Silicon / nitrogen group-containing functionalized S (EB / EP) S 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 / nitrogen group-containing functionalized S (EB / EP) S thermoplastic elastomer which is a linear / star-shaped coupled silicon / nitrogen group-containing functionalized polystyrene-(ethylene / propylene / butylene) block copolymer. The prepared S (EB / EP) S containing the silicon / nitrogen group is a macromolecule, and the viscosity is obviously improved. In the processing process, S (EB / EP) S containing a silicon / nitrogen 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, on the basis of combining the advantages of SEBS and SEPS, the polarity is improved, the performance is further improved, and good application prospects are achieved in multiple fields.

Description

Technical Field

[0001] This invention belongs to the field of polymer material synthesis and preparation technology, specifically relating to a class of silicon / nitrogen group-functionalized S(EB / EP)S thermoplastic elastomers and their preparation methods. Background Technology

[0002] Styrene-based thermoplastic elastomers (TPS) are the most produced and fastest-growing thermoplastic elastomer materials in recent years. They are block copolymers synthesized by unterminated ionic polymerization. At room temperature, TPS is characterized by the presence of hard and soft segments (or phases) within the chains of a single polymer or within an interpenetrating matrix formed by the constituent materials. TPS is a triblock copolymer, with polystyrene (PS) at both ends of its molecule and a rubber-like polyolefin (such as polybutadiene, polyisoprene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer, and polyisobutylene) in the middle. PS acts as the hard segment (plastic segment) of TPS, while the polyolefin acts as the soft segment (rubber segment). Since the hard and soft segments have two separate phases and their own glass transition temperatures, they exhibit vulcanized rubber characteristics at room temperature but undergo plastic flow at high temperatures. The glass transition temperature of the PS hard segment is approximately 70–80°C, while the glass transition temperature of the polyolefin soft segment is below -40°C. At room temperature, the PS hard segments lose fluidity, associate with each other or "crosslink" and solidify to form physically crosslinked regions, which act as reinforcing agents. The polyolefin intermediate phase is relatively flexible, giving TPS flexibility. This crosslinked network structure formed by PS hard segments and polyolefin soft segments is similar to the crosslinked network structure in vulcanized rubber, thus making TPS exhibit thermoplastic elastomer characteristics.

[0003] Styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), and styrene-butadiene / isoprene-styrene (SIBS) are mainly composed of unsaturated chains in the rubber phase. The other type consists of saturated chains in the rubber phase, including styrene-ethylene-butene-styrene (SEBS), styrene-ethylene / propylene-styrene (SEPS), styrene-ethylene / propylene / butene-styrene (SEB / EPS), and styrene-isobutylene-styrene (SIBS) block copolymers. The earliest industrialized SBS and SIS, due to the presence of numerous reactive unsaturated olefin double bonds in their molecular chains, exhibited poor heat resistance and abrasion resistance.

[0004] TPS exhibits rubber-like characteristics over a wide temperature range. At room temperature, it displays rubber-like properties while also possessing excellent processability. At high temperatures, it can be plasticized and molded, exhibiting good thermal stability and physical and mechanical properties, allowing for repeated processing. Furthermore, it demonstrates excellent biocompatibility and is friendly to humans and the environment, finding applications in in vitro medical fields such as drug and blood transfusion and storage, as well as in in vivo implantation fields such as drug-eluting stents and soft tissue replacement. The diversity of medical applications places significant demands on the varying physical, chemical, and biological properties of TPS. Therefore, further physical and chemical modifications of TPS are needed to regulate its physical and mechanical properties, improve biocompatibility, enhance its performance, and acquire new functions to meet diverse performance requirements.

[0005] In summary, how to prepare high-performance styrene-based thermoplastic elastomers, improve their comprehensive mechanical properties and compatibility, and further expand their application scope and applicable scenarios is a technical problem that this application urgently needs to solve. Summary of the Invention

[0006] To address the problems of poor compatibility and imprecise control of physical and mechanical properties in existing technologies, this invention provides a class of silicon / nitrogen-functionalized S(EB / EP)S thermoplastic elastomers. Through active anionic copolymerization, 1,1-diphenylethylene derivative comonomers containing silicon / nitrogen groups and linear / star coupling agents are added. According to different functional requirements, high-performance S(EB / EP)S thermoplastic elastomers with adjustable linear / star coupling arm numbers and precise distribution of silicon / nitrogen-functionalized 1,1-diphenylethylene derivatives at the initiation, chain, and chain ends of styrene blocks are prepared. This significantly improves the mechanical properties and compatibility of S(EB / EP)S, broadening its application areas.

[0007] The technical solution of this invention is as follows:

[0008] In a first aspect, the present invention provides a class of silicon / nitrogen-functionalized S(EB / EP)S thermoplastic elastomers, wherein the silicon / nitrogen-functionalized S(EB / EP)S thermoplastic elastomers are linearly / star-coupled silicon / nitrogen-functionalized styrene-(ethylene / propylene / butene) block copolymers, which are copolymers of linearly / star-coupled silicon / nitrogen-functionalized styrene blocks and ethylene / propylene / butene random copolymer blocks, and the structure is selected from -[(FS)-b-(EB-co-EP)]. n M[CH3] m -、-[(FS)-b-(EB-co-EP)] n At least one of the following: DVB;

[0009] Among them, F is a silicon / nitrogen group-functionalized 1,1-diphenyl ethylene derivative, F-S is a styrene block functionalized with a silicon / nitrogen group, and EB-co-EP is a selectively hydrogenated butadiene-isoprene block, specifically an ethylene / propylene / butene random copolymer block; b represents that (F-S) and (EB-co-EP) are block polymers;

[0010] Among them, the linear coupling agent is selected from M(CH3)2Cl2, 1,2-dichloroethane, 1,2-dibromoethane; the star-shaped coupling agent selects two coupling agents with different coupling mechanisms, one is selected from MCH3Cl3, MCl4, M2Cl6, M3Cl8, M is the coupling agent residue, and the other is a divinylbenzene (DVB) coupling center; n is the average number of coupling arms, and 2 < n ≤ 8; m is selected from 0, 1, 2.

[0011] Furthermore, the silicon / nitrogen group-functionalized styrene block is a copolymer block of styrene and a silicon / nitrogen group-functionalized 1,1-diphenyl ethylene derivative.

[0012] Furthermore, the silicon / nitrogen group-functionalized 1,1-diphenyl ethylene derivative is polymerized at least at one position of the chain initiation end, chain end, and chain of the polystyrene block;

[0013] The number average molecular weight (M n ) of the silicon / nitrogen group-functionalized S(EB / EP)S 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.

[0014] Furthermore, the silicon / nitrogen group-functionalized 1,1-diphenyl ethylene derivative is selected from silicon group-containing, amine group-containing, silicon group / amine group-functionalized 1,1-diphenyl ethylene derivatives; including but not limited to monomers of 1,1-diphenyl ethylene derivatives functionalized with single siloxane groups, single silicon hydride groups, single amine groups, double siloxane groups, double silicon hydride groups, double amine groups, siloxane groups / silicon hydride groups, siloxane groups / amine groups, and silicon hydride groups / amine groups; the silicon group and the silicon group / amine group are connected to the para, meta, or ortho position of the phenyl group in the 1,1-diphenyl ethylene derivative.

[0015] Furthermore, the linear / star-coupled styrene-(ethylene / propylene / butene) block copolymer with silicon / nitrogen functionalization is obtained by selective hydrogenation of the linear / star-coupled styrene-(butadiene / isoprene) block copolymer with silicon / nitrogen functionalization. The degree of hydrogenation of the linear / star-coupled styrene-(ethylene / propylene / butene) block copolymer is in the range of 50% to 100%, preferably 85% to 100%.

[0016] Furthermore, based on the mass of the silicon / nitrogen functionalized S(EB / EP)S thermoplastic elastomer as 100%, the mass percentage of the silicon / nitrogen functionalized styrene block is 20% to 50%, and the remainder is butadiene-isoprene block.

[0017] Furthermore, based on the mass of styrene blocks functionalized with silicon / nitrogen groups as 100%, the mass percentage of 1,1-diphenylethylene derivative monomers functionalized with silicon / nitrogen groups is 0.1%-50.0%, preferably 5%-30%, with the remainder being styrene.

