Silicon / nitrogen group-containing functionalized SEPS 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 SEPS (styrene-ethylene-propylene) thermoplastic elastomer which is a linear / star-shaped coupled silicon / nitrogen group-containing functionalized polystyrene-(ethylene / propylene) block copolymer. The polystyrene block is composed of a copolymer of styrene and a silicon / nitrogen-containing group functionalized 1, 1-diphenylethylene (DPE) derivative. The prepared SEPS containing the silicon / nitrogen group is a macromolecule, and the viscosity is obviously improved. In the processing process, SEPS containing silicon / nitrogen groups is easily converted into silicon hydroxyl groups, the silicon hydroxyl groups, hydroxyl groups and the like easily form covalent bonds or hydrogen bonds, the compatibility and dispersity of the material are improved, and the SEPS has good application prospects 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 polymer material synthesis and preparation, and particularly relates to a kind of functionalized SEPS thermoplastic elastomer containing silicon / nitrogen groups and a preparation method thereof. BACKGROUND

[0002] Thermoplastic elastomer is a kind of polymer material, which shows the characteristics of rubber at room temperature, but also has excellent processing performance, and can be plasticized and formed at high temperature. As the most commonly used thermoplastic elastomer, styrene-based thermoplastic elastomer shows the characteristics of rubber in a wide temperature range, and is often used in the fields of asphalt modification, adhesive, polymer modification, shoe material, lubricating oil tackifier, wire and cable, etc. SIS is a block copolymer composed of styrene and isoprene, and the soft segment in the middle is composed of polyisoprene rubber segment. The chemical properties of unsaturated conjugated diene bond are relatively active, and the performance is unstable, so their wide use in outdoor environment is limited. SEPS obtained by selective hydrogenation of SIS can greatly improve the performance of heat resistance, oxidation resistance and ozone resistance, and the degradation performance of oxidative or crosslinking reaction, and at the same time, the use temperature of the product is improved, the weather resistance, chemical resistance to acid and alkali, and wear resistance and flexibility are improved.

[0003] Hydrogenated SIS has both the thermoplasticity of non-hydrogenated products and the high elasticity of rubber at room temperature, and exhibits resin flowability at high temperatures, and can be directly processed into shape, so that SEPS is much higher than ordinary SIS in practical application, and can be applied to medical and food films and medical transparent packaging, including medical bottles / pipes / bags, etc. The blend of SEPS has good tensile strength and impact strength, and is suitable for film and catheter, and is an excellent substitute for soft PVC. At present, SEPS commodities mainly include Kraton G series products of Shell Company in the United States and SEPTON series products of Kuraray Company in Japan. However, since SEPS is a non-polar polymer material, it is difficult to be blended with polar polymer materials and polar fillers, and the adhesion with metal materials is also poor, which limits its application field, therefore, it needs to be functionally modified to broaden its application range. The method of functional modification usually includes direct copolymerization modification of monomer, graft copolymerization modification and post-click functionalization modification after copolymerization, and different methods can be used for different polymers. At present, the method of polar functionalization of SEBS is to directly copolymerize with polar monomers to introduce polar blocks in the polymer, or to post-functionalize SEBS. Hydrogenated polyisoprene products are different from hydrogenated polybutadiene, which has a shorter series of methyl units, so it will not crystallize. There is no crystallization in the EP rubber segment, so SEPS is softer than SEBS which is partially crystallized, and the elasticity and hysteresis behavior of SEPS are better than those of the corresponding SEBS. The inherent properties of hydrogenated polyisoprene polymers make the SEPS-based styrene thermoplastic elastomer have such super flexibility and high elasticity. At present, the method of polar functionalization of SEPS is to directly copolymerize with polar monomers to introduce polar blocks in the polymer, or to post-functionalize SEPS. The current polar SEPS has problems such as unclear distribution of polar functional groups in the chain and uncontrollable functionalization efficiency, therefore, it is necessary to develop SEPS with clear "quantitative" and accurate "positioning" of polar functional group distribution, so as to improve the utilization efficiency of functional groups.

[0004] Therefore, in order to solve the technical problems of uncontrolled number and position of functional groups in the modification process of thermoplastic elastomer, limited application occasions, low conversion rate, low molecular weight and poor controllability, it is urgent to develop a kind of functional SEPS and its preparation method, to improve the performance of SEPS and broaden its application field. SUMMARY

[0005] In view of the problems in the prior art, the present application provides a kind of silicon / nitrogen group functionalized SEPS thermoplastic elastomer, by adding screened silicon / nitrogen group containing 1,1-diphenyl ethylene derivative comonomer, silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative can be precisely distributed in the initiation end of styrene block, chain and chain end, different silicon / nitrogen group functionalized SEPS can be obtained according to different requirements, so as to improve the utilization efficiency of functional group, improve the mechanical properties and compatibility of SEPS, and broaden its application field.

[0006] The technical scheme of the present application is:

[0007] In the first aspect, the present application provides a kind of silicon / nitrogen group functionalized SEPS thermoplastic elastomer, the silicon / nitrogen group functionalized SEPS thermoplastic elastomer is linear / star coupling silicon / nitrogen group functionalized styrene-(ethylene / propylene) block copolymer;Specifically, it is linear / star coupling silicon / nitrogen group functionalized copolymer of styrene block and ethylene / propylene block;

[0008] The linear / star coupling silicon / nitrogen group functionalized styrene block is copolymer block of styrene and silicon / nitrogen group functionalized 1,1-diphenyl ethylene (DPE) derivative;

[0009] The ethylene / propylene block is random copolymer block of ethylene and propylene.

[0010] Further, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative is polymerized in at least one position of the chain initiation end, chain end and chain of polystyrene block;

[0011] Further, the number average molecular weight (M n ) of the silicon / nitrogen group functionalized SEPS thermoplastic elastomer ranges from 2 × 10 4 ~ 90 × 10 4 g / mol, and the molecular weight distribution (PDI) ranges from 1.02 to 1.60.

[0012] Further, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative is selected from silicon group containing group, amine group containing group, silicon group / amine group functionalized 1,1-diphenyl ethylene derivative. It includes but is not limited to silicon group containing group, amine group containing group, silicon group / amine group functionalized 1,1-diphenyl ethylene derivative monomer;The silicon group, amine group and silicon group / amine group are connected to the para, meta or ortho of phenyl in the 1,1-diphenyl ethylene derivative.

[0013] Further, the linear / star coupled silicon / nitrogen group functionalized styrene-(ethylene / propylene) block copolymer is obtained by selective hydrogenation of a linear / star coupled silicon / nitrogen group functionalized styrene-isoprene block copolymer, and the hydrogenation degree of the linear / star coupled silicon / nitrogen group functionalized styrene-(ethylene / propylene) block copolymer ranges from 50% to 100%, preferably from 85% to 100%.

[0014] Further, the linear / star coupled silicon / nitrogen group functionalized styrene block copolymer is present in an amount of 20% to 50% by mass, and the remainder is an ethylene / propylene block, based on 100% by mass of the silicon / nitrogen group functionalized SEPS thermoplastic elastomer.

