Polybutadiene material, preparation method and application thereof, and vulcanized rubber

Abstract

The invention relates to the field of polybutadiene polymerization, and discloses a polybutadiene material, a preparation method and application thereof, and vulcanized rubber. The preparation method of the polybutadiene material comprises the following steps: in the presence of a catalyst composition, butadiene is subjected to a first polymerization reaction, when the polymerization conversion rate is 75-85%, a reinforcing material is added for a second polymerization reaction, the first polymerization reaction is carried out at a first stirring linear speed, and the second polymerization reaction is carried out at a second stirring linear speed. The second polymerization reaction is carried out at a second stirring linear speed, the second stirring linear speed is greater than the first stirring linear speed, and the catalyst composition comprises a neodymium phosphonate compound, an alkyl aluminum compound, a halogen-containing compound, conjugated diene and phosphonate. According to the invention, the method has the advantage of improving the rebound resilience of the vulcanized rubber, and compared with mixing and adding of the reinforcing material, the method for adding the reinforcing material has the advantages of small dosage and more uniform distribution of the reinforcing material.

Description

Technical Field

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

[0002] Compared with polydiene elastomers prepared from traditional lithium, titanium, cobalt and nickel systems, the polydiene elastomers prepared using rare earth catalysts have higher regularity and perfect linear structure in their macromolecular chains, giving them excellent rebound performance, making them ideal materials for golf ball cores.

[0003] For materials with high requirements for rebound performance, the rebound performance is generally further improved by adding reinforcing materials to the rubber material. Silica is a commonly used reinforcing material. In order to further enhance the performance of the product, rubber product manufacturers usually add silica during the mixing process. The mixing process is to extrude different solid phases to achieve the purpose of mixing. In this process, extrusion may cause chain breakage of the polymer material and thus affect the rebound performance of the material. In addition, when silica is dispersed in the solid phase due to extrusion, it is easy to cause the aggregation of microscopic particles, which leads to uneven distribution and thus affects the performance. Summary of the invention

[0004] The purpose of the present invention is to overcome the problem of uneven distribution in the prior art and to provide a polybutadiene material, a preparation method and application thereof, and a vulcanized rubber. The polybutadiene material prepared by the polybutadiene material preparation method of the present invention has the advantage of improving the resilience of the vulcanized rubber, and compared with adding reinforcing materials (such as white carbon black) during mixing, the reinforcing material added by this method has the advantages of less dosage and more uniform distribution of the reinforcing material.

[0005] The inventors of the present invention have found through in-depth research that by subjecting butadiene to a first polymerization reaction in the presence of a specific catalyst composition of the present invention, adding reinforcing materials to a second polymerization reaction when the polymerization conversion rate is 75-85%, and controlling the second stirring line speed in the second polymerization reaction to be greater than the first stirring line speed in the first polymerization reaction, the dispersion effect can be ensured, the resilience of the vulcanized rubber can be improved, and the reinforcing materials can be reduced, thereby completing the present invention.

[0006] Therefore, on one hand, the present invention provides a method for preparing a polybutadiene material, wherein the method comprises: in the presence of a catalyst composition, subjecting butadiene to a first polymerization reaction, and when the polymerization conversion rate is 75-85%, adding a reinforcing material to conduct a second polymerization reaction, wherein the first polymerization reaction is conducted at a first stirring line speed, the second polymerization reaction is conducted at a second stirring line speed, and the second stirring line speed is greater than the first stirring line speed, and the catalyst composition comprises: a neodymium phosphonate compound, an alkyl aluminum compound, a halogen-containing compound, a conjugated diene and a phosphonate.

[0007] Preferably, the second stirring linear velocity is more than 1.1 times the first stirring linear velocity, preferably 1.1-3 times, more preferably 1.3-2.5 times, more preferably 1.5-2 times.

[0008] Preferably, the first stirring linear speed is 90-120 r / min, preferably 100-110 r / min, more preferably 103-108 r / min.

[0009] Preferably, the first stirring linear speed is 125-300 r / min, preferably 130-250 r / min, more preferably 150-220 r / min.

[0010] Preferably, the catalyst composition is a homogeneous mixture of a neodymium phosphonate compound, an alkyl aluminum compound, a halogen-containing compound, a conjugated diene, and a phosphonate.

[0011] Preferably, the catalyst composition is obtained by mixing a neodymium phosphonate compound, a conjugated diene and a phosphonate, and then sequentially mixing them with an alkyl aluminum compound and a halogen-containing compound.