[0018] Furthermore, the 1,1-diphenylethylene derivatives functionalized with silicon-containing groups, amino-containing groups, or silicon-containing / amino-containing groups are selected from:

[0019] (1) The monomer of the 1,1-diphenylethylene derivative functionalized with a single siloxy group is 1-[4-R1-ylphenyl]-1-phenylethylene; the monomer of the 1,1-diphenylethylene derivative functionalized with a bissiloxy group is 1,1-di[4-R1-ylphenyl]ethylene, wherein R1 is a siloxy group selected from trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tritert-butoxysilyl, dimethylmethoxysilyl, and diethylmethoxysilyl.

[0020] (2) The monomer of the 1,1-diphenylethylene derivative functionalized with monosilane groups is 1-[4-R2-ylphenyl]-1-phenylethylene, and the monomer of the 1,1-diphenylethylene derivative with disilane groups is generally 1,1-di[4-R2-ylphenyl]ethylene, wherein R2 is a silane group selected from dimethylsilane, diethylsilane, dipropylsilane, diisopropylsilane, and ditert-butylsilane;

[0021] (3) Monoamine group 1,1-diphenylethylene derivative monomers are generally in the range of 1-[4-R3-ylphenyl]-1-phenylethylene, and diamine group 1,1-diphenylethylene derivative monomers are generally in the range of 1,1-di[4-R3-ylphenyl]ethylene, wherein R3 is N,N-dimethylamino, N,N-diethylamino, or N,N-di-tert-butylamino;

[0022] (4) The monomer of the 1,1-diphenylethylene derivative with siloxy group / silane group is 1-[4-R1-ylphenyl]-1-[R2-ylphenyl]ethylene, wherein R1 is a siloxy group selected from trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tritert-butoxysilyl, dimethylmethoxysilyl, and diethylmethoxysilyl; and R2 is a silane group selected from dimethylsilane, diethylsilane, dipropylsilane, diisopropylsilane, and ditert-butylsilane.

[0023] (5) The monomer of the 1,1-diphenylethylene derivative of the siloxy group / amine group is 1-[4-R1-ylphenyl]-1-[4-R3-phenyl]ethylene, wherein R1 is a siloxy group selected from trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tritert-butoxysilyl, dimethylmethoxysilyl, and diethylmethoxysilyl, and R3 is an amine group selected from N,N-dimethylamino, N,N-diethylamino, and N,N-ditert-butylamino;

[0024] (6) The monomer of the 1,1-diphenylethylene derivative of the silane group / amine group is 1-[4-R2-ylphenyl]-1-[4-R3-ylphenyl]ethylene, wherein R2 is a silane group selected from dimethylsilane, diethylsilane, dipropylsilane, diisopropylsilane, and di-tert-butylsilane, and R3 is an amine group selected from N,N-dimethylamino, N,N-diethylamino, and N,N-di-tert-butylamino;

[0025] Further, 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.

[0026] Furthermore, the nitrogen-functionalized 1,1-diphenylethylene derivative is selected from at least one of 1-[4-(N,N-dimethylamino)phenyl]-1-phenylethylene and 1,1-bis[4-(N,N-dimethylamino)phenyl]ethylene.

[0027] Furthermore, 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.

[0028] Secondly, this invention provides a method for preparing a type of silicon / nitrogen group-functionalized S(EB / EP)S thermoplastic elastomer, comprising the following steps:

[0029] Step S1: Prepare polystyrene active centers functionalized with silicon / nitrogen groups:

[0030] A metered polarity modifier is added to a reactor in a non-polar hydrocarbon solvent. Depending on the monomer feeding sequence and ratio, metered amounts of styrene, silicon / nitrogen-functionalized 1,1-diphenylethylene derivative monomers, alkyl lithium initiators, and polarity modifiers are added. The mixture is stirred until homogeneous. The initiation reaction temperature is 10℃-90℃, and the reaction time is 0.5-48 h. This generates silicon / nitrogen-functionalized polystyrene active centers.

[0031] The feed ratio of styrene and silicon / nitrogen group-functionalized 1,1-diphenylethylene derivative monomers, by mass, is 1-999:1; the ratio of polarity modifier and alkyl lithium initiator is 1-20:1; and the feed ratio of initiator to raw materials is 1:1×10. 5 -2.5×10 5 .

[0032] Step S2, preparation of silicon / nitrogen group-functionalized polystyrene-butadiene / isoprene active centers: After the reaction in step S1 is completed, the measured butadiene / isoprene monomers are added to the reactor according to the monomer ratio, and the reaction temperature is controlled at 50-110℃ for 0.5-10h; a precursor polymer of linear / star-coupled silicon / nitrogen group-functionalized styrene-butadiene / isoprene block polymer is prepared, which is also the silicon / nitrogen group-functionalized polystyrene-isoprene active center; wherein, by mass, the feed ratio of styrene, styrene monomers composed of silicon / nitrogen group-functionalized 1,1-diphenylethylene derivatives, butadiene, and isoprene is 1:0.5-2:0.5-2;

[0033] Step S3, preparation of linear / star-coupled silicon / nitrogen-functionalized styrene-butadiene / isoprene block copolymer: After the reaction in step S2 is completed, a metered linear / star coupling agent is added to carry out the coupling reaction. The reaction temperature is controlled at 50-110℃ and the reaction is carried out for 30-150 min to obtain a linear / star-coupled silicon / nitrogen-functionalized styrene-butadiene / isoprene block copolymer solution.

[0034] Step S4, prepare S(EB / EP)S thermoplastic elastomer functionalized with silicon / nitrogen groups:

[0035] The linear / star-coupled styrene-butadiene / isoprene block copolymer solution containing silicon / nitrogen groups was transferred to a high-pressure hydrogenation reactor, diluted with solvent, and then a metered hydrogenation catalyst and hydrogen were added to carry out the hydrogenation reaction. The hydrogen pressure was controlled at 0.1 MPa to 10 MPa, the reaction temperature was controlled at 50℃ to 200℃, and the hydrogenation reaction was carried out for 1 to 20 hours to obtain S(EB / EP)S thermoplastic elastomer containing silicon / nitrogen groups.

[0036] Further, in step S1, a metered polar modifier is added to the reactor in a nonpolar hydrocarbon solvent as system A;

[0037] According to the monomer ratio, a measured amount of silicon / nitrogen functionalized 1,1-diphenylethylene derivative monomer and alkyl lithium initiator were added to system A. The initiation reaction temperature was 10℃-90℃. Then, a measured amount of styrene monomer was added to form system B, and a polymer with silicon / nitrogen functionalized initiation end was synthesized.

[0038] Alternatively, a measured amount of 1,1-diphenylethylene derivative and styrene monomer can be added to system A according to the monomer ratio, followed by a measured amount of alkyl lithium initiator. The initiation reaction temperature is 10℃-90℃, which is used as system C to synthesize a silicon / nitrogen functionalized polymer in the chain.

[0039] Alternatively, 1,1-diphenylethylene derivative monomers with silicon / nitrogen functionalization can be added to system B / system A to form system D, thereby synthesizing polymers with different silicon / nitrogen functionalization at the chain ends and in the chain.

[0040] In the B / C / D system, by controlling the ratio of styrene monomer, silicon / nitrogen-functionalized 1,1-diphenylethylene derivative monomer, alkyl lithium initiator and polarity modifier, as well as the silicon / nitrogen-functionalized 1,1-diphenylethylene derivative monomer, the distribution, properties (types), quantity and mass percentage of silicon / nitrogen-functionalized 1,1-diphenylethylene derivative in the chain ends and chain of polystyrene blocks can be precisely controlled.

[0041] In step S1, the silicon / nitrogen-functionalized 1,1-diphenylethylene derivative monomers added to systems B, C, and D are one or a mixture of several.

[0042] Furthermore, the total mass concentration of all monomers added in step S1 is 5%-25%, determined according to the type and amount of 1,1-diphenylethylene derivative monomers functionalized with silicon / nitrogen groups.

[0043] Furthermore, when the total mass concentration of all reactants in step SI is 5%-25%, the silicon / nitrogen functionalized 1,1-diphenylethylene derivative monomer is located at the chain end of the styrene block.