[0015] Further, the linear / star coupled silicon / nitrogen group functionalized styrene block copolymer is present in an amount of 20% to 50% by mass, and the remainder is an ethylene / propylene block, based on 100% by mass of the silicon / nitrogen group functionalized SEPS thermoplastic elastomer.

[0016] Further, the linear / star coupled silicon / nitrogen group functionalized styrene block copolymer is present in an amount of 20% to 50% by mass, and the remainder is an ethylene / propylene block, based on 100% by mass of the silicon / nitrogen group functionalized SEPS thermoplastic elastomer.

[0017] Further, the silicon group-containing, amine group-containing, silicon group / amine group functionalized 1,1-diphenyl ethylene derivative is selected from:

[0018] (1) The silicon-oxy group functionalized 1,1-diphenyl ethylene derivative monomer is 1-[4-R1phenyl]-1-phenyl ethylene, and the silicon-hydrogen group functionalized 1,1-diphenyl ethylene derivative monomer is 1,1-di[4-R2phenyl] ethylene, wherein R1 is a silicon-oxy group selected from trimethoxy silicon group, triethoxy silicon group, triisopropoxy silicon group, tri-t-butoxy silicon group, dimethyl methoxy silicon group, diethyl methoxy silicon group, and R2 is a silicon-hydrogen group selected from dimethyl silicon-hydrogen group, diethyl silicon-hydrogen group, dipropyl silicon-hydrogen group, diisopropyl silicon-hydrogen group, di-t-butyl silicon-hydrogen group.

[0019] (1) The silicon-oxy group functionalized 1,1-diphenyl ethylene derivative monomer is 1-[4-R1phenyl]-1-phenyl ethylene, and the silicon-hydrogen group functionalized 1,1-diphenyl ethylene derivative monomer is 1,1-di[4-R2phenyl] ethylene, wherein R1 is a silicon-oxy group selected from trimethoxy silicon group, triethoxy silicon group, triisopropoxy silicon group, tri-t-butoxy silicon group, dimethyl methoxy silicon group, diethyl methoxy silicon group, and R2 is a silicon-hydrogen group selected from dimethyl silicon-hydrogen group, diethyl silicon-hydrogen group, dipropyl silicon-hydrogen group, diisopropyl silicon-hydrogen group, di-t-butyl silicon-hydrogen group.

[0020] (3) Monoamine group 1,1-diphenyl ethylene derivative monomer is generally in the range of 1-[4-R3 group phenyl]-1-phenyl ethylene, and bisamine group 1,1-diphenyl ethylene derivative monomer is generally in the range of 1,1-di[4-R3 group phenyl] ethylene, wherein R3 is N,N-dimethylamine group, N,N-diethylamine group, N,N-di-tert-butylamine group;

[0021] (4) Siloxyl group / silicon hydride group 1,1-diphenyl ethylene derivative monomer is 1-[4-R1 group phenyl]-1-[R2 group phenyl] ethylene, wherein R1 is a siloxyl group selected from trimethoxysilane group, triethoxysilane group, triisopropoxysilane group, tri-tert-butoxysilane group, dimethylmethoxysilane group, diethylmethoxysilane group; R2 is a silicon hydride group selected from dimethylsilicon hydride group, diethylsilicon hydride group, dipropylsilicon hydride group, diisopropylsilicon hydride group, di-tert-butylsilicon hydride group;

[0022] (5) Siloxyl group / amine group 1,1-diphenyl ethylene derivative monomer is 1-[4-R1 group phenyl]-1-[4-R3 phenyl] ethylene, wherein R1 is a siloxyl group selected from trimethoxysilane group, triethoxysilane group, triisopropoxysilane group, tri-tert-butoxysilane group, dimethylmethoxysilane group, diethylmethoxysilane group, and R3 is an amine group selected from N,N-dimethylamine group, N,N-diethylamine group, N,N-di-tert-butylamine group;

[0023] (6) Silicon hydride group / amine group 1,1-diphenyl ethylene derivative monomer is 1-[4-R2 group phenyl]-1-[4-R3 group phenyl] ethylene, wherein R2 is a silicon hydride group selected from dimethylsilicon hydride group, diethylsilicon hydride group, dipropylsilicon hydride group, diisopropylsilicon hydride group, di-tert-butylsilicon hydride group, and R3 is an amine group selected from N,N-dimethylamine group, N,N-diethylamine group, N,N-di-tert-butylamine group;

[0024] Further, the 1,1-diphenyl ethylene derivative containing a silicon group is at least one selected from 1-[4-(triisopropoxysilane) phenyl]-1-phenyl ethylene, 1-[4-(dimethylsilicon hydride) phenyl]-1-phenyl ethylene, 1,1-di[4-(triisopropoxysilane) phenyl] ethylene, 1-[4-(dimethylsilane) phenyl]-1-phenyl ethylene, 1,1-di[4-(dimethylsilane) phenyl] ethylene, 1,1-di[4-(dimethylsilicon hydride) phenyl] ethylene, 1,1-di[4-(triisopropoxysilane) phenyl] ethylene 1-[4-(triisopropoxysilane) phenyl]-1-[4-(dimethylsilicon hydride) phenyl] ethylene, 1-[4-(triisopropoxysilane) phenyl] 1-[4-(dimethylsilicon hydride) phenyl] ethylene.

[0025] Further, the nitrogen-containing group functionalized 1,1-diphenyl ethylene derivative is at least one selected from 1-[4-(N,N dimethylamino)phenyl]-1-phenyl ethylene, 1,1-bis[4-(N,N-dimethylamino)phenyl] ethylene.

[0026] Further, the silicon / nitrogen-containing group functionalized 1,1-diphenyl ethylene derivative is at least one selected from 1-[4-(triisopropoxy silyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene, 1-[4-(dimethyl silyl hydride)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene, 1-[4-(triisopropoxy silyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene, 1-[4-(dimethyl silyl hydride)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene.

[0027] In a second aspect, the present application provides a preparation method of a silicon / nitrogen-containing group functionalized SEPS thermoplastic elastomer, comprising the following steps:

[0028] Step S1, preparing a silicon / nitrogen-containing group functionalized polystyrene active center:

[0029] 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 a silicon / nitrogen-containing group functionalized 1,1-diphenyl ethylene derivative monomer, an alkyl lithium initiator and a polar modifier are added, stirred uniformly, the initiation reaction temperature is 10-90°C, and the reaction time is 0.5-48h; a silicon / nitrogen-containing group functionalized polystyrene active center is generated;

[0030] wherein the feeding ratio of styrene and the silicon / nitrogen-containing group functionalized 1,1-diphenyl ethylene derivative monomer is 1-999:1 by mass; the addition amount ratio of the initiator and the polar modifier is 1:1-50, and the feeding ratio of the initiator and the raw materials is 1:1×10 5 -2.5×10 5 .

