CN116082648B - Functionalized star-shaped solution polymerized styrene-butadiene rubber, preparation method thereof and application thereof in new energy automobile tires - Google Patents

Functionalized star-shaped solution polymerized styrene-butadiene rubber, preparation method thereof and application thereof in new energy automobile tires Download PDF

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CN116082648B
CN116082648B CN202310286818.3A CN202310286818A CN116082648B CN 116082648 B CN116082648 B CN 116082648B CN 202310286818 A CN202310286818 A CN 202310286818A CN 116082648 B CN116082648 B CN 116082648B
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butadiene rubber
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polymerized styrene
propyl
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CN116082648A (en
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戢欢
毕吉福
邹凤朝
魏艳星
康小东
李晓帆
谢新政
张小虎
郇彦
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Huangpu Institute of Materials
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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
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0041—Compositions of the carcass layers
    • 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 

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a functionalized star-shaped solution polymerized styrene-butadiene rubber, a preparation method thereof and application thereof in a new energy automobile tire, belonging to the technical field of rubber, wherein the structural formula of the styrene-butadiene rubber is shown as a compound 1; the functionalized star-shaped solution polymerized styrene-butadiene rubber can realize star branching and functionalization at the same time, and can simultaneously realize the double effects of reducing the free chain segment at the molecular tail end of the solution polymerized styrene-butadiene rubber and hysteresis loss caused by the free chain segment, reducing the Paul effect caused by the combination effect of epoxy group functionalization or alkoxy functionalization modification strengthening and filler white carbon black, and has good mechanical strength, wet skid resistance, wear resistance and low heat generation property;

Description

Functionalized star-shaped solution polymerized styrene-butadiene rubber, preparation method thereof and application thereof in new energy automobile tires
Technical Field
The invention relates to the technical field of rubber, in particular to functionalized star-shaped solution polymerized styrene-butadiene rubber, a preparation method thereof and application thereof in a new energy automobile tire.
Background
Compared with the traditional fuel oil automobile, the new energy automobile is added with a power battery system and a motor control system, has high weight, quick start and acceleration and high braking load, and brings more severe technical requirements to the rubber of the tire tread rubber, the tire side rubber and other parts, such as wear resistance, wet skid resistance and low rolling resistance under the high modulus and high load state.
The existing new energy automobile tire part rubber technology generally adopts a scheme that high-strength natural rubber, butadiene rubber with low rolling resistance and low heat generation performance and solution polymerized styrene-butadiene rubber with high wear resistance and high wet skid resistance are physically blended and used together, and reinforcing fillers such as white carbon black and filler dispersion treatment agents such as silane coupling agents are added at the same time so as to meet the trend and requirements of green tires. Wherein, the solution polymerized styrene-butadiene rubber is subjected to end functionalization modification treatment so as to further improve the performance. The proposal of the terminal modification treatment is mainly divided into two types, wherein the first type adopts tin tetrachloride, silicon tetrachloride or methyl trichlorosilane and the like to carry out branched coupling to form multi-arm macromolecules such as star, thereby reducing hysteresis loss caused by free terminal chain segments, reducing heat generation, and increasing molecular weight and further improving mechanical strength and wear resistance; the second category is to adopt chloropropyl trimethoxyl silane and the like to carry out end-capping modification reaction to form polyalkoxyl end-capping functionalized linear molecules, so that the interaction with filler white carbon black and the like is enhanced, the Paen effect is reduced, the heat generation is reduced, and meanwhile, the mechanical strength, the wet skid resistance and the wear resistance are improved.
According to the scheme of modifying the tail end of the solution polymerized styrene-butadiene rubber which is an important component of the new energy automobile tire part rubber prepared by the existing method, star branching is tried to be achieved or functionalization is tried to be achieved, the star branching and the functionalization are not achieved at the same time, and the reduction of the free chain segment at the tail end of the solution polymerized styrene-butadiene rubber molecule and hysteresis loss brought by the free chain segment and the free chain segment can not be achieved at the same time, and the reduction of the Pair effect brought by the combination effect of the modified strengthening of the tail end alkoxy functionalization and the filler white carbon black can not be achieved at the same time.
The existing technical scheme of branching and coupling of stannic chloride, silicon tetrachloride or methyltrichlorosilane can form a star-shaped branching structure to a certain extent, but cannot realize functional modification, is very active and easy to generate hydrolysis side reaction, is inconvenient to store and use, and has large steric hindrance after branching of a single atom center part, so that complete branching is difficult to realize.
The existing technical schemes of end-capping functionalization modification such as chloropropyl trimethoxysilane can realize end-capping modification, but cannot form a star-shaped branched structure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the functionalized star-shaped solution polymerized styrene-butadiene rubber, the preparation method thereof and the application thereof in the tire of a new energy automobile, wherein the functionalized star-shaped solution polymerized styrene-butadiene rubber has good mechanical strength, wet skid resistance, wear resistance and low heat generation performance, and is particularly suitable for preparing rubber for the tire, in particular for the tire part rubber of the new energy automobile.
In order to achieve the above object, in a first aspect of the present invention, there is provided a functionalized star-shaped solution polymerized styrene-butadiene rubber having a molecular formula as shown in formula 1: [ (R) 31 R 32 R 33 SiO 0.5 ) a (R 34 R 35 SiO) b (R 36 SiO 1.5 ) c (SiO 2 ) d ] n
Formula 1;
in the formula 1, a+b+c+d=1, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and n is a positive integer greater than 0;
R 32 、R 33 、R 34 each independently selected from methyl, ethyl, propyl or phenyl;
R 31 、R 35 、R 36 each independently selected from- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
each functionalized star solution polymerized styrene-butadiene rubber molecule contains- (CH) 2 ) Z Number of- (L-SSBR) ≥3；
Each of the functionalized star-shaped solution polymerized styrene-butadiene rubber contains epoxy groups or alkoxy groups, and the number of the epoxy groups or the alkoxy groups is more than or equal to 1;
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
As a preferred embodiment of the present invention, the functionalized radial solution polymerized styrene-butadiene rubber has the formula shown in formula 2:
[(R 2 R 21 SiO) b ] m
formula 2;
in formula 2, b=1;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 2 is shown as a compound 1:
compound 1
Wherein R in formula 2 and Compound 1 2 Methyl, ethyl, propyl or phenyl;
R 21 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
m is an integer between 4 and 10;
the number of the L-SSBR is more than or equal to 3 and less than or equal to (m-1);
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
As a preferred embodiment of the present invention, the functionalized radial solution polymerized styrene-butadiene rubber has the formula shown in formula 3:
[(R 22 R 4 R 5 SiO 0.5 ) a (R 6 R 22 SiO) b ] n
formula 3;
a+b=1, 0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.1, n×a=2, 2.ltoreq.n×b.ltoreq.30 in the formula 3;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 3 is shown as a compound 2:
compound 2
Wherein R in formula 3 and Compound 2 4 And R is 5 Each independently selected from methyl, ethyl, propyl or phenyl;
R 6 methyl, ethyl or propyl;
R 22 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
n is an integer between 2 and 30;
the number of the L-SSBR is more than or equal to 3 and less than or equal to (n+1);
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
As a preferred embodiment of the present invention, the functionalized radial solution polymerized styrene-butadiene rubber has the formula shown in formula 4:
[(R 23 R 9 R 10 SiO 0.5 ) a (R 23 SiO 1.5 ) c ] n
formula 4;
a=0.75, c=0.25, n=4 in formula 4;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 4 is shown as a compound 3:
compound 3
Wherein R in formula 4 and Compound 3 9 And R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 23 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
The number of L-SSBRs = 3;
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
As a preferred embodiment of the present invention, the functionalized radial solution polymerized styrene-butadiene rubber has the formula shown in formula 5:
[(R 24 R 9 R 10 SiO 0.5 ) a (R 25 SiO 1.5 ) c ] n
formula 5;
a=2/3, c=1/3, n=6 in formula 5;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 5 is shown as a compound 4:
compound 4
Wherein R in formula 5 and Compound 4 9 And R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 24 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
R 25 Is- (CH) 2 ) Z - (L-SSBR), methyl, ethyl, propyl, octyl, lauryl, cetyl, stearyl, phenyl, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxyIsopropoxysilanylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
the number of the L-SSBR is less than or equal to 3 and less than or equal to 5, and at least contains one group selected from 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy and 3-methyldiethoxysilylpropyl methacryloyloxy;
L-SSBR is a linear butadiene-styrene copolymer; z is an integer and is more than or equal to 3 and less than or equal to 18.
