Polybutadiene glue solution and preparation method thereof, and preparation method of polybutadiene rubber

Abstract

The invention relates to the field of butadiene polymerization, and discloses a polybutadiene glue solution and a preparation method thereof, and a preparation method of polybutadiene rubber. The preparation method of the polybutadiene glue solution comprises the following steps: 1) mixing a component N and a first component B, and aging to obtain a first mixed component; 2) mixing the component A, the second component B and the component D, and aging the mixture and the first component C to obtain a second mixed component; 3) butadiene, the first mixed component and a second component C are subjected to a polymerization reaction, when the polymerization conversion rate is 70-80%, the second mixed component is added for a polymerization reaction, and a component N is nickel salt; the component B is an alkyl aluminum compound; a component C: a halogenated compound; a component D: conjugated diene; the component A is rare earth salt. According to the preparation method of the polybutadiene rubber solution and the polybutadiene rubber, the content of trans-1, 4-structure blocks in butadiene rubber can be increased, and the deflection performance of the butadiene rubber is improved.

Description

Technical Field

[0001] The invention relates to the field of butadiene polymerization, and in particular to a polybutadiene glue solution and a preparation method thereof and a preparation method of polybutadiene rubber. Background Art

[0002] Polybutadiene rubber has the characteristics of high elasticity, excellent wear resistance, good heat resistance, aging resistance, flexibility resistance, low heat generation, small hysteresis loss, etc., and the raw material resources are abundant and cheap, which is particularly suitable for manufacturing tires. Since 1960, when American companies first realized the industrial production of butadiene rubber using quinone catalysts and solution polymerization, with the development of the petrochemical industry and driven by the tire manufacturing industry, production has developed rapidly. By 1964, its production capacity jumped to the 1st place among the seven general-purpose synthetic rubbers, second only to styrene-butadiene rubber. At present, many countries and regions around the world have industrial production facilities.

[0003] In 1958, Matsumoto Takeshi and others first discovered that reduced nickel carried on acidic substances has the ability to initiate the polymerization of butadiene. From then on, the prelude to the directional polymerization of butadiene initiated by nickel was unveiled. Around 1965, Japan and other countries first used the ternary nickel system of nickel naphthenate, triethylaluminum, and boron trifluoride ether complex to initiate butadiene polymerization with toluene as solvent, and achieved industrialization. In the early 1970s, my country also used hydrogenated gasoline as solvent, the ternary nickel system of nickel naphthenate, triisobutylaluminum, and boron trifluoride ether complex, that is, the nickel-aluminum aging and dilute boron addition method, and also achieved the industrialization of nickel-based butadiene rubber.

[0004] To date, the production technology of nickel-based butadiene rubber (NiBR) has been industrialized in my country for more than 40 years, and great progress has been made in all aspects, but the product brand is single. Faced with the implementation of the tire labeling law and the continuous improvement of social development requirements for materials, the nickel-based butadiene process can no longer meet the market demand. If only the catalyst process technology can be improved accordingly based on the existing equipment, it can meet the market demand without increasing the cost of equipment transformation.

[0005] When the molecular chain of cis-1,4-block-containing butadiene rubber is stretched and deformed, it induces crystallization and produces crystalline micro-regions. The crystalline micro-regions act as physical cross-linking points, increase the tensile stress, disperse energy, and resist crack growth. Increasing the content of trans-1,4-block-structure in butadiene rubber will help improve the flexural properties of butadiene rubber. Summary of the invention

[0006] The object of the present invention is to provide a polybutadiene glue solution and a preparation method thereof and a preparation method of polybutadiene rubber. According to the polybutadiene glue solution and the preparation method of polybutadiene rubber of the present invention, the content of trans 1,4-structure block in butadiene rubber can be increased and the flexural properties of butadiene rubber can be improved.