[0031] Step S2, preparing a silicon / nitrogen-containing group functionalized polystyrene-isoprene active center: after the reaction of step S1 is completed, a measured amount of isoprene monomer is added to the reactor according to the monomer ratio, the reaction temperature is controlled at 50-110°C, and the reaction time is 0.5-10h; a linear / branched silicon / nitrogen-containing group functionalized styrene-isoprene block polymer precursor, i.e. a silicon / nitrogen-containing group functionalized polystyrene-isoprene active center, is prepared; wherein the feeding ratio of styrene and the silicon / nitrogen-containing group functionalized 1,1-diphenyl ethylene derivative, which constitute styrene monomers, and isoprene is 1:2-4 by mass;

[0032] Step S3, preparing linear / star coupling silicon / nitrogen group functionalized styrene-isoprene block copolymer: after the reaction of step S2 is completed, a metered amount of linear / star coupling agent is added to carry out coupling reaction, the temperature is 50-110℃, and the reaction time is 30-150 min, to prepare linear / star coupling silicon / nitrogen group functionalized styrene-isoprene block copolymer glue solution;

[0033] Step S4, preparing silicon / nitrogen group functionalized SEPS thermoplastic elastomer:

[0034] The linear / star coupling silicon / nitrogen group functionalized styrene-isoprene block copolymer glue solution is transferred to a high-pressure hydrogenation kettle, solvent is added for dilution, a metered amount of hydrogenation catalyst and hydrogen are added for hydrogenation reaction, the hydrogen pressure is controlled to be 0.1-10 MPa, the reaction temperature is controlled to be 50-200℃, and the hydrogenation reaction time is 1-20 h, to obtain the silicon / nitrogen group functionalized SEPS thermoplastic elastomer.

[0035] Further, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative can be selectively and accurately distributed at the initiation end, in the chain or at the chain end of the polystyrene block, specifically:

[0036] In step S1, a metered amount of polar modifier is added to the reactor in a non-polar hydrocarbon solvent as system A;

[0037] A metered amount of silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer and alkyl lithium initiator is added to system A according to monomer ratio, and the initiation reaction temperature is 10-90℃, and then a metered amount of styrene monomer is added as system B;

[0038] Or a metered amount of 1,1-diphenyl ethylene derivative and styrene monomer is added to system A according to monomer ratio, and then a metered amount of alkyl lithium initiator is added, and the initiation reaction temperature is 10-90℃ as system C;

[0039] Or the silicon / nitrogen group functionalized DPE derivative monomer is continuously added to system B / system A as system D;

[0040] In the B / C / D system, the ratio of styrene monomer, silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer, alkyl lithium initiator and polar modifier can be accurately controlled to control the distribution, nature (type), quantity and mass percentage of the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative in the chain end and chain of the polystyrene block.

[0041] The silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer added in step S1 in system B, C, D is a mixture of one or several.

[0042] Further, the mass concentration of all reaction monomers in step S1 is 5%-25%, which is determined according to the type and amount of silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer.

[0043] Further, when the mass concentration of all reaction monomers in step S1 is 5%-25%, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer is located at the chain end of the styrene block;

[0044] When the mass concentration of all reaction monomers in step S1 is less than 10%, the mass concentration of the added monosilicon hydride group functionalized 1,1-diphenyl ethylene derivative monomer, or monosilicon oxygen group functionalized 1,1-diphenyl ethylene derivative monomer, or silicon oxygen group / silicon hydride group 1,1-diphenyl ethylene derivative monomer and styrene is 5%-15%, or the mass concentration of the added silicon oxygen group / amine group 1,1-diphenyl ethylene derivative monomer, or silicon hydride group / amine group 1,1-diphenyl ethylene derivative monomer and styrene is 15%-25%, or the mass concentration of the added mon / di amine group 1,1-diphenyl ethylene derivative monomer and styrene is 10%-20%, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative in the prepared silicon / nitrogen group functionalized styrene block is located in the chain and at the chain end of the block;

[0045] When the total content of the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer is more than 10% of the mass concentration of all monomers, the mass concentration of the added monosilicon hydride group functionalized 1,1-diphenyl ethylene derivative monomer or monosilicon oxygen group functionalized 1,1-diphenyl ethylene derivative monomer or silicon oxygen group / silicon hydride group 1,1-diphenyl ethylene derivative monomer and styrene is 5%-10%, or the mass concentration of the added silicon oxygen group / amine group 1,1-diphenyl ethylene derivative monomer, or silicon hydride group / amine group 1,1-diphenyl ethylene derivative monomer and styrene is 10%-15%, or the mass concentration of the added mon / di amine group 1,1-diphenyl ethylene derivative monomer and styrene is 8%-12%, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative in the prepared silicon / nitrogen group functionalized styrene block is located in the chain and at the chain end of the block. The mass concentration unit is g / l.

[0046] 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 benzene, toluene, pentane, hexane, and cyclohexane.

[0047] Further, the polar modifier 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-tetrahydrofuryl)propane, 2,2-di(5-methyl-2-tetrahydrofuran)propane, ethyl tetrahydrofurfuryl ether, tetramethyl ethylenediamine, pentamethyl diethylene triamine, 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-isoprene microstructure.

[0048] 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 isoprene, 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 hydrocarbon group, and is preferably n-butyllithium, sec-butyllithium and tert-butyllithium.

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

[0050] Further, the star-shaped coupling agent in the 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, and is preferably tetrachlorosilane and tetrachlorotin; the other is divinylbenzene (DVB).

[0051] Further, the hydrogenation catalyst in the step S4 is selected from a nickel-based catalyst, and is preferably triisobutyl aluminum \ nickel naphthenate catalyst.

[0052] Beneficial effects:

[0053] Compared with the prior art, (1) the present application provides a kind of silicon / nitrogen group functionalized SEPS thermoplastic elastomer and preparation method thereof;(2) the present application uses composite silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative, by controlling the ratio of 1,1-diphenyl ethylene derivative and styrene monomer, the ratio of DPE derivative and alkyl lithium initiator, the ratio of DPE derivative and polarity regulator, the styrene reactivity is controlled, and by controlling the feeding sequence of 1,1-diphenyl ethylene derivative and styrene monomer, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative can be selectively and accurately distributed at the initiation end, the terminal and the chain of styrene block in a true sense, and the properties and mass fraction of silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative can be controlled, so as to realize the use of silicon / nitrogen group on demand, improve the utilization efficiency of silicon / nitrogen group;(3) compared with linear SIS generated by three-step feeding method, the present application essentially uses two-step feeding method to prepare silicon group functionalized SIS, i.e. first step to generate silicon / nitrogen group functionalized polystyrene block, second step to synthesize polystyrene-isoprene two-block polymer, then introduce coupling agent to synthesize linear / branched coupling silicon group functionalized styrene-isoprene 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 operate and better effect;(4) after preparing SIS by coupling method, the active center is consumed, so it is not necessary to add terminating agent, and the remaining active center can react with hydrogenation catalyst, which helps to improve hydrogenation efficiency;(5) by using polarity regulator to control the microstructure content of 3,4-isoprene in SIS, the microstructure content of ethylene and propylene in SEPS can be adjusted, and the mechanical properties of SEPS thermoplastic elastomer can be adjusted.