As a preferred embodiment of the present invention, the functionalized radial solution polymerized styrene-butadiene rubber has the formula shown in formula 6:
[(R 26 R 13 R 14 SiO 0.5 ) a (SiO 2 ) d ] n
formula 6;
a=0.8, d=0.2, n=5 in formula 6;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 6 is shown as a compound 5:
compound 5
Wherein R in formula 6 and Compound 5 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 26 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
The number of L-SSBRs = 3;
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
As a preferred embodiment of the present invention, the functionalized radial solution polymerized styrene-butadiene rubber has the formula shown in formula 7:
[(R 26 R 13 R 14 SiO 0.5 ) a (SiO 2 ) d ] n
formula 7;
a=0.75, c=0.25, n=8 in formula 7;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 7 is shown as a compound 6:
compound 6
Wherein R in formula 7 and Compound 6 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 26 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropylAn iminomethacryloxy group, a 3-triisopropoxysilylpropyl methacryloxy group, a 3-trimethoxysilylpropyl acryloxy group, a 3-triethoxysilylpropyl acryloxy group, a 3-triisopropoxysilylpropyl acryloxy group, a 3-methyldimethoxysilylpropyl methacryloxy group or a 3-methyldiethoxysilylpropyl methacryloxy group;
The number of the L-SSBR is more than or equal to 3 and less than or equal to 5;
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
As a preferred embodiment of the present invention, the functionalized radial solution polymerized styrene-butadiene rubber has the formula shown in formula 8:
[(R 26 R 13 R 14 SiO 0.5 ) a (SiO 2 ) d ] n
formula 8;
a=2/3, c=1/3, n=12 in formula 8;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 8 is shown as a compound 7:
compound 7
Wherein R in formula 8 and Compound 7 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 26 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy,3-methyldimethoxysilane-based propyl methacryloyloxy or 3-methyldiethoxysilyl-based propyl methacryloyloxy;
The number of L-SSBR is not less than 3 and not more than 7, L-SSBR is linear butadiene-styrene copolymer, Z is an integer, and Z is not less than 3 and not more than 18.
The functionalized star-shaped solution polymerized styrene-butadiene rubber with the specific structure (molecular formulas 1-8 and compounds 1-7) can realize star branching and functionalization at the same time, can simultaneously realize the double effects of reducing the free chain segment at the molecular tail end of the solution polymerized styrene-butadiene rubber and reducing the payon effect caused by the combination effect of epoxy group functionalization or alkoxy functionalization modification strengthening and filler white carbon black, has good mechanical strength, wet skid resistance, wear resistance and low heat generation, and is particularly suitable for preparing rubber for tires, and particularly suitable for rubber for tire parts of new energy automobiles.
In the compounds 1-7, the random copolymer structure obtained by designing butadiene-styrene according to a specific proportion range can integrate the advantages of low rolling resistance and low heat generation of polybutadiene, and the advantages of wear resistance and wet skid resistance of polystyrene; the cyclic siloxane, the oligomeric linear siloxane, the oligomeric T-shaped siloxane and the oligomeric Q-shaped siloxane are used as the inner core of the branching agent, the star branching degree is flexibly adjustable from low to high, the distribution is uniform, the stress difference is not easy to generate, the active hydrolyzable groups are not easy to remain, the stability is high, and the hysteresis loss caused by the free chain segment at the molecular tail end of the solution polymerized styrene-butadiene rubber can be reduced more remarkably as a whole; the epoxy group functionalization or alkoxy functionalization modification can be carried out singly or in a matched mode, the modification degree is flexible and adjustable, epoxy groups or alkoxy groups are used as claws of the affinity filler white carbon black, and the combination effect of rubber and the filler white carbon black can be enhanced more remarkably as a whole to bring about the reduction effect of the Pair effect; the alkane arm connected to the siloxane has flexibly adjustable length and is used as a bridge for connecting the siloxane branching inner core and the L-SSBR shell, so that star branching is easier to complete and branching is kept uniform and stable; by combining the action characteristics, the compound 1-7 is used for the rubber for the automobile tire, and achieves better mechanical strength, wet skid resistance, low heat generation performance and wear resistance.
In a second aspect of the present invention, the present invention provides a method for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber, comprising the steps of:
carrying out a first reaction on silicon-hydrogen-containing polysiloxane, halogenated alpha olefin and unsaturated compound in the presence of a first solvent and a first catalyst to obtain a solution containing a modifier;
styrene and butadiene are subjected to a second reaction in the presence of a second solvent and a second catalyst to obtain a solution containing L-SSBR;
carrying out a third reaction on the solution containing the modifier and the solution containing the L-SSBR, adding an anti-aging agent, uniformly mixing, and carrying out steam condensation and drying to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber;
the unsaturated compound includes at least one of an unsaturated epoxy compound and an unsaturated alkoxysilane.
According to the preparation method, in the first aspect, a modifier with a branching function and a functionalization function is selected, and a reaction system with specific hydrosilation reaction activity, namely, an unsaturated halogenated olefin, an unsaturated epoxy compound and/or an unsaturated alkoxy compound and a multi-element silicon hydride are adopted in the preparation process of the modifier, so that the selective catalytic reaction of the unsaturated halogenated olefin, the unsaturated epoxy compound and/or the multi-element silicon hydride by means of a transition metal catalyst is realized, and the bottleneck that branching and functionalization cannot be achieved is overcome; in the second aspect, the long-arm design of the modifier enables the halogenated hydrocarbon and the L-SSBR active anion lithium to be easier to contact and react, the grafting is complete, uniform and stable, and the halogen is not easy to be hydrolyzed and consumed in advance or remain due to steric hindrance; in the third aspect, the telechelic design ensures that epoxy groups or alkoxy groups are easier to contact with filler white carbon black for effect, and the composition is more uniform and stable; by combining the characteristics of the method, the prepared compound 1-7 is used for the rubber for the automobile tire, and achieves good mechanical strength, wet skid resistance, low heat generation and wear resistance.
As a preferred embodiment of the present invention, the structural formula of the modifier is shown as compound 8, compound 9, compound 10, compound 11, compound 12, compound 13 or compound 14:
compound 8
Wherein R is 2 Methyl, ethyl, propyl or phenyl;
R 15 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
m is an integer between 4 and 10;
3≤-(CH 2 ) Z the number of X is less than or equal to (m-1), X is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 9
Wherein R is 4 And R is 5 Each independently selected from methyl, ethyl, propyl or phenyl;
R 6 Methyl, ethyl or propyl;
R 16 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylhydroxyAlkyl propyl methacryloyloxy, 3-trimethoxy silane propyl acryloyloxy, 3-triethoxy silane propyl acryloyloxy, 3-triisopropoxy silane propyl acryloyloxy, 3-methyl dimethoxy silane propyl methacryloyloxy or 3-methyl diethoxy silane propyl methacryloyloxy;
n is an integer between 2 and 30;
the number of the- (CH 2) Z-X is more than or equal to 3 and less than or equal to (n+1), X is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 10
Wherein R is 9 And R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 17 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
-(CH 2 ) Z -number of X = 3; x is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 11
Wherein R is 9 And R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 18 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
R 19 is- (CH) 2 ) Z -X, methyl, ethyl, propyl, octyl, lauryl, cetyl, stearyl, phenyl, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
3≤-(CH 2 ) Z The number of X is less than or equal to 5, and at least contains one compound selected from 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy3-triisopropoxysilylpropylacryloyloxy, 3-methyldimethoxysilylpropyimethacryloyloxy, 3-methyldiethoxysilylpropyimethacryloyloxy;
x is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 12
Wherein R is 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 20 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
-(CH 2 ) Z -X number = 3, X being selected from fluorine, chlorine, bromine or iodine, Z being an integer, and 3.ltoreq.z.ltoreq.18;
compound 13
Wherein R is 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 20 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylhydraseEthyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
3≤-(CH 2 ) Z the number of X is less than or equal to 5, X is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 14
Wherein R is 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 20 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylethyl, 3-triethoxysilylethyl, 3-triisopropoxysilylethyl, 3-methyldimethoxysilylethyl, 3-methyldiethoxysilylethyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
3≤-(CH 2 ) Z The number of X is less than or equal to 7, X is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
wherein, the compound 8 is used for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber shown in the compound 1; compound 9 was used to prepare the functionalized star solution polymerized styrene-butadiene rubber shown in compound 2; compound 10 was used to prepare functionalized star-shaped solution polymerized styrene-butadiene rubber shown in compound 3; compound 11 was used to prepare the functionalized star solution polymerized styrene-butadiene rubber shown in compound 4; compound 12 was used to prepare the functionalized star solution polymerized styrene-butadiene rubber shown in compound 5; compound 13 was used to prepare functionalized star-shaped solution polymerized styrene-butadiene rubber shown in compound 6; compound 14 was used to prepare the functionalized star solution polymerized styrene-butadiene rubber shown in compound 7.
The modifier adopts cyclic siloxane, oligomeric linear siloxane, oligomeric T-shaped siloxane and oligomeric Q-shaped siloxane as the inner core of branching agent, and a halogenated hydrocarbon arm and a polyalkoxysilane claw connected to the siloxane as the oligomer branching structure formed by the outer shell, wherein the halogenated hydrocarbon arm is longer and is easier to contact with the active anion center and carry out coupling branching reaction, the branching degree and the functionalization degree can be flexibly regulated and controlled by adjusting the proportion of the halogenated hydrocarbon arm and the polyalkoxysilane claw, and simultaneously, the dual effects of reducing the hysteresis loss caused by free chain segments at the molecular ends of the solution polymerized styrene-butadiene rubber and reducing the payne effect caused by the combination effect of epoxy functionalization or alkoxy functionalization modification reinforcement and filler white carbon black are realized, and the adhesive for the automobile tire has better mechanical strength, wet skid resistance, low heat generation property and wear resistance.