[0044] When the total mass concentration of all reactants in step S1 is less than 10%, the mass concentration of 1,1-diphenylethylene derivative monomers functionalized with monosilane groups, or 1,1-diphenylethylene derivative monomers functionalized with monosiloxy groups, or 1,1-diphenylethylene derivative monomers containing siloxy / silane groups, combined with styrene, is 5%-15%; or the mass concentration of 1,1-diphenylethylene derivative monomers containing siloxy / amine groups, or 1,1-diphenylethylene derivative monomers containing silane / amine groups, combined with styrene, is 15%-25%; or the mass concentration of 1,1-diphenylethylene derivative monomers containing mono / diamine groups, combined with styrene, is 10%-20%. In the prepared silicon / nitrogen group-functionalized styrene block, the silicon / nitrogen group-functionalized 1,1-diphenylethylene derivative is located in the middle and at the end of the block chain.

[0045] When the total content of silicon / nitrogen functionalized 1,1-diphenylethylene derivative monomers accounts for more than 10% of the total monomer content by mass concentration, and the mass concentration of 1,1-diphenylethylene derivative monomers with monosilane groups or monosiloxy groups or siloxy / silane groups added to styrene is 5%-10%, or the mass concentration of 1,1-diphenylethylene derivative monomers with siloxy / amine groups or silane / amine groups added to styrene is 10%-15%, or the mass concentration of 1,1-diphenylethylene derivative monomers with mono / diamine groups to styrene is 8%-12%, the silicon / nitrogen functionalized 1,1-diphenylethylene derivatives in the prepared silicon / nitrogen functionalized styrene block are located in the middle and at the end of the block chain.

[0046] The nonpolar hydrocarbon solvents used in this invention are selected from at least one of nonpolar aromatic hydrocarbons and nonpolar aliphatic hydrocarbons, generally selected from: benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons (such as: mixed xylene), mixed aliphatic hydrocarbons (such as: raffinate oil), preferably selected from: benzene, toluene, pentane, hexane, cyclohexane.

[0047] Further, the polarity modifier in step S1 is selected from at least one of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and alkoxy metal compounds, preferably tetrahydrofuran, 2,2-di(2-tetrahydrofuranyl)propane, 2,2-di(5-methyl-2-tetrahydrofuran)propane, ethyl tetrahydrofuranyl ether, tetramethylethylenediamine, pentamethyldiethylenetriamine, dipiperidinyl ethane, potassium / sodium tert-butoxide, and diethylene glycol diethyl ether.

[0048] Further, in step S1, the alkyl lithium initiator is selected from at least one of the monofunctional alkyl lithium RLi initiators that can be used for the anionic polymerization of butadiene, isoprene, and styrene, where R is a hydrocarbon group with 2-20 carbon atoms, which can be an alkane group or an aromatic group, preferably n-butyllithium, sec-butyllithium, and tert-butyllithium.

[0049] Further, the linear coupling agent in step S3 is selected from M(CH3)2Cl2 or 1,2-dichloroethane or 1,2-dibromoethane, where M is selected from silicon (Si), tin (Sn), lead (Pb), titanium (Ti), germanium (Ge), and preferably dichlorodimethylsilane.

[0050] Furthermore, in step S3, the star-shaped coupling agent is selected from two coupling agents with different coupling mechanisms. One is selected from MCH3Cl3, MCl4, M2Cl6, and M3Cl8, where M is selected from silicon, tin, lead, titanium, germanium, etc., preferably tetrachlorosilane and tin tetrachloride; the other is divinylbenzene (DVB).

[0051] Furthermore, the hydrogenation catalyst in step S4 is selected from nickel-based catalysts, preferably triisobutylaluminum / nickel naphthenate catalysts.

[0052] Beneficial effects:

[0053] This invention starts with polymer design and uses 1,1-diphenylethylene derivatives functionalized with silicon / nitrogen groups as comonomers. First, based on the active anionic polymerization mechanism, linear / star-coupled styrene-butadiene / isoprene block copolymers SIBS with silicon / nitrogen groups are prepared. On this basis, linear / star-coupled styrene-(ethylene / propylene / butene) block copolymers S(EB / EP)S with silicon / nitrogen groups are obtained through selective hydrogenation. Compared with the prior art, (1) the present invention provides a novel type of silicon / nitrogen functionalized S(EB / EP)S thermoplastic elastomer and its preparation method; (2) the present invention uses a composite silicon / nitrogen functionalized 1,1-diphenylethylene derivative, and controls the polymerization rate of styrene by controlling the ratio of 1,1-diphenylethylene derivative to styrene monomer, the ratio of 1,1-diphenylethylene derivative to alkyl lithium initiator, and the ratio of 1,1-diphenylethylene derivative to polarity modifier. At the same time, by controlling the feeding sequence of 1,1-diphenylethylene derivative and styrene monomer, the silicon / nitrogen functionalized 1,1-diphenylethylene derivative can be selectively and precisely distributed in the initiation end, end and chain of styrene block, and the properties and mass fraction of silicon / nitrogen functionalized 1,1-diphenylethylene derivative can be controlled, thereby realizing the use of silicon / nitrogen groups on demand and improving the utilization efficiency of silicon / nitrogen groups; (3) the present invention essentially adopts a two-step feeding method. The preparation of silicon / nitrogen functionalized S(EB / EP)S involves the first step of generating silicon / nitrogen functionalized polystyrene blocks, the second step of synthesizing polystyrene-butadiene / isoprene diblock polymers, and then introducing a coupling agent to synthesize linear / star-coupled silicon / nitrogen functionalized styrene-butadiene / isoprene triblock copolymers with higher molecular weight. This polymer has a larger molecular weight, better melt flow properties, and better solubility. This invention has a simpler and more effective technical effect; (4) After SIBS is prepared by coupling method, the active center is consumed and no terminator is needed. The remaining active center can react with the hydrogenation catalyst, which helps to improve the hydrogenation efficiency; (5) By using polarity regulators to regulate the microstructure content of 1,2-butadiene and 3,4-isoprene in SIBS, the microstructure content of 1-butene and 1-isoprene in SEEPS can be adjusted, thereby regulating the mechanical properties of SEEPS thermoplastic elastomers.

[0054] In addition, during processing, amine groups form hydrogen bonds with hydroxyl groups and ionic bonds with carboxyl groups, while silanol groups easily form covalent or hydrogen bonds with hydroxyl groups, thus improving the compatibility and dispersibility of the material. Detailed Implementation

[0055] To better understand the above-mentioned objectives, features, and advantages of the present invention, the solutions of the present invention will be further described below. It should be noted that, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.

[0056] Many specific details are set forth in the following description in order to provide a full understanding of the invention, but the invention may also be practiced in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of the invention, and not all embodiments.

[0057] The preferred embodiments of the present invention will now be described in detail with reference to specific examples. It should be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Those skilled in the art can make various modifications and substitutions to the present invention without departing from its spirit and essence.

[0058] In this embodiment, nuclear magnetic resonance spectroscopy was used to analyze the compositional sequence distribution and microstructure of the copolymer, and gel permeation chromatography was used to analyze the molecular weight and molecular weight distribution index (the ratio of weight-average molecular weight to number-average molecular weight) of the copolymer.

[0059] Mechanical property testing: According to GBT 528-2009 standard, a universal testing machine was used for testing. The tensile rate was 500 mm / min, and the test temperature was 23℃. The tensile strength, tensile modulus, and elongation at break of the samples were recorded. Each sample was tested at least 5 times.

[0060] Hardness performance: Tested according to GB / T 531.1-2008 standard using a manual Rockwell hardness tester. The sample size was (80±2) mm × (10±2) mm × (4±2) mm. During testing, the sample was placed on a firm, flat surface. The indenter of the hardness tester was vertically pressed into the sample surface, ensuring complete contact between the indenter and the sample. A pressure of 1 kg was applied. The hardness value was read 15 seconds after the indenter had complete contact with the sample. Five tests were performed on each sample, and the final result was the average value.

[0061] Complex viscosity properties: The complex viscosity of the product prepared at 1 Hz and 170 °C was tested using an AR 2000ex rotational rheometer manufactured by TA Instruments, Inc.

[0062] Example 1

[0063] 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 (2.8g, 39mmol) and 1-[4-(dimethylsilane)phenyl]-1-phenylethylene (monosylhydrogen 1,1-diphenylethylene, 20.0g, 84mmol) were added. The mixture was stirred evenly, and n-butyllithium (2.6mmol) was added. The initiation temperature was 50℃, and the reaction was carried out for 30min. Then, styrene (110g, 1.06mol) was added to carry out the first stage polymerization reaction for 48h.

