, wherein: and (3) applying the thiosulfonate-terminated mercaptosilane coupling agent to raw rubber isoprene rubber or butylbenzene/butadiene rubber, mixing, and vulcanizing to obtain vulcanized rubber.