[0012] Preferably, the molar ratio of the neodymium phosphonate compound, the alkyl aluminum compound, the halogen-containing compound, the conjugated diene and the phosphonate is 1:2-13:2-5:10-80:0.4-0.8, preferably 1:3-10:2-5:10-80:0.4-0.8, and more preferably 1:3-10:3-5:45-55:0.4-0.6.

[0013] Preferably, the neodymium phosphonate compound is selected from one or more compounds represented by the following formula (1):

[0014]

[0015] In formula (1), R a1 , R a2 , R b1 , R b2 , R c1 and R c2are independently hydrogen, hydroxyl, C 1 ~C 20 Alkyl or C 1 ~C 20 More preferably, R a1 , R a2 , R b1 , R b2 , R c1 , R c2 Each is independently 2-ethylhexyl or 2-ethylhexyloxy.

[0016] Preferably, the alkyl aluminum compound has the general formula AlR 3 or AlHR 2 A compound or a mixture of the two, wherein R is C 1 ~C 6 of alkyl.

[0017] Preferably, the alkylaluminum compound is one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, triisobutylaluminum, diethylaluminum hydride, dipropylaluminum hydride and dibutylaluminum hydride.

[0018] Preferably, the halogen-containing compound is a compound having the general formula AlR 1 2 X is an alkyl aluminum halide having the general formula SiR 1 4-n X n The halogenated silane and the general formula Al 2 R 1 3 X 3 One or more of alkylaluminum sesquihalides, wherein R 1 C 1 ~C 6 The alkyl, benzyl and allyl groups are alkyl, benzyl and allyl groups, and X is bromine or chlorine.

[0019] Preferably, the halogen-containing compound is one or more of diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride.

[0020] Preferably, the conjugated diene is butadiene and / or isoprene.

[0021] Preferably, the phosphonate is one or more of tributyl(ethyl)phosphine diethyl phosphate, di(2-ethylhexyl)phosphate and mono(2-ethylhexyl)-2-ethylhexylphosphonate.

[0022] Preferably, the reinforcing material is one or more of white carbon black, carbon black, calcium carbonate, clay and resin, preferably white carbon black.

[0023] Preferably, based on 100 g of butadiene, the amount of the reinforcing material added is 5-15 g, more preferably 5-12 g.

[0024] Preferably, the temperatures of the first polymerization reaction and the second polymerization reaction are each independently -30°C to 90°C, and the total polymerization time is 0.5-10 hours; more preferably, the temperatures of the first polymerization reaction and the second polymerization reaction are each independently 10-60°C, and the total polymerization time is 1-5 hours.

[0025] Preferably, the polybutadiene material is used for a golf ball core.

[0026] According to a second aspect of the present invention, there is provided a polybutadiene material prepared by the method for preparing a polybutadiene material according to the first aspect of the present invention.

[0027] According to a third aspect of the present invention, there is provided a vulcanized rubber obtained by vulcanizing the polybutadiene material obtained by the method for preparing the polybutadiene material according to the first aspect of the present invention.

[0028] According to a fourth aspect of the present invention, provided is the use of the polybutadiene material prepared by the method for preparing the polybutadiene material according to the first aspect of the present invention or the polybutadiene material according to the second aspect of the present invention in preparing a golf ball core.

[0029] Through the above technical scheme, the polybutadiene material prepared by the polybutadiene material preparation method of the present invention has the advantage of improving the resilience of vulcanized rubber; and compared with adding reinforcing materials during mixing, adding reinforcing materials by this method has the advantages of less dosage and more uniform distribution of reinforcing materials; at the same time, the obtained polybutadiene can greatly facilitate the use of downstream users and avoid dust pollution during the mixing process. DETAILED DESCRIPTION

[0030] 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.

[0031] According to a first aspect of the present invention, a method for preparing a polybutadiene material is provided, wherein the method comprises: in the presence of a catalyst composition, subjecting butadiene to a first polymerization reaction, and when the polymerization conversion rate is 75-85%, adding a reinforcing material to conduct a second polymerization reaction, wherein the first polymerization reaction is conducted at a first stirring line speed, the second polymerization reaction is conducted at a second stirring line speed, and the second stirring line speed is greater than the first stirring line speed, and the catalyst composition comprises: a neodymium phosphonate compound, an alkyl aluminum compound, a halogen-containing compound, a conjugated diene, and a phosphonate.

[0032] In the present invention, by subjecting butadiene to a first polymerization reaction in the presence of the catalyst composition of the present invention, reinforcing materials are added when the polymerization conversion rate is 75-85% to conduct a second polymerization reaction, and the second stirring line speed in the second polymerization reaction is controlled to be greater than the first stirring line speed in the first polymerization reaction, the dispersion effect can be ensured, the resilience of the vulcanized rubber can be improved, and the reinforcing materials can be reduced.