[0064] Step S2, preparing styrene-butadiene / isoprene active centers functionalized with monosilane groups: add butadiene (65g, 1.2mol) and isoprene (65g, 0.96mol) to the above polymerization reactor, and carry out the second-stage polymerization reaction at a reaction temperature of 50℃ for 3h.

[0065] Step S3, prepare star-shaped coupled styrene-butadiene / isoprene block copolymer with monosilane groups: add silicon tetrachloride coupling agent (0.11g, 0.65mmol) to the above polymerization reactor, carry out the coupling reaction at 50℃ for 150min.

[0066] Step S4, Preparation of S(EB / EP)S thermoplastic elastomer functionalized with monosilane groups: The star-coupled styrene-butadiene / isoprene block copolymer solution functionalized with monosilane groups is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added to carry out hydrogenation reaction. The hydrogen pressure is controlled at 3 MPa, the reaction temperature is 50°C, and the reaction is carried out for 3 h.

[0067] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1The structure was analyzed by HNMR, and the results are as follows: The product mass was 229.3 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monosilane groups was 50.0%, with the remainder being butadiene and isoprene; based on the mass of styrene blocks as 100%, the mass percentage of DPE derivative monomers functionalized with monosilane groups was 15.3%, with the remainder being styrene monomers. The DPE derivatives functionalized with monosilane groups were distributed at the initiation ends and in the chain of polystyrene blocks, exhibiting a quasi-periodic sequence distribution in the chain; the degree of hydrogenation was 50.1%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), using narrowly distributed polystyrene with different molecular weights as... Standard curves were prepared for the standard samples, and the results are as follows: Before coupling, the styrene-butadiene / isoprene block copolymer with monosilane functionalization showed a narrow single-peak distribution, with a number-average molecular weight of 158.1 kg / mol and a molecular weight distribution of 1.14; after star-shaped coupling, the styrene-butadiene-isoprene block copolymer with monosilane functionalization showed a narrow single-peak distribution, with a coupling efficiency of approximately 100%, a number-average molecular weight of 565.7 kg / mol, and a molecular weight distribution of 1.25; after hydrogenation, the S(EB / EP)S with monosilane functionalization showed a narrow single-peak distribution, with a number-average molecular weight of 567.4 kg / mol and a molecular weight distribution of 1.26. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1830%, and the tensile strength was 15.3 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its hardness (Shore D) was 86. The complex viscosity of the product was tested at 1 Hz and 170 °C using a rotational rheometer, and the viscosity was 163 Pa·s.

[0068] Example 2

[0069] Step S1, preparation of 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 (2.8g, 39mmol) and 1-[4-(dimethylsilane)phenyl]-1-phenylethylene (monosylhydrogen DPE, 0.62g, 2.6mmol) were added. After stirring evenly, n-butyllithium (2.6mmol) 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 for 6h.

[0070] Step S2, preparing styrene-butadiene / isoprene active centers functionalized with monosilane groups: add butadiene (65g, 1.2mol) and isoprene (65g, 0.96mol) to the above polymerization reactor, and carry out the second-stage polymerization reaction at 80℃ for 3h.

[0071] Step S3, prepare star-shaped coupled styrene-butadiene / isoprene block copolymer with monosilane groups: add silicon tetrachloride coupling agent (0.07g, 0.416mmol) to the above polymerization reactor, carry out the coupling reaction at 80℃ for 120min.

[0072] Step S4, Preparation of S(EB / EP)S thermoplastic elastomer functionalized with monosilane groups: The star-coupled styrene-butadiene / isoprene block copolymer solution functionalized with monosilane groups is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added to carry out hydrogenation reaction. The hydrogen pressure is controlled at 3 MPa, the reaction temperature is 200℃, and the reaction is carried out for 1 h.

[0073] 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 product mass was 163.5 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monosilane groups was 33.5%, with the remainder being butadiene and isoprene; based on the mass of styrene blocks as 100%, the mass percentage of DPE derivative monomers functionalized with monosilane groups was 1.0%, with the remainder being styrene monomers, and the DPE derivatives functionalized with monosilane groups were distributed at the initiation end of the polystyrene blocks; the degree of hydrogenation was 99.5%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), and a standard curve was prepared using polystyrene with narrow molecular weight distributions as standard samples, and the results are as follows: styrene functionalized with monosilane groups before coupling... The number-average molecular weight of the butadiene / isoprene block copolymer was 132.2 kg / mol, with a molecular weight distribution of 1.11. The star-coupled styrene-butadiene / isoprene block copolymer with monosilylic hydrogen functionalization exhibited a bimodal distribution, with a coupling efficiency of approximately 70.1% and a molecular weight distribution of 1.42. The number-average molecular weights of the star-coupled and linear samples were 377.4 kg / mol and 134.3 kg / mol, respectively. The hydrogenated S(EB / EP)S with monosilylic hydrogen functionalization also exhibited a bimodal distribution. The number-average molecular weights of the star-coupled and linear samples were 379.1 kg / mol and 135.6 kg / mol, respectively, with a molecular weight distribution of 1.49. The mechanical properties of the product were tested using a universal testing machine, with the following results: elongation at break was 1860%, and tensile strength was 13.5 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its Shore D was 70. The complex viscosity of the product was tested at 1 Hz and 170 °C using a rotational rheometer, and the viscosity was 172 Pa·s.

[0074] Example 3

[0075] Step S1: Preparation of polystyrene active centers functionalized with monosilane and disilane groups: Under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added to a 5L polymerization reactor, and tetrahydrofuran (2.8g, 39mmol) and 1-[4-(dimethylsilane)phenyl]-1-phenylethylene (monosane DPE, 0.62g, 2.6mmol) were added and stirred evenly. Then, n-butyllithium (2.6mmol) was added, the initiation temperature was 50℃, and the reaction was carried out for 30min. Then, styrene (33g, 0.137mol) was added to carry out the first stage polymerization reaction for 2h. Then, 1,1-bis[4-(dimethylsilane)phenyl]ethylene (disilane DPE, 0.77g, 2.6mmol) was added and the reaction was carried out for 2h.

[0076] Step S2, preparing styrene-butadiene / isoprene active centers functionalized with monosilane and disilane groups: add butadiene (100g, 1.85mol) and isoprene (30g, 0.44mol) to the above polymerization reactor, and carry out the second stage polymerization reaction at 50℃ for 3h.

[0077] Step S3, prepare star-shaped styrene-butadiene / isoprene block copolymers functionalized with mono- and di-silane groups: add silicon tetrachloride coupling agent (0.11 g, 0.65 mmol) and divinylbenzene (0.05 g, 0.38 mmol) to the above polymerization reactor, carry out the coupling reaction at 50 °C for 150 min;

[0078] Step S4, preparation of S(EB / EP)S thermoplastic elastomer functionalized with mono- and di-silane groups: The star-coupled styrene-butadiene / isoprene block copolymer solution with silane groups was transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen was added as a triisobutylaluminum / nickel naphthenate catalyst. The hydrogenation reaction was carried out under the control of 5 MPa hydrogen pressure, 80 °C reaction temperature and 3 h reaction.

[0079] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1The structure was analyzed by HNMR, and the results are as follows: the product mass was 114.3 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with silanol groups was 20.9%, with the remainder being butadiene and isoprene; based on the mass of styrene blocks as 100%, the mass percentage of DPE derivative monomers functionalized with silanol groups was 4.0%, with the remainder being styrene monomers; DPE derivatives functionalized with monosilanol groups were distributed at the initiating end of the polystyrene blocks, and DPE derivatives functionalized with disilanol groups were distributed at the ends of the polystyrene blocks; the degree of hydrogenation was 94.1%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), and the molecular weights were analyzed at different molecular weights. A standard curve was prepared using narrow-distribution polystyrene as the standard sample. The results are as follows: Before coupling, the number-average molecular weight of the styrene-butadiene / isoprene block copolymer with silanol functionalization was 110.5 kg / mol, and the molecular weight distribution was 1.13; after star-shaped coupling, the styrene-butadiene / isoprene block copolymer with silanol functionalization showed a single-peak narrow distribution, with a coupling efficiency of approximately 100%, a number-average molecular weight of 391.5 kg / mol, and a molecular weight distribution of 1.21; after hydrogenation, the silanol functionalized S(EB / EP)S showed a single-peak narrow distribution, with a number-average molecular weight of 393.1 kg / mol and a molecular weight distribution of 1.23. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1880%, and the tensile strength was 11.6 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its hardness (Shore D) was 68. The complex viscosity of the product was tested at 1 Hz and 170 °C using a rotational rheometer, and the viscosity was 184 Pa·s.

