Silicon group-containing functionalized SEBS thermoplastic elastomer and preparation method thereof

Abstract

The invention belongs to the technical field of high polymer material modification, and particularly relates to a silicon group-containing functionalized SEBS thermoplastic elastomer which is a linear / star-shaped coupled silicon group-containing functionalized polystyrene-(ethylene / 1-butene) block copolymer. The polystyrene block is composed of a copolymer of styrene and a silicon-containing group functionalized 1, 1-diphenylethylene (DPE) derivative. The prepared SEBS containing the silicon group is a macromolecule, and the viscosity is obviously improved. In the processing process, the SEBS containing the silicon group is easily converted into a silicon hydroxyl group, the silicon hydroxyl group, hydroxyl and the like easily form a covalent bond or a hydrogen bond, the compatibility and the dispersity of the material are improved, and the SEBS containing the silicon group has a very good application prospect in the fields of asphalt modification, adhesive modification, polymer modification and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer material modification, and particularly relates to a kind of functionalized SEBS thermoplastic elastomer containing silicon group and a preparation method thereof. BACKGROUND

[0002] Styrene-butadiene-styrene triblock copolymer (SBS) is a kind of styrene thermoplastic elastomer with physical crosslinking points, which exhibits rubber characteristics in a wide temperature range. The polystyrene segment (PS) is uniformly distributed in the continuous phase composed of polybutadiene (PB) soft segment, and at room temperature, the PS segment acts as a physical crosslinking point to form a network structure similar to vulcanization. The material exhibits high elasticity of rubber. At high temperature, the PS aggregate state thermal deformation melts, and the material exhibits thermoplasticity, with the advantages of large surface friction coefficient, good low-temperature processing performance, etc. It is often used in asphalt modification, adhesive, polymer modification, shoe material, lubricating oil tackifier, wire and cable, etc. fields. The styrene-(ethylene / 1-butene)-styrene triblock copolymer (SEBS) obtained by selective hydrogenation of SBS retains the thermoplasticity and high elasticity of SBS, and has excellent heat resistance, oxygen resistance and resistance to ultraviolet radiation. Its application range is constantly expanding, and it can be applied in wire and cable protective sleeve, polymer modification and high-end elastomer fields. It belongs to the second generation of thermoplastic elastomers and has higher value than SBS. However, as a non-polar polymer material, SEBS is difficult to be blended with polar polymer materials and polar fillers, and its adhesion to metal materials is also poor, which limits its application field.

[0003] Functional modification is a common method to modify the properties of polymers. Different methods can be used for different polymers. Currently, the following methods are mainly used for functional SEBS technology: The polar SEBS (SEBS-P) and its preparation method disclosed in CN1749290A are obtained by polymerization of polyvinylpyridine and methacrylate polar monomers. SEBS-P has obvious polarity and better performance than ordinary SEBS. KRATON FG1901X thermoplastic rubber of SEBS of American company KRATON is a terpolymer grafted with maleic anhydride, which can effectively improve the compatibility of different raw materials: when used with other KRATON FG polymers, a copolymer with stable performance, excellent oxidation resistance and UV resistance can be obtained; when mixed with some engineering plastics, the impact strength of the engineering plastics can be greatly improved, and the compatibility between different engineering plastics can be improved. The current methods for polar functionalization of SEBS include direct copolymerization with polar monomers to introduce polar blocks into the polymer, or post-functionalization of SEBS. The current polar SEBS has the problems of unclear distribution of polar functional groups in the chain, uncontrollable functionalization efficiency, etc. Therefore, it is necessary to develop SEBS with clear "quantitative" and accurate "positioning" of polar functional group distribution, so as to improve the utilization efficiency of functional groups. CN112759730A discloses a kind of amine group multifunctional SEBS thermoplastic elastomer and its preparation method. Based on the active anion polymerization technology, a chain amine group DPE multifunctional SEBS is developed to improve the mechanical properties of SEBS thermoplastic elastomer and the compatibility with other polar materials. However, the amine group multifunctional SEBS prepared by this method has the following limitations: first, the polymer chain contains not less than 2 amine group functional DPE derivatives, and for some specific materials such as polyvinyl alcohol, there is no need for chain functionalization or too many functional groups; second, when the amine group functional SEBS is blended with other materials, the hydrogen bonding or ionic bonding mechanism between the amine group and other materials is used, but materials such as silicone rubber do not have the above mechanism with amine group, and the application occasions are limited; third, since the amine group is an electron-donating group, the activity of the amine group substituted DPE derivative is low, which reduces the reaction rate of the amine group substituted DPE derivative and styrene monomer; fourth, the amine group functional DPE and styrene monomer are added at the same time, which may lose the control of the chain initiation end and termination end, resulting in significant chain end effect of the prepared amine group multifunctional SEBS.

[0004] In order to solve the problems of uncontrollable number and position of functional groups, limited application occasions, low reaction rate and poor chain end controllability of amine group functional SEBS in the prior art, it is urgent to develop a kind of silicon group functional SEBS thermoplastic elastomer and its preparation method. SUMMARY

[0005] To solve the problems of the number of functional groups, the position of the functional groups uncontrollable, the application occasions limited, the low conversion rate and the poor controllability of the chain end of the amine group functionalized SEBS in the prior art, the application provides a kind of silicon group functionalized SEBS thermoplastic elastomer.The silicon group functionalized 1,1-diphenyl ethylene can be accurately distributed at the initiation end, the middle of the chain and the end of the chain of the styrene block by adding the silicon group containing 1,1-diphenyl ethylene derivative comonomer, and different silicon group functionalized SEBS thermoplastic elastomers with different properties can be obtained according to different requirements to meet the diversified market demand.

[0006] In the first aspect, the application provides a kind of silicon group functionalized SEBS thermoplastic elastomer, the silicon group functionalized SEBS thermoplastic elastomer is linear / star coupling silicon group functionalized styrene-(ethylene / 1-butene) block copolymer, specifically, it is linear / star coupling silicon group functionalized copolymer of styrene block and ethylene / 1-butene block;

[0007] The styrene block is a copolymer block of styrene and silicon group functionalized 1,1-diphenyl ethylene derivative;

[0008] The ethylene / 1-butene block is a random copolymer of ethylene and 1-butene.

[0009] Further, the silicon group functionalized 1,1-diphenyl ethylene derivative is polymerized at at least one position of the chain initiation end, the middle of the chain and the end of the chain of the polystyrene block.

[0010] Further, the number average molecular weight (M n ) of the silicon group functionalized SEBS thermoplastic elastomer ranges from 2×10 4 to 90×10 4 g / mol, and the molecular weight distribution (PDI) ranges from 1.02 to 1.60.

[0011] Further, the silicon group functionalized 1,1-diphenyl ethylene derivative is selected from silicon group, silicon group / amine group functionalized 1,1-diphenyl ethylene derivative, including but not limited to single silicon oxygen group, single silicon hydrogen group, double silicon oxygen group, double silicon hydrogen group, silicon oxygen group / silicon hydrogen group, silicon oxygen group / amine group, silicon hydrogen group / amine group functionalized 1,1-diphenyl ethylene derivative monomer;The silicon group and silicon group / amine group are connected to the para, meta or ortho position of the phenyl group in the 1,1-diphenyl ethylene derivative.

[0012] Further, the linear / star coupled silicon group functionalized styrene-(ethylene / 1-butene) block copolymer is obtained by selective hydrogenation of a linear / star coupled silicon group functionalized styrene-butadiene block copolymer, wherein the hydrogenation degree of the linear / star coupled styrene-(ethylene / 1-butene) block copolymer ranges from 50% to 100%, preferably from 85% to 100%.

