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CN113912798A - Star block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and preparation method thereof - Google Patents

Star block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and preparation method thereof Download PDF

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CN113912798A
CN113912798A CN202111351022.9A CN202111351022A CN113912798A CN 113912798 A CN113912798 A CN 113912798A CN 202111351022 A CN202111351022 A CN 202111351022A CN 113912798 A CN113912798 A CN 113912798A
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phenyl
butadiene
sibr
block
isoprene
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CN113912798B (en
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李杨
冷雪菲
王艳色
韩丽
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Dalian University of Technology
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/048—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers, conjugated dienes and polar monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/042—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a polyfunctional initiator
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • C08F4/48—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium
    • C08F4/486—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium at least two metal atoms in the same molecule
    • C08F4/488—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium at least two metal atoms in the same molecule at least two lithium atoms in the same molecule
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    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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Abstract

The invention belongs to the technical field of functionalized high polymer materials, provides a star block copolymer based on DPE derivatives, butadiene and styrene monomers and a preparation method thereof, and aims to solve the problems of insufficient performance, complex process and the like existing in rubber modification in the prior art, and the star block copolymer has the structure of [ (SN-SIBR) -BR ]]n-C, wherein: (SN-SIBR) is a DPE derivative, a butadiene, isoprene and styrene copolymer block, BR is a butadiene homopolymer block, C is a polyfunctional alkyl lithium initiator residue, and n is greater than or equal to 3; the number average molecular weight of the copolymer was 5X 104‑50×104(ii) a Based on 100 percent of (SN-SIBR) mass, the content of butadiene is 5 to 80 percent, the content of isoprene is 5 to 80 percent, the content of styrene is 5 to 50 percent, and the content of DPE derivative is 0.5 to 20 percent; (SN-SIBR) Block to BR Block ratios 10/90-90/10.

Description

Star block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis and preparation of high polymer materials, and particularly relates to a radial block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and a preparation method thereof.
Background
Styrene-isoprene-butadiene rubber (SIBR) is an ideal integrated rubber with better comprehensive performance, and the rolling resistance and the traction performance reach good balance, so the SIBR is a novel tread rubber type which is extremely expected. China has rich C5 resources, but the problem of comprehensive utilization of the C5 resources is not completely solved. Isoprene (I) as an important component of C5 is potentially produced in large quantities. Therefore, it is a very realistic problem in the field of synthetic materials to solve the problem of comprehensive utilization of isoprene (I). Moreover, natural rubber resources in China are very limited, so that the domestic requirements are difficult to meet, and isoprene rubber is the most ideal substitute. In the field of polymer modification, it is more desirable to directly produce synthetic materials with excellent comprehensive properties from a reactor to replace the physical blending modification of polymers. The ternary polymerization can just meet the requirement, and can realize the chemical blending of a plurality of polymers to produce integrated rubber. Therefore, abundant domestic resources are utilized to develop the styrene, isoprene and butadiene terpolymer and produce a novel material with high added value, so that a patent technology is formed, and industrialization is realized as soon as possible, so that the method has very practical significance.
Because of the problems of synthesis and purification of lithium, no industrialization has been achieved so far. The multi-lithium initiation method adopts organic lithium containing multiple functional groups as an initiator, directly initiates polymerization by an anion polymerization method, and forms a star-shaped block polymer by a one-step method. The research institute of Beijing Yanshan petrochemical company applies for a plurality of patents in the research aspect of multi-lithium system star block copolymer, a polyfunctional group organic lithium initiator initiates the copolymerization of conjugated dienes such as styrene, isoprene, butadiene and the like to obtain a series of star block copolymers, and the star polymer has the following structure: (SIBR-BR) n-C, (SIBR-IR) n-C, (SIBR-IBR) n-C, etc.