[0007] In order to achieve the above object, the first aspect of the present invention provides a method for preparing a polybutadiene adhesive, characterized in that the method comprises the following steps:

[0008] 1) performing a first mixing of component N and a first component B and then performing a first aging to obtain a first mixed component;

[0009] 2) after performing a second mixing of component A, the second component B and component D, performing a second aging of the second mixed product and the first component C to obtain a second mixed component;

[0010] 3) subjecting butadiene, the first mixed component and the second component C to a first polymerization reaction, and when the polymerization conversion rate is 70-80%, adding the second mixed component to conduct a second polymerization reaction, wherein the polymerization temperature of the second polymerization reaction is greater than 90° C. and less than 110° C.,

[0011] Among them, component N is nickel salt; component B is alkyl aluminum compound; component C is halogenated compound; component D is conjugated diene; component A is rare earth salt.

[0012] Preferably, in step 1), the molar ratio of component N to component B is 1:2-12.

[0013] Preferably, in step 2), the molar ratio of the component A, the second component B, the component D and the first component C is 1:10-25:40-55:3-4, preferably 1:12-20:43-50:3-3.5.

[0014] Preferably, in step 3), the molar ratio of the butadiene, the first mixed component calculated as component N, the second component C and the second mixed component calculated as component A is 1:5×10 -5 -1×10 -4 :1.2×10 -3 -1.5×10 -3 :1.5×10 -5 -2.5×10 -5 , preferably 1:9×10 -5 -1×10 -4 :1.3×10 -3 -1.4×10 -3 :1.7×10 -5 -2.2×10 -5 .

[0015] Preferably, the alkyl aluminum compound is selected from at least one of trialkyl aluminum and dialkyl aluminum hydride.

[0016] Preferably, the trialkylaluminum is represented by the formula Al(R)3, and 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 is independently selected from a C1-C6 alkyl group; more 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.

[0017] Preferably, the halogenated compound is selected from at least one of halogenated boron, halogenated hydrogen, halogenated alkylaluminum, halogenated silane and sesquihalogenated alkylaluminum.

[0018] 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.

[0019] Preferably, the halogenated compound is at least one of diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane tetrachlorosilane, hydrogen fluoride and boron trifluoride ether complex.

[0020] Preferably, the conjugated diene is at least one selected from 1,3-butadiene, isoprene, piperylene and 2,4-hexadiene.

[0021] Preferably, the first mixing and the second mixing each independently satisfy at least the following conditions: temperature is 10-40° C., and time is 10-200 min.

[0022] Preferably, the first aging and the second aging each independently meet at least the following conditions: temperature is 10-80°C, and time is 10-300 min.

[0023] Preferably, the first polymerization reaction temperature is 50-90°C.

[0024] Preferably, the total reaction time of the first polymerization reaction and the second polymerization reaction is 1-36 h, preferably 6-7 h.

[0025] Preferably, the polymerization conversion rate is 75-80%.

[0026] Preferably, step 1) to step 3) are each independently carried out in an inert atmosphere.

[0027] Preferably, the inert atmosphere is provided by at least one of nitrogen, helium and argon.

[0028] Preferably, the first component and the second component each independently contain a solvent, or the raw material for the first polymerization reaction contains a solvent.

[0029] Preferably, the solvent is C5-C 10 Alkanes, C5-C 10 Cycloalkanes and C6-C 12 At least one of aromatic hydrocarbons; more preferably, the solvent is at least one of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, xylene and cumene.

[0030] According to a second aspect of the present invention, a polybutadiene adhesive is provided, wherein the polybutadiene adhesive is prepared by the method for preparing the polybutadiene adhesive according to the first aspect of the present invention.

[0031] According to a third aspect of the present invention, there is provided a method for preparing polybutadiene rubber, wherein the method comprises the following steps:

[0032] 1) a step of preparing polybutadiene adhesive according to the method for preparing polybutadiene adhesive according to the first aspect of the present invention;

[0033] 2) A step of preparing polybutadiene rubber from the polybutadiene rubber solution.

[0034] Through the above technical solution, the content of trans 1,4-structure blocks in butadiene rubber can be increased, and the flexural properties of butadiene rubber can be improved.

