Preparation methods of nickel-based cis-1,4-polybutadiene latex and nickel-based cis-1,4-polybutadiene rubber

Abstract

The present invention relates to the field of butadiene polymerization, and discloses a preparation method of nickel-based cis-1,4-polybutadiene latex and nickel-based cis-1,4-polybutadiene rubber. The method comprises: 1) performing a first mixing on component N and the first component B and then performing a first aging to obtain a first mixed component; 2) performing a second mixing on component A, the second component B and the first butadiene, and then performing a second aging on the product after the second mixing and the first component C to obtain a second mixed component; 3) performing a first polymerization reaction on the second butadiene, the first mixed component and the second component C, and adding the second mixed component to perform a second polymerization reaction when the polymerization conversion rate is above 50%; wherein, component N is a nickel salt; component B is an alkylaluminum compound; component C is a halogenated compound; and component A is a rare earth salt. According to the preparation method of the nickel-based cis-1,4-polybutadiene latex of the present invention, the method can significantly improve the monomer conversion rate.

Description

Technical Field

[0001] The present invention relates to the field of butadiene polymerization, and in particular, to a method for preparing a nickel-based cis-1,4-polybutadiene rubber solution and a nickel-based cis-1,4-polybutadiene rubber. Background Art

[0002] Polybutadiene rubber has high elasticity, excellent abrasion resistance, and good heat resistance, aging resistance, flex resistance, low heat generation, and small hysteresis loss. In addition, the raw material resources are rich and the price is cheap, which is especially suitable for manufacturing tires. Since a US company first realized the industrial production of cis-1,4-polybutadiene rubber using a titanium-based catalyst and solution polymerization method in 1960, with the development of the petrochemical industry and the promotion of the tire manufacturing industry, the production has developed rapidly. By 1964, its production capacity ranked second among the seven major general synthetic rubbers, second only to styrene-butadiene rubber. Currently, industrial production plants are available in many countries and regions around the world.

[0003] Matsumoto Tsuyoshi et al. first discovered in 1958 that reduced nickel supported on an acidic substance has the ability to initiate the polymerization of butadiene. Since then, the prelude to the stereospecific polymerization of butadiene initiated by nickel has been opened. Around 1965, countries such as Japan first used a ternary nickel system of nickel naphthenate, triethylaluminum, and boron trifluoride ethyl ether complex to initiate the polymerization of butadiene with toluene as a solvent, realizing industrialization.

[0004] The polymerization technology is the core of the production technology of nickel-based cis-1,4-polybutadiene rubber (NiBR). Among them, the conversion rate is related to the energy consumption, material consumption of the product, and the production capacity of the device. So far, in the NiBR production technology, the conversion rate of butadiene is mostly 80-85%, and complete conversion cannot be achieved. The unreacted butadiene needs to be rectified and returned to the polymerization kettle to participate in the reaction again. This brings two problems: one is that the returned butadiene usually contains impurities, which will affect the stability of the polymerization; the other is that the rectification process consumes a large amount of energy. Therefore, if butadiene can be completely converted, the above problems can be avoided. Summary of the Invention

[0005] The purpose of the present invention is to overcome the problem that the monomer cannot be completely converted in the existing nickel-based cis-1,4-polybutadiene polymerization technology, and provide a method for preparing a nickel-based cis-1,4-polybutadiene rubber solution, which can significantly improve the monomer conversion rate.

[0006] To achieve the above purpose, on the one hand, the present invention provides a method for preparing a nickel-based cis-1,4-polybutadiene rubber solution, wherein the method includes the following steps:

[0007] 1) First mix component N and the first component B and then carry out first aging to obtain a first mixed component;

[0008] 2) After the second mixing of component A, the second component B, and the first butadiene, the product after the second mixing is subjected to second aging with the first component C to obtain a second mixed component;

[0009] 3) The second butadiene, the first mixed component, and the second component C are subjected to a first polymerization reaction. When the polymerization conversion rate is above 50%, the second mixed component is added for a second polymerization reaction;

[0010] Among them, component N is a nickel salt; component B is an alkyl aluminum compound; component C is a halogenated compound; component A is a rare earth salt.

[0011] Preferably, in step 1), the molar ratio of the amounts of component N and the first component B is 1:2 - 12.