Functionalization is the most effective method for realizing high performance of the solution polymerized styrene-butadiene rubber, in-chain functionalization becomes the inevitable trend of development of chain-end functionalized solution polymerized styrene-butadiene rubber, and the multi-functionalized solution polymerized styrene-butadiene rubber in a chain-end chain inevitably becomes green tire rubber with more excellent comprehensive performance. Based on a living anionic polymerization method, the multifunctional solution polymerized styrene-butadiene rubber in a synthetic chain end chain is designed most scientifically and reasonably by adopting the copolymerization reaction of a functionalized DPE derivative and butadiene and styrene. However, the synthesis and refining difficulty of the multifunctional DPE derivative monomer with a complex structure, especially the DPE derivative monomer containing silicon-oxygen group, amine group and silicon-oxygen group is large, and there is no literature report, and the mechanism of the multi-copolymerization reaction of various multifunctional DPE derivative monomers with complex structures with butadiene and styrene, and the precise regulation and control method of microstructure and sequence structure are all subject to intensive systematic research, and these problems become the bottleneck of the multifunctional solution polymerized styrene-butadiene rubber in the chain end chain to be solved. In order to further promote the development of the field of rubber toughened plastics, how to provide a functionalized polymer with good biocompatibility and excellent mechanical properties to improve the problems of low strength, poor wear resistance and the like of rubber in the prior art is a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems of low strength, poor wear resistance and the like of rubber in the prior art, the invention provides a radial block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and a preparation method thereof.
In a first aspect, the present invention provides a class of radial block copolymers based on DPE derivatives, butadiene, isoprene, styrene monomers, such radial block copolymers having the following structure: [ (SN-SIBR) -BR ] n-C,
wherein: (SN-SIBR) is a DPE derivative, butadiene, isoprene, styrene copolymer block, BR is a butadiene homopolymer block; c is a polyfunctional alkyl lithium initiator residue, n is an initiator functionality, n is a natural number, and n is greater than or equal to 3.
The number average molecular weight of the star block copolymer is 5 x 104-50×104(ii) a Based on 100 percent of the total mass of the (SN-SIBR) copolymer block, the (SN-SIBR) block contains 5 to 80 percent of butadiene, 5 to 80 percent of isoprene, 5 to 50 percent of styrene and 0.5 to 20 percent of DPE derivative; the mass ratio of the (SN-SIBR) block to the BR block in the radial block copolymer is 10/90-90/10;
the DPE derivative is selected from an amino group-containing group, a silicon group/amino group monomer 1, 1-diphenylethylene derivative; the amino group, the silicon group/the amino group are connected at the para position, the meta position or the ortho position of the phenyl in the 1, 1-diphenylethylene derivative.
Further, the value of the initiator functionality n ranges from 3 to 50.
Further, the value range of the initiator functionality n is 3-10.
Further, the number average molecular weight of the radial block copolymer is 10X 104-30×104。
Further, the butadiene content in the (SN-SIBR) block is 20 to 60% based on 100% by mass of the DPE derivative, butadiene, isoprene, and styrene copolymer (SN-SIBR) block; the content of isoprene is 20-60%; the content range of the styrene is 10-35 percent; the content range of the DPE derivative is 1-15%.
Further, the mass ratio (SN-SIBR)/BR of the DPE derivative, butadiene, isoprene, and styrene copolymer (SN-SIBR) block to the polybutadiene BR block in the radial block copolymer is in the range of 30/70 to 70/30.