[0035] In addition, 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 DESCRIPTION

[0036] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0037] In one aspect, the present invention provides a method for preparing a polybutadiene adhesive solution, wherein the method comprises the following steps:

[0038] 1) performing a first mixing of component N and a first component B and then performing a first aging to obtain a first mixed component;

[0039] 2) after performing a second mixing of component A, the second component B and component D, performing a second aging of the second mixed product and the first component C to obtain a second mixed component;

[0040] 3) subjecting butadiene, the first mixed component and the second component C to a first polymerization reaction, and when the polymerization conversion rate is 70-80%, adding the second mixed component to conduct a second polymerization reaction, wherein the polymerization temperature of the second polymerization reaction is greater than 90° C. and less than 110° C.,

[0041] Among them, component N is nickel salt; component B is alkyl aluminum compound; component C is halogenated compound; component D is conjugated diene; component A is rare earth salt.

[0042] In the present invention, the first component B, the second component B and the third component B may be the same or different. Similarly, the first component C and the second component C may be the same or different.

[0043] The present invention is described below in steps, but it should be pointed out that the order of step 1) and step 2) of the present invention is not limited, and step 1) can be performed first and then step 2), or step 2) can be performed first and then step 1), or step 1) and step 2) can be performed simultaneously.

[0044] Step 1): Component N and the first component B are first mixed and then aged to obtain a first mixed component.

[0045] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, in step 1), the molar ratio of the component N and the first component B is 1:2-12, more preferably 1:3-8, further preferably 1:5-7.5, further preferably 1:5-7.

[0046] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, the first mixing conditions include: temperature of 10-40°C, time of 10-200 min; more preferably, the first mixing conditions include: temperature of 10-40°C, time of 20-60 min.

[0047] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, the first aging conditions include: temperature of 10-80°C, time of 10-300 min; more preferably, the first aging conditions include: temperature of 15-35°C, time of 15-50 min.

[0048] According to the present invention, the component N is a nickel salt. The nickel salt may be various nickel salts commonly used in the art for butadiene polymerization. Preferably, the nickel salt is one or more of nickel naphthenate, nickel octanoate and nickel benzoate.

[0049] The nickel salt can be obtained by conventional methods in the art, for example, it can be a commercial product, or it can be prepared by conventional methods in the art, and the present invention has no particular limitation on this.

[0050] Step 2): After the component A, the second component B and the component D are mixed for the second time, the product after the second mixing is mixed with the first The first component C is subjected to a second aging to obtain a second mixed component.

[0051] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, based on the component N1mmol contained in the first mixed component, in step 2), the amount of component A can be 0.001-100mmol, the amount of the second component B is 0.012-2000mmol, the amount of component D is 0.001-5000mmol, and the amount of the first component C is 0.001-600mmol; more preferably, based on the component N1mmol contained in the first mixed component, in step 2), the The amount of component A is 0.01-1mmol, the amount of the second component B is 0.12-20mmol, the amount of the components is 2-60mmol, and the amount of the first component C is 0.2-3.5mmol; preferably, based on the component N1mmol contained in the first mixed component, in step 2), the amount of component A is 0.1-0.5mmol, the amount of the second component B is 1-10mmol, the amount of the first butadiene is 1-30mmol, and the amount of the first component C is 0.22-2mmol.

[0052] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, in step 2), the molar ratio of component A, the second component B, the component D and the first component C is 1:10-25:40-55:3-4; more preferably, in step 2), the molar ratio of component A, the second component B, the component D and the first component C is 1:12-20:43-50:3-3.5.

[0053] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, the second mixing conditions include: temperature of 10-40°C, time of 10-200 min; more preferably, the second mixing conditions include: temperature of 10-40°C, time of 20-60 min.

[0054] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, the second aging conditions include: temperature of 10-80°C, time of 10-300min; more preferably, the second aging conditions include: temperature of 50-70°C, time of 60-120min.

[0055] According to the present invention, the component A is a rare earth salt. The rare earth salt may be various rare earth salts commonly used in the art for butadiene polymerization. Preferably, the rare earth salt is one or more of a neodymium salt, a cerium salt and a praseodymium salt. Examples of the rare earth salt include neodymium octanoate, neodymium cyclohexaneate and neodymium phosphonate.

