WO2024239555A1 - 星型苯乙烯接枝丁二烯-异戊二烯改性橡胶及其制备方法和应用 - Google Patents

星型苯乙烯接枝丁二烯-异戊二烯改性橡胶及其制备方法和应用 Download PDF

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WO2024239555A1
WO2024239555A1 PCT/CN2023/130991 CN2023130991W WO2024239555A1 WO 2024239555 A1 WO2024239555 A1 WO 2024239555A1 CN 2023130991 W CN2023130991 W CN 2023130991W WO 2024239555 A1 WO2024239555 A1 WO 2024239555A1
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butadiene
isoprene
styrene
rubber
segment
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English (en)
French (fr)
Inventor
史工昌
赵志超
邵卫
王永峰
钟启林
杨海龙
董静
桂强
龚光碧
梁滔
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the invention relates to the field of rubber preparation, and in particular to a star-shaped styrene-grafted butadiene-isoprene modified rubber and a preparation method and application thereof.
  • the copolymer composed of isoprene or butadiene and styrene is generally 23-30%. If the combined styrene content is high, the obtained copolymer has greater plasticity; conversely, the copolymer has greater elasticity.
  • copolymers with a styrene combination content between 45-70% in the molecular structure are called high styrene rubbers, and those with a combined styrene content of more than 70% are called high styrene resins. Since high styrene rubber has a higher combined styrene content, its physical properties are different from general-purpose styrene-butadiene rubber.
  • High styrene rubber is generally rarely used alone. When used in combination with a variety of synthetic rubbers or natural rubbers, it can improve the rigidity, hardness, wear resistance, tear resistance, dielectric properties and other properties of rubber products. It can be widely used in the tire industry, shoemaking industry, printing industry and other industries. It can also be used for the modification of synthetic plastics and is highly valued.
  • the process flow is relatively long and requires two synthesis steps such as preparation of water phase, oil phase, initiator and degassing; secondly, in terms of production cost, since the conversion rate of the synthetic SBR-1500 or SBR-1502 latex monomer is only 70%, the unreacted monomer accounts for 30%, and this part of the monomer is difficult to recover in small and medium-sized production equipment, resulting in high production cost and relatively more equipment, auxiliary raw materials, personnel, time and energy required for the polymerization process; in addition, in terms of production cycle, since the synthesis temperature of the high-styrene resin emulsion is high-temperature polymerization, there are more structural gels in the polymerization kettle, and the polymerization kettle used usually needs to be cleaned once for 10 batches of production, so the equipment utilization rate is low.
  • high styrene rubber can be produced by blending and copolymerization, the polymers have the disadvantages of insufficient tensile strength and hardness, and poor miscibility with natural rubber and styrene-butadiene rubber.
  • the high styrene rubber produced cannot take into account the comprehensive properties of rubber and improve the dynamic mechanical properties of rubber.
  • the process is complicated, the actual operation is difficult, and the reaction The cycle is long, the cost is high, it is easy to generate gel, and it causes environmental pollution and other problems.
  • high styrene rubber is mainly produced at home and abroad by emulsion polymerization of butadiene and styrene monomers.
  • the rolling resistance, anti-skid and wear resistance of the prepared high styrene rubber are poor. Taking into account the comprehensive performance of rubber and improving the dynamic mechanical properties of rubber are problems that need to be solved in this field.
  • the purpose of the present invention is to overcome the problems of poor rolling resistance, wet skid resistance and wear resistance of high styrene rubber in the prior art, and to provide a star-shaped styrene grafted butadiene-isoprene modified rubber and a preparation method and application thereof.
  • the first aspect of the present invention provides a star-shaped styrene-grafted butadiene-isoprene modified rubber, wherein the modified rubber comprises a polymer segment from a coupling agent and a plurality of styrene homopolymer segments and butadiene-isoprene copolymer segments grafted on the polymer segment, wherein the coupling agent is selected from polyvinyl aromatic monomers.
  • the second aspect of the present invention provides a method for preparing a star-shaped styrene-grafted butadiene-isoprene modified rubber, wherein the preparation method comprises:
  • the third aspect of the present invention provides a star-shaped styrene-grafted butadiene-isoprene modified rubber obtained by the preparation method.
  • the present invention provides a star-shaped styrene-grafted butadiene-isoprene modified rubber.
  • a star-shaped styrene-grafted butadiene-isoprene modified rubber From the perspective of the structure of the polymer chain, it is a branched polymer with a star-shaped structure, that is, a plurality of molecular chains are grafted on the polymer segment to form different segments as branches, and similarly connected molecular arms (such as polybutadiene isoprene arms, styrene arms) are called mixed arms.
  • the modified rubber it is equivalent to using the polymer segment formed by the coupling agent to form polybutadiene-isoprene rubber and polystyrene rubber as the core and chaining them together, realizing the combination of different polymer molecular chains at the short-range structural level of the polymer chain, and having good compatibility, stability and adhesion, so that the polymer structure is evenly distributed in the microscopic phase, and acts in coordination with each other, having high hardness, good strength, good branching degree and the physical properties of natural rubber, improving the rubber's anti-slip property and reducing rolling resistance.
  • the invention discloses a method for preparing the star-shaped styrene grafted butadiene-isoprene modified rubber, which has the characteristics of simple process, mild polymerization conditions, stable product performance and good comprehensive performance.
  • FIG. 1 is a schematic diagram of the molecular chain structure of star-shaped styrene-grafted butadiene-isoprene modified rubber.
  • the first aspect of the present invention provides a star-shaped styrene-grafted butadiene-isoprene modified rubber, wherein the modified rubber comprises a polymer segment from a coupling agent and a plurality of styrene homopolymer segments and butadiene-isoprene copolymer segments grafted on the polymer segment, wherein the coupling agent is selected from polyvinyl aromatic monomers.
  • the star-shaped styrene-grafted butadiene-isoprene modified rubber is a branched polymer from the perspective of the structure of the polymer chain, and has a star-shaped structure, wherein the polymer segment formed by the coupling agent serves as a core, and the multiple vinyl functional groups of the coupling agent provide the polymer segment with multiple vinyl groups that can further graft other branches; the butadiene-isoprene copolymer chain and the styrene homopolymer chain can be bonded to the vinyl groups on the polymer segment through the carbon-carbon double bonds contained in each of them, forming a butadiene-isoprene copolymer segment and a styrene homopolymer segment grafted on the polymer segment, that is, a plurality of molecular chains are grafted on the polymer segment to form different segments as branches, and similarly connected molecular arms (such as polybutadiene isoprene arms,
  • the polymer chain segments formed by the coupling agent are used as the core of polybutadiene-isoprene rubber and polystyrene rubber and chained together, realizing the combination of different polymer molecular chains at the short-range structural level of the polymer chain, and having good compatibility, stability and adhesion, so that the polymer structure is evenly distributed in the microscopic phase and acts in coordination with each other, having high hardness, good strength, good branching degree and the physical properties of natural rubber, improving the rubber's anti-skid property and reducing rolling resistance.
  • the molecular arms of the polymer are connected by polymer segments from a coupling agent
  • the coupling agent is selected from polyvinyl aromatic monomers
  • the polyvinyl aromatic monomers form polymer segments with multi-terminal molecular arms by self-polymerization, as shown in Figure 1, so that multiple linear branches are connected to the same central core through chemical bonds, achieving the blending of polymers in molecular structure, making the polymer structure more evenly distributed in the microscopic phase, and the physical and mechanical properties of the rubber are better.
  • PS represents a styrene homopolymer segment
  • PIB represents a butadiene-isoprene copolymer segment.