As a preferred embodiment of the present invention, the structural formula of the L-SSBR is shown as the compound 15:
compound 15
Wherein, 10 < e+f+g+h < 100000;0.1 < e/(e+f+g+h) < 0.5; f/(e+f+g+h) < 0.1 < 0.7;0.01 < g/(e+f+g+h) < 0.5;0 < h/(e+f+g+h) < 0.4.
The butadiene-styrene random copolymer structure designed according to the proportion range can integrate the advantages of low rolling resistance and low heat generation of polybutadiene and the advantages of wear resistance and wet skid resistance of polystyrene.
As a preferred embodiment of the present invention, the unsaturated epoxy compound includes at least one of 1-allyloxy-2, 3-epoxypropane, 1, 2-epoxy-4-vinylcyclohexane;
the unsaturated alkoxysilane includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloyloxy) propyltriisopropoxysilane, 3-acryloyloxy-propyltrimethoxysilane, 3-acryloyloxy-propyltriethoxysilane, 3- (methacryloyloxy) propylmethyldimethoxysilane, 3- (methacryloyloxy) propylmethyldiethoxysilane; and/or
The halogenated alpha olefin comprises 3-chloro-1-propene, 4-chloro-1-butene, 3-chloro-3-methyl-1-butene, 5-chloro-1-pentene, 6-chloro-1-hexene, 7-chloro-1-heptene, 8-chloro-1-octene, 9-chloro-1-nonene, 10-chloro-1-decene, 11-chloro-1-undecene, 3-bromo-1-propene, 4-bromo-1-butene, 5-bromo-1-pentene, 6-bromo-1-hexene, 7-bromo-1-heptene, 8-bromo-1-octene, 9-bromo-1-nonene, 10-bromo-1-decene, 11-bromo-1-undecene, 12-bromo-1-dodecene, 13-bromo-1-tridecene, 14-bromo-1-tetradecene, 15-bromo-1-pentadecene, 16-bromo-1-hexadecene, 17-bromo-1-heptadecene, 18-bromo-1-octadecene, 3-iodo-1-butene, 4-bromo-1-butene, 4-iodo-butene, 4-fluoro-1-butene, 4-iodo-butene, 4-bromo-1-dodecene, 3-bromo-1-decene, 11-bromo-1-decene, 14-bromo-1-decene, at least one of 2-bromo-1-vinyl-4-fluorobenzene; and/or
The silicon hydrogen-containing polysiloxane comprises at least one of cyclic siloxane containing silicon hydrogen bonds, linear polysiloxane containing silicon hydrogen bonds, T-shaped polysiloxane containing silicon hydrogen bonds and Q-shaped polysiloxane containing silicon hydrogen bonds.
As a preferred embodiment of the present invention, the cyclic siloxane containing silicon-hydrogen bond has the structural formula shown in compound 16:
compound 16
Wherein R is 1 Is hydrogen;
R 2 at least one selected from methyl, ethyl, propyl or phenyl;
m is an integer between 3 and 10;
the structural formula of the linear polysiloxane containing the silicon-hydrogen bond is shown as a compound 17:
compound 17
Wherein R is 3 And R is 7 Is hydrogen;
R 4 and R is 5 Each independently selected from methyl, ethyl, propyl or phenyl;
R 6 methyl, ethyl or propyl;
n is an integer between 2 and 30;
the T-type polysiloxane containing the silicon-hydrogen bond comprises a structural formula shown as a compound 18 or a compound 19:
compound 18
Compound 19
Wherein R is 8 Is hydrogen;
R 9 and R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 11 selected from the group consisting of hydrogen, methyl, ethyl, propyl, phenyl, 3-chloropropyl, 4-chlorobutyl, 5-chloropentyl, 6-chlorohexyl, 7-chloroheptyl, 8-chlorooctyl, 9-chlorononyl, 10-chlorodecyl, 11-chloroundecyl, 3-bromopropyl, 4-bromobutyl, 5-bromopentyl, 6-bromohexyl, 7-bromoheptylAt least one of 8-bromooctyl, 9-bromononyl, 10-bromodecyl, 11-bromoundecyl, 12-bromododecyl, 13-bromotridecyl, 14-bromotetradecyl, 15-bromopentadecyl, 16-bromohexadecyl, 17-bromoheptadecyl, 18-bromooctadecyl, 3-iodopropyl, 4-iodobutyl, 5-iodopentyl, 6-iodohexyl, 4-bromo-3, 4-tetrafluorobutyl, 2-bromo-4-fluoro-phenethyl or gamma- (2, 3-epoxypropoxy) propyl, 2- (3, 4-epoxycyclohexane) ethyl;
The Q-type polysiloxane containing the silicon-hydrogen bond comprises a structural formula shown as a compound 20, a compound 21 or a compound 22:
compound 20
Compound 21
Compound 22
Wherein R is 12 Is hydrogen;
R 13 and R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
wherein, the compound 16 is used for preparing a modifier shown as the compound 8; compound 17 was used to prepare the modifier shown for compound 9; compound 18 was used to prepare the modifier shown for the preparation of compound 10; compound 19 was used to prepare the modifier shown for the preparation of compound 11; compound 20 was used to prepare the modifier shown for compound 12; compound 21 was used to prepare the modifier shown for the preparation of compound 13; compound 22 was used to prepare the modifier shown for compound 14.
The invention is obtained by adopting cyclic siloxane, oligomeric linear siloxane, oligomeric T-shaped siloxane and oligomeric Q-shaped siloxane as the inner core of branching agent, and halogenated hydrocarbon arms and polyalkoxysilane claws connected to the siloxane as the oligomer branching structure modifier formed by the outer shell to carry out coupling branching and functionalization modification on the alkyl lithium catalyzed linear butadiene-styrene random copolymer in a solvent system, the branching degree and the functionalization degree can be flexibly regulated and controlled by adjusting the proportion of the halogenated hydrocarbon arms and the polyalkoxysilane claws, the halogenated hydrocarbon arms are longer and are easier to contact with active anion centers and carry out coupling branching reaction, and simultaneously, the double effects of reducing the free chain segments at the molecular tail ends of the solution polymerized styrene-butadiene rubber and the hysteresis loss caused by the free chain segments, and reducing the Peen effect caused by the combination effect of epoxy group functionalization modification reinforcement and filler white carbon black are realized, and the rubber for automobile tires has better mechanical strength, wet skid resistance, low heat resistance and wear resistance.
As a preferred embodiment of the present invention, the mass ratio of the silicon hydride-containing polysiloxane, the halogenated alpha olefin and the unsaturated compound is 1: 0.2-4: 0.1-3; and/or
The mass ratio of the styrene to the butadiene is 1: 1-9; and/or
The mass ratio of the solution containing the modifier to the solution containing the L-SSBR is 1: 10-1000.
As a preferred embodiment of the invention, the anti-aging agent is a solution consisting of 2, 6-di-tert-butyl-4-methylphenol and isopropanol; the mass fraction of the 2, 6-di-tert-butyl-4-methylphenol is 8-20wt%.
As a preferred embodiment of the present invention, the mass ratio of the silicon hydride-containing polysiloxane, the first catalyst and the first solvent is 1: 0.00005-0.01: 0-20 parts; and/or
The mass ratio of the styrene to the second catalyst to the second solvent is 1: 0.02-1: 10-100.
As a preferred embodiment of the invention, the first catalyst is a solution of a card catalyst, and the mass fraction of the card catalyst is 0.1-2%; and/or
The first solvent comprises at least one of toluene, xylene, n-hexane, isododecane, isohexadecane, cyclohexane, cyclic siloxane, polydimethylsiloxane, tetrahydrofuran, isopropanol and ethanol; and/or
The second catalyst is a solution of n-butyl lithium, and the mass fraction of the n-butyl lithium is 1-50%; and/or
The second solvent comprises at least one of toluene, xylene, n-hexane, isododecane, isohexadecane, cyclohexane, cyclic siloxane, polydimethylsiloxane, tetrahydrofuran, isopropanol and ethanol.
As a preferred embodiment of the invention, the temperature of the first reaction is 100-120 ℃ and the time is 1-5 h; and/or
The temperature of the second reaction is 60-80 ℃ and the time is 0.5-5 h; and/or
The temperature of the third reaction is 60-100 ℃ and the time is 0.5-5 h; and/or
The temperature of the steam condensation is 100-180 ℃.
In a third aspect of the invention, the invention provides the application of the functionalized star-shaped solution polymerized styrene-butadiene rubber in preparing rubber for new energy automobile tires.
Exemplary tire gums include tire side gums, tire carcass gums, and tire tread gums.