[0056] The rare earth salt can be obtained by conventional methods in the art, for example, it can be a commercial product, or it can be prepared by conventional methods in the art, and the present invention has no particular limitation on this.

[0057] According to the present invention, the component B is an alkyl aluminum compound. The alkyl aluminum compound can be various alkyl aluminum compounds commonly used in the art for butadiene polymerization. In order to further improve the wear resistance of the obtained polybutadiene rubber, preferably, the alkyl aluminum compound is selected from at least one of trialkyl aluminum and dialkyl aluminum hydride; more preferably, the trialkyl aluminum is represented by the formula Al(R)3, and 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 the alkyl group of C1-C6; further 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, tri-isobutyl aluminum, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride and di-isobutyl aluminum hydride.

[0058] According to the present invention, the component C is a halogenated compound. The halogenated compound may be various halogenated compounds commonly used in the art for butadiene polymerization. In order to further improve the wear resistance of the obtained polybutadiene rubber, preferably, the halogenated compound is selected from at least one of halogenated boron, halogenated hydrogen, halogenated alkyl aluminum, halogenated silane and sesquihalogenated alkyl aluminum; more preferably, the halogenated alkyl aluminum is represented by the formula Al(R 1 )2X, 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 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; further preferably, the halogenated compound is at least one of diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane tetrachloride, hydrogen fluoride and boron trifluoride ether complex.

[0059] In the present invention, the conjugated diene of component D can stabilize the active center of the catalyst. Generally, the conjugated diene refers to an olefin monomer having a conjugated double bond. The conjugated diene may be the same as the polymerizable monomer or different from the polymerizable monomer. In order to further improve the catalytic activity of the composition, preferably, the components D are each independently selected from at least one of 1,3-butadiene, isoprene, piperylene and 2,4-hexadiene.

[0060] Step 3): subjecting butadiene, the first mixed component, and the second component C to a first polymerization reaction, at a polymerization conversion rate of When the content of the second mixed component is 70-80%, a second mixed component is added to carry out a second polymerization reaction, wherein the polymerization temperature of the second polymerization reaction is greater than 90°C and 110°C or less.

[0061] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, based on the component N1mmol contained in the first mixed component, in step 3), the amount of the second component C is 0.001-100mmol; more preferably, based on the component N1mmol contained in the first mixed component, in step 3), the amount of the second component C is 0.01-50mmol; more preferably, based on the component N1mmol contained in the first mixed component, in step 3), the amount of the second component C is 0.1-20mmol.

[0062] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, in step 3), the molar ratio of the butadiene, the first mixed component calculated as component N, the second component C and the second mixed component calculated as component A is 1:1×10 -5 -1×10 -3 :1×10 -3 -2×10 -3 :1×10 -8 -0.1; More preferably, in step 3), the molar ratio of the second butadiene, the first mixed component calculated as component N, the second component C and the second mixed component calculated as component A is 1:5×10 -5 -1×10 -4 :1.2×10 -3 -1.5×10 -3 :1.5×10 -5 -2.5×10 -5 Further preferably, the molar ratio of the second butadiene, the first mixed component calculated as component N, the second component C and the second mixed component calculated as component A is 1:9×10 -5 -1×10 -4 :1.3×10 -3 -1.4×10 -3 :1.7×10 -5 -2.2×10 -5 .

[0063] According to the present invention, in order to further improve the flexural properties of the obtained polybutadiene rubber, preferably, when the polymerization conversion rate is 75-80%, a second mixing component is added to carry out a second polymerization reaction.

[0064] Specific examples of the polymerization conversion rate include 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, etc., and the range consisting of any two of the above.

[0065] According to the present invention, in order to further improve the wear resistance of the obtained polybutadiene rubber, preferably, the temperature of the first polymerization reaction is 50-90°C, preferably 50-60°C.

[0066] According to the present invention, the temperature of the second polymerization reaction is greater than 90°C and below 110°C. Specifically, the temperature may be 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, etc., and a range formed by any two of the above.

