CN115991876B - Composite rubber material and application thereof in new energy automobile tires - Google Patents
Composite rubber material and application thereof in new energy automobile tires Download PDFInfo
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- CN115991876B CN115991876B CN202310286314.1A CN202310286314A CN115991876B CN 115991876 B CN115991876 B CN 115991876B CN 202310286314 A CN202310286314 A CN 202310286314A CN 115991876 B CN115991876 B CN 115991876B
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- Prior art keywords
- sio
- rubber
- catalyst
- butadiene
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 160
- 239000005060 rubber Substances 0.000 title claims abstract description 160
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 47
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 47
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims description 80
- 239000000243 solution Substances 0.000 claims description 66
- 239000003054 catalyst Substances 0.000 claims description 61
- 229920002050 silicone resin Polymers 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 41
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- 239000001257 hydrogen Substances 0.000 claims description 20
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
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- VPLNCHFJAOKWBT-UHFFFAOYSA-N phenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 VPLNCHFJAOKWBT-UHFFFAOYSA-N 0.000 claims description 2
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- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims 1
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Classifications
-
- 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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Abstract
The invention discloses a composite rubber material and application thereof in new energy automobile tires, and relates to the technical field of polymer synthesis. The invention provides modified rubber, the structural formula of which is shown in a formula II, and the difference and separation between components such as solution polymerized styrene-butadiene rubber, butadiene rubber and the like which are main components are obviously reduced. The modified rubber provided by the invention is applied to the tread rubber of the new energy automobile tire, and realizes good mechanical strength, wet skid resistance, wear resistance and rolling resistance;
Description
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a composite rubber material and application thereof in the aspect of new energy automobile tires.
Background
The polysiloxane is a material type with special properties, is called as industrial monosodium glutamate, and has excellent high and low temperature resistance, physiological inertia, insulativity and hydrophobicity, thus being widely applied to various industries such as electric power, electronics, automobiles, buildings, biomedical treatment, coating ink, personal care and the like. The polysiloxane resin is a special polysiloxane material, has the characteristics of high hardness, high light transmittance, high temperature resistance and the like besides the typical polysiloxane characteristics, and can be used for manufacturing and processing high-end materials such as LED packaging silicon rubber, additive manufacturing liquid silicon rubber and the like. At present, cross coupling application research and application practice of polysiloxane materials such as silicone resin and the like and polyacrylate, epoxy resin and polyurethane non-silicon high polymer materials are increasingly realized by means of hydrosilylations, unsaturated double bond free radical polymerization, epoxy group ring-opening polymerization or hydroxyl group esterification and the like, the beneficial effects of improving comprehensive performance are obtained, and the challenges of poor compatibility, single and difficult reaction path selection, low functional variety and the like of the polysiloxane materials such as silicone resin and the non-silicon high polymer materials are still faced. Among the non-silicon high polymer materials, main rubber materials such as butadiene rubber, styrene-butadiene rubber, natural rubber and the like are the types with very strong complementarity but most obvious difference with polysiloxane performances such as silicone resin, the requirements for multi-functional cross modification by means of various reaction paths are more and more increased when the rubber materials are modified, the rubber composite materials are modified and the like, and the beneficial attempts of chemical combination and cross modification with the polysiloxane such as the silicone resin are very few.
At present, main types of silicone resins include methyl silicone resin and phenyl silicone resin, the structure is mainly Q-type silicone resin and T-type silicone resin, most of commercialization is in a random branching structure, and the academic research is also in a POSS structure and a trapezoid structure, but the research, development and application of functional reaction type silicone resin are not enough. The silicone resin has the advantages of no need of adding catalyst in the self-catalytic reaction, lower cost of raw materials, serious equipment corrosion, waste acid water byproduct, too fast reaction rate, difficult control of the content of chloride ions, high requirement of adding organic solvent and unsuitable preparation of polysiloxane resin containing epoxy groups; the second is that sodium silicate and siloxane monomer are polycondensed under the conditions of hydrolysis and alkalinity in alkyd water system, which has the advantages of lower raw material cost, suitability for preparing resin with larger molecular weight, larger difference of monomer reaction rate, easy gelation, higher content of alkali metal ion, need of adding organic solvent, and unsuitable for preparing polysiloxane resin containing silicon hydrogen or epoxy group; the third is alkoxysilane cation catalytic cohydrolysis and anion catalytic copolycondensation, which has the advantages of weak reaction corrosiveness, mild and controllable reaction process, low content of chloride ions and alkali metal ions, and the disadvantages of residual alkoxy/silanol groups affecting stability, needing organic solvent, and being unsuitable for preparing polysiloxane resin containing silicon hydride or epoxy groups; the fourth is cationic catalytic transesterification reaction under alkoxysilane/carboxylic acid system, which has the advantages of mild reaction process, low content of chloride ions and alkali metal ions, no need of adding organic solvent, low molecular weight, high risk of influencing stability due to residual alkoxy/silanol groups, high risk of inflammability and explosiveness of byproduct carboxylate, high raw material cost, and unsuitable for preparing polysiloxane resin containing silicon hydride or epoxy group. The development of a silicon resin preparation method based on a non-oxidative high-efficiency cationic catalysis system and a carboxylic acid/alkoxy silane transesterification balance control system, which realizes the mild and controllable reaction process, low corrosiveness, safety, suitability for various siloxane monomers including hydrogen-containing siloxane monomers and epoxy silane monomers, controllable molecular weight, less residual alkoxy/silanol groups and low content of chloride ions and alkali metal ions, is of urgent importance.