The invention has the beneficial effects that: (1) The functionalized star-shaped solution polymerized styrene-butadiene rubber with the specific structure can realize star branching and functionalization at the same time, can simultaneously realize the double effects of reducing the free chain segment at the molecular tail end of the solution polymerized styrene-butadiene rubber and the hysteresis loss brought by the free chain segment, and reducing the Paul effect brought by the combination effect of epoxy functional or alkoxy functional modification strengthening and filler white carbon black, has good mechanical strength, wet skid resistance, wear resistance and low heat generation performance, and is particularly suitable for preparing rubber for tires, in particular for rubber for tire parts of new energy automobiles; (2) The invention is obtained by adopting cyclic siloxane, oligomeric linear siloxane, oligomeric T-shaped siloxane and oligomeric Q-shaped siloxane as the inner core of branching agent, and halogenated hydrocarbon arms and polyalkoxysilane claws connected to the siloxane as the oligomer branching structure modifier formed by the outer shell to carry out coupling branching and functionalization modification on the alkyl lithium catalyzed linear butadiene-styrene random copolymer in a solvent system, the branching degree and the functionalization degree can be flexibly regulated and controlled by adjusting the proportion of the halogenated hydrocarbon arms and the polyalkoxysilane claws, the halogenated hydrocarbon arms are longer and are easier to contact with active anion centers and carry out coupling branching reaction, and simultaneously, the double effects of reducing the free chain segments at the molecular tail ends of the solution polymerized styrene-butadiene rubber and the hysteresis loss caused by the free chain segments, and reducing the Peen effect caused by the combination effect of epoxy group functionalization modification reinforcement and filler white carbon black are realized, and the rubber for automobile tires has better mechanical strength, wet skid resistance, low heat resistance and wear resistance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 361 g of 1,3,5,7, 9-pentamethylcyclopentasiloxane, 635 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 1220 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.49 g of 0.5wt% toluene solution of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain toluene solution of cyclic polysiloxane containing chlorohydrocarbylcyclohexyl epoxide, namely toluene solution of modifier-1.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 6.20 g of toluene solution of the modifier-1 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-1.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-1 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-1.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-1 is as follows:
wherein, the structural formula of the modifier-1 is as follows:
。
example 2
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 361 g of 1,3,5,7,9, 11-hexamethyl-cyclohexasiloxane, 588 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane, 248 g of 3- (methacryloyloxy) propyltrimethoxysilane and 1321 g of toluene were added to a reaction vessel, the stirring speed was kept at 200rpm, and a toluene solution of 0.53 g of 0.5wt% of a card catalyst was added to the reaction vessel at 100℃to react for 3 hours, and the temperature was lowered to 30℃to obtain a toluene solution of cyclic polysiloxane containing chlorine-containing hydrocarbon-based epoxycyclohexyl and alkoxy groups, namely a toluene solution of modifier-2.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 8.25 g of toluene solution of the modifier-2 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-2.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-2 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-2.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-2 is as follows:
wherein, the structural formula of the modifier-2 is as follows:
。
example 3
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 301 g of 1,3,5,7, 9-pentamethylcyclopentasiloxane, 588 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 1013 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.41 g of 0.5wt% toluene solution of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain a toluene solution of cyclic polysiloxane containing chlorohydrocarbyloxycyclohexyl, namely a toluene solution of modifier-3.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent S (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature at 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 6.25 g of toluene solution of the modifier-3 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-3.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-3 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-3.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-3 is as follows:
wherein, the structural formula of the modifier-3 is as follows:
。
example 4
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 301 g of 1,3,5,7, 9-pentamethylcyclopentasiloxane, 441 g of 8-chloro-1-octene, 893 g of 3- (methacryloyloxy) propyltrimethoxysilane and 1114 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.45 g of 0.5wt% toluene solution of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain a toluene solution of cyclic polysiloxane containing chlorohydrocarbyloxy cyclohexyl and alkoxy, namely a toluene solution of modifier-4.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 9.33 g of toluene solution of the modifier-4 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, keeping the stirring speed at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-4.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-4 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-4.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-4 is as follows:
wherein, the structural formula of the modifier-4 is as follows:
。
example 5
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 240 g of 1,3,5,7, 9-pentamethylcyclopentasiloxane, 441 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 805 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.32 g of 0.5wt% toluene solution of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain a toluene solution of cyclic polysiloxane containing chlorohydrocarbyloxycyclohexyl, namely a toluene solution of modifier-5.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 6.67 g of toluene solution of the modifier-5 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-5.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-5 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-5.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-5 is as follows:
wherein, the structural formula of the modifier-5 is as follows:
。
example 6
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 375 g 1,1,3,5,7,9,11,11-octamethylhexasiloxane, 1470 g 8-chloro-1-octene, 124 g 1, 2-epoxy-4-vinylcyclohexane and 1234 g toluene are added into a reaction kettle, stirring speed is kept at 200rpm, 0.50 g toluene solution of 0.5wt% of a card catalyst is added to react for 3 hours under heating to 100 ℃, and cooling to 30 ℃ to obtain toluene solution of linear polysiloxane containing chloroalkyl epoxy cyclohexyl and alkoxy, namely toluene solution of modifier-6.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 6.17 g of toluene solution of the modifier-6 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-6.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-6 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-6.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-6 is as follows:
wherein, the structural formula of the modifier-6 is as follows:
1,1,3,5,7,9,11,11-octamethylhexasiloxane has the following structural formula:
。
example 7
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 375 g 1,1,3,5,7,9,11,11-octamethylhexasiloxane, 588 g 8-chloro-1-octene, 124 g 1, 2-epoxy-4-vinylcyclohexane, 248 g 3- (methacryloyloxy) propyltrimethoxysilane, 1335 g toluene were added to the reaction vessel, the stirring speed was maintained at 200rpm, heated to 100℃and 0.53 g 0.5wt% toluene solution of a card catalyst was added to react for 3 hours, and cooled to 30℃to obtain a toluene solution of a linear polysiloxane containing chlorohydrocarbyloxycyclohexyl and alkoxy groups, i.e., a toluene solution of modifier-7.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 8.50 g of toluene solution of the modifier-7 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, keeping the stirring speed at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-7.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-7 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-7.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-7 is as follows:
wherein, the structural formula of the modifier-7 is as follows:
。
example 8
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 315 g 1,1,3,5,7,9,11,11-heptamethylpentasiloxane, 588 g 8-chloro-1-octene, 124 g 1, 2-epoxy-4-vinylcyclohexane and 1026 g toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.41 g toluene solution of 0.5wt% of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain toluene solution of linear polysiloxane containing chlorohydrocarbyloxy cyclohexyl and alkoxy, namely toluene solution of modifier-8.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 6.50 g of toluene solution of the modifier-8 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, keeping the stirring speed at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-8.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-8 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-8.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-8 is as follows:
wherein, the structural formula of the modifier-8 is as follows:
the structural formula of 1,1,3,5,7,9,9-heptamethylpentasiloxane is as follows:
。
example 9
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 375 g of 1, 3-tetra (dimethylsilyloxy) disiloxane, 735 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 1234 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.50 g of 0.5wt% toluene solution of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain a toluene solution of T-type polysiloxane containing chlorohydrocarbyloxy cyclohexyl and alkoxy, namely a toluene solution of modifier-9.
(2) Under the condition of anion initiation reaction, the temperature of the materials is regulated to 35 ℃, 80 g of styrene and 720 g of butadiene are contacted with 32 g of hexane solution of n-butyl lithium (the mass percent of n-butyl lithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), initiation reaction is carried out, the kettle pressure is kept at 0.4MPa, the stirring speed is 100rpm, the temperature is kept at 70 ℃, and the polymerization reaction is carried out for 2 hours, so that the solution of L-SSBR-1 is obtained.