Further, the DPE derivative is selected from the group consisting of amino group-containing group, silicon group/amino group monomer 1, 1-diphenylethylene derivatives, including but not limited to mono-amino group-containing group, mono-siloxy group, di-amino group, di-siloxy group, siloxy/amino group, mono-siloxy/amino group monomer 1, 1-diphenylethylene derivatives;
further, the amine group-containing group, silicon group/amine group monomer 1, 1-diphenylethylene derivatives (DPE derivatives) are selected from:
(1) the amine group DPE derivative monomers generally range from 1- [ (N, N-dimethylamino) phenyl ] -1-phenylethene, 1- [ (N, N-diethylamino) phenyl ] -1-phenylethene, 1- [ (N, N-di-tert-butylamino) phenyl ] -1-phenylethene, 1- [ (N, N-diphenylamino) phenyl ] -1-phenylethene; the general ranges of the diamine group DPE derivative monomers are 1, 1-bis [ (N, N-dimethylamino) phenyl ] ethylene, 1-bis [ (N, N-diethylamino) phenyl ] ethylene, 1-bis [ (N, N-di-tert-butylamino) phenyl ] ethylene and 1, 1-bis [ (N, N-diphenylamino) phenyl ] ethylene; the most preferable ranges are 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, 1-bis [4- (N, N-dimethylamino) phenyl ] ethene.
(2) Siloxy group DPE derivative monomers generally range from 1- [4- (trimethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (triethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (tri-tert-butoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylmethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (diethylmethoxysilyl) phenyl ] -1-phenylethene; the general ranges of disiloxyl DPE derivative monomers are 1,1 bis [4- (trimethoxysilyl) phenyl ] ethylene, 1 bis [4- (triethoxysilyl) phenyl ] ethylene, 1 bis [4- (triisopropoxysilyl) phenyl ] ethylene, 1 bis [4- (tri-tert-butoxysilyl) phenyl ] ethylene, 1 bis [4- (dimethylmethoxysilyl) phenyl ] ethylene, 1 bis [4- (diethylmethoxysilyl) phenyl ] ethylene; the most preferable ranges are 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1-bis [4- (triisopropoxysilyl) phenyl ] ethylene.
(3) Silyloxy DPE derivative monomers generally range from 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, 1[3- (dimethylsilyl) phenyl ] -1-phenylethene, 1[2- (dimethylsilyl) phenyl ] -1-phenylethene, 1[4- (diethylsilyl) phenyl ] -1-phenylethene, 1[4- (dipropylsilyl) phenyl ] -1-phenylethene, 1[4- (diisopropylsilyl) phenyl ] -1-phenylethene, 1[4- (di-tert-butylsilyl) phenyl ] -1-phenylethene; bis-silyl group DPE derivative monomers generally range from 1,1 bis [4 (dimethylsilyl) phenyl ] ethylene, 1 bis [3 (dimethylsilyl) phenyl ] ethylene, 1 bis [2 (dimethylsilyl) phenyl ] ethylene, 1 bis [3,4 (dimethylsilyl) phenyl ] ethylene, 1 bis [2,3 (dimethylsilyl) phenyl ] ethylene, 1 bis [4 (diethylsilyl) phenyl ] ethylene, 1 bis [4 (dipropylsilyl) phenyl ] ethylene, 1 bis [4 (diisopropylsilyl) phenyl ] ethylene, 1 bis [4 (di-tert-butylsilyl) phenyl ] ethylene; the most preferable ranges are 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, 1 bis [4 (dimethylsilyl) phenyl ] ethene.
(4) The siloxy group/amino group DPE derivative monomers typically range from 1- [4- (trimethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (triethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (tripropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, n-dimethylamino) phenyl ] ethylene, 1- [4- (monoisopropoxydimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene; the most preferable range is 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene.
(5) The silylhydride group/amine group DPE derivative monomers typically range from 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (diethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (dipropylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (diisopropylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (di-tert-butylsilyl) phenyl ] -1- [4- (N, n-dimethylamino) phenyl ] ethylene; the most preferable range is 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene.
Further, the DPE derivative monomer is selected from the group consisting of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, 1-bis [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1-bis [4- (dimethylsilyl) phenyl ] ethene, 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, 1-bis [4- (triisopropoxysilyl) phenyl ] ethene, 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, n-dimethylamino) phenyl ] ethylene.