[0013] Further, the linear / star coupled silicon group functionalized styrene-butadiene block copolymer comprises 20% to 50% of the silicon group functionalized styrene block, and the rest is the butadiene block, based on 100% of the mass of the linear / star coupled silicon group functionalized styrene-butadiene block copolymer.

[0014] Further, the mass percentage of the silicon group functionalized 1,1-diphenyl ethylene derivative monomer in the silicon group functionalized styrene block is 0.1% to 50.0%, preferably 5.0% to 30.0%, based on 100% of the mass of the silicon group functionalized styrene block.

[0015] Further, the linear / star coupled silicon group functionalized styrene-butadiene block copolymer comprises 20% to 50% of the silicon group functionalized styrene block, and the rest is the butadiene block, based on 100% of the mass of the linear / star coupled silicon group functionalized styrene-butadiene block copolymer.

[0016] Further, the silicon group functionalized 1,1-diphenyl ethylene derivative is selected from:

[0017] (1) The silicon group functionalized 1,1-diphenyl ethylene derivative monomer is 1-[4-R1phenyl]-1-phenyl ethylene, and the silicon group functionalized 1,1-diphenyl ethylene derivative monomer is 1,1-di[4-R1phenyl] ethylene, wherein R1 is a silicon group selected from trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tri-t-butoxysilyl, dimethylmethoxysilyl, diethylmethoxysilyl;

[0018] (2) The silicon group functionalized 1,1-diphenyl ethylene derivative monomer is 1-[4-R1phenyl]-1-phenyl ethylene, and the silicon group functionalized 1,1-diphenyl ethylene derivative monomer is 1,1-di[4-R1phenyl] ethylene, wherein R1 is a silicon group selected from trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tri-t-butoxysilyl, dimethylmethoxysilyl, diethylmethoxysilyl;

[0019] (3) 1,1-diphenyl ethylene derivative monomer of siloxy group / silicon hydride group is 1-[4-R1phenyl]-1-[R2-phenyl] ethylene, wherein R1 is a siloxy group, selected from trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tri-t-butoxysilyl, dimethylmethoxysilyl, diethylmethoxysilyl; R2 is a silicon hydride group, selected from dimethylsilhydride, diethylsilhydride, dipropylsilhydride, diisopropylsilhydride, di-t-butylsilhydride;

[0020] (4) 1,1-diphenyl ethylene derivative monomer of siloxy group / amine group is 1-[4-R1phenyl]-1-[4-R3phenyl] ethylene, wherein R1 is a siloxy group, selected from trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tri-t-butoxysilyl, dimethylmethoxysilyl, diethylmethoxysilyl, R3 is an amine group, selected from N,N-dimethylamine, N,N-diethylamine, N,N-di-t-butylamine;

[0021] (5) 1,1-diphenyl ethylene derivative monomer of silicon hydride group / amine group is 1-[4-R2phenyl]-1-[4-R3phenyl] ethylene, wherein R2 is a silicon hydride group, selected from dimethylsilhydride, diethylsilhydride, dipropylsilhydride, diisopropylsilhydride, di-t-butylsilhydride, R3 is an amine group, selected from N,N-dimethylamine, N,N-diethylamine, N,N-di-t-butylamine;

[0022] Further, the 1,1-diphenyl ethylene derivative functionalized with a silicon-containing group is at least one selected from 1-[4-(triisopropoxysilyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene, 1-[4-(dimethylsilhydride)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene, 1-[4-(triisopropoxysilyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene, 1-[4-(dimethylsilhydride)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene.

[0023] In a second aspect, the present application provides a preparation method of a silicon-containing group functionalized SEBS thermoplastic elastomer, comprising the following steps:

[0024] Step S1, preparing a silicon-containing group functionalized polystyrene active center:

[0025] In a non-polar hydrocarbon solvent, a measured amount of a polar regulator is added to the reactor, and according to different monomer feeding sequences and ratios, a measured amount of styrene and a silicon group functionalized 1,1-diphenyl ethylene derivative monomer, an alkyl lithium initiator and a polar regulator are added according to the monomer ratio, stirred uniformly, the initiation reaction temperature is 10-90℃, and the reaction time is 0.5-48h;

[0026] In the formula, the feeding ratio of styrene and the silicon group functionalized 1,1-diphenyl ethylene derivative monomer is 1-999:1 by mass fraction; the addition amount ratio of the initiator and the polar regulator is 1:1-50; the feeding ratio of the initiator and the raw material is 1:1×10 5 -2.5×10 5 .

[0027] Step S2, preparation of a silicon group functionalized polystyrene-butadiene active center: after the reaction of step S1 is completed, a measured amount of butadiene monomer is added to the reactor according to the monomer ratio, the reaction temperature is controlled at 50-110℃, and the reaction time is 0.5-10h, to prepare a linear / star coupling silicon group functionalized polystyrene-butadiene block polymer precursor, i.e., a silicon group functionalized polystyrene-butadiene active center; wherein the feeding ratio of styrene and the silicon group functionalized 1,1-diphenyl ethylene derivative monomer, which are composed of styrene monomers, is 1:1-4 by mass content;

[0028] Step S3, preparation of a linear / star coupling silicon group functionalized styrene-butadiene block copolymer: after the reaction of step S2 is completed, a measured amount of a linear / star coupling agent is added to perform coupling reaction, the reaction temperature is 50-110℃, and the reaction time is 30-150min, to prepare a linear / star coupling silicon group functionalized styrene-butadiene block copolymer glue solution;

[0029] Step S4, preparation of a silicon group functionalized SEBS thermoplastic elastomer:

[0030] The linear / star coupling silicon group functionalized styrene-butadiene block copolymer glue solution is transferred to a high-pressure hydrogenation kettle, a solvent is added for dilution, a measured amount of a hydrogenation catalyst and hydrogen are added for hydrogenation reaction, the hydrogen pressure is controlled at 0.1Mpa-10Mpa, the reaction temperature is controlled at 50-200℃, and the hydrogenation reaction time is 1-20h, to obtain a silicon group functionalized SEBS thermoplastic elastomer.

[0031] Further, in step S1, a measured amount of a polar regulator is added to the reactor in a non-polar hydrocarbon solvent as system A;

[0032] The monomer ratio is added to the system A, the amount of silicon group functionalized 1,1-diphenyl ethylene derivative monomer and alkyl lithium initiator, the reaction temperature is 10-90℃, then the amount of styrene monomer is added, as system B;

[0033] The monomer ratio is added to the system A, the amount of 1,1-diphenyl ethylene derivative and styrene monomer, then the amount of alkyl lithium initiator is added, the reaction temperature is 10-90℃, as system C;

[0034] The monomer ratio is added to the system A, the amount of 1,1-diphenyl ethylene derivative and styrene monomer, then the amount of alkyl lithium initiator is added, the reaction temperature is 10-90℃, as system C;

[0035] In system B / C / D, the ratio of styrene monomer, silicon group functionalized 1,1-diphenyl ethylene derivative monomer, alkyl lithium initiator and polar modifier can accurately control the distribution, nature (type), number and mass percentage of silicon group functionalized 1,1-diphenyl ethylene derivative in the chain end and chain of styrene block.

[0036] Further, the mass concentration of all monomers added in step S1 is 5%-25%, preferably 8-12%, which is determined according to the type and amount of silicon group functionalized 1,1-diphenyl ethylene derivative monomer.

[0037] Further, when the mass concentration of all reaction monomers in step S1 is 5%-25%, the silicon group functionalized 1,1-diphenyl ethylene derivative monomer is located at the chain end of the styrene block.