[0033] That is to say, the addition of the reinforcing material can enhance the mechanical properties of the material. Since the present invention adopts the method of adding during the specific polymerization process of the present invention, its dispersion effect is better than adding during mixing, so the amount added is relatively small.

[0034] Therefore, in the present invention, there is no particular limitation on the reinforcing material, and various fillers commonly used in the art for improving mechanical properties can be used. In particular, the inventors of the present invention have found that when the reinforcing material is one or more of white carbon black, carbon black, calcium carbonate, clay and resin, and in particular when the reinforcing material is white carbon black and / or carbon black, the dispersion effect can be further ensured, the rebound performance of the vulcanized rubber can be improved, and the amount of reinforcing material used can be reduced.

[0035] According to the present invention, preferably, based on 100g of butadiene, the amount of reinforcing material added is 5-15g; more preferably, based on 100g of butadiene, the amount of reinforcing material added is 5-12g; more preferably, based on 100g of butadiene, the amount of reinforcing material added is 5-9g; more preferably, based on 100g of butadiene, the amount of reinforcing material added is 5-7g.

[0036] According to the present invention, in order to ensure the dispersion effect, the timing of addition needs to be controlled. The present invention needs to be added when the polymerization conversion rate is 75-85%. By adding within the polymerization conversion rate range, combined with the catalyst composition and the stirring line speed, the dispersion effect can be ensured, the rebound performance of the vulcanized rubber can be improved, and the reinforcing material can be reduced, so that the final polymerization conversion rate is not reduced.

[0037] Specific examples of the polymerization conversion rate include 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, etc., and the range formed by any two of them.

[0038] According to the present invention, after the reinforcing material is added, the speed of polymerization stirring also plays a key role in its dispersion. Under the premise of not significantly increasing energy consumption, increasing the stirring speed is an effective method to improve dispersion. Therefore, in order to ensure the dispersion effect, after the reinforcing material is added, the polymerization stirring line speed is adjusted.

[0039] Preferably, the second stirring line speed is more than 1.1 times the first stirring line speed; more preferably, the second stirring line speed is 1.1-3 times the first stirring line speed; more preferably, the second stirring line speed is 1.3-2.5 times the first stirring line speed; more preferably, the second stirring line speed is 1.5-2 times the first stirring line speed.

[0040] According to the present invention, the first stirring linear speed may be, for example, 90-120 r / min; preferably, the first stirring linear speed is 100-110 r / min; more preferably, the first stirring linear speed is 103-108 r / min.

[0041] In the present invention, the second stirring linear speed may be, for example, 125-300 r / min; preferably, the second stirring linear speed is 130-250 r / min; more preferably, the second stirring linear speed is 150-220 r / min.

[0042] According to the present invention, preferably, the catalyst composition comprises: a homogeneous mixture of a neodymium phosphonate compound (hereinafter also referred to as component A), an alkyl aluminum compound (hereinafter also referred to as component B), a halogen-containing compound (hereinafter also referred to as component C), a conjugated diene (hereinafter also referred to as component D) and a phosphonate (hereinafter also referred to as component E); more preferably, the catalyst composition is a homogeneous mixture of a neodymium phosphonate compound (hereinafter also referred to as component A), an alkyl aluminum compound (hereinafter also referred to as component B), a halogen-containing compound (hereinafter also referred to as component C), a conjugated diene (hereinafter also referred to as component D) and a phosphonate (hereinafter also referred to as component E); further preferably, the catalyst composition is obtained by mixing a neodymium phosphonate compound, a conjugated diene and a phosphonate, and then mixing them with an alkyl aluminum compound and a halogen-containing compound in sequence.

[0043] In a preferred embodiment of the present invention, the catalyst composition is obtained by the following steps and conditions: in a first organic solvent, component A, component D and component E are first mixed to obtain a homogeneous transparent solution ADE, and then component B is added to obtain an aging solution ABDE, and component C is continued to be added to obtain the catalyst composition.

[0044] According to the present invention, component B is added to solution ADE to obtain aged solution ABDE, which can be aged at 0-80°C for 5-250 minutes. Component C is added to aged solution ABDE, which can be aged at 0-80°C for 0.5-48 hours to obtain the catalyst composition.