[0012] Preferably, the molar ratio of component A, the second component B, the first butadiene, and the first component C is 1:5 - 50:10 - 100:1 - 10.

[0013] Preferably, based on the first mixed component containing 1 mmol of component N, in step 3), the amount of the second component C used is 0.001 - 100 mmol.

[0014] Preferably, in step 3), the molar ratio of the amounts of the second butadiene, the first mixed component, and the second mixed component is 1:8×10 -5 -1×10 -4 :7×10 -5 -1.7×10 -4 .

[0015] Preferably, the nickel salt is one or more of nickel naphthenate, nickel octanoate, and nickel benzoate.

[0016] Preferably, the alkyl aluminum compound is selected from at least one of trialkyl aluminum and dialkyl aluminum hydride.

[0017] Preferably, the trialkyl aluminum is represented by the formula Al(R)3, the dialkyl aluminum hydride is represented by the formula AlH(R)2, and each R in the formula Al(R)3 and the formula AlH(R)2 is independently selected from C1 - C6 alkyl groups.

[0018] Preferably, the alkyl aluminum compound is at least one of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-n-pentyl aluminum, tri-n-hexyl aluminum, triisobutyl aluminum, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, and diisobutyl aluminum hydride.

[0019] Preferably, the rare earth salt is one or more of neodymium salt, cerium salt, and praseodymium salt.

[0020] Preferably, the halogenated compound is selected from at least one of halogenated boron, halogenated hydrogen, halogenated alkylaluminum, halogenated silane and sesquihalogenated alkylaluminum.

[0021] Preferably, the alkyl aluminum halide is of the formula Al(R 1 )2X, the halogenated silane is represented by the formula Si(R 1 ) 4-n X n Said sesquihaloalkylaluminum is represented by the formula Al2(R 1 )3X3 represents, wherein the formula Al(R 1 )2X, formula Si(R 1 ) 4-n X n and Al2(R 1 ) Each R in 3X3 1 Each X is independently selected from C1-C6 alkyl, benzyl and allyl, each X is independently selected from halogen, and n is an integer of 1-4.

[0022] Preferably, the halogenated compound is at least one of diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, and hydrogen fluoride and boron trifluoride ether complex.

[0023] Preferably, the first mixing conditions include: temperature of 10-40° C., and time of 10-200 min.

[0024] Preferably, the first aging conditions include: temperature of 10-80°C and time of 10-90 min.

[0025] Preferably, the second mixing conditions include: temperature of 10-80° C. and time of 10-200 min.

[0026] Preferably, the second aging conditions include: temperature of 30-80°C and time of 30-300 min.

[0027] Preferably, when the polymerization conversion rate is 10-90%, the second mixed component is added to carry out the second polymerization reaction; more preferably, when the polymerization conversion rate is 50-90%, the second mixed component is added to carry out the second polymerization reaction; further preferably, when the polymerization conversion rate is 70-85%, the second mixed component is added to carry out the second polymerization reaction.

[0028] Preferably, the temperature of the first polymerization reaction is 40-90°C.

[0029] Preferably, the temperature of the second polymerization reaction is 40-90°C.

[0030] Preferably, the total reaction time of the first polymerization reaction and the second polymerization reaction is 1-36 h, more preferably 6-7 h.

[0031] Preferably, steps 1)-3) are each independently carried out in an inert atmosphere.

[0032] Preferably, the inert atmosphere is provided by at least one of nitrogen, helium and argon.

[0033] Preferably, the first mixed component and the second mixed component each independently contain a solvent, or the raw materials of the first polymerization reaction contain a solvent.

[0034] Preferably, the solvent is at least one of C5-C 10 alkanes, C5-C 10 cycloalkanes and C6-C 12 aromatics; more preferably, the solvent is at least one of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, xylene and cumene.

[0035] On the other hand, the present invention provides a method for preparing nickel-based cis-1,4-polybutadiene rubber, wherein the method comprises the following steps

[0036] 1) The step of preparing a nickel-based cis-1,4-polybutadiene rubber solution according to the method for preparing a nickel-based cis-1,4-polybutadiene rubber solution described in any one of claims 1-13;

[0037] 2) The step of preparing nickel-based cis-1,4-polybutadiene rubber from the nickel-based cis-1,4-polybutadiene rubber solution.

