CN113307912A - Silica functionalized SIBR (silicon-oxygen-functionalized-polymer-based elastomer) integrated rubber with star-shaped coupling structure and preparation method thereof - Google Patents
Silica functionalized SIBR (silicon-oxygen-functionalized-polymer-based elastomer) integrated rubber with star-shaped coupling structure and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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Abstract
The invention belongs to the technical field of high polymer materials, and provides silica functionalized SIBR (silicon-oxygen functionalized butadiene rubber) integrated rubber with a star-shaped coupling structure and a preparation method thereof, wherein the silica functionalized SIBR integrated rubber is mainly initiated by alkyl lithium, and 1, 1-diphenylethylene functional monomers of silica groups are coupled with a quadripolymer through a multi-arm star-shaped coupling agent under the action of a polar regulator. The invention adopts a three-arm, four-arm and six-arm coupling mode, and the high coupling efficiency can obviously improve the relative content of the silicon oxo 1, 1-diphenylethylene functional monomer in a copolymer chain. Compared with general rubber and linear structure rubber, the silicon-oxygen functionalized SIBR integrated rubber with a star-shaped coupling structure has the advantages that the performance is remarkably improved, the processability of the integrated rubber is improved, the compatibility of the integrated rubber and white carbon black is improved, the rolling resistance and the energy consumption of the rubber are reduced, and the silicon-oxygen functionalized SIBR integrated rubber is a high-end product of the rubber.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to silica functionalized SIBR (silicon-oxygen functionalized butadiene rubber) integrated rubber with a star-shaped coupling structure and a preparation method thereof.
Background
Rubber is an important raw material in the tire industry, the development of high-performance rubber is a necessary trend of industrial development, the automobile industry puts forward requirements on low rolling resistance, high wet skid resistance and good wear resistance on tires, but due to the existence of rubber 'magic triangles', general-purpose rubber such as Styrene Butadiene Rubber (SBR), polybutadiene rubber (BR) and Natural Rubber (NR) can only adopt a method of blending different rubber types to obtain tread rubber with expected performance, can only reach a homogeneous phase on a macroscopic scale, has serious micro phase separation, and seriously limits the comprehensive performance of the rubber. Therefore, the design concept of molecular integration is adopted, the advantages of the general rubber are integrated, and the design of the high-performance integrated rubber SIBR is an important research direction for solving the problem.
The integrated rubber SIBR is a copolymer formed by copolymerizing styrene (S), isoprene (I) and butadiene (B) serving as monomers, is an ideal novel tread rubber, becomes a hotspot for rubber research in recent years, and introduces different types of rubber to the same macromolecular chain in situ by a chemical synthesis method to obtain positive synergistic effect and realize the integration of excellent performances of several types of rubber. The integrated rubber integrates the characteristics of polybutadiene rubber (BR), Styrene Butadiene Rubber (SBR), polyisoprene rubber (SIR) and butadiene-isoprene rubber (IBR), realizes the mixing of chain end levels, different structural units can meet various different performances required by tread rubber, and overcomes the contradiction between the rolling resistance, the wear resistance and the traction performance which is difficult to realize by using general rubber.
Patent CN112142915A discloses a method for preparing liquid gum filled integral rubber by anionic living polymerization. The method realizes low molecular weight liquid integrated rubber and high molecular weight solid integrated rubber with specific structures through active polymerization and introduction of a structure regulator, and plasticizes the solid integrated rubber through the liquid integrated rubber. CN103772609A discloses a method for synthesizing integral rubber SIBR by a reactive extrusion method. At present, the research on the integrated rubber SIBR is mostly limited to the research on a synthesis method of unfunctionalized linear SIBR, CN ensures that the SIBR product has a single grade and a narrow application range, and the linear SIBR has the problems of high Mooney viscosity and difficult processing.
In the molecular structure of rubber, terminal free radicals can not be vulcanized, and side groups capable of freely moving can be formed in vulcanized rubber, which is one of the sources of tire rolling resistance.
The star-structured rubber is synthesized by two main methods, namely, the star-structured rubber is directly obtained by initiating polymerization by using a multifunctional initiator, and the star-structured rubber is obtained by adding a coupling agent for coupling after the polymerization is finished. The method for synthesizing the star-structured rubber by using the multifunctional initiator has the advantages of complex synthesis and difficult control and industrial production due to few initiator types. Although the rubber with a star structure synthesized by a method of subsequently adding a coupling agent cannot obtain the rubber with a complete star structure, the method is simple and convenient to operate and high in realizability, and is a promising synthesis mode of the star rubber. Patent CN102120798A discloses a method for synthesizing star-shaped solution-polymerized styrene-butadiene rubber by a coupling method, and the obtained solution-polymerized styrene-butadiene rubber has low rolling resistance and good wet skid resistance. At present, the synthesis method of the star-structure integrated rubber is not reported yet, and is a problem to be solved urgently.