[0045] According to the present invention, the first organic solvent is not particularly limited and can be selected from conventional organic solvents. Saturated aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons that are inert to the reaction components can be selected. C 5 -C 10 Alkanes, C 5 -C 10 Cycloalkanes, C 6 -C 12 Aromatic hydrocarbons such as pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene, cumene, etc. The amount of the first organic solvent added is not particularly limited and can be determined according to application requirements, device scale, metering equipment, etc. For example, the concentration of component A in the final catalyst composition can be 0.001-0.5 mol / L.

[0046] According to the present invention, the method of adding the first organic solvent is not particularly limited, and it can be added all at once or in steps, or added after aging or when it is pre-mixed with the components to form a solution.

[0047] According to the present invention, for ease of operation, component A and part or all of component E can be pre-formed into a solution with a first organic solvent, and then mixed with component D to form solution ADE. The concentration of the pre-formed solution is not particularly limited. For example, based on the measurement of component A, the concentration of component A can be 0.01-0.5 mol / L. In addition, component B, component C and component D can also be pre-formed into a solution with a first organic solvent for standby use. The concentration of the pre-formed solution is not particularly limited. For example, the concentration of each component can be 0.01-5 mol / L. The solvents for pre-formulating the solutions of each component can be the same or different.

[0048] According to the present invention, preferably, the molar ratio of the neodymium phosphonate compound, the alkyl aluminum compound, the halogen-containing compound, the conjugated diene and the phosphonate is 1:2-13:2-5:10-80:0.4-0.8; more preferably, the molar ratio of the neodymium phosphonate compound, the alkyl aluminum compound, the halogen-containing compound, the conjugated diene and the phosphonate is 1:3-10:2-5:10-80:0.4-0.8; further preferably, the molar ratio of the neodymium phosphonate compound, the alkyl aluminum compound, the halogen-containing compound, the conjugated diene and the phosphonate is 1:3-10:3-5:45-55:0.4-0.6.

[0049] According to the present invention, the neodymium phosphonate compound is the main catalyst of the catalyst, and the element neodymium is the central metal atom. Preferably, the neodymium phosphonate compound is selected from one or more compounds represented by the following formula (1):

[0050]

[0051] In formula (1), R a1 , R a2 , R b1 , R b2 , R c1 and R c2 are independently hydrogen, hydroxyl, C 1 ~C 20 Alkyl or C 1 ~C 20 More preferably, R a1 , R a2 , R b1 , R b2 , R c1 , R c2 Each is independently 2-ethylhexyl or 2-ethylhexyloxy.

[0052] According to the present invention, the alkyl aluminum compound is a co-catalyst of the catalyst, mainly plays an alkylation role to generate rare earth carbon active centers, and also has the functions of removing impurities, stabilizing active centers and chain transfer. In the present invention, the alkyl aluminum compound has the general formula AlR 3 Alkylaluminum and / or general formula AlHR 2 Alkyl aluminum hydride, wherein R is C 1 -C 6 alkyl; preferably, the alkyl aluminum compound is one or more of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, tripentylaluminum, trihexylaluminum, triisobutylaluminum, diethylaluminum hydride, dipropylaluminum hydride and dibutylaluminum hydride; more preferably, the alkyl aluminum compound is one or more of diethylaluminum hydride, dipropylaluminum hydride and dibutylaluminum hydride.

[0053] According to the present invention, the halogen-containing compound mainly provides halogen to promote the formation of active centers. In the present invention, the halogen-containing compound is a compound having the general formula AlR 1 2 X is an alkyl aluminum halide having the general formula SiR 1 4-n X n The halogenated silane and the general formula Al 2 R 1 3 X 3 Alkyl aluminum sesquihalide, wherein R 1 Can be C 1 ~C 6 alkyl, benzyl and allyl, X is bromine or chlorine. Preferably, it is one or more of diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride; more preferably, it is diethylaluminum monochloride and / or dichlorosilane.

[0054] According to the present invention, the conjugated diene plays a role in stabilizing the catalyst active center in the catalyst composition. Conjugated diene refers to any monomer having a conjugated double bond in its molecule. Preferably it is butadiene or isoprene or a mixture thereof. The conjugated diene in the catalyst composition may be the same or different from the butadiene used as the polymerization monomer.

[0055] According to the present invention, preferably, the phosphonate is one or more of tributyl (ethyl) phosphine diethyl phosphate, di(2-ethylhexyl) phosphate and mono(2-ethylhexyl)-2-ethylhexyl phosphonate.