[0038] According to the method of the present invention, the monomer conversion rate can be significantly improved, and the method provided by the present invention has the advantages of simple process, easy operation and mild conditions, and is suitable for large-scale industrial production. Detailed embodiments

[0039] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and a single point value, and between single point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0040] On the one hand, the present invention provides a method for preparing a nickel-based cis-1,4-polybutadiene rubber solution, wherein the method comprises the following steps

[0041] 1) Mix component N and the first component B for the first time and then carry out the first aging to obtain the first mixed component;

[0042] 2) After the second mixing of component A, the second component B and the first butadiene, the product after the second mixing is subjected to second aging with the first component C to obtain a second mixed component;

[0043] 3) The second butadiene, the first mixed component and the second component C are subjected to a first polymerization reaction. When the polymerization conversion rate is above 50%, the second mixed component is added for a second polymerization reaction;

[0044] Among them, component N is a nickel salt; component B is an alkyl aluminum compound; component C is a halogenated compound; component A is a rare earth salt.

[0045] In the present invention, the first component B and the second component B may be the same or different. Similarly, the first component C and the second component C may be the same or different.

[0046] The present invention will be described step by step below. However, it should be noted that the order of steps 1) and 2) of the present invention is not limited. It may be that step 1) is carried out first and then step 2), or step 2) is carried out first and then step 1), or steps 1) and 2) may be carried out simultaneously.

[0047] Step 1): After the first mixing of component N and the first component B, first aging is carried out to obtain a first mixed component.

[0048] According to the present invention, in order to further obtain a better monomer conversion effect, preferably, in step 1), the molar ratio of the amounts of component N and the first component B is 1:2 - 12, more preferably 1:4 - 8, and further preferably 1:5 - 6.

[0049] According to the present invention, in order to make the catalytic performance in the catalytic active center of the first mixed component more excellent, preferably, the conditions for the first mixing include: the temperature is 10 - 40°C and the time is 10 - 200 min; more preferably, the conditions for the first mixing include: the temperature is 10 - 40°C and the time is 20 - 60 min.

[0050] According to the present invention, in order to make the catalytic performance in the catalytic active center of the first mixed component more excellent, preferably, the conditions for the first aging include: the temperature is 10 - 80°C and the time is 10 - 90 min; more preferably, the conditions for the first aging include: the temperature is 15 - 35°C and the time is 15 - 50 min.

[0051] According to the present invention, component N is a nickel salt. Preferably, the nickel salt is one or more of nickel naphthenate, nickel octoate and nickel benzoate.

[0052] The above nickel salt can be obtained by conventional methods in the art. For example, it can be a commercially available product or prepared by conventional methods in the art. The present invention has no particular limitation on this.

[0053] Step 2): After the second mixing of component A, the second component B and the first butadiene, the product after the second mixing is subjected to a second aging with the first component C to obtain a second mixed component.

[0054] According to the present invention, in order to further obtain a better monomer conversion effect, preferably, in step 2), the molar ratio of component A, the second component B, the first butadiene and the first component C is 1:10 - 30:30 - 70:2 - 8; more preferably, the molar ratio of component A, the second component B, the first butadiene and the first component C is 1:15 - 20:50 - 60:3 - 5; particularly preferably, the molar ratio of component A, the second component B, the first butadiene and the first component C is 1:16 - 18:50 - 52:3 - 3.6.

[0055] According to the present invention, in order to make the catalytic performance in the catalytic active center of the second mixed component more excellent, preferably, the conditions for the second mixing include: the temperature is 10 - 40 °C and the time is 10 - 200 min; more preferably, the conditions for the second mixing include: the temperature is 10 - 40 °C and the time is 20 - 60 min.

[0056] According to the present invention, in order to make the catalytic performance in the catalytic active center of the second mixed component more excellent, preferably, the conditions for the second aging include: the temperature is 30 - 80 °C and the time is 30 - 300 min; more preferably, the conditions for the second aging include: the temperature is 50 - 70 °C and the time is 60 - 120 min.

