WO2024239554A1 - 星型接枝改性液体丁苯橡胶及其制备方法和应用 - Google Patents

星型接枝改性液体丁苯橡胶及其制备方法和应用 Download PDF

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Publication number
WO2024239554A1
WO2024239554A1 PCT/CN2023/130988 CN2023130988W WO2024239554A1 WO 2024239554 A1 WO2024239554 A1 WO 2024239554A1 CN 2023130988 W CN2023130988 W CN 2023130988W WO 2024239554 A1 WO2024239554 A1 WO 2024239554A1
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terpene resin
styrene
butadiene
modified
butadiene rubber
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French (fr)
Inventor
史工昌
赵志超
王永峰
邵卫
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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
    • 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 grafted modified liquid styrene-butadiene rubber and a preparation method and application thereof.
  • Liquid rubber generally refers to a polymer with a number-average molecular weight of 2000-15000 g/mol, and its viscosity changes with the relative molecular mass and molecular configuration of the polymer. Liquid rubber has the characteristics of fluidity and a wide range of bulk viscosity, simple processing, easy to achieve continuous and automated production, improved production efficiency, and reduced power consumption. Liquid rubber can be directly added with fillers and reinforcing agents to prepare rubber products, or it can be added to thermosetting resins and other polymers for modification.
  • Liquid rubber containing functional groups is easier to extend the chain and cross-link into solid vulcanized rubber due to the presence of active functional groups, which not only greatly improves the physical properties, but also can react with many other groups to form new materials with various structures.
  • liquid rubber There are many types of liquid rubber. According to whether there are functional groups and their locations, they can be divided into liquid rubber without functional groups, liquid rubber with random functional groups, and liquid rubber with terminal functional groups.
  • diene liquid rubbers, especially butadiene liquid rubbers were studied as "rubbers of the future" at the end of the 20th century because of their wide source of raw materials and low prices.
  • Liquid nitrile rubber, liquid styrene butadiene rubber and liquid isoprene rubber have outstanding application advantages in their respective fields.
  • Liquid styrene butadiene rubber is a copolymer with low relative molecular weight made by free radical emulsion or negative (anionic) ion polymerization with butadiene and styrene as monomers. It has a molecular weight of 2000-15000g/mol and is a light yellow or light brown transparent viscous liquid.
  • Liquid styrene butadiene rubber has excellent electrical insulation and physical properties, and is insoluble in general organic solvents and does not melt when heated.
  • Liquid styrene butadiene rubber has the characteristics of good compatibility with certain general rubbers, so they can be mixed and used, and fillers and oils can also be added at the same time.
  • these mixed components are evenly dispersed and have good pouring fluidity, they can be injection molded to produce hard rubber products. They can also be used as plasticizers for styrene butadiene rubber, nitrile rubber and chloroprene rubber, or as adhesives, sealing materials, etc. It can also be used to make high-end coatings, expanding the scope of application.
  • the purpose of the present invention is to overcome the problems of poor adhesion, stability, viscosity, adhesion performance and branching degree of liquid rubber in the prior art, and to provide a star-shaped grafted modified liquid styrene-butadiene rubber and a preparation method and application thereof.
  • the inventor of the present invention found in research that the liquid styrene butadiene rubber can be modified by using a common liquid styrene butadiene rubber anion solution polymerization method, which is simple and reliable. Thus, the present invention is obtained.
  • the first aspect of the present invention provides a star-shaped grafted modified liquid styrene butadiene rubber, wherein the modified liquid styrene butadiene rubber comprises a polymer segment from a coupling agent and a plurality of butadiene-styrene copolymer segments and cellulose ether modified terpene resin segments grafted on the polymer segment, wherein the coupling agent is selected from polyvinyl aromatic monomers.
  • a second aspect of the present invention provides a method for preparing a star-shaped graft-modified liquid styrene-butadiene rubber, wherein the preparation method comprises:
  • the third aspect of the present invention provides a star-shaped grafted modified liquid styrene-butadiene rubber obtained by the preparation method.
  • the fourth aspect of the present invention provides an application of the star-shaped grafted modified liquid styrene-butadiene rubber in the field of rubber processing.
  • the invention provides a modified liquid styrene butadiene rubber.
  • the polymer chain is a branched polymer with a star-shaped structure, that is, multiple molecular chains are grafted on the polymer chain segment to form different segments as branches, and similarly connected molecular arms (such as polybutadiene styrene arms, modified terpene resin polymer arms) are called mixed arms.
  • the polymer chain segment formed by the coupling agent is equivalent to the polybutadiene-styrene rubber and the modified terpene resin as the core 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.
  • the obtained modified liquid styrene butadiene rubber improves the viscosity, adhesion and other properties of the copolymer system, and can be used as high-end adhesives, plasticizers, coatings, and expands the scope of application.
  • FIG. 1 is a schematic diagram of the molecular chain structure of star-shaped grafted modified liquid styrene-butadiene rubber.
  • the first aspect of the present invention provides a star-shaped grafted modified liquid styrene butadiene rubber, wherein the modified liquid styrene butadiene rubber comprises a polymer segment from a coupling agent and a plurality of butadiene-styrene copolymer segments and cellulose ether modified terpene resin segments grafted on the polymer segment, wherein the coupling agent is selected from polyvinyl aromatic monomers.
  • the modified liquid styrene-butadiene rubber provided 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 the polymer core, and the multiple vinyl functional groups possessed by the coupling agent provide the polymer segment with multiple vinyl groups that can further graft other branches;
  • the butadiene-styrene copolymer chain and the cellulose ether modified terpene resin chain can be bonded to the vinyl groups on the polymer segment through the carbon-carbon double bonds contained in each of them, to form a butadiene-styrene copolymer segment and a cellulose ether modified terpene resin 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 styrene arms, modified terpene resin poly
  • the polybutadiene-styrene rubber and the modified terpene resin are chained together with the polymer chain segments formed by the coupling agent as the core, thereby 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.
  • the coupling agent is selected from polyvinyl aromatic monomers, which form polymer segments with multi-terminal molecular arms through self-polymerization, thereby forming polymers with a high degree of branching.
  • the content of the cellulose ether modified terpene resin segment is 20-80wt%, and the content of the butadiene-styrene copolymer segment is 20-80wt%.
  • the content of the cellulose ether-modified terpene resin segment can be selected from 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt% and any value in the range consisting of any two of the above values.
  • the content of the butadiene-styrene copolymer segment can be selected from 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt% and any value in the range consisting of any two of the above values.
  • the content of the butadiene structural unit is 50-90wt%, and the content of the styrene structural unit is 10-50wt%.
  • the content of the butadiene structural unit in the butadiene-styrene 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 styrene 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 content of the cellulose ether is 10-40wt%, and the content of the terpene resin is 60-90wt%.
  • the content of the cellulose ether in the cellulose ether modified terpene resin segment can be selected from 10wt%, 20wt%, 30wt%, 40wt%, and any value in the range of any two of the above values.
  • the content of the terpene resin can be selected from 60wt%, 70wt%, 80wt%, 90wt%, and any value in the range of any two of the above values.
  • the coupling agent is selected from divinylbenzene.
  • the amount of the coupling agent used is small, the polymer segment formed by the coupling agent is used as the 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 In the proportion, the amount of coupling agent used has been stated in the text.
  • the functionality is the active point on the polymer chain that can react chemically to generate new bonds.
  • the more active points are formed the more polymer segments are formed by initiating monomer polymerization, the better the branching of the modified liquid styrene-butadiene rubber, the greater the functionality.
