Modified cis-conjugated diene rubber and preparation method thereof

Abstract

The invention relates to modified cis-conjugated diene rubber and a preparation method thereof, and the modified cis-conjugated diene rubber comprises the following raw materials by mole: 0.1-10 parts of silicon modified conjugated diene; 10 to 30 parts of conjugated diene B; 0.001 to 0.1 part of a polymerization catalyst; and 60-90 parts of a solvent B. The preparation method comprises the following steps: adding a part of silicon-modified conjugated diene into a solvent B, adding a polymerization catalyst in a nitrogen atmosphere at 30-80 DEG C, reacting for 1-20 minutes, adding conjugated diene B, reacting for 6-18 hours, adding the rest of silicon-modified conjugated diene for polymerization and end capping, reacting for 5-30 minutes, filtering, washing, and drying to obtain the silicon-modified conjugated diene. And washing the obtained product, and drying at 30-60 DEG C to obtain the required modified cis-conjugated diene rubber. According to the invention, the compatibility between the rubber and polar fillers such as white carbon black can be improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of synthetic rubber, and particularly relates to a modified cis-conjugated diene rubber and a preparation method thereof. Background Art

[0002] The excellent properties of natural rubber are due to polar substances such as phospholipids and proteins at the chain ends of the molecular weight. However, traditional synthetic rubbers often do not have this structure. With the continuous development of highways and the increasing demand for vehicle energy conservation, the research and development of tire tread composites with low rolling resistance, high wet skid resistance and high wear resistance has become an important topic in the field of synthetic rubber. Compared with ordinary carbon black, silica has smaller particle size and larger specific surface area. As a tire filler, it has excellent dynamic mechanical properties and wear resistance, low rolling resistance and high wet skid resistance, meeting the requirements of current green tires. There are often a large number of silanol groups on the surface of silica, which have strong hydrophilicity and surface polarity, poor compatibility with the matrix of general synthetic rubber, difficult to disperse evenly, and difficult to process, thus increasing the Mooney viscosity of the mixed rubber and having an adverse impact on the dynamic performance of the tire. Therefore, improving the silica-rubber matrix interface has become an urgent task. Hydrophobic modification of traditional coupling agents is a commonly used method in the industry at present. However, traditional coupling agents bring increasingly severe challenges to the environment due to problems such as VOC gas emissions and high energy consumption during modification.

[0003] Grafting a silicon group to the end of a rubber molecule is the most effective and direct method to solve this problem. The introduction of silicon is beneficial to form a stable chemical interaction with the surface of silica, improve dispersion, and inhibit agglomeration. During the rubber synthesis process, coupling agents such as silicon chloride are added to in-situ modify the end-chain structure of rubber molecules. This requires the molecular chain to be an active molecule. In addition, the end of the macromolecular chain is easily embedded, and the coupling efficiency is often very low. There are also patent reports on post-modification of rubber molecular chains, which often have a series of problems such as incomplete reaction, the influence of residual modifiers on rubber properties, difficult control of the distribution of modified groups, high modification cost, and complex post-treatment processes, making it difficult to be applied on a large scale. The copolymerization method is currently an ideal method to introduce a silicon group to the chain end. Anionic copolymerization (Macromolecules 2022, 55(10), 4046 - 4055) and radical copolymerization (Macromolecules 1999, 32, 3875 - 3877) can introduce a silicon group, but the molecular chain lacks regularity and it is impossible to prepare high-regularity cis-rubber (cis content greater than 90%). Adding a terminator to the polymerization reaction system is also a modification method, but the conversion rate of end groups is not high, the reactivity of large molecular weight chains is low, and each chain can incorporate at most one modified molecule, making it difficult to improve the properties of the polymer (Macromolecules 2019, 52(3), 1210 - 1219, Macromolecules 2021, 54, 2427 - 2438). The coordination copolymerization method can prepare high-regularity rubber. There have been reports on the synthesis of hydroxyl-functionalized polyconjugated dienes (Chinese J. Polym. Sci. 2023, 41, 720 - 727, Angew. Chem. 2018, 130, 16062 - 16066), but the hydroxyl group needs to be protected by alkyl aluminum, resulting in a decrease in molecular weight. SUMMARY OF THE INVENTION

[0004] The first technical problem to be solved by the present invention is, in view of the current situation of the prior art, to provide a modified cis-conjugated diene rubber to improve its compatibility with polar fillers such as silica.

[0005] The second technical problem to be solved by the present invention is to provide a preparation method for the above-mentioned modified cis-conjugated diene rubber.

[0006] The technical solution adopted by the present invention to solve the above first technical problem is as follows: A modified cis-conjugated diene rubber, characterized in that, by mole fraction, it comprises the following raw materials:

[0007]

[0008] The silicon-modified conjugated diene is at least one of the structures shown in Formulas 1 - 4:

[0009]

[0010] Among them, the silicon-modified conjugated diene matrix is at least one of myrcene, ocimene, and albizzia olefin;

[0011] R1, R2, and R3 are at least one of alkyl, aryl, alkoxy, and aryloxy.

[0012] X is one of O, S, NMe2, NPh2, N i Pr2, N t Bu2.

[0013] Preferably, R1, R2, and R3 are at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-tert-butylphenyl, 2-phenylphenyl, 2-cumylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-di-tert-butylphenyl, 2,6-diphenylphenyl, 2,6-di-cumylphenyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, phenoxy, 2-methylphenoxy, 2-ethylphenoxy, 2-n-propylphenoxy, 2-tert-butylphenoxy, 2-phenylphenoxy, 2-cumylphenoxy, 2,6-dimethylphenoxy, 2,6-diethylphenoxy, 2,6-di-n-propylphenoxy, 2,6-di-tert-butylphenoxy, 2,6-diphenylphenoxy, 2,6-di-cumylphenoxy.