(3) Adding 6.17 g of toluene solution of the modifier-9 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-9.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-9 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-9.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-9 is as follows:
wherein, the structural formula of the modifier-9 is as follows:
the structural formula of the 1, 3-tetra (dimethylsiloxy) disiloxane is as follows:
。
example 10
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 375 g of 1, 3-bis [ di (dimethylsilyloxy) ] disiloxane, 588 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane, 248 g of 3- (methacryloyloxy) propyltrimethoxysilane, 1335 g of toluene were added to the reaction vessel, the stirring speed was maintained at 200rpm, heated to 100℃and 0.53 g of a 0.5% by weight toluene solution of a card catalyst was added to react for 3 hours, and the temperature was lowered to 30℃to obtain a toluene solution of T-type polysiloxane containing chlorohydrocarbyloxycyclohexyl and alkoxy groups, i.e., a toluene solution of modifier-10.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 8.50 g of toluene solution of the modifier-10 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-10.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-10 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-10.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-10 is as follows:
wherein, the structural formula of the modifier-10 is as follows:
。
example 11
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 255 g of tris (dimethylsilyloxy) silane, 441 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 820 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.33 g of 0.5wt% toluene solution of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain toluene solution of T-type polysiloxane containing chlorohydrocarbyloxy cyclohexyl, namely toluene solution of modifier-11.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 7.00 g of toluene solution of the modifier-11 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-11.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-11 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-11.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-11 is as follows:
wherein, the structural formula of the modifier-11 is as follows:
the structural formula of the tris (dimethylsiloxy) silane is as follows:
。
example 12
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 379 g of tris (dimethylsilyloxy) ethyl silane, 2- (3, 4-epoxycyclohexane) ethyl silane, 441 g of 8-chloro-1-octene and 820 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.33 g of toluene solution of 0.5wt% of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain toluene solution of T-type polysiloxane containing chlorohydrocarbyloxycyclohexyl, namely toluene solution of modifier-12.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 7.00 g of toluene solution of the modifier-12 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-12.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-12 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-12.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-12 is as follows:
wherein, the structural formula of the modifier-12 is as follows:
tris (dimethylsiloxy) and 2- (3, 4-epoxycyclohexane) ethylsilane have the following structural formula:
。
example 13
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 518 g of 1, 3-tetra (dimethylsilyloxy) silane, 441 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 1083 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, the mixture is heated to 100 ℃, 0.47 g of toluene solution of 0.5wt% of a card catalyst is added to react for 3 hours, and the temperature is reduced to 30 ℃ to obtain toluene solution of T-type polysiloxane containing chlorohydrocarbyloxy cyclohexyl, namely toluene solution of modifier-13.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 2.61 g of toluene solution of the modifier-13 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, maintaining the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-13.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-13 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-13.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-13 is as follows:
wherein, the structural formula of the modifier-13 is as follows:
1, 3-tetra (dimethylsilyloxy) silane the structural formula of 1, 3-bis (3-chloropropyl) silane is as follows:
。
example 14
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 518 g of 1, 3-tetra (dimethylsilyloxy) silane, 147 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane, 248 g of 3- (methacryloyloxy) propyltrimethoxysilane and 1184 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, the mixture is heated to 100 ℃, 0.44 g of 0.5wt% of toluene solution of a card catalyst is added to react for 3 hours, and the temperature is reduced to 30 ℃ to obtain toluene solution of T-type polysiloxane containing chlorohydrocarbyloxy cyclohexyl, namely toluene solution of modifier-14.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 6.75 g of toluene solution of the modifier-14 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, keeping the stirring speed at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-14.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-14 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-14.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-14 is as follows:
wherein, the structural formula of the modifier-14 is as follows:
。
example 15
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 332 g of tris (dimethylsilyloxy) (3-chloropropyl) silane, 294 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 750 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, the mixture is heated to 100 ℃, 0.30 g of 0.5wt% toluene solution of a card catalyst is added to react for 3 hours, and the temperature is reduced to 30 ℃ to obtain toluene solution of T-type polysiloxane containing chlorohydrocarbyloxycyclohexyl, namely toluene solution of modifier-15.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 6.33 g of toluene solution of the modifier-15 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-15.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-15 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-15.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-15 is as follows:
wherein, the structural formula of the modifier-15 is as follows:
the structural formula of the tris (dimethylsiloxy) (3-chloropropyl) silane is as follows:
。
example 16
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 499 g of 1, 3-tetra (dimethylsilyloxy) ethyl ] silane, 1, 3-bis [2- (3, 4-epoxycyclohexane) ethyl ] silane, 588 g of 8-chloro-1-octene and 1087 g of toluene are added into a reaction kettle, the stirring speed is kept at 200rpm, 0.43 g of 0.5wt% toluene solution of a card catalyst is added to react for 3 hours under heating to 100 ℃, and the temperature is reduced to 30 ℃ to obtain toluene solution of T-type polysiloxane containing chlorohydrocarbyloxycyclohexyl, namely toluene solution of modifier-16.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 6.75 g of toluene solution of the modifier-16 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-16.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-16 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-16.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-16 is as follows:
wherein, the structural formula of the modifier-16 is as follows:
1, 3-tetra (dimethylsilyloxy) 1, 3-bis [2- (3, 4-epoxycyclohexane) ethyl ] silane has the structural formula:
。
example 17
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 778 g of 1,3,5, 7-octa [ di (dimethylsiloxy) ] cyclotetrasiloxane, 882 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane, 248 g of 3- (methacryloyloxy) propyltrimethoxysilane and 2032 g of toluene are added into a reaction vessel, stirring speed is kept at 200rpm, heating is carried out to 100 ℃ and 0.81 g of 0.5wt% toluene solution of a card catalyst is added for reaction for 3 hours, and cooling is carried out to 30 ℃ to obtain toluene solution of Q-type polysiloxane containing chlorohydrocarbyloxycyclohexyl and alkoxy, namely toluene solution of modifier-17.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 8.50 g of toluene solution of the modifier-17 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-17.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-17 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-17.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-17 is as follows:
wherein, the structural formula of the modifier-17 is as follows:
the structural formula of 1,3,5, 7-octa [ bis (dimethylsiloxy) ] cyclotetrasiloxane is as follows:
。
example 18
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 778 g of 1,3,5, 7-octa [ bis (dimethylsilyloxy) ] cyclotetrasiloxane, 588 g of 8-chloro-1-octene, 372 g of 1, 2-epoxy-4-vinylcyclohexane, 248 g of 3- (methacryloyloxy) propyltrimethoxysilane and 1956 g of toluene were added into a reaction vessel, the stirring speed was kept at 200rpm, the mixture was heated to 100℃and 0.78 g of a toluene solution of 0.5% by weight of a card catalyst was added to react for 3 hours, and the temperature was lowered to 30℃to obtain a toluene solution of Q-type polysiloxane containing chlorohydrocarbyloxycyclohexyl and alkoxy groups, namely, a toluene solution of modifier-18.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) And (3) adding 122.5 g of toluene solution of the modifier-18 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, maintaining the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-18.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-18 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-18.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-18 is as follows:
wherein the structural formula of the modifier-18 is as follows:
。
example 19
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 523 g of 1, 3-bis [ tris (dimethylsilyloxy) ] disiloxane, 735 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 1382 g of toluene were added to the reaction vessel, the stirring speed was kept at 200rpm, and the mixture was heated to 100℃and reacted with 0.55 g of a 0.5% by weight toluene solution of a card catalyst for 3 hours, and the temperature was lowered to 30℃to obtain a toluene solution of Q-type polysiloxane containing chlorohydrocarbyloxycyclohexyl and alkoxy groups, namely, a toluene solution of modifier-19.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 7.00 g of toluene solution of the modifier-19 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-19.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-19 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-19.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-19 is as follows:
wherein the structural formula of the modifier-19 is as follows:
the structural formula of 1, 3-bis [ tris (dimethylsiloxy) ] disiloxane is as follows:
。
example 20
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 523 g of 1, 3-bis [ tris (dimethylsilyloxy) ] disiloxane, 588 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane, 248 g of 3- (methacryloyloxy) propyltrimethoxysilane, 1483 g of toluene were added to the reaction vessel, the stirring speed was kept at 200rpm, and a toluene solution of 0.59 g of 0.5wt% of a card catalyst was added to the reaction vessel to react for 3 hours while heating to 100℃and cooling to 30℃to obtain a toluene solution of Q-type polysiloxane containing chlorohydrocarbyloxycyclohexyl and alkoxy groups, i.e., a toluene solution of modifier-20.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 240 g of styrene and 360 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 9.25 g of toluene solution of the modifier-20 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-20.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-20 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-20.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-20 is as follows:
wherein, the structural formula of the modifier-20 is as follows:
。
example 21
A method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber, which comprises the following steps:
(1) 329 g of tetra (dimethylsilyloxy) silane, 441 g of 8-chloro-1-octene, 124 g of 1, 2-epoxy-4-vinylcyclohexane and 894 g of toluene are added into a reaction kettle, stirring speed is kept at 200rpm, 0.36 g of toluene solution of 0.5wt% of a card catalyst is added to react for 3 hours under heating to 100 ℃, and cooling is carried out to 30 ℃ to obtain toluene solution of Q-type polysiloxane containing chlorohydrocarbyloxy cyclohexyl, namely toluene solution of modifier-21.
(2) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(3) Adding 7.33 g of toluene solution of the modifier-21 obtained in the step (1) into 2400 g of the solution of the L-SSBR-1 obtained in the step (2), carrying out coupling modification reaction, keeping the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of the antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 30 ℃ to obtain the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-21.
(4) 1220 g of the solution of the functionalized star-shaped solution polymerized styrene-butadiene rubber-21 in the step (3) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber-21.
Wherein the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber-21 is as follows:
wherein, the structural formula of the modifier-21 is as follows:
the structural formula of the tetra (dimethylsiloxy) silane is as follows:
。
comparative example 1
A preparation method of star-shaped solution polymerized styrene-butadiene rubber comprises the following steps:
(1) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(2) Adding 0.81 g of a modifier tin tetrachloride into 2400 g of the solution of the L-SSBR-1 obtained in the step (1), performing coupling modification reaction, maintaining the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 70 ℃, performing modification reaction for 1 hour, adding 40 g of an isopropanol solution of an antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10 wt%), and cooling to 30 ℃ to obtain a solution of star-shaped solution polymerized styrene-butadiene rubber-22.
(3) 1220 g of the solution of the star-shaped solution polymerized styrene-butadiene rubber-22 in the step (2) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the star-shaped solution polymerized styrene-butadiene rubber-22.
Comparative example 2
A preparation method of star-shaped solution polymerized styrene-butadiene rubber comprises the following steps:
(1) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(2) Adding 0.53 g of silicon tetrachloride serving as a modifier into 2400 g of the L-SSBR-1 obtained in the step (1), performing coupling modification reaction, maintaining the kettle pressure at 0.4MPa, stirring at 100rpm, maintaining the temperature to 70 ℃, performing modification reaction for 1 hour, adding 40 g of isopropanol solution of an antioxidant 2, 6-di-tert-butyl-4-methylphenol (the mass percentage of the 2, 6-di-tert-butyl-4-methylphenol is 10 wt%), and cooling to 30 ℃ to obtain a solution of star-shaped solution polymerized styrene-butadiene rubber-23.