  • the amount of polymer segments formed by the coupling agent can be determined by the polymer functionality.
  • the number average molecular weight of the modified liquid styrene butadiene rubber is 3000-25000 g/mol
  • the viscosity at 25° C. is 20-60 Pa ⁇ S
  • the functionality is 4-7.
  • the higher the viscosity the better the adhesive property of the liquid styrene butadiene rubber; the higher the functionality, the better the branching property of the modified liquid styrene butadiene rubber.
  • a second aspect of the present invention provides a method for preparing a star-shaped graft-modified liquid styrene-butadiene rubber, wherein the preparation method comprises:
  • the preparation method of the modified terpene resin comprises: mixing the terpene resin and a solvent, and then adding cellulose ether to obtain the modified terpene resin.
  • the cellulose ether is selected from one or more of sodium methyl cellulose, sodium hydroxypropyl methyl cellulose, and sodium carboxymethyl cellulose.
  • the invention utilizes a negative ion solution polymerization method to prepare the star-shaped grafted modified liquid styrene butadiene rubber, and modifies the liquid styrene butadiene rubber.
  • the method is simple and reliable.
  • step (1) butadiene, styrene monomer and initiator are sequentially added to the polymerization system, and after the first monomer polymerization is completed, a coupling agent is added to carry out a coupling reaction to obtain the star-shaped grafted modified liquid styrene butadiene rubber.
  • step (3) a modified terpene resin is added and polymerized to obtain the star-shaped grafted modified liquid styrene butadiene rubber.
  • the coupling reaction is that the polymer segment formed by the coupling agent and the butadiene-styrene copolymer chain are bonded to the vinyl group on the polymer segment through the carbon-carbon double bond contained therein to obtain the active chain.
  • the solvent is selected from one or more of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene and ethylbenzene, preferably cyclohexane.
  • the polar activator is selected from diethylene glycol dimethyl ether, tetrahydrofuran, ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, triethylamine, tetramethylethylenediamine and hexamethylphosphonic triamide.
  • 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 effect, reduce its association degree, and increase the initiation reaction speed of the initiator such as n-butyl lithium.
  • the activator can also adjust the reactivity ratio of butadiene and styrene to make the two copolymerize randomly.
  • the polar activator can increase the 1,2-structure content in the butadiene unit.
  • the initiator is selected from one or more of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthalenelithium, cyclohexyllithium and dodecyllithium, preferably selected from n-butyllithium and/or sec-butyllithium.
  • the coupling agent is selected from polyvinyl aromatic hydrocarbons, preferably divinyl benzene.
  • the copolymerization reaction temperature is 50-90° C.
  • the copolymerization reaction pressure is 0.1-0.25 MPa
  • the copolymerization reaction time is 20-80 min.
  • the coupling reaction temperature is 50-90° C.
  • the coupling reaction pressure is 0.1-0.25 MPa
  • the coupling reaction time is 60-90 min.
  • the polymerization reaction temperature is 50-90° C.
  • the polymerization reaction pressure is 0.1-0.25 MPa
  • the polymerization 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 grafted modified liquid styrene butadiene rubber, and then high-performance star-shaped grafted modified liquid styrene butadiene rubber is obtained through washing, dehydration and drying.
  • the mixed monomer of butadiene and styrene is 20-80 parts by weight, wherein butadiene accounts for 60-90wt% of the mixed monomer amount, and styrene accounts for 10-40wt% of the mixed monomer amount; preferably, the mixed monomer of butadiene and styrene is 30-70 parts by weight, wherein butadiene accounts for 70-90wt% of the mixed monomer amount, and styrene accounts for 10-30wt% of the mixed monomer amount.
  • the modified terpene resin is 20-80 parts by weight, wherein the cellulose ether accounts for 10-40wt% of the modified terpene resin, and the terpene resin accounts for 60-90wt% of the modified terpene resin; preferably, the modified terpene resin is 30-70 parts by weight, wherein the cellulose ether accounts for 10-30wt% of the modified terpene resin, and the terpene resin accounts for 70-90wt% of the modified terpene resin;
  • the initiator is 0.02-0.2 parts by weight, preferably 0.025-0.1 parts by weight.
  • the molar ratio of the polar activator to the initiator is 0.1-30:1, preferably 0.1-20:1.
  • the molar ratio of the coupling agent to the initiator is 0.1-1.5:1, preferably 0.1-1:1.
  • the functionality is determined by gel permeation chromatography, and the composition and structure of the star-shaped grafted modified liquid styrene-butadiene rubber can be determined by nuclear magnetic resonance, infrared, GPC, elemental analysis, etc., or by preparing and feeding.
  • the third aspect of the present invention provides a star-shaped grafted modified liquid styrene-butadiene 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 grafted modified liquid styrene-butadiene rubber in the field of rubber processing.
  • Viscosity determination According to GJB 2050-1994, the viscosity is determined using a rotational viscometer and cone-plate viscometer method.
  • FTIR Fourier transform infrared spectroscopy
  • the conditions are carried out according to conventional conditions or conditions recommended by the manufacturer.
  • the reagents or instruments used without indicating the manufacturer are conventional products that can be obtained through commercial channels.
  • the composition and structure of the modified liquid styrene-butadiene rubber described in the following examples and comparative examples can be determined by nuclear magnetic resonance, infrared, GPC, elemental analysis, etc., or by preparing and feeding.
  • modified terpene resin In a reaction kettle, add 4212g cyclohexane and 374g terpene resin and heat to After heating to 80°C, stir until it is completely dissolved, then add 94g of dissolved sodium methyl cellulose, stir and mix evenly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin is 80wt%, and the content of cellulose ether is 20wt%).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 50wt%, and the content of styrene structural units was 50wt%), 0.249mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, the mixture of 468g of the prepared modified terpene resin and 4212g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, and 100g of water and 12g of antioxidant 1010 were added and stirred.
  • the rubber solution is coagulated by wet method and dried to obtain high-performance star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 50wt%, and the content of the butadiene-styrene copolymer segment is 50wt%).
  • modified terpene resin In a reaction kettle, 4212 g of cyclohexane and 374 g of terpene resin were added, heated to 80° C. and stirred until they were completely dissolved, then 94 g of dissolved sodium methyl cellulose was added, and stirred and mixed uniformly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin was 80 wt %, and the content of cellulose ether was 20 wt %).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 50wt%, and the content of styrene structural units was 50wt%), 0.167mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, the mixture of 468g of the prepared modified terpene resin and 4212g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the rubber solution is coagulated by wet method and dried to obtain high-performance star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 50wt%, and the content of the butadiene-styrene copolymer segment is 50wt%).
  • modified terpene resin In a reaction kettle, 4212 g of cyclohexane and 327 g of terpene resin were added, heated to 80° C. and stirred until they were completely dissolved, then 141 g of dissolved sodium methyl cellulose was added, and stirred and mixed uniformly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin was 70 wt % and the content of cellulose ether was 30 wt %).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 50wt%, and the content of styrene structural units was 50wt%), 0.374mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, the mixture of 468g of the prepared modified terpene resin and 4212g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 50wt%, and the content of the butadiene-styrene copolymer segment is 50wt%).
  • modified terpene resin In a reaction kettle, 4212 g of cyclohexane and 327 g of terpene resin were added, heated to 80° C. and stirred until they were completely dissolved, then 141 g of dissolved sodium methyl cellulose was added, and stirred and mixed uniformly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin was 70 wt % and the content of cellulose ether was 30 wt %).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 50wt%, and the content of styrene structural units was 50wt%), 0.249mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, the mixture of 468g of the prepared modified terpene resin and 4212g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 50wt%, and the content of the butadiene-styrene copolymer segment is 50wt%).