Disclosure of Invention
The invention provides silica functionalized SIBR integrated rubber with a star-shaped coupling structure and a preparation method thereof.
The technical scheme of the invention is as follows:
the silica functionalized SIBR integrated rubber with a star-shaped coupling structure is a tetrapolymer prepared by copolymerizing 1, 1-diphenylethylene functional monomers containing silica groups with styrene, butadiene and isoprene by adopting alkyl lithium initiation and coupling agent coupling; the number average molecular weight of the silica functionalized SIBR integrated rubber with the star coupling structure is 9 multiplied by 104-50×104g/mol；
The coupling agent is SiCl3CH3、SiCl4、SnCl3CH3、SnCl4、Si2Cl6Is selected from monofunctional alkyllithium, which is a mixture of one or more initiators disclosed in the prior art for anionic polymerization of butadiene and styrene, including but not limited to n-butyllithium and sec-butyllithium;
based on the mass of the quadripolymer as 100 percent, the mass of styrene accounts for 10 to 30 percent, the mass of isoprene accounts for 20 to 60 percent, and the mass of butadiene accounts for 20 to 60 percent;
the initiating end or chain of the quadripolymer at least contains 1 silicon-oxygen group-containing 1, 1-diphenylethylene functional monomer, and the number of arms of the quadripolymer is between 3.0 and 6.0.
Further, the 1, 1-diphenylethylene functional monomer containing a siloxy group includes 1- [4- (trimethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (triethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (tri-tert-butoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylmethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylisopropoxysilyl) phenyl ] -1-phenylethene, and mixtures thereof, 1- [4- (diethylmethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (diethylethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (diethylisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (methyldimethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (methyldiethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (methyldiisopropyloxysilyl) phenyl ] -1-phenylethene, 1- [4- (ethyldimethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (ethyldiethoxysilyl) phenyl ] -1-phenylethene, a salt thereof, a hydrate thereof, a solid thereof, and a pharmaceutical composition thereof, At least one of 1- [4- (ethyldiisopropoxysilyl) phenyl ] -1-phenylethene.
Further, the mass of the quadripolymer is 100%, the mass of the styrene accounts for 15% -25%, the mass of the isoprene accounts for 25% -50%, and the mass of the butadiene accounts for 25% -50%.
Furthermore, the initiation end and the chain of the quadripolymer both contain 1 silicon-oxygen group-containing 1, 1-diphenylethylene functional monomer, and the arm number of the quadripolymer is between 4.0 and 5.0.
In a second aspect, the invention provides a preparation method of a silica-functionalized SIBR integrated rubber with a star-shaped coupling structure, which comprises the following steps:
s1, according to the design component mass ratio of the silica functionalized SIBR integrated rubber with the star-shaped coupling structure, according to the ratio of 1, 1-diphenylethylene functional monomer to initiator being 1-500: 1, weighing 1, 1-diphenylethylene functional monomer in a container, adding an organic solvent, an alkyl lithium initiator and a polarity regulator according to the designed mass concentration of 5-20% of SIBR integrated rubber, and reacting for 1-3 h; wherein the molar ratio of the polarity modifier to the amount of the alkyllithium initiator is 1: 1-100;
s2, adding 15-25% of styrene, 25-50% of isoprene and 25-50% of butadiene according to 100% of the total mass of the added monomers, and reacting for 12-24h at the temperature of 20-90 ℃;
s3, adding a coupling agent into a container, and reacting at 20-90 ℃ for 12-24 h; the ratio of the initiator to the coupling agent is 1: 3-6;
and S4, adding isopropanol to terminate the reaction, settling in ethanol, and drying to obtain the silica functionalized SIBR integrated rubber with a star coupling structure.
Further, the ratio of the silicon-oxygen group-containing 1, 1-diphenylethylene functional monomer to the alkyl lithium initiator is 1: 1, the functional group of the prepared silica functionalized SIBR integrated rubber with the star coupling structure is positioned at the chain end.
Further, the ratio of the silicon-oxygen group-containing 1, 1-diphenylethylene functional monomer to the alkyl lithium initiator is 1: 1-50 hours later, the functional group of the prepared silica functionalized SIBR integrated rubber with the star-shaped coupling structure is positioned in a chain.