[0057] According to the present invention, component A is a rare earth salt. Preferably, the rare earth salt is one or more of neodymium salt, cerium salt and praseodymium salt. Examples of the rare earth salt include: neodymium octanoate, neodymium naphthenate and neodymium phosphonate.

[0058] The above rare earth salt can be obtained by conventional methods in the art. For example, it can be a commercially available product or prepared by conventional methods in the art. The present invention has no particular limitation on this.

[0059] According to the present invention, the component B is an alkylaluminum compound. In order to further obtain a better monomer conversion effect, preferably, the alkylaluminum compound is selected from at least one of trialkylaluminum and dialkylaluminum hydride; more preferably, the trialkylaluminum is represented by the formula Al(R)3, the dialkylaluminum hydride is represented by the formula AlH(R)2, and each R in the formula Al(R)3 and the formula AlH(R)2 independently represents an alkyl group having 1 to 6 carbon atoms; further preferably, the alkylaluminum compound is at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, triisobutylaluminum, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, and diisobutylaluminum hydride.

[0060] According to the present invention, the component C is a halogenated compound. In order to further obtain a better monomer conversion effect, preferably, the halogenated compound is selected from at least one of halogenated boron, hydrogen halide, halogenated alkylaluminum, halogenated silane, and sesquihalogenated alkylaluminum; more preferably, the halogenated alkylaluminum is represented by the formula Al(R 1 )2X, the halogenated silane is represented by the formula Si(R 1 ) 4-n X n represents, and the sesquihalogenated alkylaluminum is represented by the formula Al2(R 1 )3X3, where, in the formula Al(R 1 )2X, the formula Si(R 1 ) 4-n X n and the formula Al2(R 1 )3X3, each R 1 independently represents an alkyl group having 1 to 6 carbon atoms, a benzyl group, or an allyl group, each X independently represents a halogen, and n is an integer from 1 to 4; further preferably, the halogenated compound is at least one of diethylaluminum chloride, diisobutylaluminum chloride, sesquithylaluminum chloride, sesquiisobutylaluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, hydrogen fluoride, and boron trifluoride ether complex.

[0061] Step 3): Perform a first polymerization reaction on the second butadiene, the first mixed component, and the second component C, and when the polymerization conversion rate is above 50%, add the second mixed component to perform a second polymerization reaction;

[0062] According to the present invention, in order to further obtain a better monomer conversion effect, preferably, in step 3), the molar ratio of the amounts of the second butadiene, the first mixed component, and the second mixed component is 1:1×10 -5 ~1×10 -3 : 1×10 -8 ~0.1; more preferably, the molar ratio of the amounts of the second butadiene, the first mixed component, and the second mixed component is 1:8×10 -5 -1×10-4 : 7×10 -5 -1.7×10 -4 . Among them, the dosage of the first mixed component is calculated based on the molar amount of component N contained therein, and the dosage of the second mixed component is calculated based on the molar amount of component A contained therein.

[0063] According to the present invention, in order to further obtain a better monomer conversion effect, preferably, based on the first mixed component containing 1 mmol of component N, in step 3), the dosage of the second component C is 0.001 - 100 mmol; more preferably, based on the first mixed component containing 1 mmol of component N, in step 3), the dosage of the second component C is 0.1 - 10 mmol; further preferably, based on the first mixed component containing 1 mmol of component N, in step 3), the dosage of the second component C is 0.1 - 0.5 mmol; even more preferably, based on the first mixed component containing 1 mmol of component N, in step 3), the dosage of the second component C is 0.3 - 0.4 mmol.

[0064] In the present invention, in order to further obtain a better monomer conversion effect, preferably, when the polymerization conversion rate is 50 - 90%, the second mixed component is added for the second polymerization reaction; preferably, when the polymerization conversion rate is 70 - 85%, the second mixed component is added for the second polymerization reaction; more preferably, when the polymerization conversion rate is 75 - 85%, the second mixed component is added for the second polymerization reaction.

[0065] In a particularly preferred embodiment of the present invention, when the polymerization conversion rate is 75 - 85%, the second mixed component is added for the second polymerization reaction. By adding the second mixed component for the second polymerization reaction when the polymerization conversion rate is 75 - 85%, the monomer conversion effect can be significantly improved.