  • modified terpene resin In a reaction kettle, 2527 g of cyclohexane and 197 g of terpene resin were added, heated to 80° C. and stirred until they were completely dissolved, then 84 g of dissolved sodium methyl cellulose was added, and stirred and mixed uniformly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin was 70 wt % and the content of cellulose ether was 30 wt %).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 70wt%, and the content of styrene structural units was 30wt%), 0.212mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, a mixture of 281g of the prepared modified terpene resin and 2527g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 30wt%, and the content of the butadiene-styrene copolymer segment is 70wt%).
  • modified terpene resin In a reaction kettle, add 2527g of cyclohexane and 225g of terpene resin, heat to 80°C and stir until they are completely dissolved, then add 56g of dissolved sodium methyl cellulose, stir and mix evenly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin is 80wt%, and the content of cellulose ether is 20wt%).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 70wt%, and the content of styrene structural units was 30wt%), 0.131mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, a mixture of 281g of the prepared modified terpene resin and 2527g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 30wt%, and the content of the butadiene-styrene copolymer segment is 70wt%).
  • modified terpene resin In a reaction kettle, 2527 g of cyclohexane and 225 g of terpene resin (accounting for 80 wt% of the modified terpene resin segment) were added, heated to 80° C. and stirred until completely dissolved, then 56 g of dissolved sodium methyl cellulose (accounting for 20 wt% of the modified terpene resin segment) was added, and the mixture was stirred and mixed uniformly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin was 80 wt% and the content of cellulose ether was 20 wt%).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 85wt%, and the content of styrene structural units was 15wt%), 0.212mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, a mixture of 281g (30wt% of the total amount) of the prepared modified terpene resin and 2527g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 30wt%, and the content of the butadiene-styrene copolymer segment is 70wt%).
  • modified terpene resin In a reaction kettle, 2527 g of cyclohexane and 197 g of terpene resin were added, heated to 80° C. and stirred until they were completely dissolved, then 84 g of dissolved sodium methyl cellulose was added, and stirred and mixed uniformly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin was 70 wt % and the content of cellulose ether was 30 wt %).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 85wt%, and the content of styrene structural units was 15wt%), 0.301mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, a mixture of 281g of the prepared modified terpene resin and 2527g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 30wt%, and the content of the butadiene-styrene copolymer segment is 70wt%).
  • modified terpene resin In a reaction kettle, add 2611 g of cyclohexane and 211 g of terpene resin, heat to 80° C. and stir until they are completely dissolved, then add 70 g of dissolved sodium methyl cellulose, stir and mix evenly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin is 75 wt %, and the content of cellulose ether is 25 wt %).
  • the temperature was raised to 80°C (wherein, the content of butadiene structural units in the obtained butadiene-styrene copolymer segment was 85wt%, and the content of styrene structural units was 15wt%), 0.212mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, a mixture of 281g of the prepared modified terpene resin and 2527g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 30wt%, and the content of the butadiene-styrene copolymer segment is 70wt%).
  • modified terpene resin In a reaction kettle, add 2527g of cyclohexane and 225g of terpene resin, heat to 80°C and stir until they are completely dissolved, then add 56g of dissolved sodium methyl cellulose, stir and mix evenly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin is 80wt%, and the content of cellulose ether is 20wt%).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 70wt%, and the content of styrene structural units was 30wt%), 0.197mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, a mixture of 281g of the prepared modified terpene resin and 2527g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 30wt%, and the content of the butadiene-styrene copolymer segment is 70wt%).
  • modified terpene resin In a reaction kettle, add 2527g of cyclohexane and 225g of terpene resin, heat to 80°C and stir until they are completely dissolved, then add 56g of dissolved sodium methyl cellulose, stir and mix evenly to obtain a modified terpene resin (wherein, in the obtained cellulose ether modified terpene resin segment, the content of terpene resin is 80wt%, and the content of cellulose ether is 20wt%).
  • the temperature was raised to 80°C (wherein, in the obtained butadiene-styrene copolymer segment, the content of butadiene structural units was 70wt%, and the content of styrene structural units was 30wt%), 0.172mol of divinylbenzene was added to continue coupling, and after the reaction for 60min, a mixture of 281g of the prepared modified terpene resin and 2527g of cyclohexane was pressed into the polymerization reactor, and the reaction was continued for 60min. After the reaction was completed, the reaction mixture after coupling was treated with water, 100g of water and 12g of antioxidant 1010 were added, and stirred.
  • the glue solution is coagulated by wet method and dried to obtain star-shaped grafted modified liquid styrene butadiene rubber (wherein, in the modified liquid styrene butadiene rubber, the content of the cellulose ether modified terpene resin segment is 30wt%, and the content of the butadiene-styrene copolymer segment is 70wt%).
  • Example 1 The method of Example 1 is followed, except that the terpene resin is not modified, that is, the styrene-butadiene rubber segment and the terpene resin are directly coupled and then coagulated.
  • the specific preparation steps are as follows: In a 15L stainless steel reactor with a jacket, argon is passed through the system to replace 3 times. 4212g of cyclohexane, 234g of butadiene (accounting for 50wt% of the mixed monomer amount), 234g of styrene (accounting for 50wt% of the mixed monomer amount), 44.93g of tetrahydrofuran, and 0.624mol of n-butyl lithium are added to the polymerization reactor, the temperature is raised to 50°C, and the polymerization is carried out for 80min. After the monomer is completely converted, the temperature is raised to 80°C, and 0.249mol of divinylbenzene is added to continue coupling.
  • Example 2 The method of Example 2 is followed, except that the terpene resin is not modified, that is, the styrene-butadiene rubber segment and the terpene resin are directly coupled and then coagulated.
  • the specific preparation steps are as follows: In a 15L stainless steel reactor with a jacket, argon is passed through the system to replace it three times. 4212g of cyclohexane, 234g of butadiene (accounting for 50wt% of the mixed monomer amount), and 234g of styrene (accounting for 50wt% of the mixed monomer amount) are added to the polymerization reactor. 50wt% of the monomer dosage), 29.95g of tetrahydrofuran, and then 0.416mol of n-butyl lithium were added, the temperature was raised to 50°C, and the polymerization was carried out for 80min.
  • Example 3 The method of Example 3 is followed, except that the terpene resin is not modified, that is, the styrene-butadiene rubber segment and the terpene resin are directly coupled and then coagulated.
  • the specific preparation steps are as follows: In a 15L stainless steel reactor with a jacket, argon is passed through the system to replace 3 times. 4212g of cyclohexane, 234g of butadiene (accounting for 50wt% of the mixed monomer amount), 234g of styrene (accounting for 50wt% of the mixed monomer amount), 44.93g of tetrahydrofuran, and 0.936mol of n-butyl lithium are added to the polymerization reactor, the temperature is raised to 50°C, and the polymerization is carried out for 80min. After the monomer is completely converted, the temperature is raised to 80°C, and 0.374mol of divinylbenzene is added to continue coupling.
  • Example 4 The method of Example 4 is followed, except that the terpene resin is not modified, that is, the styrene-butadiene rubber segment and the terpene resin are directly coupled and then coagulated.