Further, the alkyllithium initiator is selected from monofunctional alkyllithium. Wherein, the monofunctional alkyl lithium initiator is any one or a mixture of several initiators disclosed in the prior art, which can be used for butadiene and styrene anionic polymerization, and is generally selected from the following: one or more monofunctional lithium initiators in RLi, wherein R is C2-20 alkyl, alkyl or aryl, preferably ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, or benzyl lithium.
Further, the organic solvent is selected from one or a mixture of several of non-polar aromatic hydrocarbon and non-polar aliphatic hydrocarbon. Are generally selected from: benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons (e.g., mixed xylene), mixed aliphatic hydrocarbons (e.g., raffinate oil), preferably benzene, toluene, n-hexane, cyclohexane.
Further, the polarity modifier is added in order to control the randomness of the butadiene block 1,2 structure, isoprene block 3,4 structure, and integral rubber, and to control the polymer activity and distribution in the polymer chain of the diphenylethylene derivative. The polarity regulator is one or several of oxygen-containing, sulfur-containing, phosphorus-containing polar compound and alkoxy metal compound, such as: (1) an oxygenate, typically selected from: diethyl ether, tetrahydrofuran, R1OCH2CH2OR2(wherein R1 and R2 are alkyl groups having 1 to 6 carbon atoms, and may be the same or different, and preferably R1 and R2 are different, e.g., ethylene glycol dimethyl ether and ethylene glycol diethyl ether), R1OCH2CH2OCH2CH2OR2(wherein R1 and R2 are alkyl groups having 1 to 6 carbon atoms, and may be the same or different, and R1 and R2 are preferably different from each other, e.g., diethylene glycol dimethyl ether and diethylene glycol dimethyl etherButyl ether), crown ethers; (2) a compound, typically selected from: triethylamine, Tetramethylethylenediamine (TMEDA), dipiperidine ethane (DPE); (3) a phosphorus-containing compound, generally selected from: hexamethylphosphoric triamide (HMPA); (4) metal alkoxide compounds, generally selected from ROM, wherein: r is an alkyl group having 1 to 6 carbon atoms, O is an oxygen atom, M is metallic sodium or potassium, and is preferably selected from: potassium tert-butoxide, potassium tert-pentoxide.
Further, the coupling agent is a multi-arm star coupling agent comprising SiCl3CH3、SiCl4、SnCl3CH3、SnCl4,Si2Cl6At least one of (1).
The invention has the beneficial effects that:
the invention prepares the SIBR integrated rubber by initiating diphenylethylene functional monomer containing silicon-oxygen group by alkyl lithium, copolymerizing styrene, butadiene and isoprene under the action of a polarity regulator and coupling by adopting a coupling agent. According to the invention, through topological design of rubber molecules and introduction of polar functional groups, the compatibility of a rubber matrix and fillers such as carbon black or white carbon black can be increased, the performance of rubber is improved, the dispersibility of the carbon black in the rubber matrix is improved, and the reinforcing effect of the white carbon black is improved.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. Examples the following examples are presented to analyze the copolymer compositional sequence distribution and microstructure using a nuclear magnetic resonance spectrometer and to analyze the molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the copolymer using a gel permeation chromatograph. The NMR spectrum test was performed by Bruker Avance 400M, Switzerland, the molecular weight and molecular weight distribution were measured by a volume exclusion chromatograph, model 2414 differential refractometer, model 1515 HPLC pump, manufactured by Waters, USA.
Example 1
Under the protection of argon, 100ml of benzene and 900ml of cyclohexane as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, sec-butyl lithium as an initiator is added according to the designed molecular weight of 100kg/mol, and 1- [4- (trimethoxysilyl) phenyl ] ethylene is added according to the proportion of 1.0 of a functionalized diphenylethylene monomer/initiator]1-phenyl ethylene, reacting for 1 h; adding Tetramethylethylenediamine (TMEDA), styrene 20g, isoprene 40g and butadiene 40g according to the ratio of regulator/initiator of 1.0, reacting at 20 ℃ for 24h, and adding coupling agent SiCH according to the ratio of initiator/coupling agent of 3.03Cl3After 24 hours of reaction at 30 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 19.6 percent, the mass percent of the isoprene content is 39.6 percent, and the mass percent of the butadiene content is 37.2 percent; the number average molecular weight is 291.3kg/mol, the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 76.2%, the 1, 2-polybutadiene content was 62.0%, the number of polymer arms was 2.91, and the coupling efficiency was 83.0%.