The tyre tread rubber is an inorganic reinforced filler filled composite rubber material, and the performance of the tyre tread rubber is closely related to single components such as different rubber materials, different fillers and the like, and is closely related to multiple groups of interaction relations among different rubber materials, different fillers and between rubber and fillers. In some prior attempts, chemical modification of rubber is a more efficient method to change the polarity of the rubber from molecular structure to improve its interaction with the filler. For example, star branching is carried out on the active end of the linear solution polymerized styrene-butadiene rubber anion by using branching agents such as tin tetrachloride, silicon tetrachloride, methyltrichlorosilane and the like, so that the free chain segment at the molecular end of the solution polymerized styrene-butadiene rubber and hysteresis loss brought by the free chain segment can be obviously reduced, and the defect that the affinity of rubber molecules and fillers is not improved is overcome. For example, the functionalized end capping of the anionic active end of the linear solution polymerized styrene-butadiene rubber by means of functionalized small molecules such as chloropropyl trimethoxyl silane can strengthen the combination effect of rubber molecules and filler white carbon black to reduce the Pane effect, and the defect is that the free chain segment at the tail end of the rubber molecules and hysteresis loss caused by the free chain segment cannot be reduced. For another example, the chain epoxidation modification of butadiene rubber by means of hydrogen peroxide/formic acid system can also strengthen the combination effect of rubber molecules and filler white carbon black to bring about reduction of payon effect, and has the defects of complex and severe modification process conditions, difficult control, larger damage to the rubber molecular structure and sacrifice of partial low rolling resistance performance. In general, attempts to modify rubber as described above have individually achieved certain beneficial effects in applications in composite rubber materials for tire tread rubber, but have not been able to better address many of the challenges faced by composite rubber materials for tire tread rubber.
The existing new energy automobile tire tread rubber technology generally adopts a scheme that butadiene rubber with outstanding low rolling resistance and low heat generation performance is physically blended with solution polymerized styrene-butadiene rubber with outstanding wear resistance and wet skid resistance, and simultaneously reinforcing fillers such as white carbon black and filler dispersion treatment agents such as silane coupling agents are added. At present, the new energy automobile tire tread rubber prepared by the existing method faces the 'devil triangle' difficult problem of 'low rolling resistance, wet skid resistance and low abrasion', and has no good solution, the main reason is that the main components of the tread rubber have multiple differences in molecular structure, size and polarity, and the advantages of the main components cannot be fully exerted and the disadvantages of the main components are greatly weakened by the simple physical blending and vulcanization method, so that the main aspects are as follows. First, butadiene rubber can help to reduce the rolling resistance of the tread rubber of the new energy automobile tire, but reduces the mechanical strength and the wet skid resistance, and also increases the abrasion. Secondly, the solution polymerized styrene-butadiene rubber can help to improve the mechanical strength, the wet skid resistance and the wear resistance of the tread rubber of the new energy automobile tire, but also increases the rolling resistance. Thirdly, the white carbon black filler can help to improve the mechanical strength and the wet skid resistance of the tread rubber of the new energy automobile tire, but greatly increases the rolling resistance. Particularly, the low rolling resistance performance and the high wet skid resistance performance are difficult to be balanced and balanced.
Therefore, how to improve the mechanical strength, wet skid resistance, wear resistance and rolling resistance of the tire tread rubber is an urgent problem to be solved.
Disclosure of Invention
Based on this, the present invention aims to overcome the above-mentioned shortcomings of the prior art and provide a silicone resin, modified rubber, composite rubber material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a silicone resin having the structural formula shown in formula I:
the compound of the formula I,
wherein R is 1 =hydrogen;
R 2 ，R 3 =one of methyl, ethyl, propyl, octyl, lauryl, phenyl;
R 4 =one of methyl, ethyl, propyl, octyl, lauryl, cetyl, stearyl;
R 5 =one of phenyl, benzyl, phenethyl, phenylpropyl, naphthyl;
R 6 one of γ - (2, 3-glycidoxy) propyl, 2- (3, 4-epoxycyclohexane) ethyl;
Z=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) P is a non-negative integer;
R 8 = (R 1 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When z= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When p=0, q=1, and when z= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When p is a positive integer, q=2p, and when z= (SiO) 2 ) And p=0, q=1, when z= (SiO 2 ) And p isQ=3p when positive integer;
in the silicone resin molecule, (R) 1 R 2 R 3 SiO 0.5 ) The mole fraction of the units is a1, (R) 6 R 2 R 3 SiO 0.5 ) The mole fraction of the units is a2, (R) 4 SiO 1.5 ) The mole fraction of the units is b, (R) 5 SiO 1.5 ) The mole fraction of the units is c, (SiO) 2 ) The mole fraction of the units is d; a1+a2=a, 0 < a1/a < 1,0 < a2/a < 1; a+b+c+d=1, a is more than 0 and less than or equal to 0.80,0, b is more than 0.40,0, c is more than 0.40,0, and d is more than 1.00; preferably a1+a2=a, 0.20 < a1/a < 0.80,0 < a2/a < 0.80; a+b+c+d= 1,0.10 < a.ltoreq. 0.80,0.10 < b < 0.30,0.10 < c < 0.30,0.10 < d < 0.70.
The invention provides a multifunctional reactive polysiloxane resin containing alkyl, aryl, epoxy and active silicon hydrogen. The active silicon hydrogen provides a convenient way for hydrosilylation reaction to realize the co-modification of functional polysiloxane resin of different types of non-silicone rubber composite materials, thereby obviously reducing the hysteresis loss caused by free chain segments at the molecular tail ends of linear butadiene rubber or styrene-butadiene rubber, improving the compatibility with diene rubber by alkyl, improving the compatibility with styrene-butadiene rubber by aryl, improving the interaction between modified rubber and filler by epoxy, and further reducing the Paen effect.