[0054] In addition, during processing, the amine group forms hydrogen bond with hydroxyl group, forms ionic bond with carboxyl group, and the silicon hydroxyl group forms covalent bond or hydrogen bond with hydroxyl group, etc., to improve the compatibility and dispersibility of the material. DETAILED DESCRIPTION

[0055] In order to enable the above-mentioned purposes, features and advantages of the present application to be more clearly understood, the schemes 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.

[0056] 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.

[0057] 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. Various modifications and alterations of the present application can be made by those skilled in the art without departing from the spirit and scope of the present application.

[0058] 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.

[0059] 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, the tensile rate is 500 mm / min, and the test temperature is 23℃, and each sample is repeated at least 5 times.

[0060] Example 1

[0061] Step S1, preparation of 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, stirred uniformly, and n-butyllithium (2.6mmol) is added, the initiation temperature is 50℃, the reaction is carried out for 30min, and then styrene (110g, 1.06mol) is added for the first stage of polymerization reaction, and the reaction is carried out for 48h;

[0062] Step S2, preparation of single silicon hydride group functionalized styrene-isoprene active center: isoprene (130g, 1.9mol) is added to the above polymerization kettle, the reaction temperature is 50℃, and the second stage of polymerization reaction is carried out, and the reaction is carried out for 3h;

[0063] Step S3, preparation of star-shaped coupled single silicon hydride group functionalized styrene-isoprene block copolymer: silicon tetrachloride coupling agent (0.11g, 0.65mmol) is added to the above polymerization kettle, the reaction temperature is 50℃, and the coupling reaction is carried out, and the reaction is carried out for 150min;

[0064] Step S4, preparation of SEPS thermoplastic elastomers functionalized with monosilane groups: The star-coupled styrene-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 and hydrogen gas 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.

[0065] 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 211.2 g; based on the mass of the styrene-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 isoprene; based on the mass of the styrene block 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 ends and in the chain of polystyrene blocks, exhibiting a quasi-periodic sequence distribution in the chain; the degree of hydrogenation was 85.1%; the molecular weight was analyzed by gel permeation chromatography (GPC), and a standard curve was prepared using narrowly distributed polystyrene with different molecular weights as standard samples, with tetrahydrofuran as the standard. As the mobile phase (flow rate 1.0 ml / min), the sample concentration was 2–5 mg / ml. The results are as follows: Before coupling, the styrene-isoprene block copolymer with monosilane functionalization showed a narrow single-peak distribution, with a number-average molecular weight of 160.1 kg / mol and a molecular weight distribution of 1.15; after star-shaped coupling, the styrene-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 560.4 kg / mol, and a molecular weight distribution of 1.27; after hydrogenation, the SEPS with monosilane functionalization showed a narrow single-peak distribution, with a number-average molecular weight of 560.4 kg / mol and a molecular weight distribution of 1.25. The mechanical properties of the product were tested using a universal testing machine, and the results are as follows: the elongation at break was 1530%, and the tensile strength was 7.2 MPa.

[0066] Example 2

[0067] Step S1, preparation of active center of single silicon hydride group functionalized polystyrene: under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added to a 5L polymerization kettle, and tetrahydrofuran (2.8g, 39mmol) and 1-[4-(dimethylsilyl)phenyl]-1-phenyl ethylene (single silicon hydride DPE, 0.62g, 2.6mmol) were added, stirred uniformly, and 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, and the first-stage polymerization reaction was carried out, and the reaction was carried out for 6h;

[0068] Step S2, preparation of active center of single silicon hydride group functionalized styrene-isoprene: isoprene (130g, 1.9mol) was added to the above polymerization kettle, the reaction temperature was 80℃, and the second-stage polymerization reaction was carried out, and the reaction was carried out for 3h;

[0069] Step S3, preparation of star-coupled single silicon hydride group functionalized styrene-isoprene block copolymer: silicon tetrachloride coupling agent (0.07g, 0.416mmol) and divinylbenzene (0.04g, 0.28mmol) were added to the above polymerization kettle, the reaction temperature was 80℃, and the coupling reaction was carried out, and the reaction was carried out for 120min;

[0070] Step S4, preparation of single silicon hydride group functionalized SEPS thermoplastic elastomer: the star-coupled single silicon hydride group functionalized styrene-isoprene block copolymer glue solution was transferred to 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 200℃, and the reaction was carried out for 1h.

[0071] After the reaction was completed, the polymer was post-treated by using a traditional method, and after the product was dried, the proton nuclear magnetic resonance spectrum (1H-NMR) was used to analyze the product. 1HNMR) for its structure, and the results are as follows: the prepared product is 120.2 g; the mass percentage of styrene and the DPE derivative functionalized with a single silicon hydride group styrene monomer is 34.2% based on the mass of the styrene and isoprene block copolymer being 100%, and the rest is isoprene; the mass percentage of the DPE derivative functionalized with a single silicon hydride group monomer is 0.9% 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 hydrogenation degree is 99.2%; 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 (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 DPE derivative functionalized with a single silicon hydride group before coupling is 134.8 kg / mol, and the molecular weight distribution is 1.08; the DPE derivative functionalized with a single silicon hydride group after star coupling shows a bimodal distribution, the coupling efficiency is about 66%, the molecular weight distribution is 1.46, and the number average molecular weights of the star coupling sample and the linear sample are 376.7 kg / mol and 133.8 kg / mol, respectively; the DPE derivative functionalized with a single silicon hydride after hydrogenation shows a bimodal distribution, and the number average molecular weights of the star coupling sample and the linear sample are 377.5 kg / mol and 134.2 kg / mol, respectively, and the molecular weight distribution is 1.51; the mechanical properties of the product are tested by a universal testing machine, and the results are as follows: the elongation at break is 1850%, and the tensile strength is 5.2 MPa.

[0072] Example 3

[0073] 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 thereto, stirred uniformly, and n-butyllithium (2.6 mmol) is added, the initiation temperature is 50°C, the reaction is carried out for 30 min, and 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, and 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;

[0074] Step S2, preparation of styrene-isoprene active center containing monosilicon hydride and disilicon hydride groups: isoprene (130 g, 1.9 mol) was added to the polymerization kettle, the second stage polymerization reaction was carried out at 50°C, and the reaction was carried out for 3 h;

[0075] Step S3, preparation of star-coupled styrene-isoprene block copolymer containing monosilicon hydride and disilicon hydride groups: silicon tetrachloride coupling agent (0.11 g, 0.65 mmol) and divinylbenzene (0.01 g, 0.07 mmol) were added to the polymerization kettle, the coupling reaction was carried out at 50°C, and the reaction was carried out for 150 min;

[0076] Step S4, preparation of SEPS thermoplastic elastomer containing monosilicon hydride and disilicon hydride groups: the star-coupled styrene-isoprene block copolymer containing silicon hydride group functionalization glue was transferred to a high-pressure hydrogenation kettle, diluted with a solvent, and triisobutyl aluminum \ nickel naphthenate catalyst and hydrogen were added for hydrogenation reaction, the hydrogen pressure was controlled at 5 Mpa, the reaction temperature was 80°C, and the reaction was carried out for 3 h.