  • the content of the styrene homopolymer segment is 30-70wt%, and the content of the butadiene-isoprene copolymer segment is 30-70wt%.
  • the content of the styrene homopolymer segment can be selected from 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, and any value in the range consisting of any two of the above values.
  • the content of the butadiene-isoprene copolymer segment can be selected from 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, and any value in the range consisting of any two of the above values.
  • the content of the isoprene structural unit is 50-90 wt %, and the content of the butadiene structural unit is 10-50 wt %.
  • the content of the isoprene structural unit in the butadiene-isoprene copolymer segment can be selected from 50wt%, 60wt%, 70wt%, 80wt%, 90wt%, and any value in the range of any two of the above values.
  • the content of the butadiene structural unit can be selected from 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, and any value in the range of any two of the above values.
  • the total content of 1,4-structural units of isoprene and 1,4-structural units of butadiene is 40-80wt%, and the total content of 3,4-structural units of isoprene and 1,2-structural units of butadiene is 20-60wt%.
  • the total content of 1,4-structural units of isoprene and 1,4-structural units of butadiene can be selected from 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, and any value in the range of any two of the above values.
  • the total content of 3,4-structural units of isoprene and 1,2-structural units of butadiene can be selected from 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, and any value in the range of any two of the above values. Any value in the range.
  • the coupling agent is selected from divinylbenzene.
  • the amount of the coupling agent is relatively small, the polymer segment formed by the coupling agent is used as a core, the core formed by the coupling agent is a macromolecular active species, and the macromolecular active species provides the polymer with multiple reactive active points that can further initiate polymerization of the reaction monomers, thereby initiating polymerization of the monomers to form polymer segments.
  • the proportion of the polymer segment formed by the coupling agent itself is very small relative to the amount of the macromolecular polymer, and the content can be excluded from the polymer proportion.
  • the amount of the coupling agent has been described in the text.
  • the number average molecular weight of the modified rubber is 100,000-600,000 g/mol, and the weight average molecular weight is 200,000-1,000,000 g/mol; the molecular weight distribution index is 1.2-5, and the larger the molecular weight distribution index, the better the rubber processing performance.
  • the molecular weight distribution index of the modified rubber is 1.2-5, the processing performance is good, tan ⁇ (0°C) is 0.22-0.27, tan ⁇ (60°C) is 0.009-0.119, and the coupling efficiency is 60-75%.
  • the second aspect of the present invention provides a method for preparing a star-shaped styrene-grafted butadiene-isoprene modified rubber, wherein the preparation method comprises:
  • the coupling reaction is that the polymer segment formed by the coupling agent and the styrene homopolymer segment are bonded to the vinyl group on the polymer segment through the carbon-carbon double bond contained therein to obtain the active chain.
  • the initiator is selected from one or more of n-butyl lithium, sec-butyl lithium, methylbutyl lithium, phenylbutyl lithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium, preferably selected from n-butyl lithium and/or sec-butyl lithium.
  • the amount of the initiator added is determined by the molecular weight of the designed polymer.
  • the coupling agent is selected from polyvinyl aromatic hydrocarbons, preferably divinyl benzene.
  • the coupling agent can be added once or multiple times. By adding the coupling agent multiple times, the coupling efficiency of the coupling agent can be improved.
  • the polar activator is selected from one or more of diethylene glycol dimethyl ether, tetrahydrofuran, ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, triethylamine, tetramethylethylenediamine and hexamethylphosphonic triamide, preferably selected from one or more of diethylene glycol dimethyl ether, tetrahydrofuran and tetramethylethylenediamine.
  • Polar organic compounds need to be added as activators in the polymerization system of the present invention to make the initiator produce polarization or solvation effects, thereby reducing
  • the activator can reduce the degree of association and increase the initiation reaction rate of initiators such as n-butyl lithium.
  • the activator can also adjust the reactivity ratio of butadiene and isoprene to make the two copolymerize randomly. At the same time, the activator can increase the content of 1,2-structure in butadiene units and 3,4-structure in isoprene units.
  • the mechanical properties of the star-shaped styrene grafted butadiene-isoprene modified rubber are related to the monomer ratio of styrene, isoprene and butadiene and the product molecular weight.
  • the single-arm molecular weight of the high styrene rubber determines the product molecular weight to a certain extent, thereby affecting the product performance.
  • the single-arm number average molecular weight of the styrene homopolymer segment of the present invention is 50,000-150,000 g/mol.
  • the temperature of the homopolymerization reaction is 50-80° C.
  • the pressure of the homopolymerization reaction is 0.1-0.25 MPa
  • the time of the homopolymerization reaction is 20-80 min.
  • the coupling reaction temperature is 50-80° C.
  • the coupling reaction pressure is 0.1-0.25 MPa
  • the coupling reaction time is 60-90 min.
  • the copolymerization reaction temperature is 50-80° C.
  • the copolymerization reaction pressure is 0.1-0.25 MPa
  • the copolymerization reaction time is 60-100 min.
  • the obtained polymer solution is treated with water, and the amount of water used is generally 100-300 times the amount of the initiator used, preferably 150-250 times.
  • 0.5%-1% of the polymer weight of an antioxidant can be added to the obtained star-shaped styrene grafted butadiene-isoprene modified rubber, and then high-performance star-shaped styrene grafted butadiene-isoprene modified rubber is obtained through washing, dehydration and drying.
  • styrene is 30-70 parts by weight
  • the mixed monomer of butadiene and isoprene is 30-70 parts by weight, wherein butadiene accounts for 10-50wt% of the mixed monomer amount, and isoprene accounts for 50-90wt% of the mixed monomer amount.
  • the molar ratio of the polar activator to the initiator is 0.1-30:1.
  • the molar ratio of the coupling agent to the initiator is 0.1-1.5:1.
  • the styrene monomer is 30-70 parts by weight
  • the butadiene and isoprene mixed monomer is 30-70 parts by weight, wherein butadiene accounts for 10-50wt% of the mixed monomer amount, and isoprene accounts for 50-90wt% of the mixed monomer amount.
  • the initiator is 0.0007-0.002 parts by weight.
  • the molar ratio of the polar activator to the initiator is 0.2-20:1.
  • the molar ratio of the coupling agent to the initiator is 0.15-1:1.
  • the composition and structure of the modified rubber can be determined by nuclear magnetic resonance, infrared, GPC, elemental analysis, etc., or by preparing and feeding.
  • the total content of the 1,4-structural unit of isoprene and the 1,4-structural unit of butadiene and the total content of the 3,4-structural unit of isoprene and the 1,2-structural unit of butadiene are measured by infrared spectroscopy.
  • the third aspect of the present invention provides a star-shaped styrene-grafted butadiene-isoprene modified rubber obtained by the preparation method, which may have the aforementioned composition and structural characteristics, which will not be described in detail.
  • the fourth aspect of the present invention provides an application of the star-shaped styrene-grafted butadiene-isoprene modified rubber in the field of rubber processing.
  • DMA Dynamic Mechanical Analysis
  • Mooney viscosity determination using MV2000 Mooney viscometer from Alpha Company of the United States, the Mooney viscosity test is in accordance with GB/T1232.1-2000.
  • the rubber solution is coagulated by a wet method and dried to obtain a modified rubber (in the obtained modified rubber, based on the sum of the weights of the styrene homopolymer segment and the butadiene-isoprene copolymer segment, the content of the styrene homopolymer segment is 50wt%, and the content of the butadiene-isoprene copolymer segment is 50wt%; in the butadiene-isoprene copolymer segment, based on the total weight of the butadiene-isoprene copolymer segment, the content of the isoprene structural unit is 50wt%, and the content of the butadiene structural unit is 50wt%).