[0014] Preferably, the molar ratio of the silicon-modified conjugated diene in the modified cis-conjugated diene rubber is 1.0 to 30.0%.

[0015] Preferably, the synthesis steps of the silicon-modified conjugated diene in the above formulas 1 to 4 are as follows:

[0016]

[0017] Among them, Y is O, Z is Cl or Br, and n = 1 to 10.

[0018] Calculated by mole fraction, the silicon-modified conjugated diene includes the following raw materials:

[0019]

[0020] Conjugated diene A is preferably at least one of hydroxymyrcene, aminomyrcene, bromomyrcene, chloromyrcene, myrcene, hydroxyocimene, aminoocimene, bromoocimene, chloroocimene, ocimene, hydroxyalbizzia olefin, aminoalbizzia olefin, bromoalbizzia olefin, chloroalbizzia olefin, and albizzia olefin.

[0021] The silicon modifier is preferably at least one of silicon chloride, chlorosiloxane, hydrosiloxane, hydrogenated alkylsilicon, hydrogenated arylsilicon, mercapto siloxane, amino siloxane, brominated siloxane, amino silicon, and potassium amino silicon.

[0022] When the silicon modifier is in the state of a hydrogenated silicon compound, the catalyst is a platinum catalyst;

[0023] When the silicon modifier is in a state other than a hydrogenated silicon compound, the catalyst is a Lewis base, including at least one of sodium hydroxide, potassium hydroxide, calcium hydride, sodium hydride, sodium tert-butoxide, potassium tert-butoxide, and butyl lithium.

[0024] Solvent A is at least one of n-butanol, ethanol, methanol, tert-amyl alcohol, n-propanol, isopropanol, octanol, acetone, butanone, ethyl ether, phenyl ether, methyl ethyl ether, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, n-pentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, benzene, toluene, decahydronaphthalene, dodecane, hydrogenated gasoline, and petroleum ether.

[0025] Preferably, the polymerization catalyst includes a main catalyst, and the main catalyst is one of a neodymium compound, a cobalt compound, and a nickel compound;

[0026] When the main catalyst is a neodymium compound, the polymerization catalyst further includes cocatalyst 1 and cocatalyst 2. The cocatalyst 1 is at least one of triisobutylaluminum, trioctylaluminum, trimethylaluminum, triethylaluminum, diisobutylaluminum hydride, dibutylmagnesium, ethylbutylmagnesium, diethylmagnesium, modified methylaluminoxane, methylaluminoxane, ethylmagnesium bromide, and phenylmagnesium bromide; the cocatalyst 2 is at least one of diisobutylaluminum chloride, dichlorodimethylsilane, tert-butyl chloride, carbon tetrachloride, chloroform, ethylaluminum dichloride, aluminum trichloride, diethylaluminum chloride, and ethylaluminum sesquichloride; the molar ratio of the main catalyst, cocatalyst 1, and cocatalyst 2 is 1:5 to 50:1 to 4;

[0027] When the main catalyst is a cobalt compound, the polymerization catalyst further includes cocatalyst 3. The cocatalyst 3 is at least one of triisobutylaluminum, trioctylaluminum, trimethylaluminum, triethylaluminum, diisobutylaluminum hydride, dibutylmagnesium, ethylbutylmagnesium, diethylmagnesium, modified methylaluminoxane, methylaluminoxane, ethylmagnesium bromide, phenylmagnesium bromide, diisobutylaluminum chloride, ethylaluminum dichloride, aluminum trichloride, diethylaluminum chloride, and ethylaluminum sesquichloride; the molar ratio of the main catalyst to cocatalyst 3 is 1:2 to 1200;

[0028] When the main catalyst is a nickel compound, the polymerization catalyst further includes a cocatalyst 4 and an electron donor. The cocatalyst 4 is at least one of triisobutylaluminum, trioctylaluminum, trimethylaluminum, triethylaluminum, diisobutylaluminum hydride, dibutylmagnesium, ethylbutylmagnesium, diethylmagnesium, modified methylaluminoxane, methylaluminoxane, ethylmagnesium bromide, phenylmagnesium bromide, diisobutylaluminum chloride, chloro-diethylaluminum, aluminum trichloride, diethylaluminum chloride, dichloro-triethylaluminum; the electron donor is at least one of methyl ether boron trifluoride, ethyl ether boron trifluoride, butyl ether boron trifluoride; the molar ratio of the main catalyst, the cocatalyst 4 and the electron donor is 1:3 to 50:1 to 5.

[0029] Further, the neodymium compound is at least one of neodymium carboxylate, neodymium alkoxide, neodymium phosphate ester, neodymium acetylacetonate, neodymium chloride, neodymium sulfonate;

[0030] The cobalt compound is at least one of cobalt(II) acetylacetonate, cobalt(II) acetate, cobalt(II) chloride, cobalt(II) bromide, cobalt(II) isooctanoate, cobalt(III) acetylacetonate, cobalt(III) acetate, cobalt(III) chloride, cobalt(III) bromide, cobalt(III) isooctanoate, organic cobalt(II) complex;

[0031] The organic cobalt(II) complex is at least one of the structures shown in Formulas 5 to 9:

[0032]

[0033]

[0034] Among them, R1 and R2 are at least one of methyl, ethyl, n-propyl, isopropyl, phenyl, n-butyl, tert-butyl;

[0035] Ar is at least one of phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-tert-butylphenyl, 2-phenylphenyl, 2-cumylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-di-tert-butylphenyl, 2,6-diphenylphenyl, 2,6-di-cumylphenyl;

[0036] X is at least one of chlorine, bromine, iodine;

[0037] The nickel compound is at least one of nickel(II) isooctanoate, nickel(II) naphthenate, nickel(II) acetate, nickel(II) acetylacetonate, nickel chloride, nickel bromide.