Preferably, the invention provides a preparation method of the silicone resin, which comprises the following steps:
(1) Mixing siloxane containing hydrosilyl, alkoxy silane containing long-chain alkyl, alkoxy silane containing phenyl, tetraalkoxy silane and solvent uniformly;
(2) Adding a first part of a catalyst C1 into the reaction mixture in the step (1), uniformly mixing the first part, adding water, performing a first-stage reaction, removing a water phase, adding a second part of the catalyst C1, uniformly mixing the second part, adding water, performing a second-stage reaction, washing with water, drying, and filtering to obtain a hydrogen-containing alkylphenyl silicone resin solution; the catalyst C1 is a mixed solution of trifluoroacetic acid and acetic acid, wherein the mass percentage of the trifluoroacetic acid is 1-99wt%;
(3) Adding an unsaturated epoxy monomer into the solution containing hydrogen alkyl phenyl silicone resin obtained in the step (2), uniformly mixing, heating, adding a catalyst C2, reacting to obtain a solution containing the silicone resin, and removing the solvent to obtain the silicone resin; the catalyst C2 is chloroplatinic acid, speier catalyst, karstedt's catalyst, triphenylphosphine rhodium chloride RhCl (PPh) 3 ) 3 One of them.
Preferably, in the step (1), the stirring speed of the mixing is 50-500rpm, the mixing temperature is 20-40 ℃, and the mixing time is 5-30min; in the step (2), the temperature of the first section of mixing is 25-50 ℃, the time of the first section of mixing is 10-60min, the temperature of the first section of reaction after the first part of adding water is 60-90 ℃, the time of the reaction is 1-5h, the temperature of the second section of mixing is 25-50 ℃, the time of the second section of mixing is 1-10min, the temperature of the second section of reaction after the second part of adding water is 60-100 ℃, and the time of the second section of reaction is 0.5-5h; in the step (3), the stirring speed of mixing is 50-500rpm, the temperature is raised to 90-110 ℃, the reaction time after adding the catalyst C2 is 0.5-5h, and the temperature is reduced to 20-40 ℃ to obtain the solution containing the silicone resin.
Preferably, the mass ratio of the siloxane containing the silicon hydrogen group, the alkoxysilane containing the long-chain alkyl group, the alkoxysilane containing the phenyl group, the tetraalkoxysilane and the solvent in the step (1) is the siloxane containing the silicon hydrogen group: alkoxysilanes containing long-chain alkyl groups: phenyl-containing alkoxysilanes: tetraalkoxysilanes: solvent = 1: (0.5-10): (0.5-10): (0.8-20): (0-50); the siloxane containing the hydrosilyl is one of tetramethyl disiloxane, dimethyl methoxy silane and dimethyl ethoxy silane; the alkoxy silane containing long chain alkyl is propyl trimethoxy silane, propyl triethoxy silane, butyl trimethoxy silane, butyl triethoxy silane, hexyl trimethoxy silane, hexyl triethoxy silane, euphoric trimethoxy silane, octyl triethoxy silane, decyl trimethoxy silane, decyl triethoxy silane, lauryl trimethoxy silane, lauryl triethoxy silane, cetyl trimethoxy silaneOne of cetyltriethoxysilane, stearyltrimethoxysilane, stearyltriethoxysilane; the phenyl-containing alkoxysilane is one of phenyl trimethoxysilane, phenyl triethoxysilane and phenyl triisopropoxysilane; the tetraalkoxysilane is one of tetramethoxysilane, tetraethoxysilane and polyethyl silicate; the solvent is one of hexane, heptane, isododecane, isohexadecane, C13-C16 isoparaffin, cyclohexane, benzene, toluene and xylene; in the step (2), the mass ratio of the reaction mixture, the first part of the catalyst C1, the second part of the catalyst C1, the first part of the water and the second part of the water is that: first part of catalyst C1: second part of catalyst C1: first portion of water: second portion of water = 1: (0.001-0.1): (0.0002-0.02): (0.05-0.5): (0.01-0.1); the catalyst C1 is a mixed solution of trifluoroacetic acid and acetic acid, wherein the mass percent of the trifluoroacetic acid is 5-50wt%; in the step (3), the mass ratio of the hydrogen-containing alkylphenyl silicone resin, the unsaturated epoxy monomer and the catalyst C2 is that the hydrogen-containing alkylphenyl silicone resin: unsaturated epoxy monomer: catalyst c2=1: (0.05-0.7): (5X 10) -6 -5×10 -5 ) The method comprises the steps of carrying out a first treatment on the surface of the The unsaturated epoxy monomer is one of allyl glycidyl ether, 1, 2-epoxy-4-vinyl cyclohexane and glycidyl methacrylate.
Preferably, in the step (1), the siloxane containing a hydrosilyl group is tetramethyl disiloxane, the alkoxysilane containing a long-chain alkyl group is octyl triethoxysilane, the alkoxysilane containing a phenyl group is phenyl triethoxysilane, the tetraalkoxysilane is tetraethoxysilane, and the solvent is toluene; in the step (3), the unsaturated epoxy monomer is 1, 2-epoxy-4-vinylcyclohexane, and the catalyst C2 is triphenylphosphine rhodium chloride RhCl (PPh) 3 ) 3 。
In addition, the invention provides a preparation method of the modified rubber, which comprises the following steps:
(a) Mixing the silicon resin, the solution polymerized styrene butadiene rubber, the butadiene rubber and the solvent uniformly, and heatingThen adding a catalyst C3, and reacting to obtain a mixed solution containing modified rubber; the catalyst C3 is chloroplatinic acid, speier catalyst, karstedt's catalyst, triphenylphosphine rhodium chloride RhCl (PPh) 3 ) 3 One of the following;
(b) And (c) separating the solvent from the mixed solution containing the modified rubber obtained in the step (a) to obtain the modified rubber.