[0066] In the present invention, in order to further obtain a better monomer conversion effect, preferably, each of the first polymerization reaction and the second polymerization reaction independently satisfies at least the following conditions: the temperature is 40 - 90 °C, preferably 45 - 55 °C.

[0067] In the present invention, in order to further obtain a better monomer conversion effect, preferably, the total reaction time of the first polymerization reaction and the second polymerization reaction is 1 - 36 h, more preferably 6 - 7 h.

[0068] In addition, in order to prevent oxygen from destroying the active center of the catalyst, preferably, steps 1) - 3) are each independently carried out in an inert atmosphere; more preferably, the inert atmosphere is provided by at least one of nitrogen, helium, and argon.

[0069] Meanwhile, in order to enable the smooth construction of the active centers of the catalyst and simultaneously have higher catalytic activity, preferably, the first mixed component and the second mixed component each independently contain a solvent, or the raw materials of the first polymerization reaction contain a solvent; more preferably, the solvent is at least one of C5-C 10 alkanes, C5-C 10 cycloalkanes and C6-C 12 aromatics; further preferably, the solvent is at least one of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, xylene, and cumene.

[0070] In the above embodiments, in order to further improve the activity of the catalyst, preferably, the concentration of component N in the first mixed component and the second mixed component is 0.01-1 mmol / mL, preferably 0.05-0.2 mmol / mL, and more preferably 0.08-0.12 mmol / mL.

[0071] In the above embodiments, the solvent can be added in the form of a pure substance or in the form of a solution formed with other reactants.

[0072] On this basis, component N can be provided in the form of a pure substance or in the form of a solution. When component N is provided in the form of a solution, the concentration of the solution of component N can be, for example, 0.01-0.5 mol / L. Its solvent can be selected from the solvents described above.

[0073] Similarly, component B can be provided in the form of its pure substance or in the form of a solution. When component B is provided in the form of a solution, the concentration of the solution of component B can be, for example, 0.01-5 mol / L. Its solvent can be selected from the solvents described above.

[0074] Similarly, component C can be provided in the form of its pure substance or in the form of a solution. When component C is provided in the form of a solution, the concentration of the solution of component C can be, for example, 0.0001-5 mol / L. Its solvent can be selected from the solvents described above.

[0075] Similarly, component A can be provided in the form of its pure substance or in the form of a solution. When component A is provided in the form of a solution, the concentration of the solution of component A can be, for example, 0.01-0.5 mol / L. Its solvent can be selected from the solvents described above.

[0076] In addition, butadiene can be provided in the form of its pure substance or in the form of a solution. When butadiene is provided in the form of a solution, the weight ratio of butadiene to the solvent is 100:300-1000. Among them, the solvent can be C5-C10 At least one of alkanes, C5-C 10 cycloalkanes, and C6-C 12 aromatics; more preferably, the solvent is at least one of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, xylene, and cumene.

[0077] According to another aspect of the present invention, the present invention provides a method for preparing nickel-based cis-1,4-polybutadiene rubber, wherein the method comprises the following steps:

[0078] 1) A step of preparing a nickel-based cis-1,4-polybutadiene rubber solution according to the method for preparing a nickel-based cis-1,4-polybutadiene rubber solution described in any one of claims 1-13;

[0079] 2) A step of preparing nickel-based cis-1,4-polybutadiene rubber from the nickel-based cis-1,4-polybutadiene rubber solution.

[0080] According to the present invention, there are no particular limitations on the "step of preparing nickel-based cis-1,4-polybutadiene rubber from the nickel-based cis-1,4-polybutadiene rubber solution", and conditions and methods commonly used in the art can be adopted. For example, after the reaction is completed, anhydrous ethanol and antioxidant 264 can be added to the rubber solution for termination, followed by coagulation. The obtained butadiene polymer is air-dried at room temperature and then placed in a vacuum drying oven at 40°C until constant weight.

[0081] The present invention will be described in detail below through examples, but the present invention is not limited to the following examples.

[0082] In the following examples and comparative examples, the molecular weight and molecular weight distribution were measured using a HLC-8320 gel permeation chromatograph (GPC) produced by Tosoh Corporation, Japan. Two TSKgel SuperMultipore HZ-M analytical columns were configured, THF was used as the mobile phase, narrow-distribution polystyrene was used as the standard sample, and the temperature was 40°C.