[0056] According to the present invention, the polymerization reaction can be carried out by conventional polymerization methods, such as bulk polymerization and solution polymerization. When solution polymerization is adopted, the polymerization is carried out in a second organic solvent. There is no particular restriction on the second organic solvent, and it can be a hydrocarbon solvent inert to the polymerization reaction, such as hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene. One or more. In the present invention, the first organic solvent and the second organic solvent can be the same or different, and the same organic solvent is preferably used. There is no particular restriction on the amount of the second organic solvent added, and it can ensure that the polymerization reaction proceeds. For example, the weight ratio of the weight of butadiene to the second organic solvent is 1:8-20.

[0057] In the present invention, the temperature of the first polymerization reaction and the second polymerization reaction can be independently -30°C to 90°C, and the total polymerization time is 0.5-10 hours; preferably, the temperature of the first polymerization reaction and the second polymerization reaction is independently 10-60°C, and the total polymerization time is 1-5 hours.

[0058] According to the present invention, in order to overcome the destruction of the catalyst active center by oxygen, the first polymerization reaction and / or the second polymerization reaction can be carried out in an inert atmosphere. The method for maintaining the inert atmosphere can be to evacuate the reaction vessel and then introduce an inert gas. The inert atmosphere can be, for example, conventional inert gases such as nitrogen, argon, and helium.

[0059] According to the present invention, after the polymerization reaction is completed, a terminator can be added to inactivate the active polymer chains to achieve the purpose of terminating the polymerization reaction. The type and amount of the terminator are not particularly limited, as long as the terminator can inactivate the active polymer chains. Generally, the terminator can be water, C 1 -C 6 Aliphatic alcohols, C 4 -C 12 The terminator is one or more of aliphatic carboxylic acids and aromatic polyhydroxy compounds, wherein the aromatic polyhydroxy compound refers to a compound in which at least two hydrogen atoms on the benzene ring are replaced by hydroxyl groups. Preferably, the terminator is one or more of water, methanol, ethanol and isopropanol. There is no particular limitation on the amount of the terminator, as long as the amount of the terminator can inactivate the active species in the polymer product, which will not be described in detail.

[0060] According to the present invention, the polybutadiene material has the advantage of improving the resilience performance of the vulcanized rubber, and therefore, is suitable for use in a golf ball core.

[0061] According to a second aspect of the present invention, a polybutadiene material prepared according to the first aspect of the present invention is provided.

[0062] According to a third aspect of the present invention, there is provided a vulcanized rubber obtained by vulcanizing the polybutadiene material obtained by the method according to the first aspect of the present invention.

[0063] There are no particular limitations on the formula and method for vulcanization, and the formula and method may be conventional in the art.

[0064] In a specific embodiment of the present invention, the vulcanization formula is: 100 parts by mass of polybutadiene material; 5 parts by mass of zinc oxide; 2 parts by mass of stearic acid; 1 part by mass of antioxidant 1520; 1 part by mass of antioxidant 1076; 1.4 parts by mass of sulfur, and 1 part by mass of accelerator. The accelerator may be N-cyclohexyl-2-benzothiazole sulfenamide (CBS).

[0065] According to a fourth aspect of the present invention, there is provided use of the polybutadiene material obtained by the method described in the first aspect of the present invention or the polybutadiene material described in the second aspect of claim in preparing a golf ball core.

[0066] The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

[0067] In the following examples and comparative examples, unless otherwise specified, all raw materials used were commercially available.

[0068] Preparation Example 1

[0069] Add 0.05 mol of Nd into the beaker. 2 O 3 , then continue to slowly add 0.1 mol of hydrochloric acid to beaker 1. Heat the above mixture to boiling and stir for 30 minutes to eliminate excess hydrochloric acid. The obtained NdCl aqueous solution is light purple and transparent, with no insoluble residue, and is ready for use. Place 0.3 mol of NaOH solid in beaker 2, pour in 450 g of distilled water, and dissolve it completely for use. Take 0.3 mol of di(2-ethylhexyl)phosphonate and place it in beaker 3, then pour in 180 ml of acetone, stir evenly, and standby. Pour the mixture in beaker 3 into beaker 2, stir, mix evenly, and obtain a light yellow uniform solution. Finally, pour the NdCl aqueous solution in beaker 1 into beaker 3, stir and mix evenly, and obtain a suspension containing fine white granular precipitates. Filter the suspension to obtain a white powdery di(2-ethylhexyl)phosphonate neodymium compound, wash it 3 times with appropriate amounts of distilled water and acetone, and dry it in a 60°C oven for 72 hours.