[0038] Further, the neodymium carboxylate is at least one of neodymium neodecanoate and neodymium isooctanoate; the neodymium alkoxide is at least one of neodymium ethoxide and neodymium isopropoxide; the neodymium phosphate ester is at least one of 2-ethylhexyl phosphate monoester and neodymium 2-ethylhexyl diphosphate.

[0039] In each of the above solutions, preferably, the solvent B is at least one of n-butane, n-pentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, benzene, toluene, decalin, dodecane, hydrogenated gasoline, and petroleum ether.

[0040] Preferably, the conjugated diene B is at least one of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 4-methyl-1,3-butadiene, 4,4-dimethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, myrcene, farnesene, and ocimene.

[0041] The technical solution adopted by the present invention to solve the above second technical problem is as follows: A method for preparing a modified cis-conjugated diene rubber as described above, characterized in that the steps are as follows:

[0042] Add a part of the silicon-modified conjugated diene to the solvent B, and under a nitrogen atmosphere at 30-80°C, then add a polymerization catalyst and react for 1-20 minutes, then add the conjugated diene B and react for 6-18 hours, and then add the remaining part of the silicon-modified conjugated diene for polymerization capping and react for 5-30 minutes. The obtained product is washed and then dried at 30-60°C to obtain the required silicon-modified cis-conjugated diene rubber.

[0043] Compared with the prior art, the advantages of the present invention are as follows:

[0044] (1) By the coordination copolymerization method, a silicon-modified rubber is directly introduced at the high cis-1,4 regularity (>97%) rubber chain end. The silicon group can have strong chemical interactions with inorganic fillers such as silica, montmorillonite, and calcium carbonate, providing high dispersibility for the fillers;

[0045] (2) The properties of the modified rubber, such as elongation at break, breaking strength, loss factors at 0 and 60°C, etc., are significantly improved;

[0046] (3) The direct copolymerization method avoids the problems of side reactions and residual reagents caused by the multiple steps, complex process, and uncertainties in the modification reaction of the modification method, and has important industrial application prospects. Specific Embodiments

[0047] The following further describes the present invention in detail with reference to embodiments.

[0048] First, the preparation of the silicon-modified conjugated diene is as follows:

[0049] Example 1:

[0050] Preparation of tris(isopropoxy)siloxanyl myrcene: Hydroxy myrcene (0.1 mol) and triethylamine (0.2 mol) were dissolved in 200 mL of anhydrous dichloromethane. Trichlorosilane tris(isopropoxide) (0.1 mol) was slowly added at 0 °C, and the mixture was stirred at room temperature for 2 hours. The organic solution was collected by filtration, dried over anhydrous magnesium sulfate, filtered, and distilled to obtain tris(isopropoxy)siloxanyl myrcene with a yield of 75.4%;

[0051] Tris(isopropoxy)siloxanyl ocimene was prepared by the above method, except that hydroxy ocimene was used to replace the above hydroxy myrcene, and the yield of tris(isopropoxy)siloxanyl ocimene was 80.3%;

[0052] Tris(isopropoxy)siloxanyl farnesene was prepared by the above method, except that hydroxy farnesene was used to replace the above hydroxy myrcene, and the yield of tris(isopropoxy)siloxanyl farnesene was 56.6%.

[0053] Example 2:

[0054] Preparation of propylthio tris(isopropoxy)silanyl myrcene: Propylthio tris(isopropoxy)silane (0.15 mol) was dissolved in 98 mL of anhydrous tetrahydrofuran. Sodium hydride (0.16 mol) was slowly added in portions at 0 °C. After stirring at room temperature for 3 hours, myrcenyl chloride (0.14 mol) was slowly added dropwise, and the mixture was stirred at room temperature for 8 hours. The organic solution was collected by filtration, dried over anhydrous magnesium sulfate, filtered, and distilled to obtain a colorless transparent liquid, which is propylthio tris(isopropoxy)silanyl myrcene with a yield of 48.9%;

[0055] Propylthio tris(isopropoxy)silanyl ocimene was prepared by the above method, except that ocimenyl chloride was used to replace the above myrcenyl chloride, and the yield of propylthio tris(isopropoxy)silanyl ocimene was 51.3%;

[0056] Propylthio tris(isopropoxy)silanyl farnesene was prepared by the above method, except that farnesyl chloride was used to replace the above myrcenyl chloride, and the yield of propylthio tris(isopropoxy)silanyl farnesene was 50.8%;

[0057] Example 3:

[0058] Preparation of phenylthioether tris(isopropoxy)silane myrcene: Phenylthiol tris(isopropoxy)silane (0.11 mol) was dissolved in 45 mL of anhydrous tetrahydrofuran. Sodium hydroxide (0.12 mol) was added slowly in portions at 0 °C. After stirring at room temperature for 1 hour, myrcenyl chloride (0.10 mol) was slowly added dropwise. The mixture was stirred at room temperature for 5 hours, and the organic solution was collected by filtration, dried over anhydrous magnesium sulfate, filtered, distilled, and a colorless transparent liquid, phenylthioether tris(isopropoxy)silane myrcene, was obtained with a yield of 48.9%;

[0059] Phenylthioether tris(isopropoxy)silane ocimene was prepared by the above method, except that ocimene chloride was used instead of myrcenyl chloride above. The yield of phenylthioether tris(isopropoxy)silane ocimene was 69.6%;

[0060] Phenylthioether tris(isopropoxy)silane farnesene was prepared by the above method, except that farnesene chloride was used instead of myrcenyl chloride above. The yield of phenylthioether tris(isopropoxy)silane farnesene was 78.4%.