Example 2
Argon gasUnder protection, 100ml of benzene solvent and 900ml of normal hexane are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, the initiator n-butyllithium is added according to the designed molecular weight of 100kg/mol, and 1- [4- (triisopropoxysilyl) phenyl ] is added according to the proportion of the functionalized diphenylethylene monomer/the initiator of 10.0]1-phenyl ethylene, reacting for 2 h; tetrahydrofuran (THF), 10g of styrene, 50g of isoprene and 40g of butadiene are added according to the ratio of the regulator/the initiator of 100.0, the mixture reacts for 12 hours at 40 ℃, and a coupling agent SiCl is added according to the ratio of the initiator/the coupling agent of 4.04After reaction at 40 ℃ for 12h, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 10.2 percent, the mass percent of the isoprene content is 50.8 percent, and the mass percent of the butadiene content is 39.0 percent; the number average molecular weight is 432.2kg/mol, the molecular weight distribution is 1.19; the 3.4-polyisoprene content was 56.2%, the 1, 2-polybutadiene content was 52.0%, the number of polymer arms was 4.32, and the coupling efficiency was 79.0%.
Example 3
Under the protection of argon, 100ml of benzene and 900ml of pentane as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and supplied with gas for three times, 30kg/mol of ethyl lithium as an initiator is added, and 20.0 parts of 1- [4- (triethoxysilyl) phenyl ] ethylene is added according to the proportion of functional diphenylethylene monomer/initiator]1-phenyl ethylene, reacting for 3 h; diethylene glycol dimethyl ether, 10g of styrene, 40g of isoprene and 50g of butadiene are added according to the ratio of the regulator/the initiator of 100.0, the mixture reacts for 12 hours at the temperature of 90 ℃, and a coupling agent SnCH is added according to the ratio of the initiator/the coupling agent of 3.53Cl3After reacting at 90 ℃ for 18h, degassed isopropanol is added to terminate the polymerization, the reaction solution is precipitated in excess absolute ethanol, and the resulting polymer is dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 10.5 percent, the mass percent of the isoprene content is 39.1 percent, and the mass percent of the butadiene content is 50.4 percent; number average molecular weight of 90.4kg/mol, molecular weight distribution 1.16; the content of 3.4-polyisoprene was 46.3%, the content of 1, 2-polybutadiene was 42.0%, the number of polymer arms was 3.01, and the coupling efficiency was 86.0%.
Example 4
Under the protection of argon, 100ml of benzene and 900ml of heptane, which are solvents, are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, an initiator of lithium isopropyl is added according to the designed molecular weight of 125kg/mol, and 1- [4- (tri-tert-butoxy silicon group) phenyl is added according to the proportion of a functionalized diphenylethylene monomer/initiator of 30.0]1-phenyl ethylene, reacting for 1 h; adding diethyl ether, 30g of styrene, 50g of isoprene and 20g of butadiene according to the ratio of the regulator/the initiator of 50.0, reacting for 18h at 20 ℃, and adding a coupling agent SnCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 20 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 32.6 percent, the mass percent of the isoprene content is 46.3 percent, and the mass percent of the butadiene content is 21.1 percent; the number average molecular weight is 499.1kg/mol, and the molecular weight distribution is 1.13; the content of 3.4-polyisoprene was 36.2%, the content of 1, 2-polybutadiene was 33.3%, the number of polymer arms was 4.99, and the coupling efficiency was 73.6%.
Example 5
Under the protection of argon, adding 100ml of toluene and 900ml of octane into a 2L polymerization reactor which is vacuumized and supplied with gas for three times, adding benzyl lithium as an initiator according to the designed molecular weight of 100kg/mol, and adding 1- [4- (dimethyl methoxy silicon base) phenyl according to the proportion of a functional diphenylethylene monomer/the initiator of 40.0]1-phenyl ethylene, reacting for 2 h; adding crown ether, 10g of styrene, 60g of isoprene and 30g of butadiene according to the ratio of the regulator/the initiator of 50.0, reacting for 18h at the temperature of 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. Product structure analysis knotThe following fruits were obtained: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 11.3 percent, the mass percent of the isoprene content is 59.7 percent, and the mass percent of the butadiene content is 29.0 percent; the number average molecular weight is 410.4kg/mol, and the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 36.7%, the content of 1, 2-polybutadiene was 37.5%, the number of polymer arms was 4.10, and the coupling efficiency was 73.0%.