Preferably, the structural formula of the modified rubber is shown as formula II:
wherein R is 2 ，R 3 =one of methyl, ethyl, propyl, octyl, lauryl, phenyl;
R 4 =one of methyl, ethyl, propyl, octyl, lauryl, cetyl, stearyl;
R 5 =one of phenyl, benzyl, phenethyl, phenylpropyl, naphthyl;
R 6 one of γ - (2, 3-glycidoxy) propyl, 2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR);
R 10 solution polymerized styrene butadiene rubber (SSBR);
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) The mole fraction of the units is a2, (R) 9 R 2 R 3 SiO 0.5 ) The mole fraction of the units is a3, (R) 10 R 2 R 3 SiO 0.5 ) The mole fraction of the units is a4, (R) 4 SiO 1.5 ) The mole fraction of the units is b, (R) 5 SiO 1.5 ) The mole fraction of the units is c, (SiO) 2 ) The mole fraction of the units is d; a3+a4=a1, 0 < a3/a1 < 1,0 < a4/a1 < 1; a1+a2=a, 0 < a1/a < 1,0 < a2/a < 1; a+b+c+d=1, a is more than 0 and less than or equal to 0.80,0, b is more than 0.40,0, c is more than 0.40,0, and d is more than 1.00; preferably a3+a4=a1, 0.10 < a3/a1 < 0.90,0.10 < a4/a1 < 0.90; a1+a2=a, 0.20 < a1/a < 0.80,0 < a2/a < 0.80; a+b+c+d= 1,0.10 < a.ltoreq. 0.80,0.10 < b < 0.30,0.10 < c < 0.30,0.10 < d < 0.70.
Preferably, in the step (a), the stirring speed of mixing is 50-500rpm, the temperature is raised to 90-110 ℃, the reaction time after adding the catalyst C3 is 1-10 hours, and the mixed solution containing the modified rubber is obtained; in the step (b), the process of separating the solvent is reduced pressure distillation; the reduced pressure distillation is carried out at a rotating speed of 10-30rpm, a pressure of-0.09 to-0.05 MPa, a reduced pressure distillation temperature of 80-100 ℃ and a reduced pressure distillation time of 30-90min.
Preferably, in the step (a), the mass ratio of the silicone resin, the solution polymerized styrene-butadiene rubber, the butadiene rubber and the solvent is: solution polymerized styrene-butadiene rubber: butadiene rubber: solvent = 1: (4-400): (2-200): (30-6000); the solution polymerized styrene-butadiene rubber can be linear solution polymerized styrene-butadiene rubber, the structural formula is shown in formula III, and the number average molecular weight is 2 multiplied by 10 4 -2×10 5 The Mw/Mn range is 1-2, the solution polymerized styrene-butadiene rubber can also be star-shaped solution polymerized styrene-butadiene rubber obtained by adopting silicon tetrachloride end capping, the average arm number is 2.5-3.5, the single-arm structural formula is shown in a formula III, and the number average molecular weight is 2 multiplied by 10 4 -2×10 5 The Mw/Mn range is 1-2, the structural formula of the butadiene rubber is shown as formula IV, and the number average molecular weight range is 4 multiplied by 10 4 -4×10 5 Mw/Mn is in the range of 2-5, and the catalyst C3 is triphenylphosphine rhodium chloride RhCl (PPh) 3 ) 3 ；
The compound of the formula III,
wherein in formula III the molar fraction of styrene units (St) is f, the molar fraction of cis-1, 4-butadiene units (cis-Bd) is g, the molar fraction of 1, 2-butadiene units (1, 2-Bd) is h, and the molar fraction of trans-1, 4-butadiene units (trans-Bd) is k; f+g+h+k=1, f is more than 0 and less than 0.40,0, g is more than 0.80,0, h is more than 0.80,0 and less than or equal to k is more than 0.60; preferably, f+g+h+k=1, 0.05 < f < 0.40,0 < g < 0.50, 0.01. Ltoreq.h < 0.60, 0.ltoreq.k < 0.40;
IV, the method comprises the steps of (a),
wherein the mole fraction of cis-1, 4-butadiene units (cis-Bd) in formula IV is e1, the mole fraction of 1, 2-butadiene units (1, 2-Bd) is e2, and the mole fraction of trans-1, 4-butadiene units (trans-Bd) is e3; e1+e2+e3=1, 0 < e1 < 1.00,0 < e2 < 0.80,0 < e3 < 1.00; preferably e1+e2+e3= 1,0.20 < e1 < 1.00,0.01 < e2 < 0.80,0.ltoreq.e3 < 0.50.
Further, the invention provides a composite rubber material, and the preparation method of the composite rubber material comprises the following steps: and uniformly mixing the modified rubber and the reinforcing filler to obtain the composite rubber material.
Preferably, the reinforcing filler is hydrophobically treated white carbon black.
Preferably, the preparation method of the composite rubber material can be carried out by mixing in the presence of a solvent, namely liquid phase mixing; the solvent can be derived from the preparation process of the modified rubber or can be directly added; after the mixing is completed, separating the solvent to obtain the composite rubber material; the process for separating the solvent is reduced pressure distillation or steam condensation, when reduced pressure distillation is selected, the rotating speed is 10-30rpm, the pressure is-0.09 to-0.05 MPa, the temperature of reduced pressure distillation is 80-100 ℃, the time of reduced pressure distillation is 30-90min, when steam condensation is selected, the steam temperature is 100-180 ℃, and the condensation product is dried by a blast oven, the drying temperature is 80-150 ℃ and the time is 10-240min.
Preferably, the preparation method of the composite rubber material can be carried out by mixing in the absence of solvent, namely dry mixing; the dry-mixing process is a conventional rubber and filler dry-mixing process, such as an open mill process, an internal mixing process and the like.
In addition, the invention provides application of the modified rubber in preparing tire tread rubber. The invention also provides application of the composite rubber material in preparing tire tread rubber.