[0038] When the mass concentration of all reaction monomers in step S1 is less than 10%, the mass concentration of monosilicon hydrogen group functionalized 1,1-diphenyl ethylene derivative monomer, or monosilicon oxygen group functionalized 1,1-diphenyl ethylene derivative monomer, or silicon oxygen group / silicon hydrogen group 1,1-diphenyl ethylene derivative monomer and styrene is 5%-15%, or the mass concentration of silicon oxygen group / amine group 1,1-diphenyl ethylene derivative monomer, or silicon hydrogen group / amine group 1,1-diphenyl ethylene derivative monomer and styrene is 15%-25%; the silicon group functionalized 1,1-diphenyl ethylene derivative in the group functionalized styrene block is located in the chain and the chain end of the block;

[0039] When the mass concentration of all the reaction monomers in the step S1 is higher than 10%, the mass concentration of the monosilicon hydride group functionalized 1,1-diphenyl ethylene derivative monomer, or the monosilicon oxygen group functionalized 1,1-diphenyl ethylene derivative monomer, or the 1,1-diphenyl ethylene derivative monomer of silicon oxygen group / silicon hydride group and styrene is 5%-10%, or the mass concentration of the 1,1-diphenyl ethylene derivative monomer of silicon oxygen group / amine group or the 1,1-diphenyl ethylene derivative monomer of silicon hydride group / amine group and styrene is 10%-15% is added, the silicon group functionalized 1,1-diphenyl ethylene derivative in the obtained silicon group functionalized styrene block is located in the chain and the chain end of the block. The unit of mass concentration is g / l.

[0040] The non-polar hydrocarbon solvent used in the present application is selected from at least one of non-polar aromatic hydrocarbon and non-polar aliphatic hydrocarbon, and is generally selected from benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbon (such as: mixed xylene), mixed aliphatic hydrocarbon (such as: raffinate oil), and preferably selected from benzene, toluene, pentane, hexane, cyclohexane.

[0041] Further, the polar regulator in the step S1 is selected from one or a mixture of several of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and alkoxy metal compounds, and is preferably tetrahydrofuran, 2,2-di(2-tetrahydrofuran) propane, 2,2-di(5-methyl-2-tetrahydrofuran) propane, ethyl tetrahydrofurfuryl ether, tetramethyl ethylenediamine, pentamethyldiethylenetriamine, dipiperidyl ethane, potassium tert-butoxide / sodium alcohol, diethylene glycol diethyl ether; whether to use a polar additive in the step S1 is determined according to the designed 1,2-butadiene microstructure.

[0042] Further, the alkyl lithium initiator in the step S1 is selected from one or a mixture of several of any monofunctional alkyl lithium RLi initiators that can be used for butadiene, styrene anionic polymerization, R is a hydrocarbon group with a carbon atom number of 2-20, which can be an alkane group or an aromatic group, and is preferably n-butyllithium, sec-butyllithium and tert-butyllithium.

[0043] Further, the linear coupling agent in the step S3 is selected from M(CH3)2Cl2 or 1,2-dichloroethane or 1,2-dibromoethane, and M is selected from silicon (Si), tin (Sn), lead (Pb), titanium (Ti), germanium (Ge) metal elements, and is preferably dichlorodimethylsilane.

[0044] Further, the star coupling agent in step S3 is selected from two different coupling mechanisms, one is selected from one of MCH3Cl3, MCl4, M2Cl6, M3Cl8, M is selected from silicon (Si), tin (Sn), lead (Pb), titanium (Ti), germanium (Ge) and the like, preferably tetrachlorosilane and tin tetrachloride; the other is divinylbenzene (DVB).

[0045] Further, the hydrogenation catalyst in step S4 is selected from nickel or metallocene titanium metal catalyst, preferably triisobutyl aluminum \ nickel naphthenate catalyst.

[0046] Advantages:

[0047] Compared with the prior art, (1) the complex silicon-containing group functionalized 1,1-diphenyl ethylene derivative is used in the present application, the silicon-containing group is an electron-withdrawing group, which can stabilize the carbanion more easily, so that the activity of monomer copolymerization is improved, the conversion rate of monomers is improved in the same polymerization time, the styrene reactivity is regulated by controlling the ratio of the 1,1-diphenyl ethylene derivative to the styrene monomer, the ratio of the 1,1-diphenyl ethylene derivative to the alkyl lithium initiator, and the ratio of the 1,1-diphenyl ethylene derivative to the polarity regulator, and the 1,1-diphenyl ethylene derivative is selectively and accurately distributed at the initiation end, the terminal end and the chain of the styrene block in a true sense by regulating the feeding sequence of the 1,1-diphenyl ethylene derivative and the styrene monomer, the properties and mass fraction of the silicon-containing group functionalized 1,1-diphenyl ethylene derivative can be controlled, the silicon-containing group is used on demand, and the utilization efficiency of the silicon group is improved; (2) compared with the linear SBS generated by a three-step feeding method, the silicon-containing group functionalized SBS is essentially prepared by a two-step feeding method in the present application, that is, the silicon-containing group functionalized polystyrene block is generated in the first step, the polystyrene-diene two-block polymer is synthesized in the second step, and then the coupling agent is introduced to synthesize the linear / branched coupling silicon-containing group functionalized styrene-diene three-block copolymer with higher molecular weight, better melt flow performance and better solubility, the present application has the technical effects of being more simple and easy to implement and better; (3) the active center is consumed after the SBS is prepared by the coupling method in the present application, so that the remaining active center can react with the hydrogenation catalyst, which helps to improve the hydrogenation efficiency; (4) the silicon-containing group SEBS prepared in the present application is easy to be converted into silicon hydroxyl group during the processing, the silicon hydroxyl group and the hydroxyl group can form covalent bond or hydrogen bond, which improves the compatibility and dispersibility of the material, and can be used in the fields of asphalt modification, adhesive, polymer modification and the like; (5) the microstructure content of 1,2-butadiene in the SBS is regulated by using the polarity regulator in the present application, and then the microstructure content of 1-butene in the SEBS is regulated, so that the mechanical properties of the SEBS thermoplastic elastomer can be regulated. DETAILED DESCRIPTION

[0048] In order to more clearly understand the above-mentioned purposes, features and advantages of the present application, the solutions of the present application will be further described below. It should be noted that the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.

[0049] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. However, it will be apparent to one skilled in the art that the present application can be practiced without the specific details given herein. In other instances, well-known methods have not been described in detail in order to avoid unnecessarily obscuring the present application.

[0050] The preferred embodiments of the present application will be described in detail below with reference to examples. It should be understood that the following examples are given for illustrative purposes only and are not meant to limit the scope of the present application. Those skilled in the art can make various modifications and substitutions to the present application without departing from the spirit and scope of the present application.

[0051] In this embodiment, nuclear magnetic resonance spectrometer is used to analyze the copolymer composition sequence distribution and microstructure, and gel permeation chromatograph is used to analyze the molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the copolymer.

[0052] According to the standard of GBT 528-2009, the tensile strength, tensile modulus and elongation at break of the sample are recorded by using a universal material testing machine at a tensile rate of 500 mm / min and a test temperature of 23°C, and each sample is repeated at least 5 times.