Example 6
Under the protection of argon, 100ml of solvent mixed xylene and 900ml of raffinate oil are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, initiator n-butyllithium is added according to the designed molecular weight of 100kg/mol, and 1- [4- (dimethyl ethoxy silicon base) phenyl group is added according to the proportion of 1.0 functionalized diphenylethylene monomer/initiator]1-phenyl ethylene, reacting for 2 h; adding potassium tert-butoxide, 10g of styrene, 30g of isoprene and 60g of butadiene according to the ratio of the regulator to the initiator of 10.0, reacting at 50 ℃ for 18h, and adding SiCl as a coupling agent according to the ratio of the initiator to the coupling agent of 4.04After 24 hours of reaction at 50 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100% of the polymer, the mass percent of the combined styrene content in the copolymer is 11.1%, the mass percent of the isoprene content is 31.2%, and the mass percent of the butadiene content is 57.7%; the number average molecular weight is 387.2kg/mol, and the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 41.9%, the 1, 2-polybutadiene content was 43.0%, the number of polymer arms was 3.87, and the coupling efficiency was 82.1%.
Example 7
Under the protection of argon, adding 100ml of xylene and 900ml of cyclohexane serving as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, adding n-butyllithium serving as an initiator according to the designed molecular weight of 100kg/mol, and adding 1- [4- (dimethyl isopropoxy silicon) phenyl ] according to the ratio of functionalized diphenylethylene monomer/initiator of 50.0]1-phenyl ethylene, reacting for 2 h; adding potassium tert-pentoxy, 30g of styrene, 20g of isoprene and 50g of butadiene according to the ratio of regulator/initiator of 10.0, reacting for 18h at 30 ℃,adding coupling agent SiCl according to the ratio of initiator to coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 29.9 percent, the mass percent of the isoprene content is 20.6 percent, and the mass percent of the butadiene content is 49.5 percent; the number average molecular weight is 390.1kg/mol, the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 36.2%, the content of 1, 2-polybutadiene was 32.0%, the number of polymer arms was 3.90, and the coupling efficiency was 83.0%.
Example 8
Under the protection of argon, 100ml of ethylbenzene and 900ml of normal hexane serving as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, n-butyllithium serving as an initiator is added according to the designed molecular weight of 100kg/mol, and 1- [4- (diethyl methoxy silicon) phenyl ] ethylene is added according to the proportion of 1.0 of a functionalized diphenylethylene monomer/initiator]1-phenyl ethylene, reacting for 2 h; adding hexamethylphosphoric triamide, 30g of styrene, 50g of isoprene and 20g of butadiene according to the proportion of 1.0 of a regulator/an initiator, reacting for 18h at 30 ℃, and adding a coupling agent SiCl according to the proportion of 4.0 of the initiator/the coupling agent4After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 28.8 percent, the mass percent of the isoprene content is 51.1 percent, and the mass percent of the butadiene content is 21.1 percent; the number average molecular weight is 388.8kg/mol, and the molecular weight distribution is 1.19; the 3.4-polyisoprene content was 26.2%, the 1, 2-polybutadiene content was 32.4%, the number of polymer arms was 3.89, and the coupling efficiency was 81.9%.
Example 9
Under the protection of argon, adding 100ml of benzene and 900ml of n-hexane serving as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times in sequence, adding n-butyllithium serving as an initiator into the reactor according to the designed molecular weight of 100kg/mol, and performing functionalization on diphenylVinyl monomer/initiator ratio 1.0 1- [4- (diethylethoxysilyl) phenyl group]1-phenyl ethylene, reacting for 2 h; adding triethylamine, 10g of styrene, 60g of isoprene and 30g of butadiene according to the ratio of the regulator/the initiator of 1.0, reacting for 18h at the temperature of 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 11.1 percent, the mass percent of the isoprene content is 52.0 percent, and the mass percent of the butadiene content is 36.9 percent; the number average molecular weight is 390.9kg/mol, and the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 76.2%, the content of 1, 2-polybutadiene was 62.0%, the number of polymer arms was 3.90, and the coupling efficiency was 82.2%.
Example 10
Under the protection of argon, adding 100ml of benzene and 900ml of n-hexane as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, adding n-butyllithium as an initiator according to the designed molecular weight of 100kg/mol, and adding 1- [4- (diethyl isopropoxy silicon) phenyl ] according to the ratio of the functionalized diphenylethylene monomer/the initiator of 1.0]1-phenyl ethylene, reacting for 2 h; adding ethylene glycol dimethyl ether, 10g of styrene, 30g of isoprene and 60g of butadiene according to the ratio of a regulator/an initiator of 1.0, reacting for 18h at the temperature of 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 11.0 percent, the mass percent of the isoprene content is 29.6 percent, and the mass percent of the butadiene content is 59.4 percent; the number average molecular weight is 396.6kg/mol, and the molecular weight distribution is 1.14; the content of 3.4-polyisoprene was 36.3%, the content of 1, 2-polybutadiene was 32.7%, the number of polymer arms was 3.96, and the coupling efficiency was 83.0%.