  • the specific preparation steps are as follows: In a 15L stainless steel reactor with a jacket, argon is passed through the system to replace 3 times. 4212g of cyclohexane, 234g of butadiene (accounting for 50wt% of the mixed monomer amount), 234g of styrene (accounting for 50wt% of the mixed monomer amount), 44.93g of tetrahydrofuran, and 0.624mol of n-butyl lithium are added to the polymerization reactor, the temperature is raised to 50°C, and the polymerization is carried out for 80min. After the monomer is completely converted, the temperature is raised to 80°C, and 0.249mol of divinylbenzene is added to continue coupling.
  • reaction mixture After the reaction is 60min, a mixture of 468g of terpene resin (accounting for 50wt% of the total amount) and 4212g of cyclohexane is pressed into the polymerization reactor, and the reaction is continued for 60min. After the reaction is completed, the reaction mixture after coupling is treated with water, 100g of water and 12g of antioxidant 1010 are added, and stirred. The glue solution is wet-coagulated and dried to obtain liquid styrene-butadiene rubber.
  • Example 5 The method of Example 5 was followed, except that no coupling agent was added to carry out the coupling reaction, that is, the polymerization of butadiene and styrene After the reaction is complete, the modified terpene resin is added and mixed.
  • modified terpene resin In a reaction kettle, add 2527g of cyclohexane and 187g of terpene resin (accounting for 70wt% of the modified terpene resin segment), heat to 80°C and stir until they are completely dissolved, then add 94g of dissolved sodium methylcellulose (accounting for 30wt% of the modified terpene resin segment), stir and mix evenly to obtain modified terpene resin. 2) In a 15L stainless steel reaction kettle with a jacket, replace the system 3 times with argon.
  • Example 6 The method of Example 6 is followed, except that no coupling agent is added for coupling reaction, that is, after the polymerization reaction of butadiene and styrene is completed, the modified terpene resin is added and mixed.
  • modified terpene resin In a reaction kettle, add 2527g of cyclohexane and 234g of terpene resin (accounting for 80wt% of the modified terpene resin segment), heat to 80°C and stir until they are completely dissolved, then add 47g of dissolved sodium methylcellulose (accounting for 20wt% of the modified terpene resin segment), stir and mix evenly to obtain modified terpene resin. 2) In a 15L stainless steel reactor with a jacket, replace the system 3 times with argon.
  • Example 7 The method of Example 7 is followed, except that the terpene resin is not modified, that is, the styrene-butadiene rubber segment and the terpene resin are directly coupled, and then dissolved sodium carboxymethyl cellulose is added and then coagulation is performed.
  • the terpene resin is not modified, that is, the styrene-butadiene rubber segment and the terpene resin are directly coupled, and then dissolved sodium carboxymethyl cellulose is added and then coagulation is performed.
  • the specific preparation steps are as follows: In a 15L stainless steel reactor with a jacket, argon is passed through the system to replace the system three times. 5897g of cyclohexane, 557g of butadiene (accounting for 85wt% of the mixed monomers), 98g of styrene (accounting for 15wt% of the mixed monomers), 37.73g of tetrahydrofuran, and 0.524mol of n-butyl lithium are added to the polymerization reactor, and the temperature is raised to 50°C. After 80 minutes of polymerization, the temperature was raised to 80°C after the monomers were completely converted, and 0.212 mol of divinylbenzene was added to continue coupling.
  • Example 8 The method of Example 8 was followed, except that the terpene resin was not modified, that is, the styrene-butadiene rubber segment and the terpene resin were directly coupled, and then dissolved sodium carboxymethyl cellulose was added and then coagulated.
  • Example 10 The method of Example 10 is followed, except that the terpene resin is not modified, that is, the styrene-butadiene rubber segment and the terpene resin are directly coupled, and then dissolved sodium carboxymethyl cellulose is added and then coagulation is performed.
  • the terpene resin is not modified, that is, the styrene-butadiene rubber segment and the terpene resin are directly coupled, and then dissolved sodium carboxymethyl cellulose is added and then coagulation is performed.
  • the average bonding force refers to the average value of the peel strength between the adhesive and the substrate in the peeling test, which is usually expressed by the stress per unit area. It can be used to compare the adhesive adhesion properties of the liquid styrene-butadiene rubber of the embodiments and the comparative examples under different conditions. From the comparison between the embodiments 1-10 and the comparative examples 1-9, it can be seen that as the molecular weight and viscosity of the grafted modified rubber increase, the average bonding force of the grafted modified rubber increases, and the greater the functionality of the grafted modified rubber and the higher the degree of branching, the greater the average bonding force of the grafted modified rubber.
  • Example 5-6 From the comparison between Example 5-6 and Comparative Example 5-6, it can be seen that after adding the coupling agent to couple the modified terpene resin, the modified liquid styrene butadiene rubber forms a mixed arm, so the viscosity, functionality and average binding force of the star-shaped modified liquid styrene butadiene rubber in Example 5-6 are greater than those in Comparative Example 5-6, indicating that the adhesion performance of the star-shaped modified liquid styrene butadiene rubber in Example 5-6 is better than that of the corresponding Comparative Example 5-6.
  • the coupling effect of the divinylbenzene coupling agent can chain the polybutadiene-styrene rubber and the modified terpene resin together, promote the synergistic optimization of various properties of the product, and enable the modified rubber to have good compatibility, stability and adhesion.
  • the examples 1-11 using the star-shaped grafting modified liquid styrene butadiene rubber of the present invention have the effects of high viscosity, high branching degree, and significantly better adhesive compatibility.