In another aspect, the present invention provides a method for preparing a radial block copolymer based on DPE derivatives, butadiene, isoprene, styrene monomers, comprising the steps of:
step S1, adding a first batch of butadiene monomers and polar additives into a reactor according to the monomer ratio in a nonpolar hydrocarbon solvent, adding a polyfunctional group organic lithium initiator into the reactor for 20-100min when the initiation reaction temperature reaches 10-90 ℃, and preparing butadiene homopolymer block BR;
and step S2, after the first batch of butadiene is completely reacted, adding a second batch of butadiene monomer containing polar additives, DPE derivatives, isoprene and styrene monomers into the reactor at one time according to the monomer proportion, reacting for 50-100min, and after the DPE derivatives, butadiene and styrene are completely reacted, terminating the reaction to obtain the [ (SN-SIBR) -BR ] n-C star block copolymer.
Further, the present invention relates to a method for preparing a radial block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers, wherein whether a polar additive is used is determined in step S1 according to the requirement of polybutadiene microstructure.
Further, the mass concentration of all monomers added in the steps 1 and 2 is 5-25% according to the types of polar compounds.
Further comprises a step 3 of adding a terminator after the reaction in the step 2 is finished to terminate the polymerization reaction.
Further, conventional additives, such as an anti-aging agent Irganox 1010 and an antigen BHT or 2.6.4, can be optionally added after the step 2 or 3, the polymer glue solution is subjected to post-treatment by a conventional method, and a product is dried to obtain the [ (SN-SIBR) -BR ] n-C star block copolymer.
Further, the polar additive is selected from one or a mixture of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and metal alkoxide compounds, such as: (1) an oxygenate, typically selected from: diethyl ether, tetrahydrofuran, R1OCH2CH2OR2(wherein: R1、R2Is an alkyl group having 1 to 6 carbon atoms, R1、R2May be the same or different, with R1、R2The difference is preferably as follows: ethylene glycol dimethyl ether, ethylene glycol diethyl ether), R1OCH2CH2OCH2CH2OR2(wherein：R1、R2Is an alkyl radical R having 1 to 6 carbon atoms1、R2May be the same or different, with R1、R2Preferably different, such as diethylene glycol dimethyl ether, diethylene glycol dibutyl ether), crown ethers; (2) a nitrogen-containing compound, generally selected from: triethylamine, Tetramethylethylenediamine (TMEDA), dipiperidine ethane (DPE), preferably TMEDA; (3) a phosphorus-containing compound, which is generally selected from hexamethylphosphoric triamide (HMPA); (4) the metal alkoxide compound is generally selected from the group consisting of ROMs, wherein: r is an alkyl group having 1 to 6 carbon atoms, O is an oxygen atom, M is a metal ion sodium Na or potassium K, preferably selected from: potassium tert-butoxide, potassium tert-pentoxide.
Further, the non-polar organic solvent is selected from one or a mixture of several hydrocarbon solvents 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 hydrocarbons (e.g. mixed xylenes), mixed aliphatic hydrocarbons (e.g. raffinate), preferably from: benzene, toluene, pentane, hexane, cyclohexane.
Further, the multifunctional organic lithium initiator is selected from one or a mixture of several multifunctional organic lithium initiators, such as: RLin, T (RLi) n, wherein: r is a hydrocarbon group having 4 to 20 carbon atoms, R may be an alkane group or an aromatic hydrocarbon group, and T is a metal atom, and is generally a metal element such as tin Sn, silicon Si, lead Pb, titanium Ti, germanium Ge, or the like. The polyfunctional organolithium initiator RLin may be a polychelant organolithium initiator, various polychelant organolithium initiators obtained by reacting Divinylbenzene (DVB) with alkyllithium, or a polyfunctional organolithium initiator T (RLi) n containing the above-mentioned metal, the polyfunctional organolithium initiator T (RLi) n is selected from the group consisting of Sn-containing, Si-containing polyfunctional organolithium initiators Sn (RLi) n and Si (RLi) n, and the preferable range is selected from Sn (RLi)4、Si(RLi)4。
Further, the terminator is a terminator which can be used for anionic polymerization, such as water, methanol, ethanol, isopropanol or the like.