[0053] Example 1

[0054] Step S1, preparation of a single silicon hydride group functionalized polystyrene active center: under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent is added to a 5L polymerization kettle, and tetrahydrofuran (2.8g, 39mmol) and 1-[4-(dimethylsilyl)phenyl]-1-phenyl ethylene (single silicon hydride DPE, 20.0g, 84mmol) are added thereto, stirred uniformly, and n-butyllithium (2.6mmol, 1.6mol / L) is added, the initiation temperature is 50°C, and the reaction is carried out for 30min, and then styrene (110g, 1.06mol) is added to carry out the first-stage polymerization reaction, and the reaction is carried out for 48h;

[0055] Step S2, preparation of a single silicon hydride group functionalized polystyrene active center: under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent is added to a 5L polymerization kettle, and tetrahydrofuran (2.8g, 39mmol) and 1-[4-(dimethylsilyl)phenyl]-1-phenyl ethylene (single silicon hydride DPE, 20.0g, 84mmol) are added thereto, stirred uniformly, and n-butyllithium (2.6mmol, 1.6mol / L) is added, the initiation temperature is 50°C, and the reaction is carried out for 30min, and then styrene (110g, 1.06mol) is added to carry out the first-stage polymerization reaction, and the reaction is carried out for 48h;

[0056] Step S3, preparation of a star-shaped coupled single silicon hydride group functionalized styrene-butadiene block copolymer: silicon tetrachloride coupling agent (0.11g, 0.65mmol) and divinylbenzene (0.01g, 0.07mmol) are added to the above polymerization kettle, the reaction temperature is 50°C, and the coupling reaction is carried out for 120min;

[0057] Step S4, preparing SEBS thermoplastic elastomer with silane-hydrogen functionalization: the star-coupled styrene-butadiene block copolymer solution with silane-hydrogen functionalization is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added as a triisobutylaluminum / nickel naphthenate catalyst and hydrogen to carry out hydrogenation reaction. The hydrogen pressure is controlled at 3 MPa, the reaction temperature is 60℃, and the reaction is carried out for 3 h.

[0058] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1 The structure was analyzed by HNMR, and the results are as follows: The mass of the prepared product was 234.1 g; based on the mass of the styrene-butadiene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monosilane groups was 50%, and the remainder was butadiene; based on the mass of the styrene block as 100%, the mass percentage of DPE derivative monomers functionalized with monosilane groups was 15.4%, and the remainder was styrene monomer. The DPE derivatives functionalized with monosilane groups were distributed at the initiating ends and in the chain of the polystyrene block, exhibiting a quasi-periodic sequence distribution in the chain; based on the mass of the butadiene block as 100%, the mass percentage of 1,2-butadiene was 52.4%, and the remainder was 1,4-butadiene; the degree of hydrogenation was 82%; gel permeation chromatography (GPLC) was used to analyze the structure. C) The molecular weight was analyzed, and a standard curve was prepared using polystyrene with different molecular weight narrow distributions as standard samples. Tetrahydrofuran was used as the mobile phase (flow rate 1.0 ml / min), and the sample concentration was 2–5 mg / ml. The results are as follows: Before coupling, the styrene-butadiene block copolymer with monosilylation functionalization showed a single-peak narrow distribution, with a number-average molecular weight of 168.4 kg / mol and a molecular weight distribution of 1.12; after star-shaped coupling, the styrene-butadiene block copolymer with monosilylation functionalization showed a single-peak narrow distribution, with a coupling efficiency close to 100%, a number-average molecular weight of 606.2 kg / mol, and a molecular weight distribution of 1.21; after hydrogenation, the SEBS with monosilylation functionalization showed a single-peak narrow distribution, with a number-average molecular weight of 616.4 kg / mol and a molecular weight distribution of 1.22. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1560%, and the tensile strength was 17.6 MPa.

[0059] Example 2

[0060] Step S1, preparation of active center of polystyrene functionalized with monosilicon hydride group: under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added into a 5L polymerization kettle, and tetrahydrofuran (2.8g, 39mmol) and 1-[4-(dimethylsilyl)phenyl]-1-phenyl ethylene (monosilicon hydride DPE, 0.62g, 2.6mmol) were added into the kettle, stirred uniformly, and n-butyllithium (2.6mmol, 1.6mol / L) was added, the initiation temperature was 20℃, and the reaction was carried out for 30min, then styrene (65g, 0.625mol) was added to carry out the first-stage polymerization reaction, and the reaction was carried out for 6h;

[0061] Step S2, preparation of active center of styrene-butadiene functionalized with silicon hydride group: butadiene (130g, 2.4mol) was added into the above-mentioned polymerization kettle, the reaction temperature was 80℃, and the second-stage polymerization reaction was carried out for 3h;

[0062] Step S3, preparation of star-coupled styrene-butadiene block copolymer functionalized with monosilicon hydride group: silicon tetrachloride coupling agent (0.07g, 0.416mmol) and divinylbenzene (0.02g, 0.14mmol) were added into the above-mentioned polymerization kettle, the reaction temperature was 80℃, and the coupling reaction was carried out for 120min;

[0063] Step S4, preparation of SEBS thermoplastic elastomer functionalized with silicon hydride group: the star-coupled styrene-butadiene block copolymer functionalized with silicon hydride group was transferred into a high-pressure hydrogenation kettle, solvent was added for dilution, triisobutyl aluminum \ nickel naphthenate catalyst and hydrogen were added for hydrogenation reaction, the hydrogen pressure was controlled to be 3Mpa, the reaction temperature was 100℃, and the reaction was carried out for 3h.

[0064] After the reaction was completed, the polymer was post-treated by using a traditional method, and the product was dried, then the hydrogen spectrum of nuclear magnetic resonance ( 1HNMR) for structural analysis, and the results are as follows: the product mass is 159.6 g; the mass percentage of styrene and the DPE derivative functionalized with a single silicon hydride group in the styrene monomer is 33.5% based on the mass of the styrene and butadiene block copolymer being 100%, and the rest is butadiene; the mass percentage of the DPE derivative functionalized with a single silicon hydride group in the styrene block is 0.94% based on the mass of the styrene block being 100%, and the rest is styrene monomer, and the DPE derivative functionalized with a single silicon hydride group is distributed at the initiation end of the polystyrene block; the mass percentage of 1,2-butadiene is 55.3% based on the mass of the butadiene block being 100%, and the rest is 1,4-butadiene; the hydrogenation degree is 99.5%; the molecular weight is analyzed by gel permeation chromatography (GPC) using different molecular weight narrow distribution polystyrene as a standard sample to produce a standard curve, tetrahydrofuran as a mobile phase (flow rate is 1.0 ml / min), and a sample concentration of 2-5 mg / ml, and the results are as follows: the number average molecular weight of the DPE derivative functionalized with a single silicon hydride group before coupling is 130.8 kg / mol, and the molecular weight distribution is 1.05; the DPE derivative functionalized with a single silicon hydride group after star coupling shows a bimodal distribution, the coupling efficiency is about 76%, the molecular weight distribution is 1.42, and the number average molecular weights of the star coupling sample and the linear sample are 366.2 kg / mol and 128.8 kg / mol, respectively; the DPE derivative functionalized with a single silicon hydride group after hydrogenation shows a bimodal distribution, and the number average molecular weights of the star coupling sample and the linear sample are 375.4 kg / mol and 130.2 kg / mol, respectively, and the molecular weight distribution is 1.43. The mechanical properties of the product are tested by a universal testing machine, and the results are as follows: the elongation at break is 1660%, and the tensile strength is 15.1 MPa.