[0080] Example 4

[0081] Step S1, preparation of 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 1-[4-(dimethylsilane)phenyl]-1-phenylethylene (monosylhydrogen DPE, 20.0g, 84mmol) were added. After stirring evenly, n-butyllithium (2.6mmol) was added, the initiation temperature was 60℃, and the reaction was carried out for 30min. Then, styrene (110g, 1.06mol) was added to carry out the first stage polymerization reaction for 48h.

[0082] Step S2, preparing styrene-butadiene / isoprene active centers functionalized with monosilane groups: add butadiene (30g, 0.56mol) and isoprene (100g, 1.47mol) to the above polymerization reactor, and carry out the second polymerization reaction at 50℃ for 3h.

[0083] Step S3, prepare linearly coupled styrene-butadiene / isoprene block copolymer with monosilane functionalized groups: add dimethyldichlorosilane coupling agent (0.17g, 1.3mmol) to the above polymerization reactor, carry out the coupling reaction at 60℃ for 150min;

[0084] Step S4, Preparation of S(EB / EP)S thermoplastic elastomer functionalized with silane groups: The linearly coupled styrene-butadiene / isoprene block copolymer solution functionalized with monosilane groups is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added as a triisobutylaluminum / nickel naphthenate catalyst. The hydrogenation reaction is carried out under the control of 10 MPa and 80°C for 1 h.

[0085] 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 product mass was 229.1 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monosilane groups was 50.0%, with the remainder being butadiene and isoprene; based on the mass of styrene blocks as 100%, the mass percentage of DPE derivative monomers functionalized with monosilane groups was 15.4%, with the remainder being styrene monomers. The DPE derivatives functionalized with monosilane groups were distributed at the initiation end, chain middle, and chain end of the polystyrene blocks, showing a gradual sequence distribution in the chain; the degree of hydrogenation was 96.3%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), using narrowly distributed polystyrene with different molecular weights as... Standard curves were prepared for the standard samples, and the results are as follows: Before coupling, the styrene-butadiene / isoprene block copolymer with monosilane functionalization exhibited a narrow single-peak distribution, with a number-average molecular weight of 165.1 kg / mol and a molecular weight distribution of 1.15; after linear coupling, the styrene-butadiene / isoprene block copolymer with monosilane functionalization also exhibited a narrow single-peak distribution, with a coupling efficiency close to 100%, a number-average molecular weight of 268.9 kg / mol, and a molecular weight distribution of 1.28; after hydrogenation, the S(EB / EP)S with monosilane functionalization exhibited a narrow single-peak distribution, with a number-average molecular weight of 270.2 kg / mol and a molecular weight distribution of 1.35. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1430%, and the tensile strength was 23.8 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its hardness (Shore D) was 78. The complex viscosity of the product was tested at 1 Hz and 170 °C using a rotational rheometer, and the viscosity was 194 Pa·s.

[0086] Example 5

[0087] Step S1, preparation of polystyrene active centers functionalized with siloxane and silane groups: Under the protection of nitrogen or argon, 3 L (1204 g) of cyclohexane (2.5 L, 999 g) and n-hexane (0.5 L, 205 g) in a volume ratio of 5:1 were added to a 5 L polymerization reactor, and tetramethylethylenediamine (2.6 mmol, 0.3 g), 1-[4-(triisopropoxysilyl)phenyl]-1-phenylethylene (monosilicon DPE, 0.5 g, 1.3 mmol) and 1-[4-(dimethylsilane)phenyl]-1-phenylethylene (monosilicon DPE, 0.38 g, 1.3 mmol) were added and stirred evenly. Then, n-butyllithium (2.6 mmol, 1.6 mol / L) was added, the initiation temperature was 50 °C, and the reaction was carried out for 30 min. Then, styrene (110 g, 1.06 mol) was added to carry out the first stage polymerization reaction for 3 h.

[0088] Step S2, preparing styrene-isoprene active centers functionalized with siloxane and silane groups: add butadiene (65g, 1.2mol) and isoprene (65g, 0.96mol) to the above polymerization reactor, and carry out the second-stage polymerization reaction at a reaction temperature of 90℃ for 3h.

[0089] Step S3, prepare star-shaped coupled styrene-butadiene / isoprene block copolymer with siloxane and silane groups: add selenium tetrachloride coupling agent (0.11 g, 0.52 mmol) and divinylbenzene (0.01 g, 0.07 mmol) to the above polymerization reactor, carry out the coupling reaction at 90 °C for 30 min;

[0090] Step S4, preparation of S(EB / EP)S thermoplastic elastomer functionalized with siloxane and silane groups: The star-coupled styrene-butadiene / isoprene block copolymer solution with silane groups is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added as a triisobutylaluminum / nickel naphthenate catalyst. The hydrogenation reaction is carried out under the control of 3 MPa hydrogen pressure, 60°C reaction temperature and 3 h reaction.

[0091] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1The structure was analyzed by HNMR, and the results are as follows: the product mass was 219.3 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with siloxane and silane groups was 46.0%, with the remainder being butadiene and isoprene; based on the mass of styrene block as 100%, the mass percentage of DPE derivative monomers functionalized with siloxane and silane groups was 1.0%, with the remainder being styrene monomers, and 1,1-diphenylethylene derivatives functionalized with siloxane and silane groups were distributed at the initiation end of the polystyrene block; the degree of hydrogenation was 62%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), and a standard curve was prepared using polystyrene with narrow molecular weight distributions of different molecular weights as standard samples, and the results are as follows: before coupling, it contained... The styrene-butadiene / isoprene block copolymers functionalized with siloxane and silane groups exhibit a narrow unimodal distribution, with a number-average molecular weight of 151.1 kg / mol and a molecular weight distribution of 1.20. The styrene-butadiene / isoprene block copolymers functionalized with siloxane and silane groups after star coupling show a bimodal distribution, with a coupling efficiency of 60.1%, number-average molecular weights of 392.1 kg / mol and 153.2 kg / mol, and a molecular weight distribution of 1.51, respectively. The hydrogenated S(EB / EP)S containing mono-silane functionalized groups also shows a bimodal distribution, with number-average molecular weights of 394.2 kg / mol and 155.1 kg / mol, and a molecular weight distribution of 1.51, respectively. The mechanical properties of the products were tested using a universal testing machine, and the results are as follows: elongation at break is 1760%, and tensile strength is 15.2 MPa. The hardness of the products was tested using a manual Rockwell hardness tester, and its hardness (Shore D) is 73. The complex viscosity of the product was tested at 1 Hz and 170 °C using a rotational rheometer, and the viscosity was 184 Pa·s.

[0092] Example 6

[0093] Step S1: Preparation of polystyrene active centers functionalized with silane and silane / amine groups: Under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added to a 5L polymerization reactor, and tetrahydrofuran (1.4g, 19.5mmol) and 1-[4-(dimethylsilane)phenyl]-1-phenylethylene (monosylhydrogen DPE, 15.0g, 63mmol) were added and stirred evenly. Then, n-butyllithium (1.3mmol, 1.6mol / L) was added, the initiation temperature was 50℃, and the reaction was carried out for 30min. Then, styrene (65g, 0.53mol) was added to carry out the first stage polymerization reaction for 60h. Then, 1-[4-(dimethylsilane)phenyl]-1-[4-(N,N-dimethylamino)phenyl]ethylene (silane / amine DPE, 1.3mmol, 0.37g) was added and the reaction was carried out for 2h.

[0094] Step S2, preparing styrene-butadiene / isoprene active centers functionalized with silane and silane / amine groups: add butadiene (65g, 1.2mol) and isoprene (65g, 0.96mol) to the above polymerization reactor, and carry out the second polymerization reaction at 60℃ for 3h.

[0095] Step S3, prepare star-shaped coupled styrene-butadiene / isoprene block copolymer with monosilane groups: add silicon tetrachloride coupling agent (0.11 g, 0.65 mmol) and divinylbenzene (0.03 g, 0.23 mmol) to the above polymerization reactor, carry out the coupling reaction at 60 °C for 150 min;

[0096] Step S4, Preparation of S(EB / EP)S thermoplastic elastomer functionalized with silane groups: The star-coupled styrene-butadiene / isoprene block copolymer solution containing silane and silane / amine groups is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogenation reaction is carried out by adding triisobutylaluminum / nickel naphthenate catalyst and hydrogen gas. The hydrogen pressure is controlled at 1 MPa, the reaction temperature is 200℃, and the reaction is carried out for 5 h.