The invention has the beneficial effects that:
the invention starts from polymer design, adopts polyfunctional group organic lithium initiator to firstly polymerize butadiene homopolymer block BR, and then polymerize DPE derivative, butadiene, isoprene and styrene copolymer (SN-SIBR) block to prepare [ (SN-SIBR) -BR ] n-C star block copolymer, thereby really realizing chemical compounding of DPE derivative, butadiene and styrene copolymer rubber and polybutadiene rubber.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental methods and calculation methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The polyfunctional organic lithium initiator used in the following examples is a polychelating organic lithium initiator, and the synthesis method is as follows: under the protection of high-purity nitrogen, adding 160 g of cyclohexane, 11 g of butadiene, 80mmol of Tetrahydrofuran (THF) and 100mmol of Divinylbenzene (DVB) into a 500 ml dry saline bottle according to the ratio, uniformly mixing, adding 100mmol of n-butyllithium by using a syringe, reacting at 70 ℃ for 30 minutes to generate a deep red homogeneous polychelating type organolithium initiator solution, wherein the initiator concentration is measured by adopting a double titration method. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene amount (for preparing BR block), B2 is the second butadiene amount [ for preparing (SN-SIBR) block ], SN is DPE derivative, S is styrene amount, (SN-SIBR) block contains butadiene B2, DPE derivative SN, styrene S monomer ratio, and (SN-SIBR)/BR is the weight ratio of (SN-SIBR) block to BR block.
Example 1
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 78.5 g of butadiene, 78.5 g of isoprene, 52.5 g of styrene and 4.5 g of 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene (DPE-2SiH) containing a polar additive THF are added, the reaction is continued for 60 minutes, and when the polymerization reaction of 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, butadiene, isoprene and styrene is completely finished, a terminator is added to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is the second butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, (1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, butadiene, isoprene, styrene monomer ratio (weight ratio) in SN-SIBR) block, (butadiene content 35.1% (weight percentage) in SN-SIBR block, isoprene content 35.1% (weight percentage), styrene content 23.2% (weight percentage), 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene content 6.6% (weight percentage); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 32.5 ten thousand and the molecular weight distribution index was 1.10.
Example 2
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 78.5 g of butadiene, 78.5 g of isoprene, 52.5 g of styrene and 4.5 g of 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene (DPE-2SiH) containing a polar additive THF are added, the reaction is continued for 60 minutes, and when the polymerization reaction of 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, butadiene, isoprene and styrene is completely finished, a terminator is added to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is the second butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, (1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene, butadiene, isoprene, styrene monomer ratio (weight ratio) in SN-SIBR) block, (butadiene content 36.1% (weight percentage) in SN-SIBR block, isoprene content 36.1% (weight percentage), styrene content 25.6% (weight percentage), 1, 1-bis [4- (dimethylsilyl) phenyl ] ethylene content 2.2% (weight percentage); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 48.9 ten thousand, and the molecular weight distribution index was 1.12.
Example 3
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 78.5 g of butadiene, 78.5 g of isoprene, 52.5 g of styrene, 4.4 g of 1[4- (dimethylsilyl) phenyl ] -1-phenylethene (DPE-SiH) with a molar ratio of THF/Li of 35 were added as polar additives, the reaction was continued for 60 minutes, and after the polymerization of 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, butadiene, isoprene and styrene was completed, a terminator was added to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is a second butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, (1 [4- (dimethylsilyl) phenyl ] -1-phenylethene, butadiene, isoprene, styrene monomer ratio (weight ratio) in SN-SIBR) block, (butadiene content 35.0% (weight percentage) in SN-SIBR block, isoprene content 35.0% (weight percentage), styrene content 24.3% (weight percentage), 1[4- (dimethylsilyl) phenyl ] -1-phenylethene content 5.7% (weight percentage); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 32.3 ten thousand and the molecular weight distribution index was 1.10.