[0061] Example 4:

[0062] Preparation of tris(isopropoxy)silane myrcene: Tris(isopropoxy)silane (0.21 mol) and myrcene (0.20 mol) were dissolved in 45 mL of anhydrous tetrahydrofuran. Chloroplatinic acid (H2PtCl6, 0.18 mmol) was added, and the mixture was stirred at 60 °C for 6 hours. Then the volatile solvents and reactants were removed to obtain a liquid of tris(isopropoxy)silane myrcene with a yield of 83.8%;

[0063] Tris(isopropoxy)silane ocimene was prepared by the above method, except that ocimene was used instead of myrcene above. The yield of tris(isopropoxy)silane ocimene was 61.1%;

[0064] Tris(isopropoxy)silane farnesene was prepared by the above method, except that farnesene was used instead of myrcene above. The yield of tris(isopropoxy)silane farnesene was 75.7%.

[0065] Example 5:

[0066] Preparation of trimethylsilyloxy myrcene: Hydroxy myrcene (0.22 mol) and triethylamine (0.42 mol) were dissolved in 300 mL of anhydrous dichloromethane. Trimethylsilyl chloride (0.25 mol) was added slowly at 0 °C. The mixture was stirred at room temperature for 4 hours, dried over anhydrous sodium sulfate, filtered, and separated by silica gel column (ethyl acetate: n - hexane = 20:1) to obtain trimethylsilyloxy myrcene with a yield of 81.5%;

[0067] Trimethylsilyloxy ocimene was prepared by the above method, except that hydroxy ocimene was used to replace the above-mentioned hydroxy laurene, and the yield of trimethylsilyloxy ocimene was 79.4%;

[0068] Trimethylsilyloxy albizzene was prepared by the above method, except that hydroxy albizzene was used to replace the above-mentioned hydroxy laurene, and the yield of trimethylsilyloxy albizzene was 69.4%.

[0069] Example 6:

[0070] Preparation of propylthioether trimethylsilyl laurene: Propylmercapto trimethylsilane (0.11 mol) was dissolved in 50 mL of anhydrous methanol. Sodium hydride (0.12 mol) was added slowly in batches at 0 °C. After stirring at room temperature for 1 hour, bromolaurene (0.10 mol) was slowly added dropwise. After stirring at room temperature for 8 hours, it was dried over anhydrous sodium sulfate, filtered, and separated by silica gel column (ethyl acetate: n-hexane 24:1) to obtain propylthioether trimethylsilyl laurene, with a yield of 81.0%;

[0071] Propylthioether trimethylsilyl ocimene was prepared by the above method, except that bromo ocimene was used to replace the above-mentioned bromolaurene, and the yield of propylthioether trimethylsilyl ocimene was 70.1%;

[0072] Propylthioether trimethylsilyl albizzene was prepared by the above method, except that bromo albizzene was used to replace the above-mentioned bromolaurene, and the yield of propylthioether trimethylsilyl albizzene was 66.4%.

[0073] Example 7:

[0074] Preparation of p-phenylthioether trimethylsilyl laurene: p-Phenylmercapto trimethylsilane (0.25 mol) was dissolved in 70 mL of anhydrous ethanol. Potassium hydroxide (0.30 mol) was added at 0 °C. After stirring at room temperature for 1.5 hours, bromolaurene (0.10 mol) was slowly added dropwise. After stirring at room temperature for 2 hours, it was dried over anhydrous sodium sulfate, filtered, and separated by silica gel column (ethyl acetate: n-hexane 25:1) to obtain p-phenylthioether trimethylsilyl laurene, with a yield of 56.2%;

[0075] p-Phenylthioether trimethylsilyl ocimene was prepared by the above method, except that bromo ocimene was used to replace the above-mentioned bromolaurene, and the yield of p-phenylthioether trimethylsilyl ocimene was 72.0%;

[0076] p-Phenylthioether trimethylsilyl albizzene was prepared by the above method, except that bromo albizzene was used to replace the above-mentioned bromolaurene, and the yield of p-phenylthioether trimethylsilyl albizzene was 71.1%.

[0077] Example 8:

[0078] Preparation of triethylsilyl myrcene: Triethylsilane (0.11 mol) and myrcene (0.10 mol) were dissolved in 23 mL of absolute ethanol, and chloroplatinic acid (H2PtCl6, 0.10 mmol) was added. After stirring at 58 °C for 8 hours, volatile solvents and reactants were removed to obtain triethylsilyl myrcene liquid with a yield of 92.8%;

[0079] Triethylsilyl ocimene was prepared by the above method, except that ocimene was used to replace the above-mentioned myrcene, and the yield of triethylsilyl ocimene was 78.1%;

[0080] Triethylsilyl heptatriene was prepared by the above method, except that heptatriene was used to replace the above-mentioned myrcene, and the yield of triethylsilyl heptatriene was 70.5%.