(3) 1220 g of the solution of the star-shaped solution polymerized styrene-butadiene rubber-23 in the step (2) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the star-shaped solution polymerized styrene-butadiene rubber-23.
Comparative example 3
A preparation method of star-shaped solution polymerized styrene-butadiene rubber comprises the following steps:
(1) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(2) Adding 0.63 g of modifier methyltrichlorosilane into 2400 g of the solution of L-SSBR-1 obtained in the step (1), carrying out coupling modification reaction, maintaining the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 10 ℃, carrying out modification reaction for 1 hour, adding 40 g of isopropanol solution of an antioxidant 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percent of the 2, 6-di-tert-butyl-4-methylphenol is 10 wt%), and cooling to 20-40 ℃ to obtain the solution of star-shaped solution polymerized styrene-butadiene rubber-24.
(3) 1220 g of the solution of the star-shaped solution polymerized styrene-butadiene rubber-24 in the step (2) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the star-shaped solution polymerized styrene-butadiene rubber-24.
Comparative example 4
A method for preparing functionalized solution polymerized styrene-butadiene rubber, comprising the following steps:
(1) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-1.
(2) Adding 2.49 g of 3-chloropropyl trimethoxyl silane serving as a modifier into 2400 g of the solution of the L-SSBR-1 obtained in the step (1), performing coupling modification reaction, maintaining the kettle pressure at 0.4MPa, stirring at 100rpm, preserving the temperature to 10 ℃, performing modification reaction for 1 hour, adding 40 g of isopropanol solution of the anti-aging agent of 2, 6-di-tert-butyl-4-methylphenol (wherein the mass percentage of the 2, 6-di-tert-butyl-4-methylphenol is 10wt percent), and cooling to 20-40 ℃ to obtain the solution of the functionalized solution polymerized styrene-butadiene rubber-25.
(3) 1220 g of the solution of the functionalized solution polymerized styrene-butadiene rubber-25 in the step (2) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes, so as to obtain the functionalized solution polymerized styrene-butadiene rubber-25.
Comparative example 5
A method for preparing L-SSBR, comprising the following steps:
(1) Under the condition of anion initiation reaction, regulating the temperature of the materials to 35 ℃, contacting 200 g of styrene and 600 g of butadiene with 32 g of n-butyllithium hexane solution (the mass percent of n-butyllithium is 5 wt%) in 4000 g of solvent (wherein the solvent is prepared from toluene and tetrahydrofuran according to the mass ratio of 17:3), carrying out initiation reaction, maintaining the kettle pressure of 0.4MPa, keeping the stirring speed of 100rpm, keeping the temperature to 70 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of L-SSBR-26.
(2) 1220 g of the solution of the L-SSBR-26 in the step (1) is subjected to steam condensation at 140 ℃, and the condensation product is dried by a blast oven at 110 ℃ for 60 minutes to obtain the L-SSBR-26.
Test example 1
The performance data of the functionalized star-shaped solution-polymerized styrene-butadiene rubber 1-21 obtained in examples 1-21, the star-shaped solution-polymerized styrene-butadiene rubber 22-24 obtained in comparative examples 1-3, the functionalized solution-polymerized styrene-butadiene rubber-25 obtained in comparative example 4 and the L-SSBR-26 obtained in comparative example 5 were measured by using the instruments and the measuring methods shown in Table 1, and the test results are shown in Table 2.
TABLE 1
TABLE 2
Test example 2
The functionalized star-shaped solution polymerized styrene-butadiene rubber obtained in examples 1 to 21 was used for the tread rubber formulation of new energy automobile tires to obtain effect examples 1 to 21, respectively. The tread rubber comprises the following components: 600 g of functionalized star-shaped solution polymerized styrene-butadiene rubber, 150 g of butadiene rubber (BR 9000), 450 g of white carbon black (Ultrasil 7000 GR), 10 g of zinc oxide, 2.5 g of stearic acid, 2.5 g of anti-aging agent (4020), 2.5 g of accelerator (CZ), 1.25 g of accelerator (D) and 7.5 g of sulfur.
The star-shaped solution polymerized styrene-butadiene rubber obtained in comparative examples 1 to 3 was used for the tread rubber formulation of new energy automobile tires to obtain effect examples 22 to 24, respectively. The tread rubber comprises the following components: 600 g of star-shaped solution polymerized styrene-butadiene rubber, 150 g of butadiene rubber (BR 9000), 450 g of white carbon black (Ultrasil 7000 GR), 10 g of zinc oxide, 2.5 g of stearic acid, 2.5 g of anti-aging agent (4020), 2.5 g of accelerator (CZ), 1.25 g of accelerator (D) and 7.5 g of sulfur.
The functionalized solution polymerized styrene-butadiene rubber obtained in comparative example 4 was used in the tread rubber formulation of a new energy automobile tire to obtain effect example 25. The tread rubber comprises the following components: 600 g of functionalized solution polymerized styrene-butadiene rubber, 150 g of butadiene rubber (BR 9000), 450 g of white carbon black (Ultrasil 7000 GR), 10 g of zinc oxide, 2.5 g of stearic acid, 2.5 g of anti-aging agent (4020), 2.5 g of accelerator (CZ), 1.25 g of accelerator (D) and 7.5 g of sulfur.
The L-SSBR-26 obtained in comparative example 5 was used in the tread rubber formulation of a new energy automobile tire to obtain effect example 26. The tread rubber comprises the following components: 600 g of L-SSBR-26 (linear solution polymerized styrene-butadiene rubber), 150 g of butadiene rubber (BR 9000), 450 g of white carbon black (Ultrasil 7000 GR), 10 g of zinc oxide, 2.5 g of stearic acid, 2.5 g of age inhibitor (4020), 2.5 g of accelerator (CZ), 1.25 g of accelerator (D) and 7.5 g of sulfur.
The preparation process of the effect example sample comprises the following steps: in an internal mixer, the initial temperature is 70 ℃, the rotating speed of a rotor is 30 rpm, SSBR and BR are firstly added into the internal mixer to plasticate for 2 minutes, white carbon black is added, the rotating speed of the rotor is adjusted to 45 rpm, the internal mixing is carried out for 5 minutes, a heating switch is started, the temperature of sizing material reaches 160 ℃, the sizing material is discharged after heat preservation is carried out for 1 minute, and the sizing material is cooled and flaked on an open mill and is parked for 8 hours; transferring the film which is parked for a long time to an open mill, adding zinc oxide, stearic acid, an anti-aging agent, an accelerator and sulfur into the open mill, and opening the mill for 3 minutes to obtain a lower film; and (3) after standing for 8 hours, vulcanizing in a plate vulcanizing machine at 150 ℃ until the vulcanized rubber is vulcanized, and obtaining the vulcanized rubber, namely the effect example sample.
The cured rubber property data of examples and comparative examples were measured by the apparatus and the measurement method shown in Table 3, and the test results are shown in Table 4.
TABLE 3 Table 3
8 * : for ease of comparison, after measuring the Payne effect of each example and comparative example, a Payne effect ratio (%) was obtained by comparison with the Payne effect reference of example 1, i.e., the Payne effect ratio of example 1 was 100%, and the rest were analogized.