Example 11
Under the protection of argon, adding 100ml of benzene and 900ml of n-hexane as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, adding n-butyllithium as an initiator according to the designed molecular weight of 100kg/mol, and adding 1- [4- (methyldiethoxy silicon-based) phenyl ] according to the ratio of the functionalized diphenylethylene monomer/the initiator of 1.0]1-phenyl ethylene, reacting for 2 h; adding ethylene glycol diethyl ether, 20g of styrene, 40g of isoprene and 40g of butadiene according to the ratio of a regulator/an initiator of 1.0, reacting for 18h at the temperature of 30 ℃, and adding a coupling agent SnCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 19.6 percent, the mass percent of the isoprene content is 41.6 percent, and the mass percent of the butadiene content is 38.8 percent; the number average molecular weight is 370.6kg/mol, the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 26.2%, the content of 1, 2-polybutadiene was 22.4%, the number of polymer arms was 3.70, and the coupling efficiency was 88.0%.
Example 12
Under the protection of argon, adding 100ml of benzene and 900ml of n-hexane as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, adding n-butyllithium as an initiator according to the designed molecular weight of 100kg/mol, and adding 1- [4- (methyldimethoxysilyl) phenyl ] ethyl benzene according to the ratio of the functionalized diphenylethylene monomer/the initiator of 1.0]1-phenyl ethylene, reacting for 2 h; diethylene glycol dibutyl ether, styrene 20g, isoprene 20g and butadiene 60g are added according to the proportion of 1.0 of regulator/initiator, the mixture reacts for 18h at the temperature of 30 ℃, and coupling agent SnCl is added according to the proportion of 4.0 of initiator/coupling agent4After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 19.6 percent, the mass percent of the isoprene content is 22.6 percent, and the mass percent of the butadiene content isThe fraction is 57.8%; the number average molecular weight is 411.2kg/mol, and the molecular weight distribution is 1.19; the content of 3.4-polyisoprene was 76.2%, the content of 1, 2-polybutadiene was 62.0%, the number of polymer arms was 4.11, and the coupling efficiency was 93.0%.
Example 13
Under the protection of argon, adding 100ml of benzene and 900ml of n-hexane as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, adding n-butyllithium as an initiator according to a designed molecular weight of 80kg/mol, and adding 1- [4- (methyl diisopropoxy silicon) phenyl according to a ratio of a functionalized diphenylethylene monomer/initiator of 1.0]1-phenyl ethylene, reacting for 2 h; adding dipiperidine ethane, 20g of styrene, 60g of isoprene and 20g of butadiene according to the ratio of the regulator to the initiator of 1.0, reacting for 18h at 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator to the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 19.4 percent, the mass percent of the isoprene content is 59.6 percent, and the mass percent of the butadiene content is 21.0 percent; the number average molecular weight is 320.8kg/mol, and the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 76.2%, the content of 1, 2-polybutadiene was 72.3%, the number of polymer arms was 4.01, and the coupling efficiency was 93.9%.
Example 14
Under the protection of argon, 100ml of benzene and 900ml of cyclohexane as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, initiator n-butyllithium is added according to the designed molecular weight of 80kg/mol, and 1- [4- (ethyl dimethoxy silicon) phenyl group is added according to the proportion of 1.0 of functionalized diphenylethylene monomer/initiator]1-phenyl ethylene, reacting for 1 h; adding Tetramethylethylenediamine (TMEDA), styrene 20g, isoprene 40g and butadiene 40g according to the ratio of regulator/initiator of 1.0, reacting at 20 ℃ for 24h, and adding coupling agent Si according to the ratio of initiator/coupling agent of 6.02Cl6Reacting at 30 deg.C for 24 hr, adding degassed isopropanol to terminate polymerization, and reacting the solution in excess anhydrous conditionEthanol precipitation, the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 20.4 percent, the mass percent of the isoprene content is 39.6 percent, and the mass percent of the butadiene content is 40.0 percent; the number average molecular weight is 491.2kg/mol, and the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 46.2%, the content of 1, 2-polybutadiene was 42.0%, the number of polymer arms was 6.14, and the coupling efficiency was 82.0%.