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Abstract

本发明涉及橡胶制备领域，公开了一种星型接枝改性液体丁苯橡胶及其制备方法和应用。所述改性液体丁苯橡胶包括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丁二烯-苯乙烯共聚链段和纤维素醚改性萜烯树脂链段，其中，所述偶联剂选自多乙烯基芳烃类单体。改性液体丁苯橡胶实现了聚合物在分子结构层面上的结合，具有良好的相容性、稳定性和粘合性。生成的改性液体丁苯橡胶改善了共聚物体系黏度、附着力等性能，可用于做高档胶黏剂、涂料，扩大了应用范围。

Description

星型接枝改性液体丁苯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202310587657.1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，具体涉及一种星型接枝改性液体丁苯橡胶及其制备方法和应用。
背景技术
液体橡胶一般是指数均分子量为2000-15000g/mol的聚合物，其黏度随聚合物的相对分子质量大小及分子构型而改变。液体橡胶具有流动性且本体粘度范围较宽，加工简便，易于实现连续化，自动化生产，提高生产效率，降低动力消耗等特点。液体橡胶可以直接加填充剂和补强剂制备橡胶制品，也可以加到热固性树脂及其它聚合物中进行改性。含有官能团的液体橡胶由于活性官能团的存在，更易扩链和交联成固体硫化橡胶，既大幅度提高了物理性能，还可以与其它很多基团反应，形成各种结构的新型材料。液体橡胶种类繁多，按照是否有官能团及其所在位置，可以分为无官能团液体橡胶、无规官能团液体橡胶和端官能团液体橡胶。在众多液体橡胶胶种中，双烯系液体橡胶，特别是丁二烯系，因原料来源广泛、价格便宜，在20世纪末就被作为“未来的橡胶”进行研究。液体丁腈橡胶、液体丁苯橡胶和液体异戊二烯橡胶在各自领域具有突出的应用优势。
液体丁苯橡胶(LSBR)是以丁二烯和苯乙烯为单体采用自由基乳液或负(阴)离子聚合法制得低相对分子质量的共聚物，分子量2000-15000g/mol，为浅黄色或浅棕色透明黏稠液体，液体丁苯橡胶具有优异的电绝缘性能和物理性能，且不溶于一般有机溶剂，加热不熔融。液体丁苯橡胶有与某些通用橡胶相溶性好的特点，因此它们可掺混使用，也可同时添加填充剂和油品。由于这些混合组分分散均匀，浇注流动性好，因此可注射成型制取硬橡胶制品，也可用作丁苯橡胶、丁腈橡胶和氯丁橡胶的增塑剂，或作为胶黏剂、密封材料等。以及用于做高档涂料，扩大了应用范围。
国内外的报道为液体橡胶在不同领域的利用或通过液体橡胶对各种聚合物改性，且多为液体丁腈橡胶、液体异戊二烯橡胶等，或通过端基化对液体橡胶改性。制备的液体橡胶的粘合 性、稳定性、黏度、支化度差以及提高共聚物体系黏度、附着力性能是本领域需要解决的问题。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。
发明内容
本发明的目的是为了克服现有技术存在的液体橡胶的粘合性、稳定性、黏度、附着力性能、支化度较差的问题，提供一种星型接枝改性液体丁苯橡胶及其制备方法和应用。
本发明的发明人在研究中发现，利用普通的液体丁苯橡胶负离子溶液聚合方法，对液体丁苯橡胶改性，方法简单、可靠。由此得到本发明。
为了实现上述目的，本发明第一方面提供一种星型接枝改性液体丁苯橡胶，其中，所述改性液体丁苯橡胶包括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丁二烯-苯乙烯共聚链段和纤维素醚改性萜烯树脂链段，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接枝改性液体丁苯橡胶的制备方法，其中，所述制备方法包括：
(1)在引发剂和极性活化剂存在下，将丁二烯和苯乙烯进行共聚反应，得到活性丁二烯-苯乙烯共聚段；
(2)将所述活性丁二烯-苯乙烯共聚段和偶联剂进行偶联反应，得到活性链；
(3)将所述活性链与改性萜烯树脂进行聚合反应，得到所述星型接枝改性液体丁苯橡胶。
本发明第三方面提供一种所述的制备方法得到的星型接枝改性液体丁苯橡胶。
本发明第四方面提供一种所述的星型接枝改性液体丁苯橡胶在橡胶加工领域中的应用。
通过上述技术方案，发明提供了一种改性液体丁苯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(如聚丁二烯苯乙烯臂，改性萜烯树脂聚合物臂)，称为混合臂。所述改性液体丁苯橡胶中，相当于将聚丁二烯-苯乙烯橡胶和改性萜烯树脂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。得到的改性液体丁苯橡胶改善了共聚物体系黏度、附着力等性能，可用于做高档胶黏剂、增塑剂、涂料，扩大了应用范围。
附图说明
图1是星型接枝改性液体丁苯橡胶的分子链结构示意图。
附图标记说明
PSB-代表丁二烯-苯乙烯共聚链段，PT-代表纤维素醚改性萜烯树脂链段。
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接枝改性液体丁苯橡胶，其中，所述改性液体丁苯橡胶包括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丁二烯-苯乙烯共聚链段和纤维素醚改性萜烯树脂链段，其中，所述偶联剂选自多乙烯基芳烃类单体。
在本发明中，提供的所述改性液体丁苯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作为聚合物核心，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-苯乙烯共聚物链和纤维素醚改性萜烯树脂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-苯乙烯共聚链段和纤维素醚改性萜烯树脂链段，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(如聚丁二烯苯乙烯臂，改性萜烯树脂聚合物臂)，可以称为混合臂。所述改性液体丁苯橡胶中，相当于将聚丁二烯-苯乙烯橡胶和改性萜烯树脂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。
在本发明中，所述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，进而形成支化度高的聚合物。
在本发明一些具体实施方式中，所述改性液体丁苯橡胶中，基于所述丁二烯-苯乙烯共聚链段和纤维素醚改性萜烯树脂链段的重量之和，所述纤维素醚改性萜烯树脂链段的含量为20-80wt％，所述丁二烯-苯乙烯共聚链段的含量为20-80wt％。通过限定上述含量的改性液体丁苯橡胶，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。
在本发明的一些实施方式中，所述改性液体丁苯橡胶中，基于所述丁二烯-苯乙烯共聚链段和纤维素醚改性萜烯树脂链段的重量之和，所述纤维素醚改性萜烯树脂链段的含量可选择20wt％、30wt％、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。所述丁二烯-苯乙烯共聚链段的含量可选择20wt％、30wt％、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。
在本发明一些具体实施方式中，所述丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为50-90wt％，苯乙烯结构单元的含量为10-50wt％。通过限定上述含量的改性液体丁苯橡胶，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。
在本发明的一些实施方式中，所述丁二烯-苯乙烯共聚链段中，所述丁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。所述苯乙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，所述纤维素醚改性萜烯树脂链段中，所述纤维素醚的含量为10-40wt％，所述萜烯树脂的含量为60-90wt％。通过限定上述含量的改性液体丁苯橡胶，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。其中，所述纤维素醚改性萜烯树脂链段中，萜烯树脂的含量越高，其星型接枝改性液体丁苯橡胶的平均结合力越高，液体丁苯橡胶的抗湿滑性、高温抗流动性能和附着结合力也越好。
在本发明的一些实施方式中，所述纤维素醚改性萜烯树脂链段中，所述纤维素醚的含量可选择10wt％、20wt％、30wt％、40wt％，以及上述任意两个数值组成的范围中的任意值。所述萜烯树脂的含量可选择60wt％、70wt％、80wt％、90wt％，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。
在本发明中，所述官能度为聚合物链上所具有的能起化学反应而生成新键的活性点。形成的活性点越多，引发单体聚合形成聚合物链段也越多，改性液体丁苯橡胶的支化性越好，官能度越大。通过对聚合物链段进行表征和分析，可以通过聚合物官能度可以反应偶联剂形成的聚合链段的量。
在本发明一些具体实施方式中，所述改性液体丁苯橡胶的数均分子量为3000-25000g/mol，25℃的黏度为20-60Pa·S，官能度为4-7。粘度大，液体丁苯橡胶的粘合性能好；官能度大，表明改性液体丁苯橡胶的支化性能好。
本发明第二方面提供一种星型接枝改性液体丁苯橡胶的制备方法，其中，所述制备方法包括：
(1)在引发剂和极性活化剂存在下，将丁二烯和苯乙烯进行共聚反应，得到活性丁二烯-苯乙烯共聚段；
(2)将所述活性丁二烯-苯乙烯共聚段和偶联剂进行偶联反应，得到活性链；
(3)将所述活性链与改性萜烯树脂进行聚合反应，得到所述星型接枝改性液体丁苯橡胶。
在本发明一些具体实施方式中，所述改性萜烯树脂的制备方法包括：将萜烯树脂和溶剂混合后，再加入纤维素醚制得所述改性萜烯树脂。
在本发明一些具体实施方式中，所述纤维素醚选自甲基纤维素钠、羟丙基甲基纤维素钠、羧甲基纤维素钠中的一种或几种。
本发明利用负离子溶液聚合方法制备所述星型接枝改性液体丁苯橡胶，对液体丁苯橡胶进行改性，方法简单、可靠。
在本发明中，步骤(1)中，将丁二烯、苯乙烯单体和引发剂依次加入到聚合系统，在第一次加入单体聚合结束后，再加入偶联剂进行偶联反应来制得。步骤(3)中，加入改性萜烯树脂，聚合得到所述星型接枝改性液体丁苯橡胶。
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丁二烯-苯乙烯共聚物链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，所述溶剂选自戊烷、己烷、辛烷、庚烷、环己烷、苯、甲苯和乙苯中的一种或几种，优选选自环己烷。
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苯乙烯的竞聚率，使二者无规共聚，同时所述极性活化剂能提高丁二烯单元中1,2-结构含量。