TABLE 4 Table 4
Test results
As can be seen from table 4, compared with comparative examples 1 to 5, the functionalized star-shaped solution polymerized styrene-butadiene rubber prepared in examples 1 to 21 has a hardness at a medium upper level, a significantly improved tear strength and tensile strength, a significantly improved Tan δ (0 ℃) showing a significantly enhanced wet skid resistance, a significantly reduced DIN abrasion and compression fatigue temperature rise, a significantly reduced Payne effect showing a significantly reduced hysteresis loss, a significantly reduced Tan δ (60 ℃) showing a significantly reduced rolling resistance, and a significantly advantageous application of the example scheme to tire tread rubber in combination.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (19)

1. A functionalized star-shaped solution polymerized styrene-butadiene rubber is characterized in that the molecular formula is shown in a formula 1: [ (R) 31 R 32 R 33 SiO 0.5 ) a (R 34 R 35 SiO) b (R 36 SiO 1.5 ) c (SiO 2 ) d ] n
Formula 1;
in the formula 1, a+b+c+d=1, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and n is a positive integer greater than 0;
R 32 、R 33 、R 34 each independently selected from methyl, ethyl, propyl or phenyl;
R 31 、R 35 、R 36 each independently selected from- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyryloxy;
each functionalized star solution polymerized styrene-butadiene rubber molecule contains- (CH) 2 ) Z The number of the- (L-SSBR) is more than or equal to 3;
each of the functionalized star-shaped solution polymerized styrene-butadiene rubber contains epoxy groups or alkoxy groups, and the number of the epoxy groups or the alkoxy groups is more than or equal to 1;
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
2. The functionalized radial solution polymerized styrene butadiene rubber of claim 1, wherein the functionalized radial solution polymerized styrene butadiene rubber has a formula as shown in formula 2:
[(R 2 R 21 SiO) b ] m
Formula 2;
in formula 2, b=1;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 2 is shown as a compound 1:
compound 1
Wherein R in formula 2 and Compound 1 2 Methyl, ethyl, propyl or phenyl;
R 21 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyryloxy;
m is an integer between 4 and 10;
the number of the L-SSBR is more than or equal to 3 and less than or equal to (m-1);
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
3. The functionalized radial solution polymerized styrene butadiene rubber of claim 1, wherein the functionalized radial solution polymerized styrene butadiene rubber has a formula as shown in formula 3:
[(R 22 R 4 R 5 SiO 0.5 ) a (R 6 R 22 SiO) b ] n
formula 3;
a+b=1, 0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.1, n×a=2, 2.ltoreq.n×b.ltoreq.30 in the formula 3;
The structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 3 is shown as a compound 2:
compound 2
Wherein R in formula 3 and Compound 2 4 And R is 5 Each independently selected from methyl, ethyl, propyl or phenyl;
R 6 methyl, ethyl or propyl;
R 22 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyryloxy;
n is an integer between 2 and 30;
the number of the L-SSBR is more than or equal to 3 and less than or equal to (n+1);
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
4. The functionalized radial solution polymerized styrene butadiene rubber of claim 1, wherein the functionalized radial solution polymerized styrene butadiene rubber has a formula as shown in formula 4:
[(R 23 R 9 R 10 SiO 0.5 ) a (R 23 SiO 1.5 ) c ] n
formula 4;
a=0.75, c=0.25, n=4 in formula 4;
The structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 4 is shown as a compound 3:
compound 3
Wherein R in formula 4 and Compound 3 9 And R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 23 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyryloxy;
the number of L-SSBRs = 3;
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
5. The functionalized radial solution polymerized styrene butadiene rubber of claim 1, wherein the functionalized radial solution polymerized styrene butadiene rubber has a formula as shown in formula 5:
[(R 24 R 9 R 10 SiO 0.5 ) a (R 25 SiO 1.5 ) c ] n
formula 5;
a=2/3, c=1/3, n=6 in formula 5;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 5 is shown as a compound 4:
Compound 4
Wherein R in formula 5 and Compound 4 9 And R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 24 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyryloxy;
R 25 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyloxy;
The number of the L-SSBR is less than or equal to 3 and less than or equal to 5, and at least contains one group selected from 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy and 3-methyldiethoxysilylpropyl isobutyryloxy;
L-SSBR is a linear butadiene-styrene copolymer; z is an integer and is more than or equal to 3 and less than or equal to 18.
6. The functionalized radial solution polymerized styrene butadiene rubber of claim 1, wherein the functionalized radial solution polymerized styrene butadiene rubber has a formula as shown in formula 6:
[(R 26 R 13 R 14 SiO 0.5 ) a (SiO 2 ) d ] n
formula 6;
a=0.8, d=0.2, n=5 in formula 6;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 6 is shown as a compound 5:
compound 5
Wherein R in formula 6 and Compound 5 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 26 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyryloxy;
The number of L-SSBRs = 3;
L-SSBR is a linear butadiene-styrene copolymer;
z is an integer and is more than or equal to 3 and less than or equal to 18.
7. The functionalized radial solution polymerized styrene butadiene rubber of claim 1, wherein the functionalized radial solution polymerized styrene butadiene rubber has a formula as shown in formula 7:
[(R 26 R 13 R 14 SiO 0.5 ) a (SiO 2 ) d ] n
formula 7;
a=0.75, c=0.25, n=8 in formula 7;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 7 is shown as a compound 6:
compound 6
Wherein R in formula 7 and Compound 6 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 26 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyryloxy;
the number of the L-SSBR is more than or equal to 3 and less than or equal to 5;
L-SSBR is a linear butadiene-styrene copolymer;
Z is an integer and is more than or equal to 3 and less than or equal to 18.
8. The functionalized radial solution polymerized styrene butadiene rubber of claim 1, wherein the functionalized radial solution polymerized styrene butadiene rubber has a formula as shown in formula 8:
[(R 26 R 13 R 14 SiO 0.5 ) a (SiO 2 ) d ] n
formula 8;
a=2/3, c=1/3, n=12 in formula 8;
the structural formula of the functionalized star-shaped solution polymerized styrene-butadiene rubber corresponding to the molecular formula of the formula 8 is shown as a compound 7:
compound 7
Wherein R in formula 8 and Compound 7 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 26 is- (CH) 2 ) Z - (L-SSBR), 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl isobutyryloxy, 3-triethoxysilylpropyl isobutyryloxy, 3-triisopropoxysilylpropyl isobutyryloxy, 3-trimethoxysilylpropyl propionyloxy, 3-triethoxysilylpropyl propionyloxy, 3-triisopropoxysilylpropyl propionyloxy, 3-methyldimethoxysilylpropyl isobutyryloxy or 3-methyldiethoxysilylpropyl isobutyryloxy;
the number of L-SSBR is not less than 3 and not more than 7, L-SSBR is linear butadiene-styrene copolymer, Z is an integer, and Z is not less than 3 and not more than 18.
9. The method for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber according to any one of claims 1 to 8, which is characterized by comprising the following steps:
Carrying out a first reaction on silicon-hydrogen-containing polysiloxane, halogenated alpha olefin and unsaturated compound in the presence of a first solvent and a first catalyst to obtain a solution containing a modifier;
styrene and butadiene are subjected to a second reaction in the presence of a second solvent and a second catalyst to obtain a solution containing L-SSBR;
carrying out a third reaction on the solution containing the modifier and the solution containing the L-SSBR, adding an anti-aging agent, uniformly mixing, and carrying out steam condensation and drying to obtain the functionalized star-shaped solution polymerized styrene-butadiene rubber;
the unsaturated compound includes at least one of an unsaturated epoxy compound and an unsaturated alkoxysilane.
10. The method for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 9, wherein the structural formula of the modifier is shown as a compound 8, a compound 9, a compound 10, a compound 11, a compound 12, a compound 13 or a compound 14:
compound 8
Wherein R is 2 Methyl, ethyl, propyl or phenyl;
R 15 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
m is an integer between 4 and 10;
3≤-(CH 2 ) Z the number of X is less than or equal to (m-1), X is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 9
Wherein R is 4 And R is 5 Each independently selected from methyl, ethyl, propyl or phenyl;
R 6 methyl, ethyl or propyl;
R 16 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethylOxy-silylpropyl methacryloxy or 3-methyldiethoxysilyl-propyl methacryloxy;
n is an integer between 2 and 30;
the number of the- (CH 2) Z-X is more than or equal to 3 and less than or equal to (n+1), X is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 10
Wherein R is 9 And R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 17 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
-(CH 2 ) Z -number of X = 3; x is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 11
Wherein R is 9 And R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 18 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilanePropyl acryloyloxy, 3-triisopropoxy silane propyl acryloyloxy, 3-methyl dimethoxy silane propyl methacryloyloxy or 3-methyl diethoxy silane propyl methacryloyloxy;
R 19 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
3≤-(CH 2 ) Z The number of X is less than or equal to 5, and at least contains one group selected from 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy, 3-methyldiethoxysilylpropyl methacryloxy;
x is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
compound 12
Wherein R is 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 20 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl isobutylAllyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
-(CH 2 ) Z -X number = 3, X being selected from fluorine, chlorine, bromine or iodine, Z being an integer, and 3.ltoreq.z.ltoreq.18;
compound 13
Wherein R is 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 20 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy) propyl, 3-trimethoxysilylpropyl methacryloxy, 3-triethoxysilylpropyl methacryloxy, 3-triisopropoxysilylpropyl methacryloxy, 3-trimethoxysilylpropyl acryloxy, 3-triethoxysilylpropyl acryloxy, 3-triisopropoxysilylpropyl acryloxy, 3-methyldimethoxysilylpropyl methacryloxy or 3-methyldiethoxysilylpropyl methacryloxy;
3≤-(CH 2 ) Z the number of X is less than or equal to 5, X is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
/>
compound 14
Wherein R is 13 And R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
R 20 is- (CH) 2 ) Z -X, 2- (3, 4-epoxycyclohexane) ethyl, 3- (2, 3-epoxypropoxy)) Propyl, 3-trimethoxysilylpropyl methacryloyloxy, 3-triethoxysilylpropyl methacryloyloxy, 3-triisopropoxysilylpropyl methacryloyloxy, 3-trimethoxysilylpropyl acryloyloxy, 3-triethoxysilylpropyl acryloyloxy, 3-triisopropoxysilylpropyl acryloyloxy, 3-methyldimethoxysilylpropyl methacryloyloxy or 3-methyldiethoxysilylpropyl methacryloyloxy;
3≤-(CH 2 ) Z The number of X is less than or equal to 7, X is selected from fluorine, chlorine, bromine or iodine, Z is an integer, and Z is more than or equal to 3 and less than or equal to 18;
wherein, the compound 8 is used for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber shown in the compound 1; compound 9 was used to prepare the functionalized star solution polymerized styrene-butadiene rubber shown in compound 2; compound 10 was used to prepare functionalized star-shaped solution polymerized styrene-butadiene rubber shown in compound 3; compound 11 was used to prepare the functionalized star solution polymerized styrene-butadiene rubber shown in compound 4; compound 12 was used to prepare the functionalized star solution polymerized styrene-butadiene rubber shown in compound 5; compound 13 was used to prepare functionalized star-shaped solution polymerized styrene-butadiene rubber shown in compound 6; compound 14 was used to prepare the functionalized star solution polymerized styrene-butadiene rubber shown in compound 7.