Example 15
Under the protection of argon, 100ml of benzene and 900ml of cyclohexane as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, an initiator n-butyllithium is added according to a designed molecular weight of 80kg/mol, and 1- [4- (ethyldiethoxysilyl) phenyl ] is added according to a ratio of a functionalized diphenylethylene monomer/initiator of 1.0]1-phenyl ethylene, reacting for 1 h; adding Tetramethylethylenediamine (TMEDA), styrene 20g, isoprene 40g and butadiene 40g according to the ratio of regulator/initiator of 1.0, reacting at 20 ℃ for 24h, and adding coupling agent Si according to the ratio of initiator/coupling agent of 6.02Cl6After 24 hours of reaction at 30 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 20.2 percent, the mass percent of the isoprene content is 39.8 percent, and the mass percent of the butadiene content is 40.0 percent; the number average molecular weight is 488.2kg/mol, and the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 47.2%, the content of 1, 2-polybutadiene was 41.0%, the number of polymer arms was 6.01, and the coupling efficiency was 82.0%.
Example 16
Under the protection of argon, 100ml of benzene and 900ml of cyclohexane as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, an initiator n-butyllithium is added according to a designed molecular weight of 80kg/mol, and 1- [4- (ethyldiisopropoxysilyl) phenyl ] ethylene is added according to a ratio of a functionalized diphenylethylene monomer/initiator of 1.0]1-phenyl ethylene, reacting for 1 h; according to the ratio of regulator/initiatorAdding Tetramethylethylenediamine (TMEDA), styrene 20g, isoprene 40g and butadiene 40g into the mixture at 1.0, reacting at 20 ℃ for 24h, and adding a coupling agent Si according to the initiator/coupling agent ratio of 6.02Cl6After 24 hours of reaction at 30 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 20.1 percent, the mass percent of the isoprene content is 39.9 percent, and the mass percent of the butadiene content is 40.0 percent; the number average molecular weight is 490.0kg/mol, the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 46.2%, the content of 1, 2-polybutadiene was 42.0%, the number of polymer arms was 6.11, and the coupling efficiency was 82.2%.
The foregoing are merely exemplary embodiments of the present invention to enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The silica functionalized SIBR integrated rubber with a star-shaped coupling structure is a tetrapolymer prepared by copolymerizing a 1, 1-diphenylethylene functional monomer containing a silica group with styrene, butadiene and isoprene by initiating with alkyl lithium and coupling with a coupling agent; the number average molecular weight of the silica functionalized SIBR integrated rubber with the star coupling structure is 9 multiplied by 104-50×104g/mol；
The coupling agent is SiCl3CH3、SiCl4、SnCl3CH3、SnCl4、Si2Cl6At least one of, said alkyllithium initiator is selected from the group consisting of monofunctional alkyllithium, said monofunctional alkaneThe lithium-based initiator is one or a mixture of several initiators disclosed in the prior art for the anionic polymerization of butadiene and styrene, and includes but is not limited to n-butyl lithium and sec-butyl lithium;
based on the mass of the quadripolymer as 100 percent, the mass of styrene accounts for 10 to 30 percent, the mass of isoprene accounts for 20 to 60 percent, and the mass of butadiene accounts for 20 to 60 percent;
the initiating end or chain of the quadripolymer at least contains 1 silicon-oxygen group-containing 1, 1-diphenylethylene functional monomer, and the arm number of the quadripolymer is between 3.0 and 6.0.
2. The silicone-functionalized SIBR elastomers of star-coupled structure of claim 1 wherein the silicone-containing 1, 1-diphenylethylene functional monomer comprises 1- [4- (trimethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (triethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (triisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (tri-tert-butoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylmethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (dimethylethoxysilyl) phenyl ] -1-phenylethene, a polymer of the siloxane-functionalized SIBR elastomers of star-coupled structure, and a polymer of the siloxane-functionalized SIBRs of any of the preceding claims, wherein the silicone-containing 1, 1-diphenylethylene functional monomer comprises, 1- [4- (dimethylisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (diethylmethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (diethylethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (diethylisopropoxysilyl) phenyl ] -1-phenylethene, 1- [4- (methyldimethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (methyldiethoxysilyl) phenyl ] -1-phenylethene, 1- [4- (methyldiisopropyloxysilyl) phenyl ] -1-phenylethene, 1- [4- (ethyldimethoxysilyl) phenyl ] -1-phenylethene, a salt thereof, a hydrate thereof, and a pharmaceutical composition, 1- [4- (ethyldiethoxysilyl) phenyl ] -1-phenylethene, and 1- [4- (ethyldiisopropoxysilyl) phenyl ] -1-phenylethene.