[0065] Example 3

[0066] Step S1, preparation of a polystyrene active center functionalized with a single silicon hydride and a double silicon hydride group: 3 L (2370 g) of cyclohexane solvent is added to a 5 L polymerization kettle under the protection of nitrogen or argon, and tetrahydrofuran (2.8 g, 39 mmol) and 1-[4-(dimethylsilyl)phenyl]-1-phenyl ethylene (single silicon hydride DPE, 0.62 g, 2.6 mmol) are added, stirred uniformly, and n-butyllithium (2.6 mmol, 1.6 mol / L) is added, the initiation temperature is 50°C, and the reaction is carried out for 30 min, then styrene (33 g, 0.137 mol) is added for the first stage of polymerization reaction, and the reaction is carried out for 2 h, then 1,1-di[4-(dimethylsilyl)phenyl]ethylene (double silicon hydride DPE, 0.77 g, 2.6 mmol) is added, and the reaction is carried out for 2 h;

[0067] Step S2, preparation of styrene-butadiene active center containing monosilicon hydride and disilicon hydride groups: add butadiene (130 g, 2.4 mol) to the polymerization kettle, carry out the second stage of polymerization reaction at 50℃, and react for 3 h;

[0068] Step S3, preparation of star-shaped coupled styrene-butadiene block copolymer containing monosilicon hydride and disilicon hydride groups: add silicon tetrachloride coupling agent (0.11 g, 0.65 mmol) and divinylbenzene (0.01 g, 0.07 mmol) to the polymerization kettle, carry out the coupling reaction at 50℃, and react for 120 min;

[0069] Step S4, preparation of SEBS thermoplastic elastomer containing monosilicon hydride and disilicon hydride groups: transfer the star-shaped coupled styrene-butadiene block copolymer containing silicon hydride groups to a high-pressure hydrogenation kettle, add solvent for dilution, add triisobutyl aluminum \ nickel naphthenate catalyst and hydrogen for hydrogenation reaction, control the hydrogen pressure to be 5 Mpa, the reaction temperature to be 50℃, and the reaction time to be 3 h.

[0070] After the reaction is completed, the polymer is post-treated by using a traditional method, and after the product is dried, the hydrogen spectrum (1H NMR) is used to analyze the product. 1HNMR) for structural analysis, and the results are as follows: the product quality is 119.4 g; the mass percentage of styrene and the DPE derivative functionalized with silicon hydride group styrene monomer is 20.1% based on the mass of the styrene and butadiene block copolymer being 100%, and the rest is butadiene; the mass percentage of the DPE derivative functionalized with silicon hydride group based on the mass of the styrene block being 100% is 4.0%, and the rest is styrene monomer, the DPE derivative functionalized with a single silicon hydride group is distributed at the initiation end of the polystyrene block, and the DPE derivative functionalized with a double silicon hydride group is distributed at the end of the polystyrene block; the mass percentage of 1,2-butadiene based on the mass of the butadiene block being 100% is 50.1%, and the rest is 1,4-butadiene; the hydrogenation degree is 99.1%; the molecular weight is analyzed by gel permeation chromatography (GPC) using different molecular weight narrow distribution polystyrene as the standard sample to produce a standard curve, and tetrahydrofuran is used as the mobile phase (the flow rate is 1.0 ml / min), and the sample concentration is 2-5 mg / ml, and the results are as follows: the number average molecular weight of the silicon hydride group functionalized styrene-butadiene block copolymer before coupling is 110.1 kg / mol, and the molecular weight distribution is 1.08; the silicon hydride group functionalized styrene-butadiene block copolymer after star coupling shows a single peak narrow distribution, the coupling efficiency is about 100%, the number average molecular weight is 418.4 kg / mol, and the molecular weight distribution is 1.18; the silicon hydride functionalized SEBS after hydrogenation shows a single peak narrow distribution, the number average molecular weight is 420.8 kg / mol, and the molecular weight distribution is 1.20. The mechanical properties of the product are tested by a universal testing machine, and the results are as follows: the elongation at break is 1530%, and the tensile strength is 14.7 MPa.

[0071] Example 4

[0072] Step S1, preparation of a polystyrene active center functionalized with a single silicon hydride group: 3 L (2370 g) of cyclohexane solvent is added to a 5 L polymerization kettle under the protection of nitrogen or argon, and tetrahydrofuran (93.6 mg, 1.3 mmol) and 1-[4-(dimethylsilyl hydride) phenyl]-1-phenyl ethylene (single silicon hydride DPE, 20.0 g, 84 mmol) are added, stirred uniformly, and n-butyl lithium (2.6 mmol, 1.6 mol / L) is added, the initiation temperature is 60°C, and the reaction is carried out for 30 min, and then styrene (110 g, 1.06 mol) is added for the first stage of polymerization reaction, and the reaction is carried out for 48 h;

[0073] Step S2, preparation of a styrene-butadiene active center functionalized with a single silicon hydride group: butadiene (130 g, 2.4 mol) is added to the above polymerization kettle, the reaction temperature is 50°C, and the second stage of polymerization reaction is carried out for 3 h;

[0074] Step S3, prepare linearly coupled styrene-butadiene block copolymers functionalized with monosilane groups: add dimethyldichlorosilane coupling agent (0.17g, 1.3mmol) to the above polymerization reactor, carry out the coupling reaction at 50℃ for 120min;

[0075] Step S4, preparing SEBS thermoplastic elastomer with silane-hydrogen functionalization: the linearly coupled styrene-butadiene block copolymer solution with monosilane-hydrogen functionalization is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added with titanium holocata catalyst and hydrogen to carry out hydrogenation reaction. The hydrogen pressure is controlled at 10 MPa, the reaction temperature is 50℃, and the reaction is carried out for 1 h.

[0076] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1 The structure was analyzed by HNMR, and the results are as follows: The mass of the prepared product was 210.4 g; based on the mass of the styrene-butadiene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monosilane groups was 50%, and the remainder was butadiene; based on the mass of the styrene block as 100%, the mass percentage of DPE derivative monomers functionalized with monosilane groups was 15.1%, and the remainder was styrene monomer. The DPE derivatives functionalized with monosilane groups were distributed at the initiator, chain, and chain end of the polystyrene block, showing a gradual sequence distribution in the chain; based on the mass of the butadiene block as 100%, the mass percentage of 1,2-butadiene was 8.1%, and the remainder was 1,4-butadiene; the degree of hydrogenation was 99.1%; gel permeation chromatography (GPC) was used to analyze the structure. The molecular weight of polystyrene-butadiene block copolymers (PC) was analyzed. Standard curves were constructed using polystyrene with different molecular weight distributions as standard samples. Tetrahydrofuran was used as the mobile phase (flow rate 1.0 ml / min), and sample concentrations ranged from 2 to 5 mg / ml. The results are as follows: Before coupling, the monosilylated styrene-butadiene block copolymers exhibited a single-peak narrow distribution, with a number-average molecular weight of 163.4 kg / mol and a molecular weight distribution of 1.15. After linear coupling, the monosilylated styrene-butadiene block copolymers also exhibited a single-peak narrow distribution, with a coupling efficiency close to 100%, a number-average molecular weight of 294.1 kg / mol, and a molecular weight distribution of 1.21. After hydrogenation, the monosilylated SEBS exhibited a single-peak narrow distribution, with a number-average molecular weight of 300.1 kg / mol and a molecular weight distribution of 1.22. The mechanical properties of the products were tested using a universal testing machine, and the results are as follows: elongation at break was 1410%, and tensile strength was 25.3 MPa.