Example 4
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 78.5 g of butadiene, 78.5 g of isoprene, 52.5 g of styrene, 4.4 g of 1[4- (dimethylsilyl) phenyl ] -1-phenylethene (DPE-SiH) with a molar ratio of THF/Li of 35 were added as polar additives, the reaction was continued for 60 minutes, and after the polymerization of 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, butadiene, isoprene and styrene was completed, a terminator was added to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is a second butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1[4- (dimethylsilyl) phenyl ] -1-phenylethene, (1 [4- (dimethylsilyl) phenyl ] -1-phenylethene, butadiene, isoprene, styrene monomer ratio (weight ratio) in SN-SIBR) block, (butadiene content 35.5% (weight percentage) in SN-SIBR block, isoprene content 35.5% (weight percentage), styrene content 26.6% (weight percentage), 1[4- (dimethylsilyl) phenyl ] -1-phenylethene content 2.4% (weight percentage); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 50.6 ten thousand and the molecular weight distribution index was 1.12.
Example 5
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 94.5 g of butadiene, 94.5 g of isoprene, 21 g of styrene and 25 g of 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene (DPE-2N) containing a polar additive THF are added, the reaction is continued for 60 minutes, and when the polymerization of 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene, isoprene and styrene is completely completed, a terminator is added to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is the second butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, (SN-SIBR) block 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene, isoprene, styrene monomer ratio (weight ratio), (SN-SIBR) block butadiene content 45.0% (weight percentage), isoprene content 45.0% (weight percentage), styrene content 5.5% (weight percentage), 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene content 4.5% (weight percentage); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 39.6 ten thousand and the molecular weight distribution index was 1.11.
Example 6
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 77.5 g of butadiene containing a polar additive THF, 77.5 g of isoprene, 55.0 g of styrene, 55.0 g of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene (DPE-N) with a THF/Li (molar ratio) of 35 were added, the reaction was continued for 60 minutes, and when the polymerization of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, butadiene, isoprene and styrene was completed, a terminator was added to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is a second batch of butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, (SN-SIBR) block contains 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, butadiene, isoprene, styrene monomer ratio (weight ratio), (SN-SIBR) block contains 37.7% by weight of butadiene, 37.7% by weight of isoprene, 17.8% by weight of styrene, and 6.8% by weight of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene; the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 38.5 ten thousand and the molecular weight distribution index was 1.08.
Example 7
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5 liters of benzene and 140 grams of butadiene into a 5 liter stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 78.5 g of butadiene, 78.5 g of isoprene, 52.5 g of styrene and 25.6 g of 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene (DPE-2N) containing a polar additive THF are added, the reaction is continued for 60 minutes, and when the polymerization reaction of 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene, isoprene and styrene is completely finished, a terminator is added to end the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is the second butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, (SN-SIBR) block 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene, isoprene, styrene monomer ratio (weight ratio), (SN-SIBR) block butadiene content 43.5% (weight percentage), isoprene content 43.5% (weight percentage), styrene content 11.9% (weight percentage), 1, 1-bis [4- (N, N-dimethylamino) phenyl ] ethylene content 1.1% (weight percentage); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 49.6 ten thousand and the molecular weight distribution index was 1.12.
Example 8
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5L of toluene and 140 g of butadiene into a 5L stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then, 88.5 g of butadiene, 88.5 g of isoprene, 31.5 g of styrene and 55 g of 1- [4- (triisopropoxysido) phenyl ] -1-phenylethene (DPE-SiO) containing a polar additive THF were added thereto in a molar ratio of THF/Li of 35, and the reaction was continued for 60 minutes, and after the polymerization of 1- [4- (triisopropoxysido) phenyl ] -1-phenylethene, butadiene, isoprene and styrene was completed, a terminator was added thereto to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is a second butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, (1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, butadiene, isoprene, styrene monomer ratio (weight ratio) in SN-SIBR) block, (butadiene content 34.5% (weight percentage) in SN-SIBR block, isoprene content 34.5% (weight percentage), styrene content 10.8% (weight percentage), 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene content 19.2% (weight percentage); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 36.2 ten thousand and the molecular weight distribution index was 1.12.