[0077] After the reaction was completed, the polymer was post-treated by using a conventional method, and after the product was dried, nuclear magnetic resonance hydrogen spectrum (1H-NMR) was used to analyze the product. 1HNMR) for its structure, and the results are as follows: the mass of the prepared product is 91.6 g; the mass percentage of the styrene and the DPE derivative functionalized with silicon hydride group styrene monomers is 20.9% based on the mass of the styrene and isoprene block copolymer being 100%, and the rest is isoprene; the mass percentage of the DPE derivative functionalized with silicon hydride group in the styrene block is 4.0% based on the mass of the styrene block being 100%, and the rest is styrene monomer, the DPE derivative functionalized with single silicon hydride group is distributed at the initiation end of the polystyrene block, and the DPE derivative functionalized with double silicon hydride group is distributed at the end of the polystyrene block; the hydrogenation degree is 89.1%; the molecular weight is analyzed by gel permeation chromatography (GPC) with 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-isoprene block copolymer before coupling is 115.2 kg / mol, and the molecular weight distribution is 1.11; the silicon hydride group functionalized styrene-isoprene block copolymer after star coupling shows a single peak narrow distribution, the coupling efficiency is about 100%, the number average molecular weight is 388.4 kg / mol, and the molecular weight distribution is 1.20; the silicon hydride functionalized SEPS after hydrogenation shows a single peak narrow distribution, the number average molecular weight is 389.8 kg / mol, and the molecular weight distribution is 1.21; the mechanical properties of the product are tested by a universal testing machine, and the results are as follows: the elongation at break is 2110%, and the tensile strength is 2.3 MPa.

[0078] Example 4

[0079] 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, n-butyl lithium (2.6 mmol) 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;

[0080] Step S2, preparation of a styrene-isoprene active center functionalized with a single silicon hydride group: isoprene (130 g, 1.9 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;

[0081] Step S3, prepare linearly coupled styrene-isoprene 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 60℃ for 150min;

[0082] Step S4, preparation of SEPS thermoplastic elastomer with silane-hydrogen functionalization: The linearly coupled styrene-isoprene block copolymer solution with monosilane-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 10 MPa, the reaction temperature is 80℃, and the reaction is carried out for 1 h.

[0083] 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-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 isoprene; based on the mass of the styrene block 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 end, chain middle, and chain end of the polystyrene block, showing a gradual sequence distribution in the chain; the degree of hydrogenation was 95.1%; the molecular weight was analyzed by gel permeation chromatography (GPC), and a standard curve was prepared using narrowly distributed polystyrene with different molecular weights as standard samples, with tetrahydrofuran as the standard. Using uranium as the mobile phase (flow rate 1.0 ml / min), the sample concentration was 2–5 mg / ml. The results are as follows: Before coupling, the styrene-isoprene block copolymer with monosilane functionalization showed a narrow single-peak distribution, with a number-average molecular weight of 168.8 kg / mol and a molecular weight distribution of 1.13; after linear coupling, the styrene-isoprene block copolymer with monosilane functionalization showed a narrow single-peak distribution, with a coupling efficiency close to 100%, a number-average molecular weight of 270.9 kg / mol, and a molecular weight distribution of 1.26; after hydrogenation, the SEPS with monosilane functionalization showed a narrow single-peak distribution, with a number-average molecular weight of 279.1 kg / mol and a molecular weight distribution of 1.32. The mechanical properties of the products were tested using a universal testing machine, and the results are as follows: the elongation at break was 1690%, and the tensile strength was 8.4 MPa.

[0084] Example 5

[0085] Step S1, preparation of active center of polystyrene functionalized with silicon-oxygen and silicon-hydrogen groups: 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-(triisopropoxysilyl)phenyl]-1-phenyl ethylene (monosilicon-oxygen DPE, 0.5g, 1.3mmol) and 1-[4-(dimethylsilyl hydrogen)phenyl]-1-phenyl ethylene (monosilicon-hydrogen DPE, 0.38g, 1.3mmol) were added and stirred uniformly, 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 to carry out the first-stage polymerization reaction, and the reaction was carried out for 3h;

[0086] Step S2, preparation of active center of styrene-isoprene functionalized with silicon-oxygen and silicon-hydrogen groups: isoprene (130g, 1.9mol) was added to the above polymerization kettle, the reaction temperature was 90℃, and the second-stage polymerization reaction was carried out for 3h;

[0087] Step S3, preparation of star-coupled styrene-isoprene block copolymer functionalized with silicon-oxygen and silicon-hydrogen groups: 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 30min;

[0088] Step S4, preparation of SEPS thermoplastic elastomer functionalized with silicon-oxygen and silicon-hydrogen groups: the star-coupled styrene-isoprene block copolymer functionalized with silicon-hydrogen groups was transferred to a high-pressure hydrogenation kettle, diluted with solvents, and hydrogenated by adding triisobutyl aluminum \ nickel naphthenate catalyst and hydrogen, the hydrogen pressure was controlled at 3Mpa, the reaction temperature was 60℃, and the reaction was carried out for 3h.

[0089] After the reaction was completed, the polymer was post-treated by using a traditional method, and after the product was dried, the proton nuclear magnetic resonance spectrum (1H-NMR) was used to analyze the product. 1HNMR) for its structure, and the results are as follows: the mass of the prepared product is 198.8 g; the mass percentage of the styrene and the DPE derivative functionalized with siloxyl and silicon hydride groups in the styrene monomers is 46.0% based on the mass of the styrene and isoprene block copolymer being 100%; the mass percentage of the DPE derivative functionalized with siloxyl and silicon hydride groups in the styrene block is 0.8% based on the mass of the styrene block being 100%, and the rest is styrene monomer; the DPE derivative functionalized with siloxyl and silicon hydride groups is distributed at the initiation end of the polystyrene block; the hydrogenation degree is 94.1%; the molecular weight is analyzed by using gel permeation chromatography (GPC) with 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 siloxyl and silicon hydride group functionalized styrene-isoprene block copolymer before coupling is in a single peak narrow distribution, the number average molecular weight is 153.8 kg / mol, and the molecular weight distribution is 1.22; the siloxyl and silicon hydride group functionalized styrene-isoprene block copolymer after star coupling is in a bimodal distribution, the coupling efficiency is 51.2%, the number average molecular weight is 399.9 kg / mol and 158.4 kg / mol, respectively, and the molecular weight distribution is 1.56; the single silicon hydride functionalized SEPS after hydrogenation is in a bimodal distribution, the number average molecular weight is 401.1 kg / mol and 159.7 kg / mol, respectively, and the molecular weight distribution is 1.55; the mechanical properties of the product are tested by using a universal testing machine, and the results are as follows: the elongation at break is 1720%, and the tensile strength is 8.1 MPa.