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。
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。
在本发明一些具体实施方式中，所述共聚反应的温度为50-90℃，共聚反应的压力为0.1-0.25MPa，共聚反应的时间为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50-90℃，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，所述聚合反应的温度为50-90℃，聚合反应的压力为0.1-0.25MPa，聚合反应的时间为60-100min。
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，在得到的星型接枝改性液体丁苯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接枝改性液体丁苯橡胶。
在本发明一些具体实施方式中，丁二烯和苯乙烯的混合单体为20-80重量份，其中，丁二烯占所述混合单体用量的60-90wt％，苯乙烯占所述混合单体用量的10-40wt％；优选所述丁二烯和苯乙烯混合单体为30-70重量份，其中，所述丁二烯占混合单体用量的70-90wt％，所述苯乙烯占混合单体用量的10-30wt％。
在本发明一些具体实施方式中，所述改性萜烯树脂为20-80重量份，其中，所述纤维素醚占所述改性萜烯树脂用量的10-40wt％，所述萜烯树脂占所述改性萜烯树脂用量的60-90wt％；优选所述改性萜烯树脂为30-70重量份，其中所述纤维素醚占所述改性萜烯树脂用量的10-30wt％，所述萜烯树脂占所述改性萜烯树脂用量的70-90wt％；
在本发明一些具体实施方式中，所述引发剂为0.02-0.2重量份，优选为0.025-0.1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，优选为0.1-20:1。
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，优选为 0.1-1:1。
本发明中，所述官能度用凝胶渗透色谱分析法进行测定，所述星型接枝改性液体丁苯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。
本发明第三方面提供一种所述的制备方法得到的星型接枝改性液体丁苯橡胶。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接枝改性液体丁苯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。
分子量的测定：采用美国Agilent技术公司的Viscoteck TDA 302型凝胶渗透色谱(GPC)分析试样的分子量及其分布。
黏度的测定：按GJB 2050-1994采用旋转黏度计按锥板黏度计法进行测定。
傅里叶变换红外光谱(FTIR)分析：采用美国Nicolet 560型FTIR仪进行分析，不需纯化，用溴化钾压片涂膜。用于测定改性液体丁苯橡胶结构中的苯乙烯含量和丁二烯含量。
剥离力测定：按GB/T7124-2008采用美国Instron公司的5567型万能材料试验机测试平均结合力。
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液体丁苯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
1)改性萜烯树脂的制备：在反应釜中，加入4212g环己烷和374g的萜烯树脂，加热到 80℃后搅拌至其完全溶解，然后加入94g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为80wt％，纤维素醚的含量为20wt％)。
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。向聚合釜中加入环己烷4212g，234g丁二烯，234g苯乙烯，44.93g的四氢呋喃，再加入0.624mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为50wt％，苯乙烯结构单元的含量为50wt％)，加入0.249mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂468g和4212g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得高性能星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为50wt％，所述丁二烯-苯乙烯共聚链段的含量为50wt％)。
实施例2
1)改性萜烯树脂的制备：在反应釜中，加入4212g环己烷和374g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入94g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为80wt％，纤维素醚的含量为20wt％)。
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。向聚合釜中加入环己烷4212g，234g丁二烯，234g苯乙烯，29.95g的四氢呋喃，再加入0.416mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为50wt％，苯乙烯结构单元的含量为50wt％)，加入0.167mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂468g和4212g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得高性能星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为50wt％，所述丁二烯-苯乙烯共聚链段的含量为50wt％)。
实施例3
1)改性萜烯树脂的制备：在反应釜中，加入4212g环己烷和327g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入141g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为70wt％，纤维素醚的含量为30wt％)。
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。向聚合釜中加入环己烷4212g，234g丁二烯，234g苯乙烯，44.93g的四氢呋喃，再加入0.936mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为50wt％，苯乙烯结构单元的含量为50wt％)，加入0.374mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂468g和环己烷4212g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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为50wt％，所述丁二烯-苯乙烯共聚链段的含量为50wt％)。
实施例4
1)改性萜烯树脂的制备：在反应釜中，加入4212g环己烷和327g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入141g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为70wt％，纤维素醚的含量为30wt％)。
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。向聚合釜中加入环己烷4212g，234g丁二烯，234g苯乙烯，44.93g的四氢呋喃，再加入0.624mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为50wt％，苯乙烯结构单元的含量为50wt％)，加入0.249mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂468g和环己烷4212g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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为50wt％，所述丁二烯-苯乙烯共聚链段的含量为50wt％)。
实施例5
1)改性萜烯树脂的制备：在反应釜中，加入2527g环己烷和197g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入84g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为70wt％，纤维素醚的含量为30wt％)。
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5897g的环己烷，468g丁二烯，187g苯乙烯，37.73g的四氢呋喃，再加入0.524mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为70wt％，苯乙烯结构单元的含量为30wt％)，加入0.212mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂281g和2527g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为30wt％，所述丁二烯-苯乙烯共聚链段的含量为70wt％)。
实施例6
1)改性萜烯树脂的制备：在反应釜中，加入2527g环己烷和225g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入56g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为80wt％，纤维素醚的含量为20wt％)。
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5897g的环己烷，468g丁二烯，187g苯乙烯，23.58g的四氢呋喃，再加入0.327mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为70wt％，苯乙烯结构单元的含量为30wt％)，加入0.131mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂281g和2527g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为30wt％，所述丁二烯-苯乙烯共聚链段的含量为70wt％)。
实施例7