  • the rubber solution is coagulated by a wet method and dried to obtain a modified rubber (in the obtained modified rubber, based on the sum of the weights of the styrene homopolymer segment and the butadiene-isoprene copolymer segment, the content of the styrene homopolymer segment is 50wt%, and the content of the butadiene-isoprene copolymer segment is 50wt%; in the butadiene-isoprene copolymer segment, based on the total weight of the butadiene-isoprene copolymer segment, the content of the isoprene structural unit is 50wt%, and the content of the butadiene structural unit is 50wt%).
  • the rubber solution was subjected to wet coagulation and drying to obtain a modified rubber (in the obtained modified rubber, based on the sum of the weights of the styrene homopolymer segment and the butadiene-isoprene copolymer segment, the content of the styrene homopolymer segment is 50 wt%, and the content of the butadiene-isoprene copolymer segment is 50 wt%; in the butadiene-isoprene copolymer segment, based on the total weight of the butadiene-isoprene copolymer segment, the content of the isoprene structural unit is 50 wt%, and the content of the butadiene structural unit is 50 wt%).
  • the sum of the weight of the butadiene-isoprene copolymer segments is 50 wt %, the content of the styrene homopolymer segment is 50 wt %, and the content of the butadiene-isoprene copolymer segment is 50 wt %; in the butadiene-isoprene copolymer segment, based on the total weight of the butadiene-isoprene copolymer segment, the content of the isoprene structural unit is 50 wt %, and the content of the butadiene structural unit is 50 wt %).
  • argon was passed through the system to replace the system three times.
  • 4212g of cyclohexane, 468g of styrene, and 5.85mmol of n-butyl lithium were added to the polymerization reactor, and the temperature was raised to 50°C for polymerization for 80min. After the monomers were completely converted, the temperature was raised to 80°C, and 4.68mmol of divinylbenzene was added twice (70wt% of the total amount of divinylbenzene was added in the first addition, and the remaining 30wt% was added after 30min of reaction) for coupling reaction.
  • the rubber solution was subjected to wet coagulation and drying to obtain a modified rubber (in the obtained modified rubber, based on the sum of the weights of the styrene homopolymer segment and the butadiene-isoprene copolymer segment, the content of the styrene homopolymer segment is 50 wt%, and the content of the butadiene-isoprene copolymer segment is 50 wt%; in the butadiene-isoprene copolymer segment, based on the total weight of the butadiene-isoprene copolymer segment, the content of the isoprene structural unit is 50 wt%, and the content of the butadiene structural unit is 50 wt%).
  • argon was passed through the system to replace the system three times.
  • 4212g of cyclohexane, 468g of styrene, and 11.70mmol of n-butyl lithium were added to the polymerization reactor, and the temperature was raised to 50°C for polymerization for 80min. After the monomers were completely converted, the temperature was raised to 80°C, and 2.34mmol of divinylbenzene was added twice (70wt% of the total amount of divinylbenzene was added in the first addition, and the remaining 30wt% was added after 30min of reaction) for coupling reaction.
  • the rubber solution was subjected to wet coagulation and drying to obtain a modified rubber (in the obtained modified rubber, based on the sum of the weights of the styrene homopolymer segment and the butadiene-isoprene copolymer segment, the content of the styrene homopolymer segment is 50 wt%, and the content of the butadiene-isoprene copolymer segment is 50 wt%; in the butadiene-isoprene copolymer segment, based on the total weight of the butadiene-isoprene copolymer segment, the content of the isoprene structural unit is 50 wt%, and the content of the butadiene structural unit is 50 wt%).
  • argon was passed through the system to replace the system three times.
  • 5054g of cyclohexane, 562g of styrene, and 7.03mmol of n-butyl lithium were added to the polymerization reactor, and the temperature was raised to 50°C for polymerization for 80min. After the monomers were completely converted, the temperature was raised to 80°C, and 2.81mmol of divinylbenzene was added twice (70wt% of the total amount of divinylbenzene was added in the first addition, and the remaining 30wt% was added after 30min of reaction) for coupling reaction.
  • the rubber solution was subjected to wet coagulation and drying to obtain a modified rubber (in the obtained modified rubber, based on the sum of the weights of the styrene homopolymer segment and the butadiene-isoprene copolymer segment, the content of the styrene homopolymer segment is 60 wt %, and the content of the butadiene-isoprene copolymer segment is 40 wt %; in the butadiene-isoprene copolymer segment, based on the total weight of the butadiene-isoprene copolymer segment, the content of the isoprene structural unit is 50 wt %, and the content of the butadiene structural unit is 50 wt %).
  • argon was passed through the system to replace the system three times.
  • 4212g of cyclohexane, 468g of styrene, and 5.85mmol of n-butyl lithium were added to the polymerization reactor, and the temperature was raised to 50°C for polymerization for 80min. After the monomers were completely converted, the temperature was raised to 80°C, and 2.34mmol of divinylbenzene was added three times (50wt% of the total amount of divinylbenzene was added for the first time, 30wt% was added after 15min, and the remaining 20wt% was added after 30min) for coupling reaction.
  • argon was passed through the system to replace the system three times.
  • 8424g cyclohexane, 468g styrene (accounting for 50wt% of the total monomer), 234g butadiene (accounting for 25wt% of the total monomer), 234g isoprene (accounting for 25wt% of the total monomer), 4.21g tetrahydrofuran, 11.70mmol n-butyl lithium were added to the polymerization reactor, the temperature was raised to 50°C, and the polymerization was carried out for 80min.
  • argon was passed through the system to replace the system three times. 4212g cyclohexane, 234g styrene (accounting for 25wt% of the total monomer), 234g isoprene (accounting for 25wt% of the total monomer) and 11.70mmol of n-butyl lithium were added to the polymerization reactor, and polymerization was carried out for 80min.
  • the high styrene rubber HS860 that has been commercialized on the market uses styrene and butadiene as raw materials for the polymerization reaction.
  • the difference lies in that the polymerization method is different.
  • argon was passed through the system to replace the system three times. 4212g cyclohexane, 468g styrene (accounting for 50wt% of the total monomer), 234g butadiene (accounting for 25wt% of the total monomer), 234g isoprene (accounting for 25wt% of the total monomer), 4.21g tetrahydrofuran, 11.70mmol n-butyl lithium were added to the polymerization reactor, the temperature was raised to 50°C, and the polymerization was carried out for 80min.
  • the high styrene rubber obtained by the methods of Examples 1-10 and Comparative Examples 1-7 has a rubber molecular weight and a microstructure content as shown in Table 1.
  • Ip-1,4 and Ip-3,4 represent the 1,4-structure and 3,4-structure of isoprene, respectively
  • Bd-1,4 and Bd-1,2 represent the 1,4-structure and 1,2-structure of butadiene, respectively
  • the polar activators tetrahydrofuran, diethylene glycol dimethyl ether and tetramethylethylenediamine can increase the content of 1,2-structure in butadiene units and 3,4-structure in isoprene units. It can be seen from the examples that the ability of the polar activator to adjust the 1,2-structure in butadiene units and the 3,4-structure in isoprene units is that tetramethylethylenediamine is greater than diethylene glycol dimethyl ether and greater than tetrahydrofuran.
  • the mixed arms Due to the presence of the mixed arms, it is equivalent to linking the styrene homopolymer segment and the butadiene-isoprene copolymer segment with different microstructures to the same molecular chain, realizing the blending of polymers in molecular structure, improving the performance of rubber and its vulcanization, promoting the coordinated optimization of various performances of the product, and improving the hardness and dynamic mechanical properties of the product.