[0090] Example 6

[0091] Step S1, preparation of a silicon hydride and amine group functionalized polystyrene active center: 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)phenyl]-1-phenyl ethylene (single silicon hydride DPE, 20.0 g, 84 mmol) are added thereto, stirred uniformly, n-butyl lithium (1.3 mmol, 1.6 mol / L) is added, the initiation temperature is 50°C, the reaction is carried out for 30 min, and then styrene (65 g, 0.53 mol) is added to carry out the first stage of polymerization reaction, and the reaction is carried out for 60 h, and then 1-[4-(dimethylsilyl)phenyl]-1-[4-(N,N-dimethylamino)phenyl] ethylene (silicon hydride / amine group DPE, 1.3 mmol, 0.37 g) is added to react for 2 h;

[0092] Step S2, preparation of silicon hydride and silicon hydride / amine group functionalized styrene-isoprene active center: adding isoprene (130 g, 1.9 mol) into the polymerization kettle, carrying out the second stage polymerization reaction at 60 °C for 3 h;

[0093] Step S3, preparation of star coupled silicon hydride group functionalized styrene-isoprene block copolymer: adding silicon tetrachloride coupling agent (0.11 g, 0.65 mmol) and divinylbenzene (0.02 g, 0.14 mmol) into the polymerization kettle, carrying out the coupling reaction at 60 °C for 150 min;

[0094] Step S4, preparation of silicon hydride group functionalized SEPS thermoplastic elastomer: transferring the star coupled silicon hydride and silicon hydride / amine group functionalized styrene-isoprene block copolymer solution into a high-pressure hydrogenation kettle, adding solvent for dilution, adding triisobutyl aluminum \ nickel naphthenate catalyst and hydrogen for hydrogenation reaction, controlling the hydrogen pressure to be 1 Mpa, the reaction temperature to be 200 °C, and the reaction time to be 5 h.

[0095] After the reaction, the polymer is post-treated by using the traditional method, and after drying, the product is analyzed by using nuclear magnetic resonance hydrogen spectrum (1H-NMR) and gel permeation chromatography (GPC). 1HNMR) for its structure, and the results are as follows: the prepared product is 149.5 g; the mass percentage of styrene and the styrene monomer consisting of the silicon hydride and silicon hydride / amine group functionalized DPE derivative is 39.6% based on 100% of the mass of the styrene and isoprene block copolymer, and the rest is isoprene; the mass percentage of the silicon group functionalized DPE derivative monomer is 23.9% based on 100% of the mass of the styrene block, and the rest is styrene monomer, the silicon hydride and silicon hydride / amine group functionalized DPE derivative is distributed at the initiation end and in the chain of the polystyrene block, and the silicon hydride / amine group functionalized DPE derivative is distributed at the chain end of the polystyrene block; the hydrogenation degree is 98.1%; the molecular weight is analyzed by using gel permeation chromatography (GPC), and the standard curve is prepared by using different molecular weight narrow distribution polystyrene as the standard sample, 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 silicon hydride and silicon hydride / amine group functionalized styrene-isoprene block copolymer before coupling presents a single peak narrow distribution, the number average molecular weight is 276.1 kg / mol, and the molecular weight distribution is 1.15; the silicon hydride and silicon hydride / amine group functionalized styrene-isoprene block copolymer after star coupling presents a single peak narrow distribution, the coupling efficiency is close to 100%, the number average molecular weight is 866.3 kg / mol, and the molecular weight distribution is 1.48; the single silicon hydride functionalized SEPS after hydrogenation presents a single peak narrow distribution, the number average molecular weight is 868.3 kg / mol, and the molecular weight distribution is 1.54; the mechanical properties of the product are tested by using a universal testing machine, and the results are as follows: the elongation at break is 1750%, and the tensile strength is 6.3 MPa.

[0096] Example 7

[0097] Step S1, preparation of the single amine group functionalized polystyrene active center: 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-(N,N-dimethylamine group)-phenyl]-1-phenyl ethylene (single amine DPE, 18.7 g, 84 mmol) are added thereto, stirred uniformly, and n-butyl lithium (2.6 mmol) is added, the initiation temperature is 50°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 24 h;

[0098] Step S2, preparation of the single amine group functionalized styrene-isoprene active center: isoprene (130 g, 1.9 mol) is added to the above polymerization kettle, the reaction temperature is 60°C, and the second stage of polymerization reaction is carried out for 3 h;

[0099] Step S3: Prepare star-shaped styrene-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;

[0100] Step S4, preparation of SEPS thermoplastic elastomer with monoamine functionalization: The star-coupled styrene-isoprene block copolymer solution with monoamine functionalization is transferred to a high-pressure hydrogenation reactor, solvent is added for dilution, triisobutylaluminum / nickel naphthenate catalyst and hydrogen are added for hydrogenation reaction, the hydrogen pressure is controlled at 3 MPa, the reaction temperature is 50℃, and the reaction is carried out for 3 h.

[0101] 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 201.7 g; based on the mass of the styrene-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 isoprene; based on the mass of the styrene block 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 89.6%; the molecular weight was analyzed by gel permeation chromatography (GPC), and a standard curve was prepared using polystyrene with narrow molecular weight distributions at different molecular weights as standard samples, with tetrahydrofuran as the standard. The mobile phase (flow rate 1.0 ml / min) and sample concentrations of 2–5 mg / ml yielded the following results: Before coupling, the styrene-isoprene block copolymers functionalized with diamine groups exhibited 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-isoprene block copolymers functionalized with monoamine groups exhibited a narrow, single-peak distribution with a coupling efficiency of approximately 100%, a number-average molecular weight of 559.4 kg / mol, and a molecular weight distribution of 1.28; after hydrogenation, the SEPS functionalized with monoamine groups exhibited a narrow, single-peak distribution with a number-average molecular weight of 560.1 kg / mol and a molecular weight distribution of 1.28. The mechanical properties of the products were tested using a universal testing machine, with the following results: elongation at break was 1510%, and tensile strength was 9.1 MPa.

[0102] Example 8

[0103] Step S1, preparing active center of double amine group functionalized polystyrene: under the protection of nitrogen or argon, 3L (2370g) of cyclohexane solvent was added into 5L polymerization kettle, and tetrahydrofuran (2.8g, 39mmol) and 1,1-di[4-(N,N-dimethylamine) phenyl] ethylene (double amine DPE, 0.7g, 2.6mmol) were added into the kettle, stirred uniformly, and n-butyl lithium (2.6mmol) was added, the initiation temperature was 50℃, the reaction was carried out for 30min, and then styrene (129g, 1.24mol) was added to carry out the first stage of polymerization reaction, and the reaction was carried out for 12h;

[0104] Step S2, preparing active center of double amine group functionalized styrene-isoprene: isoprene (130g, 1.9mol) was added into the above-mentioned polymerization kettle, the reaction temperature was 60℃, and the second stage of polymerization reaction was carried out, and the reaction was carried out for 3h;

[0105] Step S3, preparing star-coupled double amine group functionalized styrene-isoprene block copolymer: silicon tetrachloride coupling agent (0.11g, 0.65mmol) and divinylbenzene (0.01g, 0.07mmol) were added into the above-mentioned polymerization kettle, the reaction temperature was 60℃, and the coupling reaction was carried out, and the reaction was carried out for 150min;

[0106] Step S4, preparing double amine group functionalized SEPS thermoplastic elastomer: the star-coupled double amine group functionalized styrene-isoprene block copolymer glue solution 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.