1)改性萜烯树脂的制备：在反应釜中，加入2527g环己烷和225g的萜烯树脂(占改性萜烯树脂链段用量的80wt％)，加热到80℃后搅拌至其完全溶解，然后加入56g溶解的甲基纤维素钠(占改性萜烯树脂链段用量的20wt％)，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为80wt％，纤维素醚的含量为20wt％)。
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5897g的环己烷，557g丁二烯，98g的苯乙烯，37.73g的四氢呋喃，再加入0.524mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为85wt％，苯乙烯结构单元的含量为15wt％)，加入0.212mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂281g(占总量的30wt％)和2527g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为30wt％，所述丁二烯-苯乙烯共聚链段的含量为70wt％)。
实施例8
1)改性萜烯树脂的制备：在反应釜中，加入2527g环己烷和197g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入84g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为70wt％，纤维素醚的含量为30wt％)。
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5897g的环己烷，557g丁二烯，98g苯乙烯，53.90g的四氢呋喃，再加入0.504mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为85wt％，苯乙烯结构单元的含量为15wt％)，加入0.301mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂281g和2527g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为30wt％，所述丁二烯-苯乙烯共聚链段的含量为70wt％)。
实施例9
1)改性萜烯树脂的制备：在反应釜中，加入2611g环己烷和211g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入70g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为75wt％，纤维素醚的含量为25wt％)。
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。向聚合釜中加入环己烷5813g，478g丁二烯，84g苯乙烯，37.73g的四氢呋喃，再加入0.281mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为85wt％，苯乙烯结构单元的含量为15wt％)，加入0.212mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂281g和2527g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为30wt％，所述丁二烯-苯乙烯共聚链段的含量为70wt％)。
实施例10
1)改性萜烯树脂的制备：在反应釜中，加入2527g环己烷和225g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入56g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为80wt％，纤维素醚的含量为20wt％)。
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5897g的环己烷，468g丁二烯，187g苯乙烯，23.58g的四氢呋喃，再加入0.197mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为70wt％，苯乙烯结构单元的含量为30wt％)，加入0.197mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂281g和2527g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为30wt％，所述丁二烯-苯乙烯共聚链段的含量为70wt％)。
实施例11
1)改性萜烯树脂的制备：在反应釜中，加入2527g环己烷和225g的萜烯树脂，加热到80℃后搅拌至其完全溶解，然后加入56g溶解的甲基纤维素钠，搅拌混合均匀，制得改性萜烯树脂(其中，所得纤维素醚改性萜烯树脂链段中，萜烯树脂的含量为80wt％，纤维素醚的含量为20wt％)。
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5897g的环己烷，468g丁二烯，187g苯乙烯，23.58g的四氢呋喃，再加入0.143mol的正丁基锂，升温至50℃，聚合80min，单体完全转化后升温至80℃(其中，所得丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为70wt％，苯乙烯结构单元的含量为30wt％)，加入0.172mol二乙烯基苯继续进行偶联，反应60min后，再将制备好的改性萜烯树脂281g和2527g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得星型接枝改性液体丁苯橡胶(其中，所述改性液体丁苯橡胶中，所述纤维素醚改性萜烯树脂链段的含量为30wt％，所述丁二烯-苯乙烯共聚链段的含量为70wt％)。
对比例1
按照实施例1的方法，不同的是，未对萜烯树脂改性，即直接将丁苯橡胶段和萜烯树脂偶联后凝聚。
具体制备步骤如下：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4212g，234g丁二烯(占混合单体用量的50wt％)，234g苯乙烯(占混合单体用量的50wt％)，44.93g的四氢呋喃，再加入0.624mol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0.249mol二乙烯基苯继续进行偶联，反应60min后，再将萜烯树脂468g(占总量的50wt％)和4212g的环己烷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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对比例2
按照实施例2的方法，不同的是，未对萜烯树脂改性，即直接将丁苯橡胶段和萜烯树脂偶联后凝聚。
具体制备步骤如下：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4212g，234g丁二烯(占混合单体用量的50wt％)，234g苯乙烯(占混合 单体用量的50wt％)，29.95g的四氢呋喃，再加入0.416mol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0.167mol二乙烯基苯继续进行偶联，反应60min后，再将萜烯树脂468g(占总量的50wt％)和环己烷4212g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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对比例3
按照实施例3的方法，不同的是，未对萜烯树脂改性，即直接将丁苯橡胶段和萜烯树脂偶联后凝聚。
具体制备步骤如下：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4212g，234g丁二烯(占混合单体用量的50wt％)，234g苯乙烯(占混合单体用量的50wt％)，44.93g的四氢呋喃，再加入0.936mol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0.374mol二乙烯基苯继续进行偶联，反应60min后，再将萜烯树脂468g(占总量的50wt％)和环己烷4212g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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对比例4
按照实施例4的方法，不同的是，未对萜烯树脂改性，即直接将丁苯橡胶段和萜烯树脂偶联后凝聚。
具体制备步骤如下：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4212g，234g丁二烯(占混合单体用量的50wt％)，234g苯乙烯(占混合单体用量的50wt％)，44.93g的四氢呋喃，再加入0.624mol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0.249mol二乙烯基苯继续进行偶联，反应60min后，再将萜烯树脂468g(占总量的50wt％)和环己烷4212g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，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对比例5
按照实施例5的方法，不同的是，未加入偶联剂进行偶联反应，即对丁二烯和苯乙烯聚合 反应完成后，将改性萜烯树脂加入后混合。
具体制备步骤如下：1)改性萜烯树脂的制备：在反应釜中，加入2527g环己烷和187g的萜烯树脂(占改性萜烯树脂链段用量的70wt％)，加热到80℃后搅拌至其完全溶解，然后加入94g溶解的甲基纤维素钠(占改性萜烯树脂链段用量的30wt％)，搅拌混合均匀，制得改性萜烯树脂。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5897g的环己烷，468g丁二烯(占混合单体用量的70wt％)，187g苯乙烯(占混合单体用量的30wt％)，37.73g的四氢呋喃，再加入0.281mol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60min后，再将制备好的改性萜烯树脂281g(占总量的30wt％)和2527g的环己烷的混合物压入聚合釜，混合20min完成后加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对比例6
按照实施例6的方法，不同的是，未加入偶联剂进行偶联反应，即对丁二烯和苯乙烯聚合反应完成后，将改性萜烯树脂加入后混合。