11. The method for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 9, wherein the structural formula of the L-SSBR is shown as a compound 15:
compound 15
Wherein, 10 < e+f+g+h < 100000;0.1 < e/(e+f+g+h) < 0.5; f/(e+f+g+h) < 0.1 < 0.7;0.01 < g/(e+f+g+h) < 0.5;0 < h/(e+f+g+h) < 0.4.
12. The method for preparing a functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 9, wherein the unsaturated epoxy compound comprises at least one of 1-allyloxy-2, 3-propylene oxide, 1, 2-epoxy-4-vinylcyclohexane;
The unsaturated alkoxysilane includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloyloxy) propyltriisopropoxysilane, 3-acryloyloxy-propyltrimethoxysilane, 3-acryloyloxy-propyltriethoxysilane, 3- (methacryloyloxy) propylmethyldimethoxysilane, 3- (methacryloyloxy) propylmethyldiethoxysilane; and/or
The halogenated alpha olefin comprises 3-chloro-1-propene, 4-chloro-1-butene, 3-chloro-3-methyl-1-butene, 5-chloro-1-pentene, 6-chloro-1-hexene, 7-chloro-1-heptene, 8-chloro-1-octene, 9-chloro-1-nonene, 10-chloro-1-decene, 11-chloro-1-undecene, 3-bromo-1-propene, 4-bromo-1-butene, 5-bromo-1-pentene, 6-bromo-1-hexene, 7-bromo-1-heptene, 8-bromo-1-octene, 9-bromo-1-nonene, 10-bromo-1-decene, 11-bromo-1-undecene, 12-bromo-1-dodecene, 13-bromo-1-tridecene, 14-bromo-1-tetradecene, 15-bromo-1-pentadecene, 16-bromo-1-hexadecene, 17-bromo-1-heptadecene, 18-bromo-1-octadecene, 3-iodo-1-butene, 4-bromo-1-butene, 4-iodo-butene, 4-fluoro-1-butene, 4-iodo-butene, 4-bromo-1-dodecene, 3-bromo-1-decene, 11-bromo-1-decene, 14-bromo-1-decene, at least one of 2-bromo-1-vinyl-4-fluorobenzene; and/or
The silicon hydrogen-containing polysiloxane comprises at least one of cyclic siloxane containing silicon hydrogen bonds, linear polysiloxane containing silicon hydrogen bonds, T-shaped polysiloxane containing silicon hydrogen bonds and Q-shaped polysiloxane containing silicon hydrogen bonds.
13. The method for preparing functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 12, wherein the cyclic siloxane containing silicon-hydrogen bond has a structural formula shown in compound 16:
compound 16
Wherein R is 1 Is hydrogen;
R 2 at least one selected from methyl, ethyl, propyl or phenyl;
m is an integer between 3 and 10;
the structural formula of the linear polysiloxane containing the silicon-hydrogen bond is shown as a compound 17:
compound 17
Wherein R is 3 And R is 7 Is hydrogen;
R 4 and R is 5 Each independently selected from methyl, ethyl, propyl or phenyl;
R 6 methyl, ethyl or propyl;
n is an integer between 2 and 30;
the T-type polysiloxane containing the silicon-hydrogen bond comprises a structural formula shown as a compound 18 or a compound 19:
compound 18
Compound 19
Wherein R is 8 Is hydrogen;
R 9 and R is 10 Each independently selected from methyl, ethyl, propyl or phenyl;
R 11 selected from the group consisting of hydrogen, 3-chloropropyl, 4-chlorobutyl, 5-chloropentyl, 6-chlorohexyl, 7-chloroheptyl, 8-chlorooctyl, 9-chlorononyl, 10-chlorodecyl, 11-chloroundecyl, 3-bromopropyl, 4-bromobutyl At least one of 5-bromopentyl, 6-bromohexyl, 7-bromopeptyl, 8-bromooctyl, 9-bromononyl, 10-bromodecyl, 11-bromoundecyl, 12-bromododecyl, 13-bromotridecyl, 14-bromotetradecyl, 15-bromopentadecyl, 16-bromohexadecyl, 17-bromoheptadecyl, 18-bromooctadecyl, 3-iodopropyl, 4-iodobutyl, 5-iodopentyl, 6-iodohexyl or gamma- (2, 3-epoxypropoxy) propyl, 2- (3, 4-epoxycyclohexane) ethyl;
the Q-type polysiloxane containing the silicon-hydrogen bond comprises a structural formula shown as a compound 20, a compound 21 or a compound 22:
compound 20
Compound 21
Compound 22
Wherein R is 12 Is hydrogen;
R 13 and R is 14 Each independently selected from methyl, ethyl, propyl or phenyl;
wherein, the compound 16 is used for preparing a modifier shown as the compound 8; compound 17 was used to prepare the modifier shown for compound 9; compound 18 was used to prepare the modifier shown for the preparation of compound 10; compound 19 was used to prepare the modifier shown for the preparation of compound 11; compound 20 was used to prepare the modifier shown for compound 12; compound 21 was used to prepare the modifier shown for the preparation of compound 13; compound 22 was used to prepare the modifier shown for compound 14.
14. The method for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 9, wherein the mass ratio of the silicone containing a silicon hydride group, the halogenated alpha olefin and the unsaturated compound is 1: 0.2-4: 0.1-3; and/or
The mass ratio of the styrene to the butadiene is 1: 1-9; and/or
The mass ratio of the solution containing the modifier to the solution containing the L-SSBR is 1: 10-1000.
15. The method for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 9, wherein the anti-aging agent is a solution consisting of 2, 6-di-tert-butyl-4-methylphenol and isopropanol; the mass fraction of the 2, 6-di-tert-butyl-4-methylphenol is 8-20wt%.
16. The method for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 9, wherein the mass ratio of the silicon-hydrogen group-containing polysiloxane to the first catalyst to the first solvent is 1: 0.00005-0.01: 0-20 parts; and/or
The mass ratio of the styrene to the second catalyst to the second solvent is 1: 0.02-1: 10-100.
17. The preparation method of the functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 9, wherein the first catalyst is a solution of a card catalyst, and the mass fraction of the card catalyst is 0.1-2%; and/or
The first solvent comprises at least one of toluene, xylene, n-hexane, isododecane, isohexadecane, cyclohexane, cyclic siloxane, polydimethylsiloxane, tetrahydrofuran, isopropanol and ethanol; and/or
The second catalyst is a solution of n-butyl lithium, and the mass fraction of the n-butyl lithium is 1-50%; and/or
The second solvent comprises at least one of toluene, xylene, n-hexane, isododecane, isohexadecane, cyclohexane, cyclic siloxane, polydimethylsiloxane, tetrahydrofuran, isopropanol and ethanol.
18. The method for preparing the functionalized star-shaped solution polymerized styrene-butadiene rubber according to claim 9, wherein the temperature of the first reaction is 100-120 ℃ and the time is 1-5 h; and/or
The temperature of the second reaction is 60-80 ℃ and the time is 0.5-5 h; and/or
The temperature of the third reaction is 60-100 ℃ and the time is 0.5-5 h; and/or
The temperature of the steam condensation is 100-180 ℃.
19. The use of the functionalized star-shaped solution polymerized styrene-butadiene rubber according to any one of claims 1 to 8 for preparing a rubber for a new energy automobile tire.
CN202310286818.3A 2023-03-23 2023-03-23 Functionalized star-shaped solution polymerized styrene-butadiene rubber, preparation method thereof and application thereof in new energy automobile tires Active CN116082648B (en)

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CN105524318A (en) * 2016-01-27 2016-04-27 北京化工大学 Nanocomposite prepared from solution polymerized styrene-butadiene rubber highly filled with white carbon black
CN109384926A (en) * 2017-08-03 2019-02-26 中国石油化工股份有限公司 A kind of unsaturated ring oxidation polysiloxanes and its preparation method and application

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FR2802542A1 (en) * 1999-12-20 2001-06-22 Michelin Soc Tech VULCANIZABLE RUBBER COMPOSITION FOR THE MANUFACTURE OF A PNEUMATIC AND PNEUMATIC TIRE WHERE THE TREAD BAND INCLUDES SUCH A COMPOSITION
FR3037590B1 (en) * 2015-06-18 2017-06-02 Michelin & Cie RUBBER COMPOSITION COMPRISING STYRENE AND BUTADIENE COPOLYMER WITH LOW GLASS TRANSITION TEMPERATURE, AND HIGH LOAD AND PLASTICIZING RATE

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CN105524318A (en) * 2016-01-27 2016-04-27 北京化工大学 Nanocomposite prepared from solution polymerized styrene-butadiene rubber highly filled with white carbon black
CN109384926A (en) * 2017-08-03 2019-02-26 中国石油化工股份有限公司 A kind of unsaturated ring oxidation polysiloxanes and its preparation method and application

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