When the modified rubber is applied to the preparation of tire tread rubber, the modified rubber can be directly dry-mixed or mixed in the presence of a solvent. The modified rubber and the reinforcing filler can be directly dry-mixed with the reinforcing filler and the auxiliary agent, or the modified rubber and the reinforcing filler are dry-mixed first to obtain the composite rubber material, and the composite rubber material is dry-mixed with the auxiliary agent when being applied to tread rubber. The modified rubber and the reinforcing filler are subjected to liquid phase mixing in a solvent, the solvent is separated, and the composite rubber material is obtained and dry-mixed with an auxiliary agent when the composite rubber material is applied to tread rubber; the solvent may be added when mixed with the reinforcing filler, or may be contained and not removed when the modified rubber is prepared at the front end.
Compared with the prior art, the invention has the beneficial effects that: the invention provides modified rubber, which obviously reduces the difference and separation between components such as solution polymerized styrene-butadiene rubber, butadiene rubber and the like of main components, and the adopted silicon resin chemical modifier containing alkyl, aryl, epoxy and active silicon hydrogen has the functions of branching, reinforcing, promoting filler dispersion and improving the content of bonding rubber. The modified rubber provided by the invention is applied to the tread rubber of the new energy automobile tire, and realizes good mechanical strength, wet skid resistance, wear resistance and rolling resistance.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available. In the present invention, the specific dispersing and stirring treatment method is not particularly limited.
Examples 1 to 9 and examples 10 to 11
The formulation proportions of examples 1-9 are shown in tables 1, 2 and 3 (i.e., examples 1-9 differ in the amount of raw materials or the choice of raw materials), respectively, wherein examples 1-9 are a composite rubber material, and the preparation method of the composite rubber material comprises the following steps:
(1) Adding silicon hydride-containing siloxane, alkoxy silane containing long-chain alkyl, alkoxy silane containing phenyl, tetraalkoxy silane and solvent into a reaction kettle, and uniformly mixing to obtain a reaction mixture; the stirring speed of the mixing is 250rpm, the temperature of the mixing is 30 ℃, and the mixing time is 20min;
(2) Adding a first part of a catalyst C1 into the reaction mixture obtained in the step (1), uniformly mixing the first part, adding water, performing a first-stage reaction, removing a water phase, adding a second part of the catalyst C1, uniformly mixing the second part, adding water, performing a second-stage reaction, washing with water, drying, and filtering to obtain a hydrogen-containing alkylphenyl silicone resin solution; the temperature of the first section of mixing is 25 ℃, the time of the first section of mixing is 30min, the temperature of the first section of reaction after the first part of adding water is 70 ℃, the time of the first section of reaction is 2h, the temperature of the second section of mixing is 25 ℃, the time of the second section of mixing is 3min, the temperature of the second section of reaction after the second part of adding water is 80 ℃, and the time of the second section of reaction is 1h;
(3) Adding an unsaturated epoxy monomer into the solution containing hydrogen alkyl phenyl silicone resin obtained in the step (2), uniformly mixing, heating, adding a catalyst C2, reacting to obtain the solution containing the silicone resin, heating to 100 ℃ at the stirring speed of 250rpm, adding the catalyst C2, reacting for 2 hours, and cooling to 25 ℃ to obtain the solution containing the silicone resin;
(4) Uniformly mixing the solution containing the silicone resin, solution polymerized styrene-butadiene rubber, butadiene rubber and a solvent, heating, adding a catalyst C3, and reacting to obtain a mixed solution containing modified rubber; the stirring speed of the mixing is 250rpm, the temperature is raised to 100 ℃, the reaction time after adding the catalyst C3 is 5 hours, and the mixed solution containing the modified rubber is obtained;
(5) Uniformly mixing the mixed solution containing the modified rubber and the reinforcing filler white carbon black, and separating the solvent after the mixing is completed to obtain the composite rubber material; the process for separating the solvent comprises reduced pressure distillation, the rotating speed is 20rpm, the pressure is-0.09 MPa, the temperature of the reduced pressure distillation is 100 ℃, and the time of the reduced pressure distillation is 60min.
TABLE 1
TABLE 2
TABLE 3 Table 3
Example 10 (modified rubber + reinforcing filler + post-solubilizing agent)
The formulation ratio of example 10 is shown in table 4, and the difference between the example 10 and the example 1 is that the modified rubber without solvent is obtained first, then the modified rubber and the reinforcing filler are dissolved and dispersed uniformly by adding the solvent, and the preparation process is different, and the preparation method of the composite rubber material comprises the following steps:
(1) Adding silicon hydride-containing siloxane, alkoxy silane containing long-chain alkyl, alkoxy silane containing phenyl, tetraalkoxy silane and solvent into a reaction kettle, and uniformly mixing to obtain a reaction mixture; the stirring speed of the mixing is 250rpm, the temperature of the mixing is 30 ℃, and the mixing time is 20min;
(2) Adding a first part of a catalyst C1 into the reaction mixture obtained in the step (1), uniformly mixing the first part, adding water, performing a first-stage reaction, removing a water phase, adding a second part of the catalyst C1, uniformly mixing the second part, adding water, performing a second-stage reaction, washing with water, drying, and filtering to obtain a hydrogen-containing alkylphenyl silicone resin solution; the temperature of the first section of mixing is 25 ℃, the time of the first section of mixing is 30min, the temperature of the first section of reaction after the first part of adding water is 70 ℃, the time of the first section of reaction is 2h, the temperature of the second section of mixing is 25 ℃, the time of the second section of mixing is 3min, the temperature of the second section of reaction after the second part of adding water is 80 ℃, and the time of the second section of reaction is 1h;
(3) Adding an unsaturated epoxy monomer into the solution containing hydrogen alkyl phenyl silicone resin obtained in the step (2), uniformly mixing, heating, adding a catalyst C2, reacting to obtain the solution containing the silicone resin, heating to 100 ℃ at the stirring speed of 250rpm, adding the catalyst C2, reacting for 2 hours, and cooling to 25 ℃ to obtain the solution containing the silicone resin;
(4) Uniformly mixing the solution containing the silicone resin, solution polymerized styrene-butadiene rubber, butadiene rubber and a solvent, heating, adding a catalyst C3, and reacting to obtain a mixed solution containing modified rubber; the stirring speed of the mixing is 250rpm, the temperature is raised to 100 ℃, the reaction time after adding the catalyst C3 is 5 hours, and the mixed solution containing the modified rubber is obtained;
(5) Separating the solvent from the mixed solution containing the modified rubber obtained in the step (4) to obtain the modified rubber; the process for separating the solvent comprises reduced pressure distillation, the rotating speed is 20rpm, the pressure is-0.09 MPa, the temperature of the reduced pressure distillation is 100 ℃, and the time of the reduced pressure distillation is 60min;
(6) And uniformly mixing the modified rubber, the reinforcing filler white carbon black and the solvent to obtain the composite rubber material.