[0070] Example 1

[0071] Under nitrogen protection, 164g of hexane, 10g of di(2-ethylhexyl)phosphonate neodymium solution, 1.45g of di(2-ethylhexyl)phosphonate and 5.9g of butadiene were added to a clean and dry aging kettle. After mixing, 6.75ml of 1mol / L diisobutylaluminum monohydrogen solution was added at 30°C and stirred for reaction for 30 minutes. Then the reactor was heated to 60°C and 6.8ml of 1mol / L diethylaluminum monochloride solution was added. The molar ratio of di(2-ethylhexyl)phosphonate neodymium, diisobutylaluminum monohydrogen, diethylaluminum monochloride, butadiene and di(2-ethylhexyl)phosphonate was 1:3:3:50:0.5. The aging was continued for 2 hours to obtain a yellow-green homogeneous catalyst, which was stored at 60°C for 2 hours for polymerization. The catalyst prepared according to the above steps was in a homogeneous solution state.

[0072] Under nitrogen protection, 900g hexane, 200g butadiene and 9.8ml catalyst were added to the polymerization kettle in sequence, and reacted at about 50°C and a stirring speed of 105r / min. When the polymerization conversion rate was 75%, 14g white carbon black was added to the polymerization kettle, and the stirring speed was increased to 158r / min, until the polymerization reaction reached 5 hours, butadiene was completely converted, and the glue was released. After coagulation and drying, polybutadiene was obtained. The test results of the obtained polymer after mixing and vulcanization according to the formula are shown in Table 1.

[0073] Example 2

[0074] Under nitrogen protection, 164g of hexane, 10g of neodymium di(2-ethylhexyl)phosphonate, 1.45g of di(2-ethylhexyl)phosphonate and 5.9g of butadiene were added to a clean and dry aging kettle. After mixing, 11.25ml of 1mol / L diisobutylaluminum monohydrogenate solution was added at 30°C and stirred for reaction for 30 minutes. Then the reactor was heated to 60°C and 6.8ml of 1mol / L diethylaluminum monochloride solution was added. The molar ratio of neodymium di(2-ethylhexyl)phosphonate, diisobutylaluminum monohydrogenate, diethylaluminum monochloride, butadiene and di(2-ethylhexyl)phosphonate was 1:5:3:50:0.5. The aging was continued for 2 hours to obtain a yellow-green homogeneous catalyst, which was stored at 60°C for 2 hours for polymerization. The catalyst prepared according to the above steps was in a homogeneous solution state.

[0075] Under nitrogen protection, 900g hexane, 200g butadiene and 7.8ml catalyst were added to the polymerization kettle in sequence, and reacted at about 50°C and a stirring speed of 105r / min. When the polymerization conversion rate was 80%, 18g white carbon black was added to the polymerization kettle, and the stirring speed was increased to 180r / min, until the polymerization reaction reached 5 hours, butadiene was completely converted, and the glue was released. After coagulation and drying, polybutadiene was obtained. The test results of the obtained polymer after mixing and vulcanization according to the formula are shown in Table 1.

[0076] Example 3

[0077] Under nitrogen protection, 164g of hexane, 10g of di(2-ethylhexyl)phosphonate neodymium solution, 1.45g of di(2-ethylhexyl)phosphonate and 5.9g of butadiene were added to a clean and dry aging kettle. After mixing, 18ml of 1mol / L diisobutylaluminum monohydrogen solution was added at 30°C and stirred for reaction for 30 minutes. Then the reactor was heated to 60°C and 6.8ml of 1mol / L diethylaluminum monochloride solution was added. The molar ratio of di(2-ethylhexyl)phosphonate neodymium, diisobutylaluminum monohydrogen, diethylaluminum monochloride, butadiene and di(2-ethylhexyl)phosphonate was 1:8:3:50:0.5. The aging was continued for 2 hours to obtain a yellow-green homogeneous catalyst, which was stored at 60°C for 2 hours for polymerization. The catalyst prepared according to the above steps was in a homogeneous solution state.

[0078] Under nitrogen protection, 900g hexane, 200g butadiene and 6.9ml catalyst were added to the polymerization kettle in sequence, and reacted at about 50°C and a stirring speed of 105r / min. When the polymerization conversion rate was 82%, 24g carbon black was added to the polymerization kettle, and the stirring speed was increased to 210r / min, until the polymerization reaction reached 5 hours, butadiene was completely converted, and the glue was released. After coagulation and drying, polybutadiene was obtained. The test results of the obtained polymer after mixing and vulcanization according to the formula are shown in Table 1.