[0097] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1The structure was analyzed by HNMR, and the results are as follows: The product mass was 173.7 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with silane and silane / amine groups was 38.2%, with the remainder being butadiene and isoprene; based on the mass of styrene blocks as 100%, the mass percentage of DPE derivative monomers functionalized with silicon groups was 18.0%, with the remainder being styrene monomers; the DPE derivatives functionalized with silane and silane / amine groups were distributed at the initiation ends and chains of polystyrene blocks, while the DPE derivatives functionalized with silane / amine groups were distributed at the chain ends of polystyrene blocks; the degree of hydrogenation was 99.1%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), and the molecular weight was analyzed by narrow-band fractionation. A standard curve was prepared using polystyrene as the standard sample, and the results are as follows: Before coupling, the styrene-butadiene / isoprene block copolymer containing silane and silane / amine functionalization groups exhibited a narrow single-peak distribution, with a number-average molecular weight of 274.8 kg / mol and a molecular weight distribution of 1.13; after star-shaped coupling, the styrene-butadiene / isoprene block copolymer containing silane and silane / amine functionalization groups also exhibited a narrow single-peak distribution, with a coupling efficiency close to 100%, a number-average molecular weight of 865.1 kg / mol, and a molecular weight distribution of 1.42; after hydrogenation, the S(EB / EP)S containing mono-silane functionalization exhibited a narrow single-peak distribution, with a number-average molecular weight of 868.4 kg / mol and a molecular weight distribution of 1.44. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1730%, and the tensile strength was 15.7 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its hardness (Shore D) was 71. The complex viscosity of the product was tested at 1 Hz and 170 °C using a rotational rheometer, and the viscosity was 201 Pa·s.

[0098] Example 7

[0099] Step S1, preparation of polystyrene active centers functionalized with monoamine groups: Under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added to a 5L polymerization reactor, and tetrahydrofuran (2.8g, 39mmol) and 1-[4-(N,N-dimethylamino)phenyl]-1-phenylethylene (monoamine DPE, 18.7g, 84mmol) were added. After stirring evenly, n-butyllithium (2.6mmol) was added, the initiation temperature was 50℃, and the reaction was carried out for 30min. Then, styrene (110g, 1.06mol) was added to carry out the first stage polymerization reaction for 24h.

[0100] Step S2, preparing styrene-butadiene / isoprene active centers functionalized with monoamine groups: add butadiene (65g, 1.2mol) and isoprene (65g, 0.96mol) to the above polymerization reactor, carry out the second stage polymerization reaction at 60℃, and react for 3h;

[0101] Step S3: Prepare star-shaped styrene-butadiene / isoprene block copolymer with monoamine functionalized groups: Add silicon tetrachloride coupling agent (0.11 g, 0.65 mmol) and divinylbenzene (0.01 g, 0.07 mmol) to the above polymerization reactor, carry out the coupling reaction at 50 °C for 150 min;

[0102] Step S4, Preparation of S(EB / EP)S thermoplastic elastomer functionalized with monoamine groups: The star-coupled styrene-butadiene / isoprene block copolymer solution functionalized with monoamine groups is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added as a triisobutylaluminum / nickel naphthenate catalyst. The hydrogenation reaction is carried out under the control of 3 MPa hydrogen pressure, 50°C reaction temperature and 3 h reaction.

[0103] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1The structure was analyzed by HNMR, and the results are as follows: the product mass was 223.9 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monoamine groups was 49.7%, with the remainder being butadiene and isoprene; based on the mass of styrene blocks as 100%, the mass percentage of DPE derivative monomers functionalized with monoamine groups was 14.5%, with the remainder being styrene monomers. The DPE derivatives functionalized with monoamine groups were distributed at the initiation ends and in the chain of polystyrene blocks, exhibiting a gradient sequence distribution in the chain; the degree of hydrogenation was 53.6%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), using narrowly distributed polystyrene with different molecular weights as standard samples. A standard curve was constructed, and the results are as follows: Before coupling, the styrene-butadiene / isoprene block copolymer with diamine groups exhibited a narrow single-peak distribution, with a number-average molecular weight of 156.1 kg / mol and a molecular weight distribution of 1.13; after star-shaped coupling, the styrene-butadiene / isoprene block copolymer with monoamine groups exhibited a narrow single-peak distribution, with a coupling efficiency of approximately 100%, a number-average molecular weight of 558.3 ​​kg / mol, and a molecular weight distribution of 1.25; after hydrogenation, the S(EB / EP)S with monoamine groups exhibited a narrow single-peak distribution, with a number-average molecular weight of 560.2 kg / mol and a molecular weight distribution of 1.27. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1720%, and the tensile strength was 13.6 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its hardness (Shore D) was 79. The complex viscosity of the product was tested at 1 Hz and 170 °C using a rotational rheometer, and the viscosity was 210 Pa·s.

[0104] Example 8

[0105] Step S1, preparing polystyrene active centers functionalized with diamine groups: Under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added to a 5L polymerization reactor, and tetrahydrofuran (2.8g, 39mmol) and 1,1-bis[4-(N,N-dimethylamino)phenyl]ethylene (diamine DPE, 0.7g, 2.6mmol) were added. After stirring evenly, n-butyllithium (2.6mmol) was added, the initiation temperature was 50℃, and the reaction was carried out for 30min. Then, styrene (129g, 1.24mol) was added to carry out the first stage polymerization reaction for 12h.

[0106] Step S2, preparing styrene-isoprene active centers functionalized with diamine groups: add butadiene (65g, 1.2mol) and isoprene (65g, 0.96mol) to the above polymerization reactor, and carry out the second-stage polymerization reaction at a reaction temperature of 60℃ for 3h;

[0107] Step S3, prepare star-shaped coupled styrene-butadiene / isoprene block copolymer with diamine groups: add silicon tetrachloride coupling agent (0.11g, 0.65mmol) to the above polymerization reactor, react at 60℃, and carry out the coupling reaction for 150min;

[0108] Step S4, Preparation of S(EB / EP)S thermoplastic elastomer functionalized with diamine groups: The star-coupled styrene-butadiene / isoprene block copolymer solution functionalized with diamine groups is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added with triisobutylaluminum / nickel naphthenate catalyst and hydrogen gas to carry out hydrogenation reaction. The hydrogen pressure is controlled at 3 MPa, the reaction temperature is 100℃, and the reaction is carried out for 3 h.

[0109] 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 product mass was 218.2 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with diamine groups was 50.1%, with the remainder being butadiene and isoprene; based on the mass of styrene blocks as 100%, the mass percentage of DPE derivative monomers functionalized with diamine groups was 0.54%, with the remainder being styrene monomers, and the DPE derivatives functionalized with diamine groups were distributed at the initiation ends of the polystyrene blocks; the degree of hydrogenation was 99.1%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), and a standard curve was prepared using narrow-distribution polystyrene with different molecular weights as standard samples. The results are as follows: Before coupling, the styrene-butadiene / isoprene block copolymer with diamine groups exhibited a narrow, single-peak molecular weight distribution, with a number-average molecular weight of 167.1 kg / mol and a molecular weight distribution of 1.13; after star-shaped coupling, the styrene-butadiene / isoprene block copolymer with diamine groups exhibited a narrow, single-peak molecular weight distribution, with a coupling efficiency of approximately 100%, a number-average molecular weight of 564.6 kg / mol, and a molecular weight distribution of 1.25; after hydrogenation, the S(EB / EP)S with diamine groups exhibited a narrow, single-peak molecular weight distribution, with a number-average molecular weight of 567.6 kg / mol and a molecular weight distribution of 1.31. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1780%, and the tensile strength was 12.3 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its hardness (Shore D) was 80. The complex viscosity of the product was tested at 1 Hz and 170 °C using a rotational rheometer, and the viscosity was 162 Pa·s.