  • the isoprene structural unit in the polymer is very similar to that of natural rubber, so that the product has the characteristics of performance and use closer to natural rubber. In application, it can be better mixed with natural rubber and styrene-butadiene rubber, fully improving the compatibility and reducing the phase separation of the blended rubber.
  • a mixing arm is formed, and the styrene homopolymer segment and the butadiene-isoprene copolymer segment with different microstructures are linked to the same molecular chain, thereby achieving the blending of the polymers in the molecular structure, making the polymer structure evenly distributed in the microphase and coordinating with each other, thus avoiding the shortcomings of uneven distribution, poor product quality and performance, and high energy consumption when the star-shaped styrene grafted butadiene-isoprene modified rubber is mechanically mixed with natural rubber.
  • the star-shaped high styrene rubber of the present invention has high hardness and good strength.
  • the formed polymer has a high degree of branching and has the physical properties of natural rubber, thereby achieving the blending of the polymers in the molecular structure.
  • it can improve the rigidity, hardness, wear resistance, tear resistance, dielectric properties and other properties of rubber products. It is widely used in many rubber processing fields such as tires, belts, hoses, rubber shoes and other industries.
  • the method for preparing the star-shaped styrene grafted butadiene-isoprene modified rubber provided by the present invention has the characteristics of simple process, mild polymerization conditions, high coupling efficiency, stable product performance, and good comprehensive performance.
  • the coupling efficiency of the embodiment is higher than that of the comparative example, indicating that the better the coupling performance of divinylbenzene, the greater the activity of the macromolecular active species formed, the more linear branches connected to the central core formed by divinylbenzene by chemical bonds, and the higher the branching degree of the star-shaped polymer formed.
  • the performance of the embodiment is better than that of the comparative example in many aspects, the tensile strength and elongation at break of the embodiment are higher than those of the comparative example, the hardness of the embodiment is relatively high, the Mooney viscosity of the embodiment is also slightly better, and the permanent deformation of the embodiment is slightly lower than that of the comparative example. Therefore, it can be seen that the synthesized star-shaped styrene-grafted butadiene-isoprene modified rubber has excellent dynamic mechanical properties.

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Abstract

本发明涉及橡胶制备领域，公开了一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶及其制备方法和应用。所述改性橡胶包含来自偶联剂的聚合链段以及接枝在所述聚合链段上的多个苯乙烯均聚链段和丁二烯-异戊二烯共聚链段，其中，所述偶联剂选自多乙烯基芳烃类单体。通过聚合过程中结构设计，形成混合臂，使聚合物结构在微观相上分布均匀，相互协调作用，具有高硬度，强度好，支化度好且又具有天然橡胶的物理性能，提高橡胶抗湿滑性，降低滚动阻力，在与多种合成橡胶或天然橡胶并用时，能够提高橡胶制品的刚性、硬度、耐磨性、抗撕裂性、介电性等性能，广泛用于轮胎、胶带、胶管、胶鞋等众多橡胶加工领域及其它工业。

Description

星型苯乙烯接枝丁二烯-异戊二烯改性橡胶及其制备方法和应用
相关申请的交叉引用
本申请要求2023年05月23日提交的中国专利申请202310589831.6的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及橡胶制备领域，具体涉及一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶及其制备方法和应用。
背景技术
异戊二烯或丁二烯和苯乙烯组成的共聚物，结合苯乙烯一般为23-30％，若结合苯乙烯含量高，得到的共聚物塑性较大；反之，则共聚物的弹性较大。通常把分子结构中苯乙烯结合量在45-70％之间的共聚物称为高苯乙烯橡胶，结合苯乙烯量在70％以上者称为高苯乙烯树脂。由于高苯乙烯橡胶的结合苯乙烯量较高，因此其物性不同于通用型丁苯橡胶。高苯乙烯橡胶一般很少单独使用，在与多种合成橡胶或天然橡胶并用时，能够提高橡胶制品的刚性、硬度、耐磨性、抗撕裂性、介电性等性能，可广泛应用于轮胎工业、制鞋工业、印刷工业及其它工业，也可用于合成塑料的改性，而倍受重视。
现有技术中大多采用胶乳共凝聚技术，虽然这种工艺过程能够得到性能较好的高苯乙烯橡胶，但该法存在的主要问题是：首先在工艺上，需要先分别合成SBR-1500或SBR-1502胶乳和高苯乙烯树脂乳液，将分析合格的两种乳液按一定比例再进行混合，然后经凝聚干燥得到高苯乙烯橡胶，其工艺流程相对较长需要两次水相、油相、引发剂的配制及脱气等合成工序；其次在生产成本上，由于合成SBR-1500或SBR-1502胶乳单体转化率仅70％，未反应单体占30％，且这部分单体在中小规模的生产装置中难以回收，导致生产成本较高且聚合反应过程所需的设备、辅助原料、人员、时间、能源相对较多；另外在生产周期上，由于高苯乙烯树脂乳液的合成温度为高温聚合，聚合釜内结构凝胶较多，所用的聚合釜通常生产10批次需要进行一次清釜作业，因此设备利用率较低。