[0079] Example 4

[0080] Under nitrogen protection, 164g of hexane, 10g of di(2-ethylhexyl)phosphonate neodymium solution, 1.45g of di(2-ethylhexyl)phosphonate and 5.9g of butadiene were added to a clean and dry aging kettle. After mixing, 22.5ml of 1mol / L diisobutylaluminum monohydrogen solution was added at 30°C and stirred for reaction for 30 minutes. Then the reactor was heated to 60°C and 6.8ml of 1mol / L diethylaluminum monochloride solution was added. The molar ratio of di(2-ethylhexyl)phosphonate neodymium, diisobutylaluminum monohydrogen, diethylaluminum monochloride, butadiene and di(2-ethylhexyl)phosphonate was 1:10:3:50:0.5. The aging was continued for 2 hours to obtain a yellow-green homogeneous catalyst, which was stored at 60°C for 2 hours for polymerization. The catalyst prepared according to the above steps was in a homogeneous solution state.

[0081] Under nitrogen protection, 900g hexane, 200g butadiene and 7.0ml catalyst were added to the polymerization kettle in sequence, and reacted at about 50°C and a stirring speed of 105r / min. When the polymerization conversion rate was 85%, 10g white carbon black was added to the polymerization kettle, and the stirring speed was increased to 193r / min, until the polymerization reaction reached 5 hours, butadiene was completely converted, and the glue was released. After coagulation and drying, polybutadiene was obtained. The test results of the obtained polymer after mixing and vulcanization according to the formula are shown in Table 1.

[0082] Comparative Example 1

[0083] The polymerization method described in Example 2 is different in that white carbon black is added during mixing. The test results after vulcanization are shown in Table 1.

[0084] Comparative Example 2

[0085] The polymerization method described in Example 2 was used, except that white carbon black was added during mixing, and the amount of white carbon black added was 40 g. The test results after vulcanization are shown in Table 1.

[0086] Comparative Example 3

[0087] The polymerization method described in Example 2 was used, except that white carbon black was added when the conversion rate was 70%. The test results after vulcanization are shown in Table 1.

[0088] Comparative Example 4

[0089] The polymerization method described in Example 2 was used, except that white carbon black was added when the conversion rate was 90%. The test results after vulcanization are shown in Table 1.

[0090] Comparative Example 5

[0091] The polymerization method described in Example 2 is different in that when the stirring rate remains unchanged, the test results after vulcanization are shown in Table 1.

[0092] Test Example 1

[0093] The polybutadiene obtained in Examples 1-4 and Comparative Examples 1-5 was vulcanized according to the following formulation.

[0094] The vulcanization method is: vulcanizing at 150°C for 2 hours using a flat vulcanizing machine.

[0095] Mixing and vulcanization formula: 100 parts of polybutadiene rubber; 5 parts of zinc oxide; 2 parts of stearic acid; 1 part of antioxidant 1520; 1 part of antioxidant 1076; 1.4 parts of sulfur, 1 part of accelerator. The accelerator is N-cyclohexyl-2-benzothiazole sulfenamide (CBS).

[0096] The following properties of the vulcanized rubber were tested and the results are shown in Table 1.

[0097] Molecular weight distribution of polymers: measured using a HLC-8320 gel permeation chromatograph (GPC) produced by Tosoh, Japan, equipped with two TSKgel SuperMultiporeHZ-M analytical columns, THF as the mobile phase, narrow distribution polystyrene as the standard sample, and the temperature at 40°C.

[0098] Mooney viscosity: tested according to the method of GBT 1232.1-2016.

[0099] Rebound value: tested according to the method of GBT 1681-2009.

[0100] Table 1

[0101] PDI Mooney Rebound value% Example 1 2.25 76 61 Example 2 2.33 67 63 Example 3 2.42 65 62 Example 4 2.59 63 59 Comparative Example 1 2.37 68 54 Comparative Example 2 2.34 74 61 Comparative Example 3 2.34 65 55 Comparative Example 4 2.36 66 53 Comparative Example 5 2.31 62 52

[0102] From the results in Table 1, it can be seen that the reinforcing material needs to be added in the range of 75-85% polymerization conversion rate and the stirring rate should be increased at the same time to ensure high rebound performance. In addition, under the same reinforcing material addition conditions, adding in the polymerization process is better than adding in the mixing process; and to achieve similar rebound performance, the amount of reinforcing material added in the mixing method is more than that added in the polymerization method, which shows that the dispersion effect of reinforcing material added in the polymerization process is better than that in the mixing method.