Example 11 (modified rubber+reinforcing filler)
Example 11 formulation ratios such as shown in table 4, a composite rubber material, the difference between the example 11 and the example 1 is that a modified rubber without solvent is obtained first, then the modified rubber and the reinforcing filler are directly and uniformly mixed without solvent, and the preparation process is different, the preparation method of the composite rubber material comprises the following steps:
(1) Adding silicon hydride-containing siloxane, alkoxy silane containing long-chain alkyl, alkoxy silane containing phenyl, tetraalkoxy silane and solvent into a reaction kettle, and uniformly mixing to obtain a reaction mixture; the stirring speed of the mixing is 250rpm, the temperature of the mixing is 30 ℃, and the mixing time is 20min;
(2) Adding a first part of a catalyst C1 into the reaction mixture obtained in the step (1), uniformly mixing the first part, adding water, performing a first-stage reaction, removing a water phase, adding a second part of the catalyst C1, uniformly mixing the second part, adding water, performing a second-stage reaction, washing with water, drying, and filtering to obtain a hydrogen-containing alkylphenyl silicone resin solution; the temperature of the first section of mixing is 25 ℃, the time of the first section of mixing is 30min, the temperature of the first section of reaction after the first part of adding water is 70 ℃, the time of the first section of reaction is 2h, the temperature of the second section of mixing is 25 ℃, the time of the second section of mixing is 3min, the temperature of the second section of reaction after the second part of adding water is 80 ℃, and the time of the second section of reaction is 1h;
(3) Adding an unsaturated epoxy monomer into the solution containing hydrogen alkyl phenyl silicone resin obtained in the step (2), uniformly mixing, heating, adding a catalyst C2, reacting to obtain the solution containing the silicone resin, heating to 100 ℃ at the stirring speed of 250rpm, adding the catalyst C2, reacting for 2 hours, and cooling to 25 ℃ to obtain the solution containing the silicone resin;
(4) Uniformly mixing the solution containing the silicone resin, solution polymerized styrene-butadiene rubber, butadiene rubber and a solvent, heating, adding a catalyst C3, and reacting to obtain a mixed solution containing modified rubber; the stirring speed of the mixing is 250rpm, the temperature is raised to 100 ℃, the reaction time after adding the catalyst C3 is 5 hours, and the mixed solution containing the modified rubber is obtained;
(5) Separating the solvent from the mixed solution containing the modified rubber obtained in the step (4) to obtain the modified rubber; the process for separating the solvent comprises reduced pressure distillation, the rotating speed is 20rpm, the pressure is-0.09 MPa, the temperature of the reduced pressure distillation is 100 ℃, and the time of the reduced pressure distillation is 60min;
(6) And uniformly mixing the modified rubber and the reinforcing filler white carbon black to obtain the composite rubber material.
TABLE 4 Table 4
The structural formula of the modified rubber prepared in examples 1-11 is shown in formula II.
The groups of the modified rubber prepared in example 1 are as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integerR=2s, when y= (SiO 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in example 2 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, whenY=(R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.578, (R) 9 R 2 R 3 SiO 0.5 ) Parts by mole a3=0.009, (R) 10 R 2 R 3 SiO 0.5 ) Molar fraction a4=0.071, (R) of units 4 SiO 1.5 ) Molar fraction of units b=0.08, (R) 5 SiO 1.5 ) Molar fraction of units c=0.092, (SiO) 2 ) The molar fraction of units d=0.17.
The groups of the modified rubber prepared in example 3 were as follows:
Wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.023, (R) 9 R 2 R 3 SiO 0.5 ) Parts by mole a3=0.006, (R) 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.05, (R) 4 SiO 1.5 ) Molar fraction of units b=0.192, (R) 5 SiO 1.5 ) Molar fraction of units c=0.22, (SiO) 2 ) The molar fraction of units d=0.509.
The groups of the modified rubber prepared in example 4 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in example 5 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =lauryl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in example 6 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in example 7 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn range is 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, the molar fraction of trans-1, 4-butadiene units (trans-Bd) is 0.55k=0.15；
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in example 8 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =γ - (2, 3-glycidoxy) propyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ratio is in the range of 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, 1,2-mole fraction h=0.55 of butadiene units (1, 2-Bd) and mole fraction k=0.15 of trans-1, 4-butadiene units (trans-Bd);
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in example 9 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =γ - (2, 3-glycidoxy) propyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Star-shaped solution polymerized styrene-butadiene rubber obtained by blocking silicon tetrachloride and having average arm number of 3 and single-arm structural formula shown in formula III and number average molecular weight of 9 multiplied by 10 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Parts by mole of units a3=0.042, (R) 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.112, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in example 10 were as follows:
Wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =γ - (2, 3-glycidoxy) propyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in example 11 were as follows:
Wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =γ - (2, 3-glycidoxy) propyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
Comparative examples 1 to 4
Comparative examples 1 to 4 the formulation ratios are shown in, for example, table 5 (the difference between the amounts of raw materials or the selection of raw materials is different from example 1), wherein comparative examples 1 to 4, a composite rubber material, the preparation method of which is exactly the same as example 1.