[0081] II. Secondly, preparation of chain-end silicon-modified cis-conjugated diene rubber:

[0082] Example 1: Preparation of chain-end tris(isopropoxy)siloxy myrcene-modified cis-isoprene rubber: Tris(isopropoxy)siloxy myrcene (3.5 mmol) was added to a polymerization flask containing 80 mL of anhydrous and anaerobic toluene. At 50 °C, 0.07 mmol of neodymium(III) neodecanoate, 1.4 mmol of triisobutylaluminum, and 0.14 mmol of diethylaluminum chloride were added to initiate polymerization. After 1.0 hour, the monomers completely reacted. Then, isoprene (0.35 mol) was added and reacted for 8 hours. Then, tris(isopropoxy)siloxy myrcene (3.5 mmol) was added. After 4 hours, 0.5 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration, and drying, with a yield of 95.2%;

[0083] Characterization of the copolymer: 1 HNMR (400 MHz, ppm, δ), (1.14~1.31, 1.67~1.88, 1.91~2.28, 2.59~2.80, 3.35~4.08, 4.85~4.95, 5.30~5.45); The cis-1,4 content was 97.1 mol-%, the insertion rate of tris(isopropoxy)siloxy myrcene was 1.90 mol-%, and the insertion mode was chain-end block. The number-average molecular weight of the copolymer was 24.7x10 4 g / mol, and the molecular weight distribution was 2.2.

[0084] The copolymer was vulcanized according to the formulations in Table 1 and Table 2, and the properties of the vulcanizate are shown in Table 2.

[0085] Example 2: Preparation of chain-end tris(isopropoxy)siloxanyl myrcene-modified cis-1,4-polybutadiene rubber: Tris(isopropoxy)siloxanyl myrcene (3.0 mmol) was added to a 65 mL anhydrous and anaerobic toluene polymerization flask. At 35 °C, 0.06 mmol of cobalt(II) isooctanoate and 1.2 mmol of diethylaluminum chloride were added to initiate polymerization. After 2.5 hours, the monomers completely reacted. Then, butadiene (0.24 mol) was added and reacted for 6 hours. After that, tris(isopropoxy)siloxanyl myrcene (3.0 mmol) was added. After 8 hours, 0.5 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration, and drying, with a yield of 90.2%;

[0086] Copolymer characterization: 1 HNMR (400 MHz, ppm, δ), (1.10 - 1.37, 1.61 - 1.84, 1.90 - 2.20, 2.41 - 2.88, 3.30 - 3.88, 4.88 - 4.99, 5.17 - 5.40); The cis-1,4 content was 97.5 mol-%, the insertion rate of tris(isopropoxy)siloxanyl myrcene was 2.13 mol-%, the insertion mode: chain-end block, and the number-average molecular weight of the copolymer was 18.8x10 4 g / mol, and the molecular weight distribution was 2.5.

[0087] The copolymer was vulcanized according to the formulations in Table 1 and Table 3, and the properties of the vulcanizate are shown in Table 3.

[0088] Example 3: Preparation of chain-end propylthioether tris(isopropoxy)silane myrcene-modified cis-1,4-polyisoprene rubber: Propylthioether tris(isopropoxy)silane myrcene (5.0 mmol) was added to 100 mL of anhydrous and anaerobic toluene. At 40 °C, 0.20 mmol of neodymium(III) naphthenate was added, and then 6.0 mmol of triisobutylaluminum and 0.40 mmol of diethylaluminum chloride were added to initiate polymerization. After 1.5 hours, the monomers completely reacted. Then, isoprene (0.40 mol) was added and reacted for 4 hours. After that, propylthioether tris(isopropoxy)silane myrcene (5.0 mmol) was added. After 2 hours, 0.4 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration, and drying, with a yield of 98.8%;

[0089] Copolymer characterization: 1 HNMR (400 MHz, ppm, δ), (0.05 - 0.12, 1.01 - 1.30, 1.61 - 1.81, 1.94 - 2.24, 2.49 - 2.89, 4.80 - 5.05, 5.18 - 5.41); The cis-1,4 content was 97.8 mol-%, the insertion rate of propylthioether tris(isopropoxy)silane myrcene was 1.29 mol-%, the insertion mode: chain-end block, and the number-average molecular weight of the copolymer was 20.5x10 4g / mol, molecular weight distribution 2.9.

[0090] The copolymer was vulcanized according to the formulations in Table 1 and Table 4, and the properties of the vulcanizate are shown in Table 4.

[0091] Example 4: Preparation of chain-end propylthioether tris(isopropoxy)silane-modified cis-1,4-polybutadiene rubber: Propylthioether tris(isopropoxy)silane laurylene (1.5 mmol) was added to a polymerization flask containing 73 mL of anhydrous and oxygen-free toluene. At 28 °C, 0.05 mmol of cobalt(II) acetylacetonate and 1.5 mmol of diethylaluminum chloride were added to initiate polymerization. After 4 hours, the monomers were completely reacted. Then, butadiene (0.30 mol) was added and reacted for 6 hours. Then, tris(isopropoxy)siloxane laurylene (2.0 mmol) was added. After 1 hour, 0.5 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration, and drying, with a yield of 85.2%.

[0092] Copolymer characterization: 1 HNMR (400 MHz, ppm, δ), (0.10 - 0.15, 1.09 - 1.29, 1.60 - 1.80, 1.94 - 2.28, 2.44 - 2.80, 4.92 - 5.04, 5.10 - 5.40); the content of cis-1,4 is 97.0 mol-%, the insertion rate of tris(isopropoxy)siloxane laurylene is 1.01 mol-%, insertion mode: chain-end block, the number-average molecular weight of the copolymer is 15.0x10 4 g / mol, molecular weight distribution 2.9.

[0093] The copolymer was vulcanized according to the formulations in Table 1 and Table 5, and the properties of the vulcanizate are shown in Table 5.