[0110] Example 9 (Adjusting the type, sequence, and topological structure of the stilbene derivative; other parameters are the same as in Example 2)

[0111]

[0112] Example 10 (DPE type adjusted, other parameters same as Example 2)

[0113]

[0114]

[0115]

[0116] Example 11 (Adjusting the block weight, other parameters are the same as in Example 4)

[0117]

[0118] When the styrene block content is less than 20%, the tensile strength and elongation at break of SEEPS are low, and the performance is poor. When the styrene block content is greater than 50%, the tensile strength of SEEPS does not improve significantly, and the elongation at break gradually decreases. Therefore, the preferred styrene block content in this patent is 20-50%.

[0119] Example 12 (Adjusting the proportion of stilbene derivative in the styrene block, other parameters are the same as in Example 6)

[0120]

[0121] When the DPE content is less than 0.1%, the tensile strength of SEEPS is below 11.0 MPa, indicating low strength. When the DPE content is greater than 0.5% and less than 20%, the tensile strength and tensile modulus of SEEPS are significantly improved. When the DPE content is greater than 50%, the tensile strength and tensile modulus do not change much, and excessive DPE will increase the production cost of SEEPS. Therefore, the preferred DPE content in this patent is 0.5-20%.

[0122] Example 13 (Vinyl content adjusted, other parameters same as in Example 6)

[0123]

[0124]

[0125] Example 14 (Adjusting the position of the stilbene derivative in the chain, other parameters are the same as in Example 6)

[0126]

[0127] Comparative Example 1 (using Example 5 as an example, with the hydrogenation step reduced)

[0128] Step S1, preparation of polystyrene active centers functionalized with siloxane and silane groups: Under the protection of nitrogen or argon, 3 L (1204 g) of cyclohexane (2.5 L, 999 g) and n-hexane (0.5 L, 205 g) in a volume ratio of 5:1 were added to a 5 L polymerization reactor, and tetramethylethylenediamine (2.6 mmol, 0.3 g), 1-[4-(triisopropoxysilyl)phenyl]-1-phenylethylene (monosilicon DPE, 0.5 g, 1.3 mmol) and 1-[4-(dimethylsilane)phenyl]-1-phenylethylene (monosilicon DPE, 0.38 g, 1.3 mmol) were added and stirred evenly. Then, n-butyllithium (2.6 mmol, 1.6 mol / L) was added, the initiation temperature was 50 °C, and the reaction was carried out for 30 min. Then, styrene (110 g, 1.06 mol) was added to carry out the first stage polymerization reaction for 3 h.

[0129] Step S2, preparing styrene-isoprene active centers functionalized with siloxane and silane groups: add butadiene (65g, 1.2mol) and isoprene (65g, 0.96mol) to the above polymerization reactor, carry out the second stage polymerization reaction at 50℃ for 3h;

[0130] Step S3, prepare star-shaped coupled styrene-butadiene / isoprene block copolymer with silicon oxygen and silicon hydrogen groups: add selenium tetrachloride coupling agent (0.11g, 0.52mmol) to the above polymerization reactor, carry out the coupling reaction at 60℃ for 30min;

[0131] After the reaction, the polymer was post-treated using traditional methods, and the product was dried and then subjected to 1H NMR spectroscopy. 1The structure was analyzed by HNMR, and the results are as follows: The product mass was 198.3 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with siloxane and silane groups was 46.0%, with the remainder being butadiene and isoprene; based on the mass of styrene blocks as 100%, the mass percentage of DPE derivative monomers functionalized with siloxane and silane groups was 1.0%, with the remainder being styrene monomers, and the DPE derivatives functionalized with siloxane and silane groups were distributed at the initiation ends of the polystyrene blocks; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), and the molecular weights were analyzed at different molecular weights. A standard curve was prepared using narrow-distribution polystyrene as the standard sample. The results are as follows: Before coupling, the styrene-butadiene / isoprene block copolymer functionalized with siloxane and silane groups exhibited a single-peak narrow distribution, with a number-average molecular weight of 121.1 kg / mol and a molecular weight distribution of 1.10. After star-shaped coupling, the styrene-butadiene / isoprene block copolymer functionalized with siloxane and silane groups exhibited a bimodal distribution, with a coupling efficiency of 60.1%, number-average molecular weights of 381.1 kg / mol and 123.2 kg / mol, and a molecular weight distribution of 1.41, respectively. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 670%, and the tensile strength was 2.1 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its hardness (Shore D) was 43.

[0132] Comparative Example 2 (using Example 5 as an example, replacing monosilicon hydrogen DPE with the same amount of styrene)

[0133] Step S1, preparing polystyrene active centers functionalized with siloxane and silane groups: Under the protection of nitrogen or argon, 3L (1204g) of cyclohexane (2.5L, 999g) and n-hexane (0.5L, 205g) in a volume ratio of 5:1 were added to a 5L polymerization reactor, and styrene (110.3g, 1.06mol) and tetramethylethylenediamine (2.6mmol, 0.3g) were added. The mixture was stirred until homogeneous, and n-butyllithium (2.6mmol, 1.6mol / L) was added. The initiation temperature was 50℃, and the reaction was carried out for 3h.

[0134] Step S2, preparing styrene-isoprene active centers functionalized with siloxane and silane groups: add butadiene (65g, 1.2mol) and isoprene (65g, 0.96mol) to the above polymerization reactor, carry out the second stage polymerization reaction at 50℃ for 3h;

[0135] Step S3, prepare star-shaped coupled styrene-butadiene / isoprene block copolymer with silicon oxygen and silicon hydrogen groups: add selenium tetrachloride coupling agent (0.11g, 0.52mmol) to the above polymerization reactor, carry out the coupling reaction at 60℃ for 30min;

[0136] Step S4, preparation of S(EB / EP)S thermoplastic elastomer functionalized with siloxane and silane groups: The star-coupled styrene-butadiene / isoprene block copolymer solution with silane groups is transferred to a high-pressure hydrogenation reactor, diluted with solvent, and hydrogen is added as a triisobutylaluminum / nickel naphthenate catalyst. The hydrogenation reaction is carried out under the control of 3 MPa hydrogen pressure, 60°C reaction temperature and 3 h reaction.

[0137] 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 product mass was 201.6 g; based on the mass of styrene and butadiene / isoprene block copolymer as 100%, the mass percentage of styrene was 46.0%, with the remainder being butadiene and isoprene; the degree of hydrogenation was 98.1%; the molecular weight was analyzed by high-temperature gel permeation chromatography (GPC), and a standard curve was prepared using polystyrene with narrow molecular weight distributions as standard samples. The results are as follows: before coupling, the styrene-butadiene / isoprene block copolymer showed a single-peak narrow distribution, with a number-average molecular weight of 147.3 kg / mol. The molecular weight distribution was 1.08; the star-coupled styrene-butadiene / isoprene block copolymer exhibited a bimodal distribution with a coupling efficiency of 60.1%, number-average molecular weights of 376.4 kg / mol and 148.2 kg / mol, and a molecular weight distribution of 1.51; the hydrogenated S(EB / EP)S also exhibited a bimodal distribution with number-average molecular weights of 391.2 kg / mol and 156.1 kg / mol, and a molecular weight distribution of 1.51; the mechanical properties of the product were tested using a universal testing machine, and the results are as follows: elongation at break was 1130%, and tensile strength was 10.2 MPa. The hardness of the product was tested using a manual Rockwell hardness tester, and its hardness (Shore D) was 63. The complex viscosity of the product was tested using a rotational rheometer at 1 Hz and 170 °C, and the viscosity was 164 Pa·s.