虽然通过共混法、共聚法可以生产出高苯乙烯橡胶，但是聚合物都存在产品拉伸强度及硬度不够高的缺点，与天然橡胶、丁苯橡胶混溶性不好的问题，所生产的高苯乙烯橡胶无法兼顾橡胶的综合性能以及提高橡胶的动态力学性能。并且还存在工艺复杂，实际操作困难，反应 周期长，成本高，容易生成凝胶，造成环境污染等问题。
现有技术中，国内外生产高苯乙烯橡胶主要采用丁二烯和苯乙烯单体进行乳液聚合反应制得，制备的高苯乙烯橡胶的滚动阻力、抗湿滑性和耐磨性较差，兼顾橡胶的综合性能以及提高了橡胶的动态力学性能是本领域需要解决的问题。
发明内容
本发明的目的是为了克服现有技术存在的高苯乙烯橡胶的滚动阻力、抗湿滑性和耐磨性较差的问题，提供一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶及其制备方法和应用。
为了实现上述目的，本发明第一方面提供一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶，其中，所述改性橡胶包含来自偶联剂的聚合链段以及接枝在所述聚合链段上的多个苯乙烯均聚链段和丁二烯-异戊二烯共聚链段，其中，所述偶联剂选自多乙烯基芳烃类单体。
本发明第二方面提供一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶的制备方法，其中，所述制备方法包括：
(1)在引发剂存在下，苯乙烯进行均聚反应，得到活性苯乙烯均聚段；
(2)将所述活性苯乙烯均聚段与偶联剂进行偶联反应，得到活性链；
(3)在极性活化剂存在下，将所述活性链、丁二烯和异戊二烯进行共聚反应，得到所述星型混合臂高苯乙烯橡胶。
本发明第三方面提供一种所述的制备方法得到的星型苯乙烯接枝丁二烯-异戊二烯改性橡胶。
本发明第四方面提供一种所述的星型苯乙烯接枝丁二烯-异戊二烯改性橡胶在橡胶加工领域中的应用。
通过上述技术方案，本发明提供了一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶从高分子链的构造上看，为支化高聚物，具有星型结构，即在所述聚合链段上接枝有多条分子链组成不同的链段作为支链，类似连接的分子臂(如聚丁二烯异戊二烯臂，苯乙烯臂)，称为混合臂。所述改性橡胶中，相当于将聚丁二烯-异戊二烯橡胶和聚苯乙烯橡胶通过所述偶联剂形成的聚合链段当作的核心而链合在一起，实现了不同聚合物分子链在高分子链的近程结构层面上的结合，能够具有良好的相容性、稳定性和粘合性，使聚合物结构在微观相上分布均匀，相互协调作用，具有高硬度，强度好，支化度好且又具有天然橡胶的物理性能，提高橡胶抗湿滑性，降低滚动阻力。在与多种合成橡胶或天然橡胶并用时，能够提高橡胶制品的刚性、硬度、耐磨性、 抗撕裂性、介电性等性能，广泛用于轮胎、胶带、胶管、胶鞋等众多橡胶加工领域及其它工业。本发明所提供的制备该星型苯乙烯接枝丁二烯-异戊二烯改性橡胶的方法具有工艺简单，聚合条件温和，产品性能稳定，综合性能良好的特点。
附图说明
图1是星型苯乙烯接枝丁二烯-异戊二烯改性橡胶分子链结构示意图。
附图标记说明
PS-代表苯乙烯均聚链段，PIB-代表丁二烯-异戊二烯共聚链段。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶，其中，所述改性橡胶包含来自偶联剂的聚合链段以及接枝在所述聚合链段上的多个苯乙烯均聚链段和丁二烯-异戊二烯共聚链段，其中，所述偶联剂选自多乙烯基芳烃类单体。
在本发明中，提供的所述星型苯乙烯接枝丁二烯-异戊二烯改性橡胶从高分子链的构造上看为支化高聚物，具有星型结构，其中，所述偶联剂形成的聚合链段当作核心，所述偶联剂具有的多个乙烯基官能团为所述聚合链段提供多个能够进一步接枝其他支链的乙烯基；丁二烯-异戊二烯共聚物链和苯乙烯均聚链可以通过各自含有的碳碳双键与所述聚合链段上的乙烯基进行键合，形成接枝在所述聚合链段上的丁二烯-异戊二烯共聚链段和苯乙烯均聚链段，即在所述聚合链段上接枝有多条分子链组成不同的链段作为支链，类似连接的分子臂(如聚丁二烯异戊二烯臂，苯乙烯臂)，称为混合臂。所述改性橡胶中，相当于将聚丁二烯-异戊二烯橡胶和聚苯乙烯橡胶通过所述偶联剂形成的聚合链段当作的核心而链合在一起，实现了不同聚合物分子链在高分子链的近程结构层面上的结合，能够具有良好的相容性、稳定性和粘合性，使聚合物结构在微观相上分布均匀，相互协调作用，具有高硬度，强度好，支化度好且又具有天然橡胶的物理性能，提高橡胶抗湿滑性，降低滚动阻力。
在本发明中，所述聚合物的分子臂通过来自偶联剂的聚合链段连接，偶联剂选自多乙烯基芳烃类单体，多乙烯基芳烃类单体通过自身聚合形成具有多端分子臂的聚合链段，如图1所示，使多个线型支链通过化学键连接到同一个中心核上，实现了聚合物在分子结构上的共混，使聚合物结构在微观相上分布更均匀，橡胶的物理机械性能更佳。其中PS代表苯乙烯均聚链段，PIB代表丁二烯-异戊二烯共聚链段。
在本发明一些具体实施方式中，所述改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，所述苯乙烯均聚链段的含量为30-70wt％，所述丁二烯-异戊二烯共聚链段的含量为30-70wt％。通过限定上述含量的改性橡胶，实现了不同聚合物分子链在高分子链的近程结构层面上的结合，能够具有良好的相容性、稳定性和粘合性，使聚合物结构在微观相上分布均匀，相互协调作用，具有高硬度，强度好。
在本发明一些具体实施方式中，所述改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，所述苯乙烯均聚链段的含量可选择30wt％、40wt％、50wt％、60wt％、70wt％，以及上述任意两个数值组成的范围中的任意值。所述丁二烯-异戊二烯共聚链段的含量可选择30wt％、40wt％、50wt％、60wt％、70wt％，以及上述任意两个数值组成的范围中的任意值。
在本发明一些具体实施方式中，所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50-90wt％，丁二烯结构单元的含量为10-50wt％。
在本发明一些具体实施方式中，所述丁二烯-异戊二烯共聚链段中，异戊二烯结构单元的含量可选择50wt％、60wt％、70wt％、80wt％、90wt％，以及上述任意两个数值组成的范围中的任意值。丁二烯结构单元的含量可选择10wt％、20wt％、30wt％、40wt％、50wt％，以及上述任意两个数值组成的范围中的任意值。
在本发明一些具体实施方式中，所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯的1,4-结构单元和丁二烯的1,4-结构单元的总含量为40-80wt％，异戊二烯的3,4-结构单元和丁二烯的1,2-结构单元的总含量为20-60wt％。
在本发明一些具体实施方式中，所述丁二烯-异戊二烯共聚链段中，异戊二烯的1,4-结构单元和丁二烯的1,4-结构单元的总含量可选择40wt％、50wt％、60wt％、70wt％、80wt％，以及上述任意两个数值组成的范围中的任意值。异戊二烯的3,4-结构单元和丁二烯的1,2-结构单元的总含量可选择20wt％、30wt％、40wt％、50wt％、60wt％，以及上述任意两个数值组成的 范围中的任意值。
在本发明一些具体实施方式中，优选地，所述偶联剂选自二乙烯基苯。
在本发明一些具体实施方式中，所述改性液体丁苯橡胶中，所述偶联剂的用量较少，所述偶联剂形成的聚合链段当作核心，所述偶联剂形成的核心为大分子活性种，大分子活性种为聚合物提供多个能够进一步引发反应单体聚合的反应活性点，从而引发单体聚合形成聚合物链段，偶联剂自身形成的聚合链段的占比相对于大分子聚合物的量很少，含量可以不计入聚合物占比中，偶联剂用量已在文中进行说明。
在本发明一些具体实施方式中，所述改性橡胶的数均分子量为10万-60万g/mol，重均分子量为20万-100万g/mol；分子量分布指数为1.2-5，分子量分布指数越大，橡胶加工性能更好，改性橡胶的分子量分布指数为1.2-5，加工性能较好，tanδ(0℃)为0.22-0.27，tanδ(60℃)为0.009-0.119，偶联效率为60-75％。
本发明第二方面提供一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶的制备方法，其中，所述制备方法包括：
(1)在引发剂存在下，苯乙烯进行均聚反应，得到活性苯乙烯均聚段；
(2)将所述活性苯乙烯均聚段与偶联剂进行偶联反应，得到活性链；
(3)在极性活化剂存在下，将所述活性链、丁二烯和异戊二烯进行共聚反应，得到所述星型混合臂高苯乙烯橡胶。
在本发明一些具体实施方式中，所述偶联反应为所述偶联剂形成的聚合链段与苯乙烯均聚段通过含有的碳碳双键与所述聚合链段上的乙烯基进行键合，得到所述活性链。
在本发明一些具体实施方式中，所述引发剂选自正丁基锂、仲丁基锂、甲基丁基锂、苯基丁基锂、萘锂、环己基锂和十二烷基锂中的一种或几种，优选选自正丁基锂和/或仲丁基锂。引发剂的加入量由设计的聚合物的分子量决定。
在本发明一些具体实施方式中，所述偶联剂选自多乙烯基芳烃类，优选选自二乙烯基苯。偶联反应过程中，偶联剂可以一次加入，也可以多次加入。通过多次加入偶联剂，可以提高偶联剂的偶联效率。