[0094] Example 5: Preparation of chain-end trimethylsiloxy laurylene-modified cis-1,4-polyisoprene rubber: Trimethylsiloxy laurylene (5.0 mmol) was added to 95 mL of anhydrous and oxygen-free toluene solvent. At 48 °C, 0.10 mmol of neodymium(III) naphthenate was added, and then 5.0 mmol of triisobutylaluminum and 0.10 mmol of sesquiethylaluminum were added to initiate polymerization. After 2.0 hours, the monomers were completely reacted. Isoprene (0.40 mol) was added and reacted for 4 hours. Then, trimethylsiloxy laurylene (5.0 mmol) was added. After 3 hours, 0.4 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration, and drying, with a yield of 84.7%;

[0095] Copolymer characterization: 1HNMR (400 MHz, ppm, δ), (0.04 - 0.10, 1.11 - 1.24, 1.60 - 1.80, 1.90 - 2.27, 2.50 - 2.79, 4.85 - 5.00, 5.14 - 5.40); the content of cis-1,4 is 97.2 mol-%, the insertion rate of trimethylsilyloxy myrcene is 2.58 mol-%, the insertion mode: chain-end block, the number-average molecular weight of the copolymer is 21.0x10 4 g / mol, and the molecular weight distribution is 2.7.

[0096] The copolymer is vulcanized according to the formulations in Table 1 and Table 6, and the properties of the vulcanizate are shown in Table 6.

[0097] Example 6: Preparation of chain-end trimethylsilyloxy myrcene modified cis-1,4-polybutadiene rubber: Trimethylsilyloxy myrcene (1.5 mmol) was added to a polymerization flask containing 55 mL of anhydrous and oxygen-free toluene. At 37 °C, 0.05 mmol of cobalt(II) naphthenate and 1.5 mmol of diethylaluminum chloride were added to initiate polymerization. After 2 hours, the monomers completely reacted. Then, butadiene (0.20 mol) was added and reacted for 8 hours, and then trimethylsilyloxy myrcene (3.0 mmol) was added. After 5 hours, 0.5 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration, and drying, and the yield was 97.4%.

[0098] Copolymer characterization: 1 HNMR (400 MHz, ppm, δ), (0.04 - 0.09, 1.08 - 1.19, 1.58 - 1.81, 1.90 - 2.21, 2.48 - 2.78, 4.90 - 5.09, 5.18 - 5.41); the content of cis-1,4 is 97.9 mol-%, the insertion rate of trimethylsilyloxy myrcene is 1.95 mol-%, the insertion mode: chain-end block, the number-average molecular weight of the copolymer is 12.7x10 4 g / mol, and the molecular weight distribution is 2.4.

[0099] The copolymer is vulcanized according to the formulations in Table 1 and Table 7, and the properties of the vulcanizate are shown in Table 7.

[0100] Example 7: Preparation of chain-end phenylthioether trimethylsilane myrcene modified cis-isoprene rubber: Phenylthioether trimethylsilane myrcene (0.04 mol) was added to 100 mL of anhydrous and oxygen-free n-hexane. At 55 °C, 0.04 mmol of neodymium(III) isopropoxide was added, followed by 0.12 mmol of triisobutylaluminum and 0.08 mmol of dibutylaluminum dichloride to initiate polymerization. After 1.0 hour, the monomers completely reacted. Isoprene (0.32 mol) was added and reacted for 5 hours. Then phenylthioether trimethylsilane myrcene (0.04 mol) was added. After 3 hours, 0.4 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration and drying, with a yield of 98.8%;

[0101] Characterization of the copolymer: 1 HNMR (400 MHz, ppm, δ), (0.04 - 0.11, 1.17 - 1.30, 1.59 - 1.70, 1.90 - 2.25, 4.87 - 5.07, 5.17 - 5.47, 6.87 - 7.40); The cis-1,4 content was 97.0 mol-%, the insertion rate of phenylthioether trimethylsilane myrcene was 19.5 mol-%, and the insertion mode was chain-end block. The number-average molecular weight of the copolymer was 38.5x10 4 g / mol, and the molecular weight distribution was 2.5.

[0102] The copolymer was vulcanized according to the formulations in Table 1 and Table 8, and the properties of the vulcanizate are shown in Table 8.

[0103] Example 8: Preparation of chain-end phenylthioether trimethylsilane myrcene modified cis-butadiene rubber: Phenylthioether trimethylsilane myrcene (0.1 mmol) was added to a polymerization flask containing 58 mL of anhydrous and oxygen-free toluene. At 45 °C, 0.04 mmol of cobalt(II) isooctanoate and 0.80 mmol of sesquiethylaluminum were added to initiate polymerization. After 4 hours, the monomers completely reacted. Then butadiene (0.40 mol) was added and reacted for 8 hours. Then phenylthioether trimethylsilane myrcene (0.10 mol) was added. After 7 hours, 0.5 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration and drying, with a yield of 96.2%.

[0104] Characterization of the copolymer: 1 HNMR (400 MHz, ppm, δ), (0.02 - 0.10, 1.01 - 1.22, 1.59 - 1.79, 1.94 - 2.20, 4.90 - 5.11, 5.21 - 5.41, 6.81 - 7.39); The cis-1,4 content was 97.8 mol-%, the insertion rate of phenylthioether trimethylsilane myrcene was 31.8 mol-%, and the insertion mode was chain-end block. The number-average molecular weight of the copolymer was 24.0x10 4 g / mol, and the molecular weight distribution was 2.5.

[0105] The copolymer is vulcanized according to the formulations in Appendix 1 and Appendix 9, and the properties of the vulcanizate are shown in Appendix 9.