[0138] While the specific embodiments of the present invention have been described above, they are not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art without creative effort based on the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims

1. A silicon / nitrogen group functionalized S(EB / EP)S thermoplastic elastomer characterized in that, The silicon / nitrogen group-functionalized S(EB / EP)S thermoplastic elastomer is a linear / star coupled silicon / nitrogen group-functionalized styrene-(ethylene / propylene / butylene) block copolymer, a linear / star coupled silicon / nitrogen group-functionalized copolymer of styrene blocks and ethylene / propylene / butylene random copolymer blocks, having the structure -[(F-S)-b-(EB-co-EP)] n M[CH3] m -、-[(F-S)-b-(EB-co-EP)] n at least one of DVB, Among them, F is a silicon / nitrogen group-functionalized 1,1-diphenyl ethylene derivative, F-S is a silicon / nitrogen group-functionalized styrene block, and EB-co-EP is a selectively hydrogenated butadiene-isoprene block, specifically an ethylene / propylene / butene random copolymer block; b indicates that (F-S) and (EB-co-EP) are block polymers, M is a coupling agent residue, DVB is a diethylbenzene coupling center, n is the average number of coupling arms, and 2 < n ≤ 8; m is selected from 0, 1, 2; Among them, the linear coupling agent is selected from M(CH3)2Cl2, 1,2-dichloroethane, 1,2-dibromoethane; the star-shaped coupling agent is selected from MCH3Cl3, MCl4, M2Cl6, M3Cl8 or divinylbenzene; The linear / star-shaped coupled silicon / nitrogen group-functionalized styrene block is a copolymer block of styrene and a silicon / nitrogen group-functionalized 1,1-diphenyl ethylene derivative; The number average molecular weight M of the silicon / nitrogen group- functionalized S(EB / EP)S 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 / nitrogen-containing functionalized S(EB / EP)S thermoplastic elastomer according to claim 1, characterized in that, The linear / star-shaped coupled silicon / nitrogen group-functionalized styrene-(ethylene / propylene / butene) block copolymer is obtained by selectively hydrogenating the linear / star-shaped coupled silicon / nitrogen group-functionalized styrene-(butadiene / isoprene) block copolymer, and the hydrogenation degree range of the linear / star-shaped coupled styrene-(ethylene / propylene / butene) block copolymer is 50% to 100%.

3. The silicon / nitrogen-functionalized S(EB / EP)S thermoplastic elastomer according to claim 1, characterized in that, Based on the mass of the silicon / nitrogen group-functionalized S(EB / EP)S thermoplastic elastomer being 100%, among them, the mass percentage of the linear / star-shaped coupled silicon / nitrogen group-functionalized styrene block is 20% to 50%, and the rest is the butadiene-isoprene block.

4. The silicon / nitrogen-containing functionalized S(EB / EP)S thermoplastic elastomer according to claim 1, characterized in that, Based on the mass of the silicon / nitrogen group-functionalized styrene block being 100%, among them, the mass percentage of the silicon / nitrogen group-functionalized 1,1-diphenyl ethylene derivative monomer is 0.1% - 50.0%.

5. The silicon / nitrogen-functionalized S(EB / EP)S thermoplastic elastomer according to claim 1, characterized in that, The silicon / nitrogen group-functionalized 1,1-diphenyl ethylene derivative is selected from silicon group-containing, amine group-containing, silicon group / amine group-functionalized 1,1-diphenyl ethylene derivatives; The silicon group-functionalized 1,1-diphenyl ethylene derivative is selected from at least one of 1-[4-(triisopropoxysilyl)phenyl]-1-phenyl ethylene, 1-[4-(dimethylsilylhydride)phenyl]-1-phenyl ethylene, 1,1-di[4-(triisopropoxysilyl)phenyl]ethylene, 1-[4-(dimethylsilyl)phenyl]-1-phenyl ethylene, 1,1-di[4-(dimethylsilyl)phenyl]ethylene, 1,1-di[4-(dimethylsilylhydride)phenyl]ethylene, 1,1-di[4-(triisopropoxysilyl)phenyl]ethylene 1-[4-(triisopropoxysilyl)phenyl]-1-[4-(dimethylsilylhydride)phenyl]ethylene, 1-[4-(triisopropoxysilyl)phenyl] 1-[4-(dimethylsilylhydride)phenyl]ethylene; The nitrogen-functionalized 1,1-diphenylethylene derivative is selected from at least one of 1-[4-(N,N-dimethylamino)phenyl]-1-phenylethylene and 1,1-bis[4-(N,N-dimethylamino)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 method for preparing a silicon / nitrogen group functionalized S(EB / EP)S thermoplastic elastomer as described in any one of claims 1-5, characterized in that, Includes the following steps: Step S1: Prepare polystyrene active centers functionalized with silicon / nitrogen groups: A metered polar modifier is added to the reactor in a non-polar hydrocarbon solvent. According to different monomer feeding sequences and ratios, metered styrene and silicon / nitrogen functionalized 1,1-diphenylethylene derivative monomers, alkyl lithium initiators and polar modifiers are added. The mixture is stirred evenly. The initiation reaction temperature is 10℃-90℃ and the reaction time is 0.5-48h. The feed ratio of styrene and silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer by mass is 1-999:1; the addition amount of polar modifier and alkyl lithium initiator is 1-20:1; the feed ratio of initiator and raw material is 1:1x10 5 -2.5x10 5 ; Step S2, preparation of silicon / nitrogen group-functionalized polystyrene-butadiene / isoprene active centers: After the reaction in step S1 is completed, the measured butadiene / isoprene monomers are 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, thus generating silicon / nitrogen group-functionalized polystyrene-butadiene / isoprene active centers; wherein, by mass, the feeding ratio of styrene, styrene monomers composed of silicon / nitrogen group-functionalized 1,1-diphenylethylene derivatives, butadiene, and isoprene is 1:0.5-2:0.5-2; Step S3, preparation of linear / star-coupled silicon / nitrogen-functionalized styrene-butadiene / isoprene block copolymer: After the reaction in step S2 is completed, a metered linear / star coupling agent is added to carry out the coupling reaction. The reaction temperature is controlled at 50-110℃ and the reaction is carried out for 30-150 min to obtain a linear / star-coupled silicon / nitrogen-functionalized styrene-butadiene / isoprene block copolymer solution. Step S4, prepare S(EB / EP)S thermoplastic elastomer functionalized with silicon / nitrogen groups: The linear / star-coupled silicon / nitrogen-functionalized styrene-butadiene / isoprene block copolymer solution was transferred to a high-pressure hydrogenation reactor, diluted with solvent, and then a metered hydrogenation catalyst and hydrogen were added to carry out the hydrogenation reaction. The hydrogen pressure was controlled at 0.1 MPa to 10 MPa, the reaction temperature was controlled at 50℃ to 200℃, and the hydrogenation reaction was carried out for 1 to 20 hours to obtain silicon / nitrogen-functionalized S(EB / EP)S thermoplastic elastomer. The hydrogenation catalyst is selected from nickel-based catalysts.

7. The preparation method according to claim 6, characterized in that, When the mass concentration of all reactants in step SI is 5%-25%, the 1,1-diphenylethylene derivative monomer with silicon / nitrogen functionalization is located at the chain end of the styrene block.

8. The preparation method according to claim 6, characterized in that, When the total mass concentration of all reactants in step S1 is less than 10%, the mass concentration of 1,1-diphenylethylene derivative monomers functionalized with monosilane groups, or 1,1-diphenylethylene derivative monomers functionalized with monosiloxy groups, or 1,1-diphenylethylene derivative monomers containing siloxy / silane groups, combined with styrene, is 5%-15%; or the mass concentration of 1,1-diphenylethylene derivative monomers containing siloxy / amine groups, or 1,1-diphenylethylene derivative monomers containing silane / amine groups, combined with styrene, is 15%-25%; or the mass concentration of 1,1-diphenylethylene derivative monomers containing mono / diamine groups, combined with styrene, is 10%-20%. In the prepared silicon / nitrogen group-functionalized styrene block, the silicon / nitrogen group-functionalized 1,1-diphenylethylene derivative is located in the middle and at the end of the block chain.

9. The preparation method according to claim 6, characterized in that, When the total content of silicon / nitrogen functionalized 1,1-diphenylethylene derivative monomers accounts for more than 10% of the total monomer content by mass concentration, and the mass concentration of 1,1-diphenylethylene derivative monomers with monosilane groups or monosiloxy groups or siloxy / silane groups added to styrene is 5%-10%, or the mass concentration of 1,1-diphenylethylene derivative monomers with siloxy / amine groups or silane / amine groups added to styrene is 10%-15%, or the mass concentration of 1,1-diphenylethylene derivative monomers with mono / diamine groups to styrene is 8%-12%, the silicon / nitrogen functionalized 1,1-diphenylethylene derivatives in the prepared silicon / nitrogen functionalized styrene block are located in the middle and at the end of the block chain.

10. The preparation method according to claim 6, characterized in that, The solvent is selected from benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons, and mixed aliphatic hydrocarbons; The polarity modifier 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 initiators, where R is a hydrocarbon group with 2-20 carbon atoms; The linear coupling agent is selected from one of M(CH3)2Cl2, 1,2-dichloroethane, and 1,2-dibromoethane; the star coupling agent is selected from one of MCH3Cl3, MCl4, M2Cl6, M3Cl8, and divinylbenzene; and M is selected from one of silicon, tin, lead, titanium, and germanium.

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