TABLE 5
The structural formula of the modified rubber prepared in comparative examples 1-4 is shown in formula II.
The groups of the modified rubber prepared in comparative example 1 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 methyl group;
R 9 methyl group;
R 10 methyl group;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in comparative example 2 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2-cyclohexylethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Unit moleMole fraction c=0.167, (SiO) 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in comparative example 3 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 =2- (3, 4-epoxycyclohexane) ethyl;
R 10 =2- (3, 4-epoxycyclohexane) ethyl;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Parts by mole of units a2=0.179, (R) 9 R 2 R 3 SiO 0.5 ) Molar fraction a3=0.017, (R) of units 10 R 2 R 3 SiO 0.5 ) Parts by mole a4=0.137, (R) 4 SiO 1.5 ) Molar fraction of units b=0.167, (R) 5 SiO 1.5 ) Molar fraction of units c=0.167, (SiO 2 ) The molar fraction of units d=0.333.
The groups of the modified rubber prepared in comparative example 4 were as follows:
wherein R is 2 ，R 3 Methyl group;
R 4 =octyl;
R 5 phenyl;
R 6 =2- (3, 4-epoxycyclohexane) ethyl;
R 9 butadiene Rubber (BR) as shown in formula iv, number average molecular weight=3.5×10 5 ，Mw/Mn=2.4；
R 10 Linear solution polymerized styrene butadiene rubber (SSBR) with number average molecular weight 9×10 as shown in formula III 4 The Mw/Mn ranges from 1.45, wherein the molar fraction f of styrene units (St) is=0.15, the molar fraction g of cis-1, 4-butadiene units (cis-Bd) is=0.15, the molar fraction h of 1, 2-butadiene units (1, 2-Bd) is=0.55, and the molar fraction k of trans-1, 4-butadiene units (trans-Bd) is=0.15;
Y=(R 4 SiO 1.5 )、(R 5 SiO 1.5 )、(SiO 2 ) S is a non-negative integer;
R 11 =(R 9 R 2 R 3 SiO 0.5 ) And/or (R) 10 R 2 R 3 SiO 0.5 ) And/or (R) 6 R 2 R 3 SiO 0.5 ) When y= (R 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s=0, r=1, and when y= (R) 4 SiO 1.5 )、(R 5 SiO 1.5 ) When s is a positive integer, r=2s, and when y= (SiO) 2 ) And s=0, r=1, when y= (SiO) 2 ) And s is a positive integer, r=3s;
in the molecule of the modified rubber, (R) 6 R 2 R 3 SiO 0.5 ) Molar fraction a2=0.054 of units, (R) 9 R 2 R 3 SiO 0.5 ) Parts by mole a3=0.006, (R) 10 R 2 R 3 SiO 0.5 ) Parts by mole of units a4=0.049, (R) 4 SiO 1.5 ) Molar fraction of units b=0.054, (R) 5 SiO 1.5 ) Molar fraction of units c=0.054, (SiO) 2 ) The molar fraction of units d=0.783.
Performance testing
The testing process comprises the following steps: the composite rubber materials prepared in the examples and the comparative examples are used in the tread rubber formula of the new energy automobile tire, and in the test process, the tread rubber formula comprises the following components: 750 g of composite rubber, 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 test sample preparation process comprises the following steps: in an internal mixer, the initial temperature is 70 ℃, the rotating speed of a rotor is 30 rpm, the composite rubber is firstly added into the internal mixer for plasticating for 2 minutes, 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 the rubber material reaches 160 ℃, the rubber is discharged after the heat preservation is carried out for 1 minute, and the rubber material is cooled and sheet-fed 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 6, and the test results are shown in Table 7.
TABLE 6
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 7
As can be seen from table 7, examples 1 to 11 showed a significant increase in tear strength and tensile strength, a significant increase in Tan δ (0 ℃) showing a significant increase in wet skid resistance, a significant decrease in DIN abrasion and compression fatigue temperature rise, a significant decrease in Payne effect showing a significant decrease in hysteresis loss, a significant decrease in Tan δ (60 ℃) showing a significant decrease in rolling resistance, as compared to comparative examples 1 to 4, and the application of the example embodiments to tire tread rubber had significant advantages.