在本发明一些具体实施方式中，所述极性活化剂选自二乙二醇二甲醚、四氢呋喃、乙醚、乙基甲醚、苯甲醚、二苯醚、乙二醇二甲醚、三乙胺、四甲基乙烯基二胺和六甲基膦酰三胺中的一种或几种，优选选自二乙二醇二甲醚、四氢呋喃和四甲基乙烯基二胺中的一种或几种。本发明所述聚合系统中需加入极性有机化合物作为活性剂，使引发剂产生极化或溶剂化效应，降 低其缔合度，提高引发剂如正丁基锂的引发反应速度，活化剂还能调节丁二烯与异戊二烯的竞聚率，使二者无规共聚，同时活化剂能提高丁二烯单元中1,2-结构和异戊二烯单元中3,4-结构含量。
在本发明一些具体实施方式中，星型苯乙烯接枝丁二烯-异戊二烯改性橡的力学性能与苯乙烯、异戊二烯以及丁二烯的单体配比及产品分子量相关。一般来说，苯乙烯含量高，其硬度高，扯断伸长率小；异戊二烯和丁二烯含量高，其硬度低，扯断伸长率高。同时，高苯乙烯橡胶的单臂分子量在一定程度上决定产品分子量，从而影响产品性能。本发明苯乙烯均聚链段的单臂数均分子量为50000-150000g/mol。
在本发明一些具体实施方式中，所述均聚反应的温度为50-80℃，均聚反应的压力为0.1-0.25MPa，均聚反应的时间为20-80min。
在本发明一些具体实施方式中，所述偶联反应的温度为50-80℃，偶联反应的压力为0.1-0.25MPa，偶联反应的时间为60-90min。
在本发明一些具体实施方式中，所述共聚反应的温度为50-80℃，共聚反应的压力为0.1-0.25MPa，共聚反应的时间为60-100min。
在本发明一些具体实施方式中，所述星型苯乙烯接枝丁二烯-异戊二烯改性橡胶聚合物的偶联效率为61-74％。偶联效率通过将偶联得到的混合物进行GPC分析，对应于偶联形成的聚合物的峰面积与偶联形成的聚合物的峰面积以及偶联后剩余的共聚物的峰面积之和的比值即为偶联效率(CE)。偶联效率越高，说明二乙烯基苯的偶联性能越好，形成的大分子活性种的活性也越大，通过化学键连接到二乙烯基苯形成的中心核上的线型支链数也越多。
在本发明一些具体实施方式中，反应完全后，将得到的聚合物溶液用水处理，水的用量一般为引发剂用量的100-300倍，优选为150-250倍。
在本发明一些具体实施方式中，在得到的星型苯乙烯接枝丁二烯-异戊二烯改性橡胶中可以加入聚合物重量0.5％-1％的防老剂，然后经洗涤、脱水、干燥得到高性能星型苯乙烯接枝丁二烯-异戊二烯改性橡胶。
在本发明一些具体实施方式中，苯乙烯为30-70重量份，所述丁二烯和异戊二烯混合单体为30-70重量份，其中，丁二烯占所述混合单体用量的10-50wt％，异戊二烯占所述混合单体用量的50-90wt％。
在本发明一些具体实施方式中，所述引发剂为0.0005-0.002重量份，
在本发明一些具体实施方式中，所述极性活化剂与所述引发剂的摩尔比为0.1-30：1。
在本发明一些具体实施方式中，所述偶联剂与所述引发剂的摩尔比为0.1-1.5：1。
在本发明一些具体实施方式中，优选地，苯乙烯单体为30-70重量份，丁二烯和异戊二烯混合单体为30-70重量份，其中，丁二烯占所述混合单体用量的10-50wt％，异戊二烯占所述混合单体用量的50-90wt％。
在本发明一些具体实施方式中，优选地，所述引发剂为0.0007-0.002重量份。
在本发明一些具体实施方式中，优选地，所述极性活化剂与所述引发剂的摩尔比为0.2-20：1。
在本发明一些具体实施方式中，优选地，所述偶联剂与所述引发剂的摩尔比为0.15-1：1。
本发明中，所述改性橡胶的组成和结构可以通过核磁、红外、GPC、元素分析等测定确定，或者通过制备投料确定，所述异戊二烯的1,4-结构单元和丁二烯的1,4-结构单元的总含量以及异戊二烯的3,4-结构单元和丁二烯的1,2-结构单元的总含量通过红外光谱测得。
本发明第三方面提供一种所述的制备方法得到的星型苯乙烯接枝丁二烯-异戊二烯改性橡胶。可以具有前述的组成和结构特征，不再赘述。
本发明第四方面提供一种所述的星型苯乙烯接枝丁二烯-异戊二烯改性橡胶在橡胶加工领域中的应用。
以下将通过实施例对本发明进行详细描述。
分子量和偶联效率的测定：采用美国Agilent技术公司生产的Viscoteck TDA302型凝胶渗透色谱(GPC)分析试样的分子量及其分布，以THF为流动相，测试温度为30℃。
傅里叶变换红外光谱(FTIR)分析：采用美国Nicolet560型FTIR仪进行分析，不需纯化，用溴化钾压片涂膜。用于测定改性橡胶中的苯乙烯结构含量、丁二烯结构含量以及异戊二烯结构含量。
动态力学分析(DMA)：用法国01db-Metravib公司生产的Va3000型动态热机械分析(DMA)仪测试试样的动态力学性能，条件为剪切型、形变幅度5％。
力学机械性能分析：用美国Instron公司生产的5567型万能材料试验机测试试样的力学性能。
门尼粘度测定：用美国阿尔法公司的MV2000型门尼粘度计，门尼粘度测试按照GB/T1232.1－2000。
以下实施例和对比例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购途径获得的常规产品。以下实施例和对比例所述改性橡胶的组成和结构可以通过核磁、红外、GPC、元素分析等测定确定，或者通过制备投料确定。
实施例1
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，468g苯乙烯，加入5.85mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，加入2.34mmol二乙烯基苯继续进行偶联，反应60min后，再将2.11g的四氢呋喃，4212g环己烷和234g丁二烯、234g异戊二烯的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为50wt％，丁二烯-异戊二烯共聚链段的含量为50wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
实施例2
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，468g苯乙烯(占单体总量的50wt％)，加入5.85mmol的正丁基锂，升温至50℃，聚 合80min，单体完全转化后升温至80℃，加入2.34mmol二乙烯基苯继续进行偶联，反应60min后，再将0.339g四甲基乙烯基二胺，4212g环己烷和234g丁二烯(占混合单体用量的50wt％)、234g异戊二烯(占混合单体用量的50wt％)的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为50wt％，丁二烯-异戊二烯共聚链段的含量为50wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
实施例3
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，468g苯乙烯，加入5.85mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，加入2.34mmol二乙烯基苯继续进行偶联，反应60min后，再将0.392g二乙二醇二甲醚(2G)，4212g环己烷和234g丁二烯、234g异戊二烯的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，加入10g抗氧剂1076，5g抗氧剂1010，搅拌均匀，胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为50wt％，丁二烯-异戊二烯共聚链段的含量为50wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
实施例4
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，468g苯乙烯，加入5.85mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，分二次加入2.34mmol二乙烯基苯(第一次加入二乙烯基苯总量的70wt％，反应30min后加入剩余的30wt％)进行偶联反应，反应80min后，再将2.11g的四氢呋喃，4212g环己烷和234g丁二烯、234g异戊二烯的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量 之和，苯乙烯均聚链段的含量为50wt％，丁二烯-异戊二烯共聚链段的含量为50wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
实施例5
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，468g苯乙烯，加入5.85mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，分二次加入4.68mmol二乙烯基苯(第一次加入二乙烯基苯总量的70wt％，反应30min后加入剩余的30wt％)进行偶联反应，反应80min后，再将2.11g的四氢呋喃，4212g环己烷和234g丁二烯、234g异戊二烯的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，加入10g抗氧剂1076，5g抗氧剂1010，搅拌均匀，胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为50wt％，丁二烯-异戊二烯共聚链段的含量为50wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