Example 9
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5L of toluene and 140 g of butadiene into a 5L stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then, 52.5 g of butadiene, 52.5 g of isoprene, 105.0 g of styrene, and 25.0 g of 1- [4- (triisopropoxysido) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene (DPE-N/SiO) containing a polar additive THF were added, the reaction was continued for 60 minutes while the THF/Li molar ratio was 35, and after the polymerization reaction of 1- [4- (triisopropoxysido) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene, isoprene and styrene was completed, a terminator was added to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is a second batch of butadiene [ used for preparing (SN-SIBR) block ], isoprene, styrene, 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, (weight ratio of 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene, isoprene, styrene monomer in (SN-SIBR) block), (weight ratio of butadiene content in SN-SIBR) block is 44.1% (weight ratio), isoprene content is 44.1% (weight ratio), styrene content is 8.3% (weight ratio), 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, the content of N-dimethylamino) phenyl ] ethylene was 3.5% (by weight); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 44.6 ten thousand and the molecular weight distribution index was 1.09.
Example 10
[ (SN-SIBR) -BR ] n-C radial block copolymer: adding 3.5L of toluene and 140 g of butadiene into a 5L stainless steel reaction kettle with a stirrer, heating to 50 ℃, adding a polyfunctional group lithium initiator, and completing the polymerization reaction of the butadiene when the polymerization reaction is carried out for 30 minutes; then 75 g of butadiene, 75 g of isoprene, 60 g of styrene and 20 g of 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene (DPE-N/SiO) containing the polar additive THF were added, the reaction was continued for 60 minutes with a THF/Li molar ratio of 35, and after the polymerization of 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene, isoprene and styrene had been completed, a terminator was added to terminate the reaction. [ (SN-SIBR) -BR ] n-C radial block copolymer: b1 is the first butadiene (used to make the BR block); b2 is a second batch of butadiene [ used for preparing the (SN-SIBR) block ], isoprene, styrene, 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, (weight ratio of 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene, butadiene, isoprene, styrene monomer in the SN-SIBR block), (weight ratio of butadiene content 33.6% in the SN-SIBR) block, isoprene content 33.6% by weight, styrene content 26.6% by weight, 1- [4- (dimethylethoxysilyl) phenyl ] -1- [4- (N, the N-dimethylamino) phenyl ] ethylene content was 6.2% (weight percentage); the (SN-SIBR) block to BR block ratio (SN-SIBR)/BR is 60/40 (weight ratio); the number average molecular weight was 34.6 ten thousand and the molecular weight distribution index was 1.12.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A class of radial block copolymers based on DPE derivatives, butadiene, styrene monomers, characterized in that said radial block copolymers have the following structure: [ (SN-SIBR) -BR ] n-C,
wherein: (SN-SIBR) is a DPE derivative, butadiene, isoprene, styrene copolymer block, BR is a butadiene homopolymer block; c is a polyfunctional alkyl lithium initiator residue, n is initiator functionality, n is a natural number, and the value range is 3-50; the number average molecular weight of the radial block copolymer was 5X 104-50×104(ii) a Based on 100% of the mass of the (SN-SIBR) copolymer block, the (SN-SIBR) block contains 5-80% of butadiene, 5-80% of isoprene, 5-50% of styrene and 0.5-20% of DPE derivative; the mass ratio of the (SN-SIBR) block to the BR block in the radial block copolymer is 10/90-90/10;
the DPE derivative is selected from an amino group-containing group, a silicon group/amino group monomer 1, 1-diphenylethylene derivative; the amino group, the silicon group/the amino group are connected at the para position, the meta position or the ortho position of the phenyl in the 1, 1-diphenylethylene derivative.