[0077] Example 5

[0078] Step S1, preparation of silicon-oxygen and silicon-hydrogen group functionalized polystyrene active center: under the protection of nitrogen or argon, 3L (1204g) of cyclohexane (2.5L, 999g) and n-hexane (0.5L, 205g) solvents in a volume ratio of 5:1 were added to a 5L polymerization kettle, and tetramethyl ethylenediamine (2.6mmol, 0.3g), 1-[4-(trisilyloxyphenyl)-1-phenyl ethylene (monosilicon DPE, 0.5g, 1.3mmol) and 1-[4-(dimethylsilyl hydrogen) phenyl]-1-phenyl ethylene (monosilicon DPE, 0.38g, 1.3mmol) were added and stirred uniformly, then n-butyllithium (2.6mmol, 1.6mol / L) was added, the initiation temperature was 50℃, and the reaction was carried out for 30min, then styrene (110g, 1.06mol) was added for the first stage of polymerization reaction, and the reaction was carried out for 3h;

[0079] Step S2, preparation of silicon-oxygen and silicon-hydrogen group functionalized styrene-butadiene active center: butadiene (130g, 2.4mol) was added to the above polymerization kettle, the reaction temperature was 90℃, and the second stage of polymerization reaction was carried out for 3h;

[0080] Step S3, preparation of star-shaped coupled silicon-oxygen and silicon-hydrogen group functionalized styrene-butadiene block copolymer: tetra-chloro selenium coupling agent (0.11g, 0.52mmol) and divinyl benzene (0.03g, 0.21mmol) were added to the above polymerization kettle, the reaction temperature was 90℃, and the coupling reaction was carried out for 120min;

[0081] Step S4, preparation of silicon-hydrogen group functionalized SEBS thermoplastic elastomer: the star-shaped coupled silicon-hydrogen group functionalized styrene-butadiene block copolymer solution was transferred to a high-pressure hydrogenation kettle, diluted with solvent, and then triisobutyl aluminum \ nickel naphthenate catalyst and hydrogen were added for hydrogenation reaction, the hydrogen pressure was controlled at 3Mpa, the reaction temperature was 60℃, and the reaction was carried out for 3h.

[0082] After the reaction was completed, the polymer was post-treated by using the traditional method, and after the product was dried, the proton nuclear magnetic resonance spectrum (1H-NMR) was used to analyze the product. 1HNMR) for structural analysis, and the results are as follows: the product mass is 214.1 g; the mass percentage of styrene and the DPE derivative functionalized with a single silicon hydride group in the styrene monomer is 46% based on the mass of the styrene and butadiene block copolymer being 100%, and the rest is butadiene; the mass percentage of the DPE derivative functionalized with a single silicon hydride group in the styrene block is 0.8% based on the mass of the styrene block being 100%, and the rest is styrene monomer, and the DPE derivative functionalized with a silicon-oxygen and silicon hydride group is distributed at the initiation end of the polystyrene block; the mass percentage of 1,2-butadiene is 70.1% based on the mass of the butadiene block being 100%, and the rest is 1,4-butadiene; the hydrogenation degree is 84%; the molecular weight is analyzed by gel permeation chromatography (GPC) using different molecular weight narrow distribution polystyrene as a standard sample to produce a standard curve, and tetrahydrofuran is used as a mobile phase (the flow rate is 1.0 ml / min), and the sample concentration is 2-5 mg / ml, and the results are as follows: the silicon-oxygen and silicon hydride group functionalized styrene-butadiene block copolymer before coupling shows a single peak narrow distribution, and the number average molecular weight is 163.8 kg / mol, and the molecular weight distribution is 1.10; the silicon-oxygen and silicon hydride group functionalized styrene-butadiene block copolymer after star coupling shows a bimodal distribution, the coupling efficiency is 91.2%, the number average molecular weight is 507.8 kg / mol and 165.4 kg / mol, and the molecular weight distribution is 1.51; the single silicon hydride functionalized SEBS after hydrogenation shows a bimodal distribution, the number average molecular weight is 510.2 kg / mol and 166.7 kg / mol, and the molecular weight distribution is 1.50. The mechanical properties of the product are tested by a universal testing machine, and the results are as follows: the elongation at break is 1510%, and the tensile strength is 18.2 MPa.

[0083] Example 6

[0084] Step S1, preparation of a polystyrene active center functionalized with a silicon hydride and a silicon-oxygen group: 3 L (2370 g) of cyclohexane solvent is added to a 5 L polymerization kettle under the protection of nitrogen or argon, and tetrahydrofuran (1.4 g, 19.5 mmol) and 1-[4-(dimethylsilyl hydride) phenyl]-1-phenyl ethylene (single silicon hydride DPE, 20.0 g, 84 mmol) are added, stirred uniformly, and n-butyl lithium (1.3 mmol, 1.6 mol / L) is added, the initiation temperature is 50°C, and the reaction is carried out for 30 min, then styrene (65 g, 0.53 mol) is added, and the first stage of polymerization is carried out, the reaction is carried out for 60 h, then 1-[4-(dimethylsilyl hydride) phenyl]-1-[4-(N,N-dimethyl amine) phenyl] ethylene (silicon hydride / amine DPE, 1.3 mmol, 0.37 g) is added, and the reaction is carried out for 2 h;

[0085] Step S2, preparation of styrene-butadiene active center functionalized with silicon hydride and siloxy group: add butadiene (130 g, 2.4 mol) to the polymerization kettle, carry out the second stage polymerization reaction at 50℃, and react for 3 h;

[0086] Step S3, preparation of star-shaped coupled styrene-butadiene block copolymer functionalized with silicon hydride and siloxy group: add silicon tetrachloride coupling agent (0.11 g, 0.65 mmol) and divinylbenzene (0.01 g, 0.07 mmol) to the polymerization kettle, carry out the coupling reaction at 50℃, and react for 120 min;

[0087] Step S4, preparation of SEBS thermoplastic elastomer functionalized with silicon hydride and siloxy group: transfer the star-shaped coupled styrene-butadiene block copolymer functionalized with silicon hydride group solution to a high-pressure hydrogenation kettle, add solvent for dilution, add triisobutyl aluminum \ nickel naphthenate catalyst and hydrogen for hydrogenation reaction, control the hydrogen pressure to be 1 Mpa, the reaction temperature to be 100℃, and the reaction time to be 5 h.

[0088] After the reaction is completed, the polymer is post-treated by using a traditional method, and after the product is dried, the hydrogen spectrum (1H NMR) is used to analyze the product. 1HNMR) for its structure, and the results are as follows: the product mass is 174.9 g; the mass percentage of styrene and the DPE derivative functionalized with the silicon group styrene monomer is 40% based on the mass of the styrene and butadiene block copolymer being 100%, and the rest is butadiene; the mass percentage of the DPE derivative functionalized with the silicon group in the styrene block is 23.8% based on the mass of the styrene block being 100%, and the rest is styrene monomer, the DPE derivative functionalized with the silicon hydrogen group is distributed at the initiation end and in the chain of the polystyrene block, and the DPE derivative functionalized with the silicon hydrogen and silicon oxygen groups is distributed at the chain end of the polystyrene block; the mass percentage of 1,2-butadiene is 27.4% based on the mass of the butadiene block being 100%, and the rest is 1,4-butadiene; the hydrogenation degree is 98.1%; the molecular weight is analyzed by gel permeation chromatography (GPC) using different molecular weight narrow distribution polystyrene as the standard sample to produce a standard curve, tetrahydrofuran as the mobile phase (the flow rate is 1.0 ml / min), and the sample concentration is 2-5 mg / ml, and the results are as follows: the styrene-butadiene block copolymer functionalized with the single silicon hydrogen group before coupling shows a single peak narrow distribution, the number average molecular weight is 270.4 kg / mol, and the molecular weight distribution is 1.12; the styrene-butadiene block copolymer functionalized with the silicon hydrogen and silicon hydrogen / amine groups after star coupling shows a single peak narrow distribution, the coupling efficiency is close to 100%, the number average molecular weight is 865.3 kg / mol, and the molecular weight distribution is 1.41; the SEBS functionalized with the single silicon hydrogen group after hydrogenation shows a single peak narrow distribution, the number average molecular weight is 868.3 kg / mol, and the molecular weight distribution is 1.55. The mechanical properties of the product are tested by a universal testing machine, and the results are as follows: the elongation at break is 1620%, and the tensile strength is 15.7 MPa.