[0107] After the reaction, the polymer was post-treated by conventional method, and the product was dried and then analyzed by 1H nuclear magnetic resonance (1H NMR) for its structure, and the results were as follows: the mass of the prepared product was 200.4 g; the mass percentage of the styrene and the DPE derivative containing the double amine group functionalized monomer was 49.9% based on 100% of the mass of the styrene and isoprene block copolymer, and the rest was isoprene; the mass percentage of the DPE derivative containing the double amine group functionalized monomer was 0.5% based on 100% of the mass of the styrene block, and the rest was styrene monomer, and the DPE derivative containing the double amine group functionalized monomer was distributed at the initiation end of the polystyrene block; the hydrogenation degree was 97.6%; the molecular weight was analyzed by gel permeation chromatography (GPC) with different molecular weight narrow distribution polystyrene as the standard sample to produce a standard curve, and tetrahydrofuran was used as the mobile phase (the flow rate was 1.0 ml / min), and the sample concentration was 2-5 mg / ml, and the results were as follows: the double amine group functionalized styrene-isoprene block copolymer before coupling showed a single peak narrow distribution, the number average molecular weight was 168.1 kg / mol, and the molecular weight distribution was 1.14; the double amine group functionalized styrene-isoprene block copolymer after star coupling showed a single peak narrow distribution, the coupling efficiency was about 100%, the number average molecular weight was 565.1 kg / mol, and the molecular weight distribution was 1.28; the double amine group functionalized SEPS after hydrogenation showed a single peak narrow distribution, the number average molecular weight was 568.1 kg / mol, and the molecular weight distribution was 1.30; the mechanical properties of the product were tested by a universal testing machine, and the results were as follows: the elongation at break was 1550%, and the tensile strength was 8.7 MPa.

[0108] Example 9 (adjusting the type and sequence of DPE and the topological structure, and other parameters are the same as in Example 2)

[0109]

[0110]

[0111] Example 10 (adjusting the type of DPE, and other parameters are the same as in Example 2)

[0112]

[0113] Example 11 (adjusting the block ratio, and other parameters are the same as in Example 4)

[0114]

[0115] When the styrene block content is less than 20%, the tensile strength of SEPS is low and the performance is poor; when the styrene block content is greater than 50%, the tensile strength of SEPS does not increase significantly, and the elongation at break decreases, so the styrene block content of the patent is preferably 20-50%.

[0116] Example 12 (adjusting the proportion of DPE derivative in the styrene block, other parameters are the same as in Example 4)

[0117]

[0118] When the DPE content is less than 0.1%, the tensile strength of SEPS is less than 5.5 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 SEPS 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 SEPS, so the DPE content of the patent is preferably 0.5-20%.

[0119] Example 13 (adjusting the vinyl content, other parameters are the same as in Example 6)

[0120]

[0121] Example 14 (adjusting the vinyl content, other parameters are the same as in Example 6)

[0122] Comparative Example 1 (reducing the hydrogenation step based on Example 5)

[0123] Step S1, preparation of a functionalized polystyrene active center containing silicon-oxygen and silicon-hydrogen groups: 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-(triisopropoxysilyl)phenyl]-1-phenyl ethylene (monosilicon-oxygen DPE, 0.5g, 1.3mmol) and 1-[4-(dimethylsilyl hydrogen)phenyl]-1-phenyl ethylene (monosilicon-hydrogen DPE, 0.38g, 1.3mmol) were added thereto, stirred uniformly, and n-butyl lithium (2.6mmol, 1.6mol / L) was added to initiate the reaction at a temperature of 50°C, reacted for 30min, and then styrene (110g, 1.06mol) was added to carry out the first-stage polymerization reaction for 3h;

[0124] Step S2, preparation of a functionalized styrene-isoprene active center containing silicon-oxygen and silicon-hydrogen groups: isoprene (130g, 1.9mol) was added to the above polymerization kettle, the reaction temperature was 50°C, and the second-stage polymerization reaction was carried out for 3h.

[0125] Step S3, prepare star-shaped coupled styrene-isoprene block copolymers functionalized with siloxane and silane groups: add selenium tetrachloride coupling agent (0.11g, 0.52mmol) to the above polymerization reactor, carry out the coupling reaction at 60℃ for 30min;

[0126] 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 208.8 g; based on the mass of the styrene-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 isoprene; based on the mass of the styrene block as 100%, the mass percentage of DPE derivative monomers functionalized with siloxane and silane groups was 0.8%, 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 gel permeation chromatography (GPC), and standard curves were prepared using narrow-distribution polystyrene with different molecular weights as standard samples. The sample concentration was 2–5 mg / ml, using tetrahydrofuran as the mobile phase (flow rate 1.0 ml / min). The results are as follows: Before coupling, the styrene-isoprene block copolymers functionalized with siloxane and silane groups exhibited a narrow unimodal distribution with a number-average molecular weight of 131.6 kg / mol and a molecular weight distribution of 1.19. After star-shaped coupling, the styrene-isoprene block copolymers functionalized with siloxane and silane groups exhibited a bimodal distribution with a coupling efficiency of 55.2% and number-average molecular weights of 359.9 kg / mol and 131.6 kg / mol, respectively, and a molecular weight distribution of 1.55. The mechanical properties of the products were tested using a universal testing machine, and the results are as follows: the elongation at break was 820%, and the tensile strength was 1.1 MPa.

[0127] Comparative Example 2 (using Example 5 as an example, replacing monosilicon hydrogen DPE with the same amount of styrene)

[0128] 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, 1.12mol) were added. After stirring evenly, n-butyllithium (2.6mmol) was added, the initiation temperature was 60℃, and the reaction was carried out for 30min for the first stage of polymerization reaction, which was carried out for 2h.

[0129] Step S2, preparing styrene-isoprene active centers functionalized with monosilane groups: add isoprene (130g, 1.9mol) to the above polymerization reactor, react at 50℃, and carry out the second stage polymerization reaction for 3h.

[0130] Step S3, prepare linearly coupled styrene-isoprene 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 60℃ for 150min;

[0131] Step S4, preparation of SEPS thermoplastic elastomer with silane-hydrogen functionalization: The linearly coupled styrene-isoprene block copolymer solution with monosilane-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 10 MPa, the reaction temperature is 80℃, and the reaction is carried out for 1 h.

[0132] 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 189.1 g; based on the mass of the styrene-isoprene block copolymer as 100%, the mass percentage of styrene monomers composed of styrene and DPE derivatives functionalized with monosilane groups was 47.7%, with the remainder being isoprene; based on the mass of styrene blocks as 100%; the degree of hydrogenation was 98.1%; the molecular weight was analyzed by gel permeation chromatography (GPC), and a standard curve was prepared using narrow-distribution polystyrene with different molecular weights as standard samples. Tetrahydrofuran was used as the mobile phase (flow rate of 1.0 ml / min), and the sample concentration was 2–5 mg / ml. The results are as follows: before coupling, it contained... The styrene-isoprene block copolymer functionalized with monosilane groups exhibits a narrow, single-peak molecular weight distribution with a number-average molecular weight of 171.1 kg / mol and a molecular weight distribution of 1.13. The styrene-isoprene block copolymer functionalized with monosilane groups after linear coupling also exhibits a narrow, single-peak molecular weight distribution with a coupling efficiency close to 100%, a number-average molecular weight of 267.3 kg / mol, and a molecular weight distribution of 1.25. The SEPS functionalized with monosilane groups after hydrogenation also exhibits a narrow, single-peak molecular weight distribution with a number-average molecular weight of 281.1 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 is 1610%, and tensile strength is 3.2 MPa.