实施例6
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，468g苯乙烯，加入11.70mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，分二次加入2.34mmol二乙烯基苯(第一次加入二乙烯基苯总量的70wt％，反应30min后加入剩余的30wt％)进行偶联反应，反应80min后，再将4.22g的四氢呋喃，4212g环己烷和234g丁二烯、234g异戊二烯的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，加入10g抗氧剂1076，5g抗氧剂1010，搅拌均匀，胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为50wt％，丁二烯-异戊二烯共聚链段的含量为50wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
实施例7
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入环己烷5054g，苯乙烯562g，加入7.03mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，分二次加入2.81mmol二乙烯基苯(第一次加入二乙烯基苯总量的70wt％，反应30min后加入剩余的30wt％)进行偶联反应，反应80min后，再将2.54g的四氢呋喃，3370g环己烷和187g丁二烯、187g异戊二烯的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，加入10g抗氧剂1076，5g抗氧剂1010，搅拌均匀，胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为60wt％，丁二烯-异戊二烯共聚链段的含量为40wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
实施例8
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入环己烷5475g，苯乙烯608g，加入7.60mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，分二次加入3.04mmol二乙烯基苯(第一次加入二乙烯基苯总量的70wt％，反应30min后加入剩余的30wt％)进行偶联反应，反应80min后，再将2.74g的四氢呋喃，2949g环己烷和131g丁二烯、196g异戊二烯的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，加入10g抗氧剂1076，5g抗氧剂1010，搅拌均匀，胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为65wt％，丁二烯-异戊二烯共聚链段的含量为35wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为40wt％，丁二烯结构单元的含量为60wt％)。
实施例9
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，468g苯乙烯，加入5.85mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，分三次加入2.34mmol二乙烯基苯(第一次加入二乙烯基苯总量的50wt％，15min后加入30wt％，30min后加入剩余的20wt％)进行偶联反应，反应80min后，再将0.39g二乙二醇二甲醚(2G)，4212g环己烷和234g丁二烯、234g异戊二烯的混合物压入聚合釜，继续 反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，加入10g抗氧剂1076，5g抗氧剂1010，搅拌均匀，胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为50wt％，丁二烯-异戊二烯共聚链段的含量为50wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
实施例10
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g戊烷，468g苯乙烯，加入5.85mmol的正丁基锂，升温至50℃，聚合60min，单体完全转化后，分二次加入2.34mmol二乙烯基苯(第一次加入二乙烯基苯总量的50wt％，反应30min后加入剩余的50wt％)进行偶联反应，反应80min后，再将2.11g的四氢呋喃，4212g戊烷和234g丁二烯、234g异戊二烯的混合物压入聚合釜，继续反应60min，反应完成后用水处理偶联后的反应混合物，加入100g水，加入15g抗氧剂1010，搅拌均匀，胶液经湿法凝聚、烘干得到改性橡胶(所得改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，苯乙烯均聚链段的含量为50wt％，丁二烯-异戊二烯共聚链段的含量为50wt％；所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50wt％，丁二烯结构单元的含量为50wt％)。
对比例1
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入8424g环己烷，468g苯乙烯(占单体总量的50wt％)、234g丁二烯(占单体总量的25wt％)、234g异戊二烯(占单体总量的25wt％)，4.21g的四氢呋喃，加入11.70mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，反应至聚合反应中无游离单体存在，加入2.93mmol的SnCl4偶联剂进行偶联反应，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干。
对比例2
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环 己烷，苯乙烯234g(占单体总量的25wt％)，丁二烯234g(占单体总量的25wt％)，加入11.70mmol的正丁基锂，聚合80min，再将0.679g四甲基乙烯基二胺，4212g环己烷和234g苯乙烯(占单体总量的25wt％)，234g丁二烯(占单体总量的25wt％)的混合物压入聚合釜继续反应60min，单体完全转化后，加入2.93mmol的SnCl4偶联剂进行偶联反应，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干。
对比例3
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，苯乙烯234g(占单体总量的25wt％)，异戊二烯234g(占单体总量的25wt％)，加入11.70mmol的正丁基锂，聚合80min，再将0.784g二乙二醇二甲醚，4212g环己烷和234g苯乙烯(占单体总量的25wt％)，234g异戊二烯(占单体总量的25wt％)的混合物压入聚合釜继续反应60min，单体完全转化后，加入2.93mmol的SnCl4偶联剂进行偶联反应，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干。
对比例4
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入8424g环己烷，468g苯乙烯(占单体总量的50wt％)、234g丁二烯(占单体总量的25wt％)、234g异戊二烯(占单体总量的25wt％)，4.21g的四氢呋喃，加入11.70mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，反应至聚合反应中无游离单体存在，分二次加入2.93mmol的SnCl4(第一次加入SnCl4总量的80wt％，反应30min后加入剩余的20wt％)进行偶联反应，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干。
对比例5
市场上已商品化的高苯乙烯橡胶HS860，聚合反应原料采用苯乙烯、丁二烯，不同之处在于：聚合方法不同，首先乳液聚合制备高苯乙烯树脂(苯乙烯/丁二烯＝80/20)，然后与乳聚丁苯橡胶(苯乙烯/丁二烯＝23/77)掺混，最后制得高苯乙烯橡胶。
对比例6