[0067] In the present invention, 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, step 1) to step 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] At the same time, in order to enable the active center of the catalyst to be smoothly constructed and have higher catalytic activity, preferably, the first mixed component and the second mixed component each independently contain a solvent, or the raw material of the first polymerization reaction contains a solvent; more preferably, the solvent is at least one of C5-C10 alkanes, C5-C10 cycloalkanes and C6-C12 aromatics; further preferably, the solvent is at least one of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, xylene and isopropylbenzene.

[0070] In the above embodiment, in order to further improve the activity of the catalyst, preferably, the concentration of component N in the first 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 embodiment, the solvent may be added in the form of a pure substance or in the form of a solution 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. The solvent can be selected from the solvents described above.

[0073] Similarly, component B can be provided in the form of a 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. The solvent can be selected from the solvents described above.

[0074] Similarly, component C can be provided in the form of a 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. The solvent can be selected from the solvents described above.

[0075] Similarly, component D can be provided in the form of a pure substance or in the form of a solution. When component D is provided in the form of a solution, the concentration of the solution of component D can be, for example, 0.01-5 mol / L. The solvent can be selected from the solvents described above.

[0076] Similarly, component A can be provided in the form of a 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. The solvent can be selected from the solvents described above.

[0077] In addition, butadiene can be provided in the form of a 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. The solvent can be C5-C 10 Alkanes, C5-C 10 Cycloalkanes and C6-C 12 more preferably, the solvent is at least one of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, xylene and cumene.

[0078] According to a second aspect of the present invention, a polybutadiene adhesive is provided, wherein the polybutadiene adhesive is prepared by the method for preparing the polybutadiene adhesive according to the first aspect of the present invention.

[0079] According to a third aspect of the present invention, there is provided a method for preparing polybutadiene rubber, characterized in that the method comprises the following steps:

[0080] 1) a step of preparing polybutadiene adhesive according to the method for preparing polybutadiene adhesive according to the first aspect of the present invention;

[0081] 2) A step of preparing polybutadiene rubber from the polybutadiene rubber solution.

[0082] According to the present invention, there is no particular limitation on the step of "preparing polybutadiene rubber from the polybutadiene glue solution", and the conditions and methods commonly used in the art can be adopted. For example, after the reaction is completed, anhydrous ethanol and antioxidant 1076 can be added to the glue solution to terminate the reaction, and then condense the reaction. The obtained butadiene polymer is dried at room temperature and placed in a 50°C vacuum drying oven until constant weight is reached.

[0083] The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

[0084] In the following examples and comparative examples, unless otherwise specified, all raw materials used were commercially available.

[0085] The polymerization monomer conversion rate was calculated as follows.

[0086]

[0087] The method for determining the “polymer structure content” is as follows:

[0088] The microstructure of the polymer was determined by FTIR. The polybutadiene rubber was prepared into a 5 wt% n-hexane solution and coated on a KBr window. The infrared spectra (400-2000 cm) were collected by a ThermoFisher Nicolet IS5 infrared spectrometer. -1 ), the number of scans is 32, and the resolution is 4cm -1 , and calculate the content of each microstructure. There are three types of BR microstructures, namely cis-1,4-structure content, trans-1,4-structure content and 1,2-structure content, which correspond to the FTIR spectrum at 738cm -1 、967cm -1 and 911cm -1 The absorption peak at 738 , A 967 and A 911 ), the content of each configuration can be calculated using the formula:

[0089]

[0090]

[0091] Where A = 17667A 738 +4741.4A 967 +3673.8A 911 .

[0092] Example 1

[0093] Under nitrogen protection, 100 mL of hexane, 5 mmol of neodymium octanoate, and then 75 mL of a 1 mol / L hexane solution of diisobutylaluminum hydride and 250 mmol of butadiene were added, stirred and mixed at 30°C for 30 min, then the temperature was raised to 60°C, and 15 mL of a 1 mol / L hexane solution of diethylaluminum chloride was added, and the mixture was aged for 2 h to obtain a catalyst in a homogeneous solution state, i.e., homogeneous rare earth catalyst C1.