具体制备步骤如下：1)改性萜烯树脂的制备：在反应釜中，加入2527g环己烷和234g的萜烯树脂(占改性萜烯树脂链段用量的80wt％)，加热到80℃后搅拌至其完全溶解，然后加入47g溶解的甲基纤维素钠(占改性萜烯树脂链段用量的20wt％)，搅拌混合均匀，制得改性萜烯树脂。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5897g的环己烷，468g丁二烯(占混合单体用量的70wt％)，187g苯乙烯(占混合单体用量的30wt％)，23.58g的四氢呋喃，再加入0.327mol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60min后，再将制备好的改性萜烯树脂281g(占总量的30wt％)和2527g的环己烷的混合物压入聚合釜，混合20min完成后加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对比例7
按照实施例7的方法，不同的是，未对萜烯树脂改性，即直接将丁苯橡胶段和萜烯树脂偶联后，加入溶解的羧甲基纤维素钠，然后进行凝聚。
具体制备步骤如下：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5897g的环己烷，557g丁二烯((占混合单体用量的85wt％)，98g的苯乙烯(占混合单体用量的15wt％)，37.73g的四氢呋喃，再加入0.524mol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0.212mol二乙烯基苯继续进行偶联，反应60min后，再加入225g的萜烯树脂(占总量的21wt％)和1685g的环己烷的混合物压入聚合釜，继续反应60min，再加入溶解的羧甲基纤维素钠56g(占总量的9wt％)和842g的环己烷的混合物，混合20min后用水处理偶联后的反应混合物，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对比例8
按照实施例8的方法，不同的是，未对萜烯树脂改性，即直接将丁苯橡胶段和萜烯树脂偶联后，加入溶解的羧甲基纤维素钠，然后进行凝聚。
具体制备步骤如下：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5897g的环己烷，557g丁二烯(占混合单体用量的85wt％)，98g苯乙烯(占混合单体用量的15wt％)，53.90g的四氢呋喃，再加入0.504mol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0.301mol二乙烯基苯继续进行偶联，反应60min后，再加入萜烯树脂197g(占总量的21wt％)和1685g的环己烷的混合物压入聚合釜，继续反应60min，再加入溶解的羧甲基纤维素钠84g(占总量的9wt％)和842g的环己烷的混合物，混合20min后用水处理偶联后的反应混合物，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对比例9
按照实施例10的方法，不同的是，未对萜烯树脂改性，即直接将丁苯橡胶段和萜烯树脂偶联后，加入溶解的羧甲基纤维素钠，然后进行凝聚。
具体制备步骤如下：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5897g的环己烷，468g丁二烯(占混合单体用量的70wt％)，187g苯乙烯(占混合单体用量的30wt％)，23.58g的四氢呋喃，再加入0.262mol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0.131mol二乙烯基苯继续进行偶联，反应60min后，再加入萜烯树脂225g(占总量的24wt％)和2527g的环己烷的混合物压入聚合釜，继续反应60min，再加入溶解的羧甲基纤维素钠56g(占总量的6wt％)和842g的环己烷的混合物，混合20min后用水处理偶联后的反应混合物，加入水100g，12g抗氧剂1010，搅拌。胶液经湿法凝聚、干燥制得液体丁苯橡胶。
对实施例1-11以及对比例1-9的结果进行相关性能测定，结果如表1所示，其中，所述苯乙烯含量是以总的改性液体丁苯橡胶为基准。
表1
通过表1的结果可以看出，本发明星型接枝改性液体丁苯橡胶的合成过程中，采用二次加料(分丁二烯-苯乙烯共聚链段单体加料和纤维素醚改性萜烯树脂链段加料)的方法合成具有混合臂(如聚丁二烯苯乙烯臂，改性萜烯树脂聚合物臂)的星型接枝改性液体丁苯橡胶，由于混合臂的存在，相当于将聚丁二烯-苯乙烯橡胶和改性萜烯树脂通过所述偶联剂形成的聚合链段核心而链合在一起，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，能促进产品各种性能的协同优化，能够使改性橡胶具有良好的相容性、稳定性和粘合性。
平均结合力是指在剥离实验中，粘结剂与基材之间的剥离强度的平均值，通常使用单位面积内的应力来表示。可以用来比较不同条件下实施例和对比例的液体丁苯橡胶的粘合附着性能。从实施例1-10和对比例1-9之间的比较可以看出，随着接枝改性橡胶的分子量，黏度的增大，接枝改性橡胶的平均结合力增大，接枝改性橡胶的官能度越大，支化度越高，接枝改性橡胶的平均结合力越大。
由实施例1-11可以看出，随着聚合物分子量的增大，聚合物的黏度也逐渐增大，改性橡胶的平均结合力也逐渐增大，随着聚合物的官能度的增大，改性橡胶的平均结合力也逐渐增大，接枝改性橡胶的附着性能越好。从实施例和相应对比例比较可以看出，实施例比对比例的平均结合力数值要高，说明对比例的附着性能不如实施例中的液体丁苯橡胶样品，实施例中液体丁苯橡胶的官能度也较高，官能度越大，液体丁苯橡胶的支化度就越大，黏度也越大。黏度越大，液体丁苯橡胶的附着性能也越好。
从实施例1-4和对比例1-4比较可以看出，当对萜烯树脂改性后，接枝改性橡胶的黏度和平均结合力都增大，表明实施例中改性液体丁苯橡胶的附着性能要好于对比例的，说明改性的纤维素醚起到了良好的粘合效果。所述纤维素醚改性萜烯树脂链段影响所制备的橡胶的平均结合力，本发明的结构的橡胶的粘合性较好。
从实施例5-6和对比例5-6比较可以看出，当加入偶联剂对改性萜烯树脂进行偶联后，改性液体丁苯橡胶就形成了混合臂，所以实施例5-6中的星型改性液体丁苯橡胶的黏度和官能度以及平均结合力都大于对比例5-6的，说明实施例5-6中的星型改性液体丁苯橡胶附着性能要好于相应对比例5-6的。因此二乙烯基苯偶联剂的偶联作用能够将聚丁二烯-苯乙烯橡胶和改性萜烯树脂链合在一起，能促进产品各种性能的协同优化，能够使改性橡胶具有良好的相容性、稳定性和粘合性。
通过表1的结果可以看出，实施例1和实施例3对比，实施例2和实施例4对比，相同苯乙烯和丁二烯的含量下，纤维素醚改性萜烯树脂链段中，萜烯树脂的含量增大，其制备的改性橡胶的平均结合力变大，橡胶的粘合性较好。
采用本发明星型接枝改性液体丁苯橡胶的实施例1-11具有黏度大、支化度高、粘合性相容性明显更好的效果，附着结合力越大，粘度越大，液体丁苯橡胶的粘合性越好。表明改性液体丁苯橡胶具有抗湿滑性、高温抗流动性能和附着结合力好等优点，拓宽了应用范围。
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. 一种星型接枝改性液体丁苯橡胶，其特征在于，所述改性液体丁苯橡胶包括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丁二烯-苯乙烯共聚链段和纤维素醚改性萜烯树脂链段，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所述的改性液体丁苯橡胶，其特征在于，所述改性液体丁苯橡胶中，基于所述丁二烯-苯乙烯共聚链段和纤维素醚改性萜烯树脂链段的重量之和，所述纤维素醚改性萜烯树脂链段的含量为20-80wt％，所述丁二烯-苯乙烯共聚链段的含量为20-80wt％；
    优选地，所述丁二烯-苯乙烯共聚链段中，丁二烯结构单元的含量为50-90wt％，苯乙烯结构单元的含量为10-50wt％；
    优选地，所述纤维素醚改性萜烯树脂链段中，所述纤维素醚的含量为10-40wt％，所述萜烯树脂的含量为60-90wt％；
    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所述的改性液体丁苯橡胶，其特征在于，所述改性液体丁苯橡胶的数均分子量为3000-25000g/mol，25℃的黏度为20-60Pa·S，官能度为4-7。
  4. 一种星型接枝改性液体丁苯橡胶的制备方法，其特征在于，所述制备方法包括：
    (1)在引发剂和极性活化剂存在下，将丁二烯和苯乙烯进行共聚反应，得到活性丁二烯-苯乙烯共聚段；
    (2)将所述活性丁二烯-苯乙烯共聚段和偶联剂进行偶联反应，得到活性链；
    (3)将所述活性链与改性萜烯树脂进行聚合反应，得到所述星型接枝改性液体丁苯橡胶。
  5. 根据权利要求4所述的制备方法，其特征在于，所述改性萜烯树脂的制备方法包括：将萜烯树脂和溶剂混合后，再加入纤维素醚制得所述改性萜烯树脂。
  6. 根据权利要求4或5所述的制备方法，其特征在于，所述溶剂选自戊烷、己烷、辛烷、庚烷、环己烷、苯、甲苯和乙苯中的一种或几种，优选选自环己烷；
    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；
    优选地，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。
  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，所述共聚反应的温度为50-90℃，共聚反应的压力为0.1-0.25MPa，共聚反应的时间为20-80min；
    优选地，所述偶联反应的温度为50-90℃，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，所述聚合反应的温度为50-90℃，聚合反应的压力为0.1-0.25MPa，聚合反应的时间为60-100min。
  8. 根据权利要求4-7中任意一项所述的制备方法，其特征在于，丁二烯和苯乙烯的混合单体为20-80重量份，其中，丁二烯占所述混合单体用量的60-90wt％，苯乙烯占所述混合单体用量的10-40wt％；优选所述丁二烯和苯乙烯混合单体为30-70重量份，其中，所述丁二烯占混合单体用量的70-90wt％，所述苯乙烯占混合单体用量的10-30wt％；
    优选地，所述改性萜烯树脂为20-80重量份，其中，所述纤维素醚占所述改性萜烯树脂用量的10-40wt％，所述萜烯树脂占所述改性萜烯树脂用量的60-90wt％；优选所述改性萜烯树脂为30-70重量份，其中所述纤维素醚占所述改性萜烯树脂用量的10-30wt％，所述萜烯树脂占所述改性萜烯树脂用量的70-90wt％；
    优选地，所述引发剂为0.02-0.2重量份，优选为0.025-0.1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，优选为0.1-20:1；
    优选地，所述偶联剂与所述引发剂的摩尔比为0.1-1.5:1，优选为0.1-1：1。
  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接枝改性液体丁苯橡胶。
  10. 一种权利要求1-3和9中任意一项所述的星型接枝改性液体丁苯橡胶在橡胶加工领域中的应用。
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