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 the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the modified rubber is characterized by comprising the following steps:
(a) Uniformly mixing silicone resin, solution polymerized styrene-butadiene rubber, butadiene rubber and a solvent, heating, adding a catalyst C3, and reacting to obtain a mixed solution containing modified rubber; the catalyst C3 is chloroplatinic acid, speier catalyst, karstedt's catalyst, triphenylphosphine rhodium chloride RhCl (PPh) 3 ) 3 One of the following;
(b) Separating the solvent from the mixed solution containing the modified rubber obtained in the step (a) to obtain the modified rubber;
the preparation method of the silicone resin comprises the following steps:
(1) Uniformly mixing silicon containing hydrosilyl or silane containing hydrosilyl, alkoxy silane containing long-chain alkyl, alkoxy silane containing phenyl, tetraalkoxy silane and solvent; the silicon hydride-containing siloxane is tetramethyl disiloxane, and the silicon hydride-containing silane is one of dimethyl methoxy silane and dimethyl ethoxy silane;
(2) Adding a first part of the catalyst C1 into the reaction mixture in the step (1), uniformly mixing the first part, adding water, performing a first-stage reaction, removing a water phase, adding a second part of the catalyst C1, uniformly mixing the second part, adding water, performing a second-stage reaction, washing with water, drying, and filtering to obtain a hydrogen-containing alkylphenyl silicone resin solution; the catalyst C1 is a mixed solution of trifluoroacetic acid and acetic acid, wherein the mass percentage of the trifluoroacetic acid is 1-99wt%;
(3) Adding an unsaturated epoxy monomer into the solution containing hydrogen alkyl phenyl silicone resin obtained in the step (2), uniformly mixing, heating, adding a catalyst C2, reacting to obtain a solution containing the silicone resin, and removing the solvent to obtain the silicone resin; the catalyst C2 is chloroplatinic acid, speier catalyst, karstedt's catalyst, triphenylphosphine rhodium chloride RhCl (PPh) 3 ) 3 One of the following;
in the step (1), the mass ratio of the siloxane containing the hydrosilyl, the alkoxysilane containing the long-chain alkyl, the alkoxysilane containing the phenyl, the tetraalkoxysilane and the solvent is the siloxane containing the hydrosilyl: alkoxysilanes containing long-chain alkyl groups: phenyl-containing alkoxysilanes: tetraalkoxysilanes: solvent = 1: (0.5-10): (0.5-10): (0.8-20): (0-50);
in the step (3), the mass ratio of the hydrogen-containing alkylphenyl silicone resin, the unsaturated epoxy monomer and the catalyst C2 is that the hydrogen-containing alkylphenyl silicone resin: unsaturated epoxy monomer: catalyst c2=1: (0.05-0.7): (5X 10) -6 -5×10 -5 ）。
2. The method for producing a modified rubber as claimed in claim 1, wherein in said step (1), the stirring speed of mixing is 50 to 500rpm, the mixing temperature is 20 to 40℃and the mixing time is 5 to 30 minutes; in the step (2), the temperature of the first section of mixing is 25-50 ℃, the time of the first section of mixing is 10-60min, the temperature of the first section of reaction after adding the first part of water is 60-90 ℃, the time of the first section of reaction is 1-5h, the temperature of the second section of mixing is 25-50 ℃, the time of the second section of mixing is 1-10min, the temperature of the second section of reaction after adding the second part of water is 60-100 ℃, and the time of the second section of reaction is 0.5-5h; in the step (3), the stirring speed of mixing is 50-500rpm, the temperature is raised to 90-110 ℃, the reaction time after adding the catalyst C2 is 0.5-5h, and the temperature is reduced to 20-40 ℃ to obtain the solution containing the silicone resin.
3. The method for producing a modified rubber as described in claim 1, wherein said alkoxysilane containing a long chain alkyl group is one of octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, lauryltrimethoxysilane, lauryltriethoxysilane, cetyltrimethoxysilane, stearyltrimethoxysilane, stearyltriethoxysilane; the phenyl-containing alkoxysilane is one of phenyl trimethoxysilane, phenyl triethoxysilane and phenyl triisopropoxysilane; the tetraalkoxysilane is one of tetramethoxysilane and tetraethoxysilane; the solvent is one of hexane, heptane, isododecane, C13-C16 isoparaffin, cyclohexane, benzene, toluene and xylene; in the step (2), the mass ratio of the reaction mixture, the first part of the catalyst C1, the second part of the catalyst C1, the first part of the water and the second part of the water is that: first part of catalyst C1: second part of catalyst C1: first portion of water: second portion of water = 1: (0.001-0.1): (0.0002-0.02): (0.05-0.5): (0.01-0.1); the unsaturated epoxy monomer is one of allyl glycidyl ether, 1, 2-epoxy-4-vinyl cyclohexane and glycidyl methacrylate.
4. The method for producing a modified rubber as defined in claim 1, wherein in said step (a), the stirring speed of mixing is 50 to 500rpm, the temperature is raised to 90 to 110 ℃, the reaction time after adding the catalyst C3 is 1 to 10 hours, and a mixed solution containing the modified rubber is obtained; in the step (b), the process of separating the solvent is reduced pressure distillation; the reduced pressure distillation is carried out at a rotating speed of 10-30rpm, a pressure of-0.09 to-0.05 MPa, a reduced pressure distillation temperature of 80-100 ℃ and a reduced pressure distillation time of 30-90min.
5. The method for producing a modified rubber according to claim 1, wherein in the step (a), the mass ratio of the silicone resin, the solution polymerized styrene-butadiene rubber, the butadiene rubber, and the solvent is: solution polymerized styrene-butadiene rubber:butadiene rubber: solvent = 1: (4-400): (2-200): (30-6000); the solution polymerized styrene-butadiene rubber is linear solution polymerized styrene-butadiene rubber with the number average molecular weight of 2 multiplied by 10 4 -2×10 5 The solution polymerized styrene-butadiene rubber or star-shaped solution polymerized styrene-butadiene rubber obtained by capping silicon tetrachloride has an average arm number of 2.5-3.5 and a number average molecular weight of 2 multiplied by 10 4 -2×10 5 Mw/Mn ranges from 1 to 2 and butadiene rubber number average molecular weight ranges from 4X 10 4 -4×10 5 Mw/Mn is in the range of 2-5, and the catalyst C3 is triphenylphosphine rhodium chloride RhCl (PPh) 3 ) 3 ；
The solution polymerized styrene-butadiene rubber comprises f, g and h of cis-1, 4-butadiene units, and k of trans-1, 4-butadiene units; f+g+h+k=1, f is more than 0 and less than 0.40,0, g is more than 0.80,0, h is more than 0.80,0 and less than or equal to k is more than 0.60;
the cis-1, 4-butadiene unit in the butadiene rubber has a mole fraction of e1, 2-butadiene unit as e2, and trans-1, 4-butadiene unit as e3; e1+e2+e3=1, 0 < e1 < 1.00,0 < e2 < 0.80,0.ltoreq.e3 < 1.00.
6. The preparation method of the composite rubber material is characterized by comprising the following steps of: uniformly mixing the modified rubber prepared by the preparation method of any one of claims 1-5 with a reinforcing filler to obtain the composite rubber material.
7. Use of the modified rubber produced by the production method according to any one of claims 1 to 5 for producing a tread rubber for a tire.
8. Use of the composite rubber material of claim 6 for the preparation of a tread band for a tire.
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