[0094] Under nitrogen protection, 10 mL of hexane, 0.37 mmol of nickel cyclohexane, and 5.26 mmol of triisobutylaluminum were mixed at 30°C and aged for 30 minutes. Then, the above solution was put into a reactor containing 220 g of butadiene (monomer) and 1000 g of hexane, and then 0.13 mmol of boron trifluoride ether complex, mixed, and polymerized at 55°C. When the conversion rate of the reaction reached 78%, 3.8 mL of catalyst C1 (the molar ratio of butadiene to the catalyst calculated as neodymium octanoate was 1:1×10 -4 ), continue to react at 98°C until the polymerization reaction reaches 5 hours to obtain a glue solution. Then, add 1 ml of ethanol and 1 g of antioxidant 1076 to the obtained glue solution, stir evenly, dry at room temperature, and place in a 50°C vacuum drying oven until constant weight to obtain polybutadiene rubber. In addition, the content of cis-1,4-polymer structure and the content of trans-1,4-polymer structure block are shown in Table 1.

[0095] Example 2

[0096] Under nitrogen protection, 100 mL of hexane, 5 mmol of neodymium octanoate, and then 80 mL of a 1 mol / L hexane solution of diisobutylaluminum hydride and 230 mmol of butadiene were added, stirred and mixed at 30°C for 30 min, then the temperature was raised to 60°C, and 15 mL of a 1 mol / L hexane solution of diethylaluminum chloride was added, and the mixture was aged for 2 h to obtain a catalyst in a homogeneous solution state, i.e., homogeneous rare earth catalyst C2.

[0097] Under nitrogen protection, 10 mL of hexane, 0.37 mmol of nickel cyclohexane, and 5.31 mmol of triisobutylaluminum were mixed at 30°C and aged for 30 minutes. The above solution was then added to a reactor containing 220 g of butadiene (monomer) and 1000 g of hexane, followed by 0.12 mmol of boron trifluoride ether complex, mixed, and polymerized at 50°C. When the conversion rate of the reaction reached 75%, 3.9 mL of catalyst C2 (the molar ratio of butadiene to the catalyst in terms of neodymium octanoate was 1:9×10 -5 ), continue to react at 95°C until the polymerization reaction reaches 5 hours to obtain a glue solution. Then, add 1 ml of ethanol and 1 g of antioxidant 1076 to the obtained glue solution, stir evenly, dry at room temperature and place in a 50°C vacuum drying oven until constant weight to obtain polybutadiene rubber. In addition, the content of cis-1,4-polymer structure and the content of trans-1,4-polymer structure block are shown in Table 1.

[0098] Example 3

[0099] Under nitrogen protection, 100 mL of hexane, 5 mmol of neodymium octanoate, and then 90 mL of a 1 mol / L hexane solution of diisobutylaluminum hydride and 225 mmol of butadiene were added, stirred and mixed at 30°C for 30 min, then the temperature was raised to 60°C, 17.5 mL of a 1 mol / L hexane solution of diethylaluminum chloride was added, and the mixture was aged for 2 h to obtain a catalyst in a homogeneous solution state, i.e., homogeneous rare earth catalyst C3.

[0100] Under nitrogen protection, 10 mL of hexane, 0.34 mmol of nickel cyclohexane, and 5.69 mmol of triisobutylaluminum were mixed at 30°C and aged for 30 min. The above solution was then added to a reactor containing 220 g of butadiene (monomer) and 1000 g of hexane, followed by 0.14 mmol of boron trifluoride ether complex, mixed, and polymerized at 60°C. When the conversion rate of the reaction reached 75%, 3.9 mL of catalyst C3 (the molar ratio of butadiene to the catalyst in terms of neodymium octanoate was 1:9.5×10 -5 ), continue to react at 105°C until the polymerization reaction reaches 5 hours to obtain a glue solution. Then, add 1 ml of ethanol and 1 g of antioxidant 1076 to the obtained glue solution, stir evenly, dry at room temperature, and place in a 50°C vacuum drying oven until constant weight to obtain polybutadiene rubber. In addition, the content of cis-1,4-polymerization structure and the content of trans-1,4-polymerization structure block are shown in Table 1.