2. The radial block copolymer of claim 1, wherein the radial block copolymer has a number average molecular weight of 10 x 104-30×104。
3. The radial block copolymer according to claim 1, wherein the (SN-SIBR) block has a butadiene content of 20 to 60%, an isoprene content of 20 to 60%, a styrene content of 10 to 35%, and a DPE derivative content of 1 to 15%, based on 100% by mass of the total (SN-SIBR) copolymer block.
4. The radial block copolymer of claim 1, wherein the mass ratio of (SN-SIBR) blocks to BR blocks in the radial block copolymer is from 30/70 to 70/30.
5. The radial block copolymer of claim 2, wherein the DPE derivative is selected from the group consisting of 1- [4- (N, N-dimethylamino) phenyl ] -1-phenylethene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylsilyl) phenyl ] -1-phenylethene, 1-bis [4- (N, N-dimethylamino) phenyl ] ethene, 1-bis [4- (triisopropoxysilyl) phenyl ] ethene, 1-bis [4- (dimethylsilyl) phenyl ] ethene, 1- [4- (triisopropoxysilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethene, and mixtures thereof, 1- [4- (dimethylsilyl) phenyl ] -1- [4- (N, N-dimethylamino) phenyl ] ethylene.
6. The process for preparing a radial block copolymer according to any one of claims 1 to 5, comprising the steps of:
adding a first batch of butadiene monomer and a polar additive into a reactor according to the monomer ratio in a nonpolar hydrocarbon solvent, enabling the initiation reaction temperature to reach 10-90 ℃, and the reaction time to be 20-100min, and then adding a polyfunctional group organic lithium initiator to prepare a butadiene homopolymer block BR;
adding a second batch of butadiene monomer containing polar additives, DPE derivatives, isoprene and styrene into the reactor at one time according to the monomer ratio, and reacting for 50-100min to obtain [ (SN-SIBR) -BR ] n-C star block copolymer;
the multifunctional organic lithium initiator is selected from one or a mixture of several multifunctional lithium initiators in RLin and T (RLi) n, wherein: r is a hydrocarbon group with 4-20 carbon atoms, and T is a metal atom of Sn, Si, Pb, Ti and Ge;
the polar additive is one or a mixture of oxygen-containing, nitrogen-containing, sulfur-containing and phosphorus-containing polar compounds and metal alkoxide compounds.
7. The method of claim 6, wherein the polyfunctional organolithium initiator is selected from the group consisting of Sn (RLi)4、Si(RLi)4。
8. The method of claim 6, wherein the polar additive is at least one selected from the group consisting of diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, hexamethylphosphoric triamide, tetramethylethylenediamine, potassium tert-butoxide, and potassium tert-pentoxide.
9. The method for preparing radial block copolymer [ (SN-SIBR) -BR ] n-C according to claims 6-7, wherein said non-polar hydrocarbon solvent is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, xylene, raffinate oil.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020120069A1 (en) * 2000-10-19 2002-08-29 Yang Li Star-block interpolymers and preparation of the same
US20100010154A1 (en) * 2008-07-08 2010-01-14 Kraton Polymers U.S. Llc Gels prepared from dpe containing block copolymers
CN113307912A (en) * 2021-05-31 2021-08-27 大连理工大学 Silica functionalized SIBR (silicon-oxygen-functionalized-polymer-based elastomer) integrated rubber with star-shaped coupling structure and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020120069A1 (en) * 2000-10-19 2002-08-29 Yang Li Star-block interpolymers and preparation of the same
US20100010154A1 (en) * 2008-07-08 2010-01-14 Kraton Polymers U.S. Llc Gels prepared from dpe containing block copolymers
CN113307912A (en) * 2021-05-31 2021-08-27 大连理工大学 Silica functionalized SIBR (silicon-oxygen-functionalized-polymer-based elastomer) integrated rubber with star-shaped coupling structure and preparation method thereof

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