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入环己烷5054g，苯乙烯562g(占单体总量的60wt％)，加入11.70mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，再将4.21g的四氢呋喃，1685g环己烷和187g异戊二烯(占单体总量的20wt％)的混合物压入聚合釜，继续反应60min，单体完全转化后向聚合釜中加入1685g环己烷和187g丁二烯(占单体总量的20wt％)，反应完全后加入2.93mmol的SnCl4偶联剂进行偶联反应，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干。
对比例7
在带有夹套的15L不锈钢反应釜中，通氩气将系统置换3次。向聚合釜中加入4212g环己烷，468g苯乙烯(占单体总量的50wt％)、234g丁二烯(占单体总量的25wt％)、234g异戊二烯(占单体总量的25wt％)，4.21g的四氢呋喃，加入11.70mmol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃，反应至聚合反应中无游离单体存在，加入2.93mmol的二乙烯基苯进行偶联反应，反应完成后用水处理偶联后的反应混合物，加入100g水，12g抗氧剂1010，搅拌。胶液经湿法凝聚、烘干。
按照实施例1-10以及对比例1-7的方法得到的高苯乙烯橡胶，橡胶分子量及微观结构含量如表1所示。(Ip-1,4和Ip-3,4分别代表异戊二烯的1,4-结构和3,4-结构，Bd-1,4和Bd-1,2分别代表丁二烯的1,4-结构和1,2-结构)
表1
表1(续表)

表1(续表)
从表1可以看出，极性活化剂四氢呋喃、二乙二醇二甲醚和四甲基乙烯基二胺能够提高丁二烯单元中1,2-结构和异戊二烯单元中3,4-结构的含量。从实施例中可以看出极性活化剂调节丁二烯单元中1,2-结构和异戊二烯单元中3,4-结构的能力是四甲基乙烯基二胺大于二乙二醇二甲醚大于四氢呋喃的能力。
按照实施例1-10以及对比例1-7的方法得到的液体橡胶，测试性能结果如表2所示。
表2
表2(续表)
表2(续表)
表2(续表)
通过表2的结果可以看出，在星型苯乙烯接枝丁二烯-异戊二烯改性橡胶的合成过程中，采用二次加料(苯乙烯均聚链段单体加料和丁二烯-异戊二烯共聚链段单体加料)的方法合成具有混合臂(如聚苯乙烯臂，丁二烯异戊二烯共聚物臂)，以及不同丁二烯单元中1,2-结构和异戊二烯单元中3,4-结构含量的星型苯乙烯接枝丁二烯-异戊二烯改性橡胶，由于混合臂的存在，使其相当于将苯乙烯均聚链段和不同微观结构的丁二烯-异戊二烯共聚链段链合到同一分子链上，实现了聚合物在分子结构上的共混，改善橡胶及其硫化的性能，能促进产品各种性能的协同优化，提高产品的硬度以及动态力学性能。聚合物中异戊二烯结构单元与天然橡胶的结构单元很相似，使产品具有性能及用途与天然橡胶更接近的特点，在应用中可以更好的和天然橡胶和丁苯橡胶混合，充分提高相容性，降低共混橡胶的相分离。并且通过聚合过程中结构设计，形成混合臂，将苯乙烯均聚链段和不同微观结构的丁二烯-异戊二烯共聚链段链合到同一分子链上，实现了聚合物在分子结构上的共混，使聚合物结构在微观相上分布均匀，相互协调作用，避免了星型苯乙烯接枝丁二烯-异戊二烯改性橡胶与天然橡胶机械混炼时，分布不均匀，产品质量和性能较差，能耗大等缺点。本发明的星型高苯乙烯橡胶具有高硬度，强度好，形成的聚合物支化度高且又具有天然橡胶的物理性能，实现了聚合物在分子结构上的共混，在与多 种合成橡胶或天然橡胶并用时，能够提高橡胶制品的刚性、硬度、耐磨性、抗撕裂性、介电性等性能，广泛用于轮胎、胶带、胶管、胶鞋等众多橡胶加工领域及其它工业。
本发明所提供的制备该星型苯乙烯接枝丁二烯-异戊二烯改性橡胶的方法具有工艺简单，聚合条件温和，偶联效率高，产品性能稳定，综合性能良好的特点，同时tanδ/0℃值越大，表明橡胶的抗湿滑性越好，tanδ/60℃值越小，表明橡胶的滚动阻力越小，由表2可以看出，本申请实施例的橡胶的tanδ/0℃值均好于对比例，说明实施例的橡胶抗湿滑性能更好，实施例橡胶的tanδ/60℃值均小于对比例，说明实施例的橡胶滚动阻力更小。其中，实施例1、3、5的抗湿滑性能和滚动阻力更好一些。
由表2可以看出，实施例相比于对比例的偶联效率高，说明二乙烯基苯的偶联性能越好，形成的大分子活性种的活性也越大，通过化学键连接到二乙烯基苯形成的中心核上的线型支链数也越多，形成的星型聚合物支化度高。由表2可以看出，实施例的性能在多个方面均优于对比例，实施例的拉伸强度、断裂伸长率相比于对比例要高，实施例的硬度相对较高，实施例的门尼黏度也较略好，实施例的永久变形比对比例略低。因此可以看出合成的星型苯乙烯接枝丁二烯-异戊二烯改性橡胶具有优良的动态力学性能。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶，其特征在于，所述改性橡胶包含来自偶联剂的聚合链段以及接枝在所述聚合链段上的多个苯乙烯均聚链段和丁二烯-异戊二烯共聚链段，其中，所述偶联剂选自多乙烯基芳烃类单体。
  2. 根据权利要求1所述的改性橡胶，其特征在于，所述改性橡胶中，基于所述苯乙烯均聚链段和丁二烯-异戊二烯共聚链段的重量之和，所述苯乙烯均聚链段的含量为30-70wt％，所述丁二烯-异戊二烯共聚链段的含量为30-70wt％；
    优选地，所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯结构单元的含量为50-90wt％，丁二烯结构单元的含量为10-50wt％；
    优选地，所述丁二烯-异戊二烯共聚链段中，基于所述丁二烯-异戊二烯共聚链段的总重量，异戊二烯的1,4-结构单元和丁二烯的1,4-结构单元的总含量为40-80wt％，异戊二烯的3,4-结构单元和丁二烯的1,2-结构单元的总含量为20-60wt％；
    优选地，所述偶联剂选自二乙烯基苯。
  3. 根据权利要求1或2所述的改性橡胶，其特征在于，所述改性橡胶的数均分子量为10万-60万g/mol，重均分子量为20万-100万g/mol；分子量分布指数为1.2-5，tanδ(0℃)为0.22-0.27，tanδ(60℃)为0.009-0.119，偶联效率为60-75％。
  4. 一种星型苯乙烯接枝丁二烯-异戊二烯改性橡胶的制备方法，其特征在于，所述制备方法包括：
    (1)在引发剂存在下，苯乙烯进行均聚反应，得到活性苯乙烯均聚段；
    (2)将所述活性苯乙烯均聚段与偶联剂进行偶联反应，得到活性链；
    (3)在极性活化剂存在下，将所述活性链、丁二烯和异戊二烯进行共聚反应，得到所述星型苯乙烯接枝丁二烯-异戊二烯改性橡胶。
  5. 根据权利要求4所述的制备方法，其特征在于，所述引发剂选自正丁基锂、仲丁基锂、甲基丁基锂、苯基丁基锂、萘锂、环己基锂和十二烷基锂中的一种或几种，优选选自正丁基锂和/或仲丁基锂；
    优选地，所述偶联剂选自多乙烯基芳烃类，优选选自二乙烯基苯；
    优选地，偶联反应过程中，偶联剂可以一次加入，也可以多次加入；
    优选地，所述极性活化剂选自二乙二醇二甲醚、四氢呋喃、乙醚、乙基甲醚、苯甲醚、二苯醚、乙二醇二甲醚、三乙胺、四甲基乙烯基二胺和六甲基膦酰三胺中的一种或几种，优选选自二乙二醇二甲醚、四氢呋喃和四甲基乙烯基二胺中的一种或几种。
  6. 根据权利要求4或5所述的制备方法，其特征在于，所述均聚反应的温度为50-80℃，均聚反应的压力为0.1-0.25MPa，均聚反应的时间为20-80min；
    优选地，所述偶联反应的温度为50-80℃，偶联反应的压力为0.1-0.25MPa，偶联反应的时间为60-90min；
    优选地，所述共聚反应的温度为50-80℃，共聚反应的压力为0.1-0.25MPa，共聚反应的时间为60-100min；
    优选地，所述星型苯乙烯接枝丁二烯-异戊二烯改性橡胶的偶联效率为61-74％。
  7. 根据权利要求4-6中任意一项所述的制备方法，其特征在于，苯乙烯为30-70重量份，所述丁二烯和异戊二烯混合单体为30-70重量份，其中，丁二烯占所述混合单体用量的10-50wt％，异戊二烯占所述混合单体用量的50-90wt％；
    优选地，所述引发剂为0.0005-0.002重量份；
    优选地，所述极性活化剂与所述引发剂的摩尔比为0.1-30：1；
    优选地，所述偶联剂与所述引发剂的摩尔比为0.1-1.5:1。
  8. 根据权利要求7所述的制备方法，其特征在于，苯乙烯单体为30-70重量份，丁二烯和异戊二烯混合单体为30-70重量份，其中，丁二烯占所述混合单体用量的10-50wt％，异戊二烯占所述混合单体用量的50-90wt％；
    优选地，所述引发剂为0.0007-0.002重量份；
    优选地，所述极性活化剂与所述引发剂的摩尔比为0.2-20：1；
    优选地，所述偶联剂与所述引发剂的摩尔比为0.15-1:1。
  9. 由权利要求4-8中任意一项所述的制备方法得到的星型苯乙烯接枝丁二烯-异戊二烯改 性橡胶。
  10. 一种权利要求1-3和9中任意一项所述的星型苯乙烯接枝丁二烯-异戊二烯改性橡胶在橡胶加工领域中的应用。
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