[0106] Example 9: Preparation of cis - isoprene rubber modified with triethylsilyl myrcene at the chain end: Triethylsilyl myrcene (80.0 mmol) was added to 100 mL of anhydrous and oxygen - free n - hexane. At 45 °C, 0.04 mmol of neodymium(III) isooctanoate was added, followed by 0.12 mmol of triisobutylaluminum and 0.08 mmol of diethylaluminum chloride to initiate polymerization. After 0.5 h, the monomers completely reacted. Then isoprene (0.40 mol) was added and reacted for 3 h. After the monomers completely reacted, triethylsilyl myrcene (80.0 mmol) was added. After 1 h, 0.4 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration and drying, with a yield of 98.8%.

[0107] Characterization of the copolymer: 1 HNMR (400 MHz, ppm, δ), (0.05 - 0.12, 1.21 - 1.35, 1.58 - 1.74, 1.95 - 2.20, 4.85 - 5.08, 5.10 - 5.40); The cis - 1,4 content is 98.1 mol - %, the insertion rate of triethylsilyl myrcene is 27.9 mol - %, the insertion mode: block at the chain end, the number - average molecular weight of the copolymer is 36.5x10 4 g / mol, and the molecular weight distribution is 2.0.

[0108] The copolymer is vulcanized according to the formulations in Appendix 1 and Appendix 10, and the properties of the vulcanizate are shown in Appendix 10.

[0109] Example 10: Preparation of cis - butadiene rubber modified with triethylsilyl myrcene at the chain end: Triethylsilyl myrcene (0.1 mmol) was added to a polymerization flask containing 61 mL of anhydrous and oxygen - free toluene. At 30 °C, 0.04 mmol of cobalt(II) chloride and 12 mmol of MAO aluminum were added to initiate polymerization. After 2 h, the monomers completely reacted. Then butadiene (0.20 mol) was added and reacted for 8 h. After the monomers completely reacted, triethylsilyl myrcene (0.10 mol) was added. After 7 h, 0.5 mL of methanol was added to terminate the reaction. The product was obtained by methanol coagulation, washing, filtration and drying, with a yield of 96.2%.

[0110] Characterization of the copolymer: 1HNMR (400 MHz, ppm, δ), (0.07 - 0.12, 1.05 - 1.20, 1.58 - 1.77, 1.90 - 2.29, 4.90 - 5.09, 5.21 - 5.42); The content of cis-1,4 is 97.5 mol-%, the insertion rate of triethylsilyl myrcene is 50.1 mol-%, insertion mode: chain-end block, the number-average molecular weight of the copolymer is 29.0 x 10 4 g / mol, and the molecular weight distribution is 2.4.

[0111] The copolymer is vulcanized according to the formula in Table 1-11, and the properties of the vulcanizate are shown in Table 2-11.

[0112] Table 1 Vulcanization Formula

[0113] Material Parts by weight (wt-%) Copolymer 100 Carbon black (C) 0-50 <![CDATA[Silica (SiO2)]]> 0-50 Zinc oxide (ZnO) 4 Stearic acid (SA) 2 CZ 1.5 D 0.5 4010N / A 1 Sulfur (S) 1.5

[0114] Table 2 Mechanical Properties of Vulcanizates Corresponding to the Polymer in Example 1 under Different Silica / Carbon Black Formulas

[0115]

[0116] Table 3 Mechanical Properties of Vulcanizates Corresponding to the Polymer in Example 2 under Different Silica / Carbon Black Formulas

[0117]

[0118] Table 4 Mechanical Properties of Vulcanizates Corresponding to the Polymer in Example 3 under Different Silica / Carbon Black Formulas

[0119]

[0120]

[0121] Table 5 Mechanical Properties of Vulcanizates Corresponding to the Polymer in Example 4 under Different Silica / Carbon Black Formulas

[0122]

[0123] Table 6 Mechanical Properties of Vulcanizates Corresponding to the Polymer in Example 5 under Different Silica / Carbon Black Formulas

[0124]

[0125] Table 7 Mechanical Properties of Vulcanizates Corresponding to the Polymer in Example 6 under Different Silica / Carbon Black Formulas

[0126]

[0127] Table 8 Mechanical Properties of Vulcanizates Corresponding to the Polymer in Example 7 under Different Silica / Carbon Black Formulas

[0128]

[0129] Table 9 Mechanical properties of vulcanizates corresponding to the polymers in Example 8 under different silica / carbon black formulations

[0130]

[0131]

[0132] Table 10 Mechanical properties of vulcanizates corresponding to the polymers in Example 9 under different silica / carbon black formulations

[0133]

[0134] Table 11 Mechanical properties of vulcanizates corresponding to the polymers in Example 10 under different silica / carbon black formulations

[0135]

Claims

1. A modified cis-conjugated diene rubber, characterized in that: By mole fraction, it includes the following raw materials: The silicon-modified conjugated diene is at least one of the structures shown in Formulas 1-4: Among them, the silicon-modified conjugated diene matrix is at least one of myrcene, ocimene, and acacia olefins; R1, R2, and R3 are at least one of alkyl, aryl, alkoxy, and aryloxy; X is one of O, S, NMe2, NPh2, N i Pr2, N t Bu2.

2. The modified cis-conjugated diene rubber according to claim 1, wherein: The synthesis steps of the silicon-modified conjugated diene in the above Formulas 1-4 are as follows: Among them, Y is O, Z is Cl or Br, and n = 1-10.

3. The modified cis-conjugated diene rubber according to claim 1, characterized in that: R1, R2, and R3 are at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-tert-butylphenyl, 2-phenylphenyl, 2-cumylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-di-tert-butylphenyl, 2,6-diphenylphenyl, 2,6-di-cumylphenyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, phenoxy, 2-methylphenoxy, 2-ethylphenoxy, 2-n-propylphenoxy, 2-tert-butylphenoxy, 2-phenylphenoxy, 2-cumylphenoxy, 2,6-dimethylphenoxy, 2,6-diethylphenoxy, 2,6-di-n-propylphenoxy, 2,6-di-tert-butylphenoxy, 2,6-diphenylphenoxy, 2,6-di-cumylphenoxy.