[0083] Example 1

[0084] Under nitrogen protection, 100 mL of hexane, 4.6 mmol of neodymium octoate, then 73.6 mL of a 1 mol / L hexane solution of diisobutylaluminum hydride and 230 mmol of butadiene were added, and the mixture was stirred at 30°C for 30 min. Then, the temperature was raised to 60°C, and 13.8 mL of a 1 mol / L hexane solution of diethylaluminum chloride was added, and the mixture was aged for 2 h to obtain a second mixed component in a homogeneous solution state, namely homogeneous rare earth catalyst C1.

[0085] Under nitrogen protection, 10 mL of hexane, 0.37 mmol of nickel naphthenate, and 2.2 mmol of triisobutylaluminum were mixed at 30 °C and aged at 30 °C for 30 min to obtain a first mixed component. Then, the first mixed component was put into a reaction kettle containing 200 g of butadiene (monomer) and 900 g of hexane (the molar ratio of butadiene to the first mixed component based on nickel naphthenate is 1:1×10 -4 ), and then 0.15 mmol of boron trifluoride ethyl ether complex was added, mixed evenly, and a polymerization reaction was carried out at a polymerization temperature of 50 °C. When the conversion rate of the reaction reached 85%, 3.8 mL of catalyst C1 was added to the reaction kettle (the molar ratio of butadiene to the catalyst based on neodymium octanoate is 1:1.5×10 -4 ), and the reaction was continued at a polymerization temperature of 50 °C for 6 hours, and the conversion rate was measured to be 100%.

[0086] Example 2

[0087] Under nitrogen protection, 10 mL of hexane, 0.30 mmol of nickel naphthenate, and 1.6 mmol of triisobutylaluminum were mixed at 30 °C and aged at 30 °C for 30 min to obtain a first mixed component. Then, the first mixed component was put into a reaction kettle containing 200 g of butadiene (monomer) and 900 g of hexane (the molar ratio of butadiene to the first mixed component based on nickel naphthenate is 1:8×10 -5 ), and then 0.10 mmol of boron trifluoride ethyl ether complex was added, mixed evenly, and a polymerization reaction was carried out at a polymerization temperature of 50 °C. When the conversion rate of the reaction reached 79%, 5.6 mL of catalyst C1 was added to the reaction kettle (the molar ratio of butadiene to the catalyst based on neodymium octanoate is 1:1.6×10 -4 ), and the reaction was continued at a polymerization temperature of 50 °C for 6.5 hours, and the conversion rate was measured to be 100%.

[0088] Example 3

[0089] Under nitrogen protection, 100 mL of hexane, 4.3 mmol of neodymium octanoate, then 77.4 mL of a hexane solution of diisobutylaluminum hydride with a concentration of 1 mol / L and 223.6 mmol of butadiene were stirred and mixed at 30 °C for 30 min, then the temperature was raised to 60 °C, and then 15.1 mL of a hexane solution of diethylaluminum chloride with a concentration of 1 mol / L was added and aged for 2 h to obtain a first mixed component in a homogeneous solution state, that is, a homogeneous rare earth catalyst C2.

[0090] Under nitrogen protection, 10 mL of hexane, 0.30 mmol of nickel naphthenate, and 1.6 mmol of triisobutylaluminum were mixed at 30 °C and then aged for 30 min to obtain a second mixed component. Subsequently, the first mixed component was introduced into a reaction kettle containing 200 g of butadiene (monomer) and 900 g of hexane (the molar ratio of butadiene to the first mixed component based on nickel naphthenate is 1:8×10 -5 ). Then, 0.10 mmol of boron trifluoride ethyl ether complex was added, and after mixing evenly, a polymerization reaction was carried out at a polymerization temperature of 50 °C. When the conversion rate of the reaction reached 75%, 7.8 mL of catalyst C2 was added to the reaction kettle (the molar ratio of butadiene to the catalyst based on neodymium octanoate is 1:1.7×10 -4 ), and the reaction was continued at a polymerization temperature of 50 °C for 6.5 hours, and the measured conversion rate was 98%.