[0089] Example 7 (adjusting the DPE type and sequence and topology, and other parameters are the same as in Example 2)

[0090]

[0091] Example 8 (adjusting the DPE type, and other parameters are the same as in Example 2)

[0092]

[0093] Example 9 (adjusting the block ratio, and other parameters are the same as in Example 2)

[0094] When the styrene block content is less than 20%, the tensile strength and elongation at break of SEBS are low, and the performance is poor; when the styrene block content is greater than 50%, the tensile strength of SEBS does not increase significantly, and the elongation at break gradually decreases, therefore the styrene block content of the present patent is preferably 20-50%.

[0095] Example 10 (adjusting the proportion of DPE derivative in the styrene block, other parameters are the same as in Example 4)

[0096]

[0097]

[0098] When the DPE content is less than 0.1%, the tensile strength of SEBS is less than 19.0 MPa, and the strength is low; when the DPE content is greater than 0.5% and less than 20%, the tensile strength and tensile modulus of SEEPS increase significantly; when the DPE content is greater than 50%, the tensile strength and tensile modulus change little, and excessive DPE will increase the production cost of SEBS, therefore the DPE content of the present patent is preferably 0.5-20%.

[0099] Example 11 (adjusting the vinyl content, other parameters are the same as in Example 6)

[0100]

[0101] Example 12 (adjusting the vinyl content, other parameters are the same as in Example 6)

[0102] Comparative Example 1 (reducing the hydrogenation step based on Example 4)

[0103] Step S1, preparation of a polystyrene active center containing a single silicon hydride group functional group: under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added to a 5L polymerization kettle, and tetrahydrofuran (93.6mg, 1.3mmol) and 1-[4-(dimethylsilyl)phenyl]-1-phenyl ethylene (single silicon hydride DPE, 20.0g, 84mmol) were added, stirred uniformly, and n-butyllithium (2.6mmol, 1.6mol / L) was added, the initiation temperature was 60°C, and the reaction was carried out for 30min, then styrene (110g, 1.06mol) was added, and the first-stage polymerization reaction was carried out, and the reaction was carried out for 48h;

[0104] Step S2, preparation of a styrene-butadiene active center containing a single silicon hydride group functional group: butadiene (130g, 2.4mol) was added to the above polymerization kettle, the reaction temperature was 50°C, and the second-stage polymerization reaction was carried out, and the reaction was carried out for 3h;

[0105] Step S3, prepare linearly coupled styrene-butadiene block copolymers functionalized with monosilane groups: add dimethyldichlorosilane coupling agent (0.17g, 1.3mmol) to the above polymerization reactor, carry out the coupling reaction at 50℃ for 120min;

[0106] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1 The structure was analyzed by ¹H NMR, and the results are as follows: The mass of the prepared product was 203.4 g; based on the mass of the styrene-butadiene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monosilane groups was 50%, and the remainder was butadiene; based on the mass of the styrene block as 100%, the mass percentage of DPE derivative monomers functionalized with monosilane groups was 15.1%, and the remainder was styrene monomer. The DPE derivatives functionalized with monosilane groups were distributed at the initiator, chain, and chain end of the polystyrene block, showing a gradual sequence distribution in the chain; based on the mass of the butadiene block as 100%, the mass percentage of 1,2-butadiene was 8.1%, and the remainder was 1... 4-Butadiene; degree of hydrogenation 99.1%; molecular weight was analyzed by gel permeation chromatography (GPC). A standard curve was constructed using polystyrene with different molecular weight narrow distributions as standard samples. Tetrahydrofuran was used as the mobile phase (flow rate 1.0 ml / min), and sample concentrations ranged from 2 to 5 mg / ml. The results are as follows: Before coupling, the styrene-butadiene block copolymer with monosilylated functionalized groups exhibited a single-peak narrow distribution, with a number-average molecular weight of 163.4 kg / mol and a molecular weight distribution of 1.15. After linear coupling, the styrene-butadiene block copolymer with monosilylated functionalized groups also exhibited a single-peak narrow distribution, with a coupling efficiency close to 100%, a number-average molecular weight of 294.1 kg / mol, and a molecular weight distribution of 1.21. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: elongation at break 710%, tensile strength 1.3 MPa.

[0107] Comparative Example 2 (using Example 4 as an example, with the same amount of styrene replacing monosilicon hydrogen DPE)

[0108] Step S1, preparing polystyrene active centers functionalized with monosilane groups: Under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added to a 5L polymerization reactor, and tetrahydrofuran (93.6mg, 1.3mmol) and styrene (118.7g, 1.14mol) were added. After stirring evenly, n-butyllithium (2.6mmol, 1.6mol / L) was added. The initiation temperature was 60℃, and the reaction was carried out for 30min to carry out the first stage of polymerization reaction for 48h.

[0109] Step S2, preparation of styrene-butadiene active centers functionalized with monosilane groups: add butadiene (130g, 2.4mol) to the above polymerization reactor, react at 50℃, and carry out the second stage polymerization reaction for 3h;

[0110] Step S3, prepare linearly coupled styrene-butadiene block copolymers functionalized with monosilane groups: add dimethyldichlorosilane coupling agent (0.17g, 1.3mmol) to the above polymerization reactor, carry out the coupling reaction at 50℃ for 120min;

[0111] Step S4, preparing SEBS thermoplastic elastomer with silane-hydrogen functionalization: the linearly coupled styrene-butadiene block copolymer solution with monosilane-hydrogen functionalization is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added with titanium holocata catalyst and hydrogen to carry out hydrogenation reaction. The hydrogen pressure is controlled at 10 MPa, the reaction temperature is 50℃, and the reaction is carried out for 1 h.

[0112] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1 The structure was analyzed by HNMR, and the results are as follows: The mass of the prepared product was 198.4 g; based on the mass of the styrene-butadiene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monosilane groups was 50%, and the remainder was butadiene; based on the mass of the butadiene block as 100%, the mass percentage of 1,2-butadiene was 8.1%, and the remainder was 1,4-butadiene; the degree of hydrogenation was 99.1%; the molecular weight was analyzed by gel permeation chromatography (GPC), and a standard curve was prepared using polystyrene with different molecular weight narrow distributions as standard samples, with tetrahydrofuran as the mobile phase. The flow rate was 1.0 ml / min, and the sample concentration was 2–5 mg / ml. The results are as follows: Before coupling, the styrene-butadiene block copolymer with monosilylic hydrogen functionalization showed a narrow single-peak distribution, with a number-average molecular weight of 143.4 kg / mol and a molecular weight distribution of 1.05; after linear coupling, the styrene-butadiene block copolymer with monosilylic hydrogen functionalization showed a narrow single-peak distribution, with a coupling efficiency close to 100%, a number-average molecular weight of 294.1 kg / mol, and a molecular weight distribution of 1.21; after hydrogenation, the SEBS with monosilylic hydrogen functionalization showed a narrow single-peak distribution, with a number-average molecular weight of 302.1 kg / mol and a molecular weight distribution of 1.22. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1110%, and the tensile strength was 19.3 MPa.

[0113] The above describes the specific embodiments of the present application, but is not a limitation on the protection scope of the present application. Those skilled in the art should understand that various modifications or variations made on the basis of the technical solutions of the present application without creative labor are still within the protection scope of the present application.

Claims

1. A silicon group functionalized SEBS thermoplastic elastomer characterized in that, The silicon-functionalized SEBS thermoplastic elastomer is a linear / star-coupled silicon-functionalized styrene-(ethylene / 1-butene) block copolymer, which is a copolymer of linear / star-coupled silicon-functionalized styrene blocks and ethylene / 1-butene blocks. The linear / star-coupled silicon-functionalized styrene block is a copolymer block of styrene and a silicon-functionalized 1,1-diphenylethylene derivative; the ethylene / 1-butene block is a random copolymer block of ethylene and 1-butene. The number average molecular weight M of the silicon group functionalized SEBS thermoplastic elastomer n in the range of 2 x 10 4 - 90 x 10 4 g / mol, with a molecular weight distribution PDI in the range of 1.02 - 1.