4. The modified cis-conjugated diene rubber according to claim 1, wherein: The polymerization catalyst includes a main catalyst, and the main catalyst is one of neodymium compounds, cobalt compounds, and nickel compounds; When the main catalyst is a neodymium compound, the polymerization catalyst further includes cocatalyst 1 and cocatalyst 2. The cocatalyst 1 is at least one of triisobutylaluminum, trioctylaluminum, trimethylaluminum, triethylaluminum, diisobutylaluminum hydride, dibutylmagnesium, ethylbutylmagnesium, diethylmagnesium, modified methylaluminoxane, methylaluminoxane, ethylmagnesium bromide, phenylmagnesium bromide; The cocatalyst 2 is at least one of diisobutylaluminum chloride, dichlorodimethylsilane, tert-butyl chloride, carbon tetrachloride, chloroform, ethylaluminum dichloride, aluminum trichloride, diethylaluminum chloride, triethylaluminum dichloride; The molar ratio of the main catalyst, cocatalyst 1, and cocatalyst 2 is 1:5-50:1-4; When the main catalyst is a cobalt compound, the polymerization catalyst further includes cocatalyst 3. The cocatalyst 3 is at least one of triisobutylaluminum, trioctylaluminum, trimethylaluminum, triethylaluminum, diisobutylaluminum hydride, dibutylmagnesium, ethylbutylmagnesium, diethylmagnesium, modified methylaluminoxane, methylaluminoxane, ethylmagnesium bromide, phenylmagnesium bromide, diisobutylaluminum chloride, ethylaluminum dichloride, aluminum trichloride, diethylaluminum chloride, triethylaluminum dichloride; The molar ratio of the main catalyst and cocatalyst 3 is 1:2-1200; When the main catalyst is a nickel compound, the polymerization catalyst further includes a cocatalyst 4 and an electron donor. The cocatalyst 4 is at least one of triisobutylaluminum, trioctylaluminum, trimethylaluminum, triethylaluminum, diisobutylaluminum hydride, dibutylmagnesium, ethylbutylmagnesium, diethylmagnesium, modified methylaluminoxane, methylaluminoxane, ethylmagnesium bromide, phenylmagnesium bromide, diisobutylaluminum chloride, chloro-diethylaluminum, aluminum trichloride, diethylaluminum chloride, dichloro-triethylaluminum; the electron donor is at least one of methyl ether boron trifluoride, ethyl ether boron trifluoride, butyl ether boron trifluoride; the molar ratio of the main catalyst, cocatalyst 4 and electron donor is 1:3 to 50:1 to 5.

5. The modified cis-conjugated diene rubber according to claim 4, characterized in that: The neodymium compound is at least one of neodymium carboxylate, neodymium alkoxide, neodymium phosphate ester, neodymium acetylacetonate, neodymium chloride, neodymium sulfonate; The cobalt compound is at least one of cobalt(II) acetylacetonate, cobalt(II) acetate, cobalt(II) chloride, cobalt(II) bromide, cobalt(II) isooctanoate, cobalt(III) acetylacetonate, cobalt(III) acetate, cobalt(III) chloride, cobalt(III) bromide, cobalt(III) isooctanoate, at least one of organic cobalt(II) complexes; The organic cobalt(II) complex is at least one of the structures shown in Formulas 5 to 9: Wherein, R1 and R2 are at least one of methyl, ethyl, n-propyl, isopropyl, phenyl, n-butyl, tert-butyl; Ar is at least one of phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-tert-butylphenyl, 2-phenylphenyl, 2-cumenylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-di-tert-butylphenyl, 2,6-diphenylphenyl, 2,6-di-cumenylphenyl; X is at least one of chlorine, bromine, iodine; The nickel compound is at least one of nickel(II) isooctanoate, nickel(II) naphthenate, nickel(II) acetate, nickel(II) acetylacetonate, nickel chloride, nickel bromide.

6. The modified cis-conjugated diene rubber according to claim 5, characterized in that: The neodymium carboxylate is at least one of neodymium neodecanoate or neodymium isooctanoate; the neodymium alkoxide is at least one of neodymium ethoxide, neodymium isopropoxide; the neodymium phosphate ester is at least one of 2-ethylhexyl phosphate monoester, 2-ethylhexyl diester neodymium salt.

7. The modified cis-conjugated diene rubber according to any one of claims 1 to 6, characterized in that: The solvent B is at least one of n-butane, n-pentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, benzene, toluene, decalin, dodecane, hydrogenated gasoline, petroleum ether.

8. The modified cis-conjugated diene rubber according to any one of claims 1 to 6, characterized in that: The conjugated diene B is at least one of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 4-methyl-1,3-butadiene, 4,4-dimethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene.

9. A method for preparing a modified cis-conjugated diene rubber as described in any one of claims 1 to 8, characterized in that The steps are as follows: Add a part of the silicon-modified conjugated diene to Solvent B. Under a nitrogen atmosphere at 30 to 80 °C, then add a polymerization catalyst and react for 1 to 20 minutes. Then add conjugated diene B and react for 6 to 18 hours. Then add the remaining part of the silicon-modified conjugated diene for polymerization capping and react for 5 to 30 minutes. The obtained product is washed and then dried at 30 to 60 °C to obtain the desired modified cis-conjugated diene rubber.

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