[0091] Example 4

[0092] Under nitrogen protection, 10 mL of hexane, 0.30 mmol of nickel naphthenate, and 1.6 mmol of triisobutylaluminum were mixed at 30 °C and then aged at 30 °C for 30 min to obtain a first mixed component. Subsequently, the first mixed component was introduced into a reaction kettle containing 200 g of butadiene (monomer) and 900 g of hexane (the molar ratio of butadiene to the first mixed component based on nickel naphthenate is 1:8×10 -5 ). Then, 0.10 mmol of boron trifluoride ethyl ether complex was added, and after mixing evenly, a polymerization reaction was carried out at a polymerization temperature of 50 °C. When the conversion rate of the reaction reached 62%, 2.8 mL of catalyst C2 was added to the reaction kettle (the molar ratio of butadiene to the catalyst based on neodymium octanoate is 1:7×10 -5 ), and the reaction was continued at a polymerization temperature of 50 °C for 13 hours, and the measured conversion rate was 86%.

[0093] Example 5

[0094] Under nitrogen protection, 10 mL of hexane, 0.30 mmol of nickel naphthenate, and 1.6 mmol of triisobutylaluminum were mixed at 30 °C and then aged at 30 °C for 30 min to obtain a first mixed component. Subsequently, the first mixed component was introduced into a reaction kettle containing 200 g of butadiene (monomer) and 900 g of hexane (the molar ratio of butadiene to the first mixed component based on nickel naphthenate is 1:8×10 -5 ). Then, 0.10 mmol of boron trifluoride ethyl ether complex was added, and after mixing evenly, a polymerization reaction was carried out at a polymerization temperature of 50 °C. When the conversion rate of the reaction reached 55%, 12.3 mL of catalyst C2 was added to the reaction kettle (the molar ratio of butadiene to the catalyst based on neodymium octanoate is 1:1.5×10 -4), the reaction was continued at a polymerization temperature of 50 °C for 6.5 hours, and the conversion rate was measured to be 85%.

[0095] Comparative Example 1

[0096] According to the method described in Example 1, except that the amount of catalyst C1 used was 0, and the corresponding conversion rate of butadiene was 82%.

[0097] Comparative Example 2

[0098] According to the method described in Example 1, except that the conversion rate when adding catalyst C1 was 40%, and the corresponding conversion rate of butadiene was 57%.

[0099] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A preparation method of nickel-based cis-1,4-polybutadiene rubber solution, characterized in that, The method comprises the following steps: 1) First, components N and the first component B are subjected to first mixing and then first aging to obtain a first mixed component; 2) Second, components A, the second component B, and the first butadiene are subjected to second mixing, and then the product after the second mixing is subjected to second aging with the first component C to obtain a second mixed component; 3) Third, the second butadiene, the first mixed component, and the second component C are subjected to a first polymerization reaction. When the polymerization conversion rate is above 50%, the second mixed component is added for a second polymerization reaction; wherein, component N is a nickel salt; component B is an alkylaluminum compound; component C is a halogenated compound; component A is a rare earth salt. In step 1), the molar ratio of the amounts of component N and the first component B used is 1:2 - 12. In step 2), the molar ratio of component A, the second component B, the first butadiene, and the first component C is 1:5 - 50:10 - 100:1 - 10. Based on the first mixed component containing 1 mmol of component N, in step 3), the amount of the second component C used is 0.001 - 100 mmol. In step 3), the molar ratio of the second butadiene, the first mixed component, and the second mixed component is 1:8×10 -5 -1×10 -4 :7×10 -5 -1.7×10 -4 , the amount of the first mixed component is calculated based on the molar amount of the component N contained therein, and the amounts of the second mixed component are all calculated based on the molar amount of the component A contained therein.

2. The method according to claim 1, wherein, The nickel salt is one or more of nickel naphthenate, nickel octanoate, and nickel benzoate.

3. The method according to claim 1, wherein, The alkylaluminum compound is selected from at least one of trialkylaluminum and dialkylaluminum hydride.

4. The method according to claim 3, wherein, The trialkylaluminum is represented by the formula Al(R)3, and the dialkylaluminum hydride is represented by the formula AlH(R)2. Each R in the formula Al(R)3 and the formula AlH(R)2 independently represents an alkyl group of C1 - C6.