60.

2. The silicon group-functionalized SEBS thermoplastic elastomer of claim 1, wherein, The linear / star-coupled silicon-functionalized styrene-(ethylene / 1-butene) block copolymer is obtained by selective hydrogenation of the linear / star-coupled silicon-functionalized styrene-butadiene block copolymer, and the degree of hydrogenation of the linear / star-coupled styrene-(ethylene / 1-butene) block copolymer ranges from 50% to 100%.

3. The silicon group-functionalized SEBS thermoplastic elastomer of claim 1, wherein, Based on the mass of 100% of the linear / star-coupled silicon-functionalized styrene-butadiene block copolymer, the silicon-functionalized styrene blocks account for 20% to 50%, and the remainder are butadiene blocks.

4. The silicon group-functionalized SEBS thermoplastic elastomer of claim 1, wherein, Based on the mass of the silicon-functionalized styrene block as 100%, the mass percentage of the silicon-functionalized 1,1-diphenylethylene derivative monomer is 0.1%-50.0%.

5. The silicon group-functionalized SEBS thermoplastic elastomer of claim 1, wherein, The silicon-functionalized 1,1-diphenylethylene derivatives are selected from silicon-functionalized and silicon / amine-functionalized 1,1-diphenylethylene derivatives. The silicon-functionalized 1,1-diphenylethylene derivative is selected from at least one of 1-[4-(triisopropoxysilyl)phenyl]-1-phenylethylene, 1-[4-(dimethylsilyl)phenyl]-1-phenylethylene, 1,1-di[4-(triisopropoxysilyl)phenyl]ethylene, 1-[4-(dimethylsilyl)phenyl]-1-phenylethylene, 1,1-di[4-(dimethylsilyl)phenyl]ethylene, 1,1-di[4-(dimethylsilyl)phenyl]ethylene, 1,1-di[4-(triisopropoxysilyl)phenyl]ethylene, 1-[4-(triisopropoxysilyl)phenyl]phenyl]-1-[4-(dimethylsilyl)phenyl]ethylene, and 1-[4-(triisopropoxysilyl)phenyl]-1-[4-(dimethylsilyl)phenyl]ethylene; The silicon / nitrogen-functionalized 1,1-diphenylethylene derivative is selected from at least one of 1-[4-(triisopropoxysilyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl]ethylene, 1-[4-(dimethylsilyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl]ethylene, 1-[4-(triisopropoxysilyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl]ethylene, and 1-[4-(dimethylsilyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl]ethylene.

6. A process for the preparation of a silicon group functionalized SEBS thermoplastic elastomer as claimed in any one of claims 1 to 5, characterized in that, Includes the following steps: Step S1, preparing silicon-functionalized polystyrene active centers: In a non-polar hydrocarbon solvent, a measured amount of a polar modifier is added to a reactor, and according to different monomer feeding sequences and ratios, a measured amount of styrene and silicon group functionalized 1,1-diphenyl ethylene derivative monomers, alkyl lithium initiator and polar modifier are added according to the monomer ratio, stirred uniformly, the initiation reaction temperature is 10-90℃, and the reaction time is 0.5-48h; the feeding ratio of the styrene and silicon group functionalized 1,1-diphenyl ethylene derivative monomers is 1-999:1 by mass; the alkyl lithium initiator and the polar modifier are added in a proportion of 1:1-50; the initiator and the raw material feeding ratio is 1:1x10 5 -2.5x10 5 ; Step S2, preparing the silicon group functionalized polystyrene-butadiene active center: after the reaction of step S1 is completed, the measured butadiene monomer is added to the reactor according to the monomer ratio, the reaction temperature is controlled at 50-110℃, and the reaction time is 0.5-10h; wherein the mass ratio of styrene monomers composed of styrene and silicon-hydrogen functionalized 1,1-diphenyl ethylene derivative and butadiene is 1:1-4; Step S3, preparing the linear / star coupling silicon group functionalized styrene-butadiene block copolymer: after the reaction of step S2 is completed, the measured linear / star coupling agent is added for coupling reaction, the reaction temperature is 50-110℃, and the reaction time is 30-150min, to obtain the linear / star coupling silicon group functionalized styrene-butadiene block copolymer glue solution; Step S4, preparing the silicon group functionalized SEBS thermoplastic elastomer: the linear / star coupling silicon group functionalized styrene-butadiene block copolymer glue solution is transferred to a high-pressure hydrogenation kettle, the measured hydrogenation catalyst and hydrogen are added for hydrogenation reaction, the hydrogen pressure is controlled at 0.1Mpa-10Mpa, the reaction temperature is 50℃-200℃, the hydrogenation reaction time is 1-20h, and the silicon group functionalized SEBS thermoplastic elastomer is obtained. The hydrogenation catalyst is selected from nickel-based or metallocene titanium metal catalysts.

7. The preparation method according to claim 6, characterized in that, When the mass concentration of all reaction monomers in step S1 is 5%-25%, the silicon group functionalized 1,1-diphenyl ethylene derivative monomer is located at the chain end of the styrene block.

8. The preparation method according to claim 6, characterized in that, When the mass fraction of all reaction monomers in step S1 is less than 10%, the mass concentration of the single silicon-hydrogen group functionalized 1,1-diphenyl ethylene derivative monomer, or the single silicon-oxygen group functionalized 1,1-diphenyl ethylene derivative monomer, or the 1,1-diphenyl ethylene derivative monomer with silicon-oxygen group / silicon-hydrogen group and styrene is 5%-15%, or the mass concentration of the 1,1-diphenyl ethylene derivative monomer with silicon-oxygen group / amine group, or the 1,1-diphenyl ethylene derivative monomer with silicon-hydrogen group / amine group and styrene is 15%-25%; the silicon group functionalized 1,1-diphenyl ethylene derivative in the prepared silicon group functionalized styrene block is located in the chain and at the chain end of the block.

9. The preparation method according to claim 6, characterized in that, When the mass fraction of all reaction monomers in step S1 is higher than 10%, the mass concentration of the single silicon-hydrogen group functionalized 1,1-diphenyl ethylene derivative monomer, or the single silicon-oxygen group functionalized 1,1-diphenyl ethylene derivative monomer, or the 1,1-diphenyl ethylene derivative monomer with silicon-oxygen group / silicon-hydrogen group and styrene is 5%-10%, or the mass concentration of the 1,1-diphenyl ethylene derivative monomer with silicon-oxygen group / amine group, or the 1,1-diphenyl ethylene derivative monomer with silicon-hydrogen group / amine group and styrene is 10%-15%; the silicon group functionalized 1,1-diphenyl ethylene derivative in the prepared silicon group functionalized styrene block is located in the chain and at the chain end of the block.

10. The method of claim 6, wherein, The solvent is selected from benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons, mixed aliphatic hydrocarbons; The polar regulator is selected from at least one of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and alkoxy metal compounds; The alkyl lithium initiator is selected from at least one of monofunctional alkyl lithium RLi initiator, R is a hydrocarbon group with carbon atom number of 2-20; The linear coupling agent is selected from at least one of M(CH3)2Cl2, 1,2-dichloroethane, 1,2-dibromoethane; the star coupling agent is selected from one of MCH3Cl3, MCl4, M2Cl6, M3Cl8, divinylbenzene (DVB), M is selected from silicon, tin, lead, titanium, germanium.

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