[0133] 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 / nitrogen group functionalized SEPS thermoplastic elastomer characterized in that, The silicon / nitrogen group functionalized SEPS thermoplastic elastomer is a linear / star coupled silicon / nitrogen group functionalized styrene-(ethylene / propylene) block copolymer, a linear / star coupled silicon / nitrogen group functionalized copolymer of styrene block and ethylene / propylene block; The linear / star coupled silicon / nitrogen group functionalized styrene block is a copolymer block of styrene and a silicon / nitrogen group functionalized 1,1-diphenyl ethylene (DPE) derivative; the ethylene / propylene block is a random copolymer block of ethylene and propylene; The number average molecular weight of the silicon / nitrogen group- functionalized SEPS thermoplastic elastomer ranges from 2 x 10 4 to 90 x 10 4 g / mol, and the molecular weight distribution ranges from 1.02 to 1.

60.

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

3. The silicon / nitrogen group functionalized SEPS thermoplastic elastomer of claim 1, wherein, In terms of 100% by mass of the silicon / nitrogen group functionalized SEPS thermoplastic elastomer, the mass percentage of the linear / star coupled silicon / nitrogen group functionalized styrene block ranges from 20% to 50%, and the rest is the ethylene / propylene block.

4. The silicon / nitrogen group functionalized SEPS thermoplastic elastomer of claim 1, wherein, In terms of 100% by mass of the linear / star coupled silicon / nitrogen group functionalized styrene block, the mass percentage of the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer ranges from 0.1% to 50.0%, and the rest is styrene.

5. The silicon / nitrogen group functionalized SEPS thermoplastic elastomer of claim 1, wherein, The silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative is selected from a silicon group functionalized 1,1-diphenyl ethylene derivative, an amine group functionalized 1,1-diphenyl ethylene derivative, and a silicon group / amine group functionalized 1,1-diphenyl ethylene derivative; 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-(dimethylsilyl)phenyl]-1-phenyl ethylene, 1,1-di[4-(triisopropoxysilyl)phenyl] ethylene, 1,1-di[4-(dimethylsilyl)phenyl] ethylene, 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]-1-[4-(dimethylsilyl)phenyl] ethylene, and 1-[4-(triisopropoxysilyl)phenyl] 1-[4-(dimethylsilyl)phenyl] ethylene; The nitrogen group functionalized 1,1-diphenyl ethylene derivative is selected from at least one of 1-[4-(N,N dimethylamino)phenyl]-1-phenyl ethylene and 1,1-bis[4-(N,N-dimethylamino)phenyl] ethylene; The silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative is 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 / nitrogen group functionalized SEPS thermoplastic elastomer as claimed in any one of claims 1 to 5, characterized in that, The method comprises the following steps: Step S1, preparing a silicon / nitrogen group functionalized polystyrene active center: In a non-polar hydrocarbon solvent, a metered polar modifier is added to the reactor, and according to different monomer feeding sequences and ratios, a metered styrene and a silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer, an alkyl lithium initiator and a polar modifier are added, stirred uniformly, the initiation reaction temperature is 10-90℃, and the reaction time is 0.5-48h; wherein the feed ratio of styrene and silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer is 1-999:1 by mass; the initiator and polar modifier are added in a ratio of 1:1-50, and the feed ratio of the initiator and the raw material is 1:1 x 10 5 -2.5 x 10 5 ; Step S2, preparing a silicon / nitrogen group functionalized polystyrene-isoprene active center: After the reaction in step S1 is completed, a metered isoprene monomer is added to the reactor according to the monomer ratio, the reaction temperature is controlled to be 50-110℃, and the reaction time is 0.5-10h; wherein the feeding ratio of the styrene monomer composed of styrene and the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative and isoprene is 1:2-4 in mass fraction; Step S3, preparing a linear / branched coupled silicon / nitrogen group functionalized styrene-isoprene block copolymer: after the reaction in step S2 is completed, a metered linear / branched coupling agent is added to perform coupling reaction, the temperature is 50-110℃, the reaction time is 30-150min, and a linear / branched coupled silicon / nitrogen group functionalized styrene-isoprene block copolymer glue solution is prepared; Step S4, preparing a silicon / nitrogen group functionalized SEPS thermoplastic elastomer: The linear / branched coupled silicon / nitrogen group functionalized styrene-isoprene block copolymer glue solution is transferred to a high-pressure hydrogenation kettle, a metered hydrogenation catalyst and hydrogen are added to perform hydrogenation reaction, the hydrogen pressure is controlled to be 0.1Mpa-10Mpa, the reaction temperature is controlled to be 50℃-200℃, the hydrogenation reaction time is 1-20h, and a silicon / nitrogen group functionalized SEPS thermoplastic elastomer is obtained. The hydrogenation catalyst is a nickel catalyst.

7. The production method according to claim 6, characterized by, When the mass concentration of all the reaction monomers in step S1 is 5%-25%, the silicon / nitrogen 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 concentration of all reaction monomers in the step SI is less 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 silicon oxygen group / silicon hydride group 1,1-diphenyl ethylene derivative monomer and styrene is 5%-15%, or the mass concentration of the silicon oxygen group / amine group 1,1-diphenyl ethylene derivative monomer, or the silicon hydride group / amine group 1,1-diphenyl ethylene derivative monomer and styrene is 15%-25%, or the mass concentration of the mon / di amine group 1,1-diphenyl ethylene derivative monomer and styrene is 10%-20%, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative in the prepared silicon / nitrogen group functionalized styrene block is located in the chain and the chain end of the block.

9. The preparation method according to claim 6, characterized in that, When the total content of the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative monomer is more than 10% of the mass concentration of all monomers, 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 silicon oxygen group / silicon hydride group 1,1-diphenyl ethylene derivative monomer and styrene is 5%-10%, or the mass concentration of the silicon oxygen group / amine group 1,1-diphenyl ethylene derivative monomer, or the silicon hydride group / amine group 1,1-diphenyl ethylene derivative monomer and styrene is 10%-15%, or the mass concentration of the mon / di amine group 1,1-diphenyl ethylene derivative monomer and styrene is 8%-12%, the silicon / nitrogen group functionalized 1,1-diphenyl ethylene derivative in the prepared silicon / nitrogen group functionalized styrene block is located in the chain and the chain end of the block.

10. The method of claim 6, wherein, 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 solvent is selected from benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons, mixed aliphatic hydrocarbons; The linear coupling agent is selected from at least one of M(CH3)2Cl2, 1,2-dichloroethane or 1,2-dibromoethane; the star coupling agent is selected from one of divinylbenzene, MCH3Cl3, MCl4, M2Cl6, M3Cl8, M is selected from silicon, tin, lead, titanium, germanium.

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