[0103] 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 material, characterized in that: The method comprises: in the presence of a catalyst composition, subjecting butadiene to a first polymerization reaction, and when the polymerization conversion rate is 75-85%, adding a reinforcing material to conduct a second polymerization reaction, wherein the first polymerization reaction is conducted at a first stirring line speed, the second polymerization reaction is conducted at a second stirring line speed, and the second stirring line speed is greater than the first stirring line speed, The catalyst composition comprises: a neodymium phosphonate compound, an alkyl aluminum compound, a halogen-containing compound, a conjugated diene and a phosphonate.

2. The method according to claim 1, wherein: The second stirring linear velocity is 1.1 times or more of the first stirring linear velocity, preferably 1.1-3 times, more preferably 1.3-2.5 times, more preferably 1.5-2 times; Preferably, the first stirring linear speed is 90-120 r / min, preferably 100-110 r / min, more preferably 103-108 r / min; Preferably, the second stirring linear speed is 125-300 r / min, preferably 130-250 r / min, more preferably 150-220 r / min.

3. The method according to claim 1, wherein: The catalyst composition comprises: a homogeneous mixture of a neodymium phosphonate compound, an alkyl aluminum compound, a halogen-containing compound, a conjugated diene and a phosphonate; Preferably, the catalyst composition is obtained by mixing a neodymium phosphonate compound, a conjugated diene and a phosphonate, and then sequentially mixing them with an alkyl aluminum compound and a halogen-containing compound.

4. The method according to claim 1, wherein: The molar ratio of the neodymium phosphonate compound, the alkyl aluminum compound, the halogen-containing compound, the conjugated diene and the phosphonate is 1:2-13:2-5:10-80:0.4-0.8, preferably 1:3-10:2-5:10-80:0.4-0.8, and more preferably 1:3-10:3-5:45-55:0.4-0.

6.

5. The method according to any one of claims 1 to 4, wherein: The neodymium phosphonate compound is selected from one or more compounds represented by the following formula (1): In formula (1), R a1 , R a2 , R b1 , R b2 , R c1 and R c2 are independently hydrogen, hydroxyl, C1-C 20 Alkyl or C1~C 20 Alkoxyl groups; Preferably, R a1 , R a2 , R b1 , R b2 , R c1 , R c2 Each is independently 2-ethylhexyl or 2-ethylhexyloxy.

6. The method according to any one of claims 1 to 4, wherein: The alkyl aluminum compound is a compound having the general formula of AlR3 or AlHR2 or a mixture of the two, wherein R is a C1-C6 alkyl group; Preferably, the alkylaluminum compound is one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, triisobutylaluminum, diethylaluminum hydride, dipropylaluminum hydride and dibutylaluminum hydride.

7. The method according to any one of claims 1 to 4, wherein: The halogen-containing compound has the general formula AlR 1 2X alkylaluminum halide, having the general formula SiR 1 4-n X n The silane halide and the general formula Al2R 1 One or more of 3X3 alkylaluminum sesquihalides, wherein R 1 is C1-C6 alkyl, benzyl or allyl, and X is bromine or chlorine; Preferably, the halogen-containing compound is one or more of diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, monochlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride.

8. The method according to any one of claims 1 to 4, wherein: The conjugated diene is butadiene and / or isoprene.

9. The method according to any one of claims 1 to 4, wherein: The phosphonate is one or more of tributyl (ethyl) phosphine diethyl phosphate, di(2-ethylhexyl) phosphate and mono(2-ethylhexyl)-2-ethylhexyl phosphonate.

10. The method according to any one of claims 1 to 4, wherein: The reinforcing material is one or more of white carbon black, carbon black, calcium carbonate, clay and resin, preferably white carbon black; Based on 100g of butadiene, the added amount of the reinforcing material is 5-15g, more preferably 5-12g.

11. The method according to any one of claims 1 to 4, wherein: The temperatures of the first polymerization reaction and the second polymerization reaction are independently -30°C to 90°C, and the total polymerization time is 0.5-10 hours; Preferably, the temperatures of the first polymerization reaction and the second polymerization reaction are independently 10-60° C., and the total polymerization time is 1-5 hours.

12. The method according to any one of claims 1 to 4, wherein: The polybutadiene material is used for a golf ball core.

13. The polybutadiene material prepared by the method for preparing the polybutadiene material according to any one of claims 1 to 12.

14. A vulcanized rubber obtained by vulcanizing a polybutadiene material obtained by the method for preparing a polybutadiene material according to any one of claims 1 to 12.

15. Use of the polybutadiene material prepared by the method for preparing the polybutadiene material according to any one of claims 1 to 12 or the polybutadiene material according to claim 13 in preparing a golf ball core.

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