[0101] Example 4

[0102] Under nitrogen protection, 100 mL of hexane, 5 mmol of neodymium octanoate, and then 60 mL of a 1 mol / L hexane solution of diisobutylaluminum hydride and 240 mmol of butadiene were added, stirred and mixed at 30°C for 30 min, then the temperature was raised to 60°C, and 17.5 mL of a 1 mol / L hexane solution of diethylaluminum chloride was added, and the mixture was aged for 2 h to obtain a catalyst in a homogeneous solution state, i.e., homogeneous rare earth catalyst C4.

[0103] Under nitrogen protection, 10 mL of hexane, 0.35 mmol of nickel cyclohexane, and 6.26 mmol of triisobutylaluminum were mixed at 30°C and aged for 30 minutes. The above solution was then added to a reactor containing 220 g of butadiene (monomer) and 1000 g of hexane, followed by 0.14 mmol of boron trifluoride ether complex, mixed, and polymerized at 52°C. When the conversion rate of the reaction reached 78%, 2.8 mL of catalyst C4 (the molar ratio of butadiene to the catalyst in terms of neodymium octanoate was 1:8×10 -5), continue to react at 100°C until the polymerization reaction reaches 13 hours to obtain a glue solution. Then, add 1 ml of ethanol and 1 g of antioxidant 1076 to the obtained glue solution, stir evenly, dry at room temperature and place in a 50°C vacuum drying oven until constant weight to obtain polybutadiene rubber. In addition, the content of cis-1,4-polymerization structure and the content of trans-1,4-polymerization structure block are shown in Table 1.

[0104] Example 5

[0105] Under nitrogen protection, 100 mL of hexane, 5 mmol of neodymium octanoate, and then 100 mL of a 1 mol / L hexane solution of diisobutylaluminum hydride and 215 mmol of butadiene were added, stirred and mixed at 30°C for 30 min, then the temperature was raised to 60°C, 17.5 mL of a 1 mol / L hexane solution of diethylaluminum chloride was added, and the mixture was aged for 2 h to obtain a catalyst in a homogeneous solution state, i.e., homogeneous rare earth catalyst C5.

[0106] Under nitrogen protection, 10 mL of hexane, 0.37 mmol of nickel cyclohexane, and 5.17 mmol of triisobutylaluminum were mixed at 30°C and aged for 30 min. The above solution was then put into a reactor containing 220 g of butadiene (monomer) and 1000 g of hexane, and then 0.12 mmol of boron trifluoride ether complex was added, mixed, and polymerized at 58°C. When the conversion rate of the reaction reached 80%, 4.2 mL of catalyst C5 (the molar ratio of butadiene to the catalyst calculated as neodymium octanoate was 1:1.1×10 -4 ), continue to react at 110°C until the polymerization reaction reaches 5 hours to obtain a glue solution. Then, add 1 ml of ethanol and 1 g of antioxidant 1076 to the obtained glue solution, stir evenly, dry at room temperature, and place in a 50°C vacuum drying oven until constant weight to obtain polybutadiene rubber. In addition, the content of cis-1,4-polymer structure and the content of trans-1,4-polymer structure block are shown in Table 1.

[0107] Comparative Example 1

[0108] The method described in Example 1 was used, except that the amount of catalyst C1 was 0. The polymerization test results are shown in Table 1.

[0109] Comparative Example 2

[0110] The method described in Example 1 was used, except that the reaction temperature after adding catalyst C1 was 80° C. The polymerization test results are shown in Table 1.

[0111] Comparative Example 3

[0112] The method described in Example 1 was used, except that the reaction temperature after adding the catalyst C1 was 120°C. The polymerization test results are shown in Table 1, and the catalyst activity decreased.

[0113] Test Example 1

[0114] The rubber obtained in Examples 1-5 and Comparative Examples 1-3 was tested for fatigue flexure using the method of GB / T 13934-2006. The instrument used for the test was WPL-100 produced by New Zhenwei Testing Machinery Factory, the ambient temperature was 25°C, during the test, the specimen was loaded into the fixture, the equipment was started, and the number of flexures of level 3 cracks was recorded.