5. The method according to claim 3, wherein The alkylaluminum compound is at least one of trimethylaluminum, triethylaluminum, tri - n - propylaluminum, tri - n - butylaluminum, tri - n - pentylaluminum, tri - n - hexylaluminum, triisobutylaluminum, diethylaluminum hydride, di - n - propylaluminum hydride, di - n - butylaluminum hydride, and diisobutylaluminum hydride.

6. The method according to any one of claims 1-5, wherein, The rare earth salt is one or more of neodymium salts, cerium salts, and praseodymium salts.

7. The method according to any one of claims 1-5, wherein The halogenated compound is selected from at least one of halogenated boron, hydrogen halide, halogenated alkylaluminum, halogenated silane, and sesquihalogenated alkylaluminum.

8. The method according to claim 7, wherein, The haloalkylaluminum is represented by the formula Al(R 1 )2X, the halosilane is represented by the formula Si(R 1 ) 4-n X n , and the sesquialter haloalkylaluminum is represented by the formula Al2(R 1 )3X3. Among them, in the formulas Al(R 1 )2X, Si(R 1 ) 4-n X n and Al2(R 1 )3X3, each R 1 is independently selected from alkyl groups having 1 to 6 carbon atoms, benzyl, and allyl, and each X is independently selected from halogens, and n is an integer from 1 to 4.

9. The method according to claim 7, wherein The halogenated compound is at least one of diethylaluminum chloride, diisobutylaluminum chloride, sesquithylaluminum chloride, sesquiisobutylaluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, hydrogen fluoride, and boron trifluoride ether complex.

10. The method according to any one of claims 1-5, wherein, The conditions for the first mixing include: temperature is 10 - 40°C, and time is 10 - 200 min.

11. The method according to any one of claims 1-5, wherein The conditions for the first aging include: temperature is 10 - 80°C, and time is 10 - 90 min.

12. The method according to any one of claims 1-5, wherein The conditions for the second mixing include: temperature is 10 - 80°C, and time is 10 - 200 min.

13. The method according to any one of claims 1-5, wherein The conditions for the second aging include: temperature is 30 - 80°C, and time is 30 - 300 min.

14. The method according to any one of claims 1-5, wherein, When the polymerization conversion rate is 10 - 90%, the second mixed component is added for the second polymerization reaction.

15. The method according to claim 14, wherein, When the polymerization conversion rate is 50 - 90%, the second mixed component is added for the second polymerization reaction.

16. The method according to claim 15, wherein, When the polymerization conversion rate is 70 - 85%, the second mixed component is added for the second polymerization reaction.

17. The method according to any one of claims 1-5, wherein, The temperature of the first polymerization reaction is 40 - 90°C.

18. The method according to any one of claims 1-5, wherein, The temperature of the second polymerization reaction is 40 - 90°C.

19. The method according to any one of claims 1-5, wherein, The total reaction time of the first polymerization reaction and the second polymerization reaction is 1 - 36 h.

20. The method according to claim 19, wherein The total reaction time of the first polymerization reaction and the second polymerization reaction is 6 - 7 h.

21. The method according to any one of claims 1-5, wherein, Steps 1) - 3) are each independently carried out in an inert atmosphere.

22. The method according to claim 21, wherein, The inert atmosphere is provided by at least one of nitrogen, helium, and argon.

23. The method according to any one of claims 1-5, wherein, Each of the first mixed component and the second mixed component independently contains a solvent, or the raw materials of the first polymerization reaction contain a solvent.

24. The method according to claim 23, wherein The solvent is at least one of C5-C 10 alkanes, C5-C 10 cycloalkanes and C6-C 12 aromatics.

25. The method according to claim 23, wherein, The solvent is at least one of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, n - heptane, n - octane, benzene, toluene, xylene, and cumene.

26. A preparation method of nickel-based cis-1,4-polybutadiene rubber, characterized in that, This method includes the following steps 1) A step of preparing a nickel - based cis - 1,4 - polybutadiene latex according to the preparation method of the nickel - based cis - 1,4 - polybutadiene latex described in any one of claims 1 - 25; 2) A step of preparing nickel - based cis - 1,4 - polybutadiene rubber from the nickel - based cis - 1,4 - polybutadiene latex.