3. The silicone-functionalized SIBR integrated rubber with a star-coupled structure according to claim 1, wherein the mass ratio of styrene is 15% to 25%, the mass ratio of isoprene is 25% to 50%, and the mass ratio of butadiene is 25% to 50%, based on 100% by mass of the tetrapolymer.
4. The silicone-functionalized SIBR integral rubber of star-coupled structure according to claim 3, wherein the tetrapolymer comprises 1 silicone-containing 1, 1-diphenylethylene functional monomer at both the initiation end and the chain, and the number of arms of the tetrapolymer is between 4.0 and 5.0.
5. A method for preparing the silicone-functionalized SIBR integral rubber with a star-shaped coupling structure as claimed in any one of claims 1 to 4, comprising the following steps:
s1, weighing a certain amount of the 1, 1-diphenylethylene functional monomer containing the silicon-oxygen group in the silicon-oxygen functionalized SIBR integrated rubber with the star-shaped coupling structure, styrene, isoprene and butadiene according to the designed mass ratio, adding an organic solvent, an alkyl lithium initiator and a polarity regulator into a container, and reacting for 1-3 h; the molar ratio of the polarity modifier to the amount of the alkyllithium initiator is 1: 1-100;
s2, adding styrene, isoprene and butadiene according to the designed mass ratio, and reacting for 12-24h at 20-90 ℃;
s3, adding a coupling agent, and reacting at 20-90 ℃ for 12-24 h; the dosage ratio of the initiator to the coupling agent is 1: 3-6;
and S4, adding isopropanol to terminate the reaction, settling in ethanol, and drying to obtain the silica functionalized SIBR integrated rubber with a star coupling structure.
6. The method of claim 5, wherein the ratio of the silicone-functionalized 1, 1-diphenylethylene-containing functional monomer to initiator is 1: 1, the functional group of the prepared silica functionalized SIBR integrated rubber with the star coupling structure is positioned at the chain end.
7. The method of claim 5, wherein the ratio of the silicone-functionalized 1, 1-diphenylethylene-containing functional monomer to initiator is 1: 1-50 hours later, the functional group of the prepared silica functionalized SIBR integrated rubber with the star-shaped coupling structure is positioned in a chain.
8. The method for preparing the silicone-functionalized SIBR integral rubber with star-coupled structure according to claim 5, wherein the alkyl lithium initiator is selected from monofunctional alkyl lithium, and the monofunctional alkyl lithium initiator is one or a mixture of several initiators disclosed in the prior art for butadiene and styrene anionic polymerization; the organic solvent is selected from at least one of non-polar aromatic hydrocarbon and non-polar aliphatic hydrocarbon, including but not limited to n-hexane, cyclohexane and cyclopentane.
9. The method of claim 5, wherein the polarity modifier is selected from at least one of oxygen-containing, sulfur-containing, phosphorus-containing polar compounds, and metal alkoxide compounds.
10. The method of claim 5, wherein the coupling agent is a multi-arm star coupling agent comprising SiCl3CH3、SiCl4、SnCl3CH3、SnCl4、Si2Cl6At least one of (1).
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| CN113698542A (en) * | 2021-09-10 | 2021-11-26 | 大连理工大学 | Soluble polymerized A-DPE derivative SIBR star-shaped integrated rubber toughened ABS resin and preparation method thereof |
| CN113817111A (en) * | 2021-09-10 | 2021-12-21 | 大连理工大学 | Soluble polymerized A-DPE derivative SIBR star-shaped integrated rubber toughened HIPS resin and preparation method thereof |
| CN113912798A (en) * | 2021-11-15 | 2022-01-11 | 大连理工大学 | Star block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and preparation method thereof |
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| CN105837751A (en) * | 2016-04-05 | 2016-08-10 | 大连理工大学 | Siloxy-containing chain-end in-chain multi-functional solution polymerized styrene-butadiene rubber and a preparing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698542A (en) * | 2021-09-10 | 2021-11-26 | 大连理工大学 | Soluble polymerized A-DPE derivative SIBR star-shaped integrated rubber toughened ABS resin and preparation method thereof |
| CN113817111A (en) * | 2021-09-10 | 2021-12-21 | 大连理工大学 | Soluble polymerized A-DPE derivative SIBR star-shaped integrated rubber toughened HIPS resin and preparation method thereof |
| CN113817111B (en) * | 2021-09-10 | 2022-11-11 | 大连理工大学 | Soluble polymerized A-DPE derivative SIBR star-shaped integrated rubber toughened HIPS resin and preparation method thereof |
| CN113912798A (en) * | 2021-11-15 | 2022-01-11 | 大连理工大学 | Star block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and preparation method thereof |
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