[0115] Table 1

[0116]

[0117] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a polybutadiene adhesive, characterized in that: The Method The following steps are included: 1) performing a first mixing of component N and a first component B and then performing a first aging to obtain a first mixed component; 2) after performing a second mixing of component A, the second component B and component D, performing a second aging of the second mixed product and the first component C to obtain a second mixed component; 3) subjecting butadiene, the first mixed component and the second component C to a first polymerization reaction, and when the polymerization conversion rate is 70-80%, adding the second mixed component to conduct a second polymerization reaction, wherein the polymerization temperature of the second polymerization reaction is greater than 90° C. and less than 110° C., Among them, component N is nickel salt; component B is alkyl aluminum compound; component C is halogenated compound; component D is conjugated diene; component A is rare earth salt.

2. The method according to claim 1, wherein: In step 1), the molar ratio of component N to component B is 1:2-12.

3. The method according to claim 1 or 2, wherein: In step 2), the molar ratio of the component A, the second component B, the component D and the first component C is 1:10-25:40-55:3-4, preferably 1:12-20:43-50:3-3.

5.

4. The method according to claim 1, 2 or 3, wherein: In step 3), the molar ratio of butadiene, the first mixed component calculated as component N, the second component C and the second mixed component calculated as component A is 1:5×10 -5 -1×10 -4 :1.2×10 -3 -1.5×10 -3 :1.5×10 -5 -2.5×10 -5 , preferably 1:9×10 -5 -1×10 -4 :1.3×10 -3 -1.4×10 -3 :1.7×10 -5 -2.2×10 -5 .

5. The method according to any one of claims 1 to 3, wherein: The alkyl aluminum compound is selected from at least one of trialkyl aluminum and dialkyl aluminum hydride; Preferably, the trialkylaluminum is represented by the formula Al(R)3, and 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 is independently selected from a C1-C6 alkyl group; More 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.

6. The method according to any one of claims 1 to 3, wherein: The halogenated compound is selected from at least one of halogenated boron, halogenated hydrogen, halogenated alkylaluminum, halogenated silane and sesquihalogenated alkylaluminum; 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 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; Preferably, the halogenated compound is at least one of diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, monochlorosilane, dichlorosilane, trichlorosilane tetrachlorosilane, hydrogen fluoride and boron trifluoride ether complex.

7. The method according to any one of claims 1 to 3, wherein: The conjugated diene is at least one selected from 1,3-butadiene, isoprene, piperylene and 2,4-hexadiene.

8. The method according to any one of claims 1 to 3, wherein the first mixing and the second mixing independently satisfy at least the following conditions: temperature is 10-40°C, time is 10-200 min; Preferably, the first aging and the second aging each independently meet at least the following conditions: temperature is 10-80°C, and time is 10-300 min.

9. The method according to any one of claims 1 to 8, wherein: The first polymerization reaction temperature is 50-90°C; Preferably, the total reaction time of the first polymerization reaction and the second polymerization reaction is 1-36h, preferably 6-7h; More preferably, the polymerization conversion rate is 75-80%.

10. The method according to any one of claims 1 to 3, wherein: Step 1) to step 3) are each independently carried out in an inert atmosphere; Preferably, the inert atmosphere is provided by at least one of nitrogen, helium and argon.

11. The method according to any one of claims 1 to 3, wherein: The first component and the second component each independently contain a solvent, or the raw material of the first polymerization reaction contains a solvent; Preferably, the solvent is C5-C 10 Alkanes, C5-C 10 Cycloalkanes and C6-C 12 At least one of the aromatic hydrocarbons; More preferably, the solvent is at least one of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, xylene and cumene.

12. A polybutadiene adhesive, characterized in that: The polybutadiene adhesive is prepared by the method for preparing the polybutadiene adhesive according to any one of claims 1 to 11.

13. A method for preparing polybutadiene rubber, characterized in that: The Method The following steps are included: 1) a step of preparing the polybutadiene adhesive according to the method for preparing the polybutadiene adhesive according to any one of claims 1 to 11; 2) A step of preparing polybutadiene rubber from the polybutadiene rubber solution.

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