KR100490337B1 - Manufacturing method of 1,4-cis polybutadiene using tris(pentafluorophenyl)borane - Google Patents

Abstract

The present invention relates to a process for producing polybutadiene having a high 1,4-cis content of 80% or more through 1,3-butadiene polymerization, wherein a bis (1,5-cyclooctadiene) nickel salt compound is used as a main catalyst. By using a tris (pentafluorophenyl) borane compound as a catalyst activator to polymerize 1,3-butadiene monomers, thereby producing a catalyst in the production of polybutadiene having a high 1,4-cis content, usually using a nickel salt compound as the main catalyst. To prepare polybutadiene having a high 1,4-cis content of at least 80% without using trialkylaluminum or alkylaluminoxane compounds which have been essentially used as catalyst components for the production of polybutadiene having high activity and high molecular weight. Provide a method.

Description

Manufacturing method of 1,4-cis polybutadiene using tris (pentafluorophenyl) borane compound as a catalyst activator {Manufacturing method of 1,4-cis polybutadiene using tris (pentafluorophenyl) borane}

The present invention relates to a method for producing polybutadiene having a high 1,4-cis content of 80% or more through 1,3-butadiene polymerization, and more particularly, bis (1,5-cycloocta) serving as a main catalyst. To a polybutadiene having a high 1,4-cis content of at least 80% by polymerizing a 1,3-butadiene monomer using a tris (pentafluorophenyl) borane compound as a catalyst activator to a diene) nickel salt compound will be.

Conventionally, a method for preparing polybutadiene (hereinafter referred to as high-cis BR) having a high 1,4-cis content, US Pat. No. 5,100,982 discloses an organic nickel compound, an organoaluminum compound, and a boron trifluoride compound. A method of controlling the molecular weight and molecular weight distribution of hysbial is disclosed by preparing a hycisbial using a catalyst component, but using a phenol derivative substituted with a halogen atom as an additive and adjusting the addition amount thereof.

U.S. Patent No. 5,451,646 discloses a hysvial using an organic nickel compound, an organoaluminum compound, and a fluoride compound as main catalysts, and uses a para-styrenate diphenylamine as an additive to determine the molecular weight of the hysvial. A method of improving workability by adjusting is disclosed.

As another example, Japanese Patent Laid-Open No. 78-51,286 discloses a method for producing a hysvial having a narrow molecular weight distribution using nickel compounds, boron compounds, alkyllithium and alkylbenzenesulfonates.

In addition, U.S. Patent No. 4,533,711 uses hydrocarbons containing rare earth metal compounds, organoaluminum compounds, and halogenated aluminum compounds with atomic numbers 57 to 71 as catalyst components, and hydrocarbons containing organoaluminum hydrides or activated hydrogen compounds. Discloses a method for producing a hysvial, characterized by using as a molecular weight regulator.

However, such a conventional method for producing a hysyl vial may lead to an increase in manufacturing cost, gelation of the product, and preparation of a bimodal hysvial with the use of a large amount of organoaluminum compound as a promoter. And there is a problem that the process is complicated in commercial production.

Accordingly, the present inventors have been working to solve the known problems in the preparation of the conventional hysis vial, while tris (penta) as a catalyst activator to the bis (1,5-cyclooctadiene) nickel salt compound acting as a main catalyst As a result of polymerizing 1,3-butadiene monomer using a mixture produced by adding a fluorophenyl) borane compound as a catalyst, without using an organoaluminum compound or an alkylaluminoxane compound that acts as an alkylating agent in the production of a conventional hysvial The present invention has been completed to realize that polybutadiene having a high 1,4-cis content of 80% or more can be prepared.

According to the present invention, the molecular weight of the polymer can be controlled according to the amount of the tris (pentafluorophenyl) borane compound acting as a catalyst activator, thereby easily controlling the molecular weight affecting the physical properties such as processability or strength of the polymer. Can be.

Accordingly, it is an object of the present invention to eliminate process complexity by using tris (pentafluorophenyl) borane compounds as activators of bis (1,5-cyclooctadiene) nickel salt compounds without the addition of additional compounds, The present invention provides a method for producing a polybutadiene having a high 1,4-cis content, which enables the molecular weight of the hycisvial to be adjusted according to the use so as to optimize the processability and physical properties of the rubber.

The method for producing a polybutadiene having a high 1,4-cis content of the present invention for achieving the above object is a bis (1,5-cyclooctadiene) nickel salt compound as a polymerization catalyst in the presence of an inert organic solvent. A tris (pentafluorophenyl) borane compound is mixed and used as a catalyst activator in a 1: 2 to 1: 5 molar ratio to carry out a polymerization reaction with 1,3-butadiene at 0 to 60 ° C.

The present invention will be described in more detail as follows.

In the preparation of 1,4-cis polybutadiene according to the present invention, the characteristics of the catalyst structure are characterized by the activity of the catalyst in the preparation of polybutadiene having a high 1,4-cis content using a nickel salt compound as a main catalyst. Catalytically active species are produced in the absence of trialkylaluminum or alkylaluminoxane compounds, known as constituents of the catalyst necessary for the preparation of polybutadiene with high molecular weight, and high stereoregularity (1,4-cis selectivity). And 1,4-cis polybutadiene having a high molecular weight.

In the present invention, the catalyst structure used in the preparation of 1,4-cis polybutadiene is a combination of a bis (1,5-cyclooctadiene) nickel salt compound and a tris (pentafluorophenyl) borane compound, and a bis (1,5- Increasing the number of moles of the tris (pentafluorophenyl) borane compound to the cyclooctadiene) nickel salt compound increases the yield, 1,4-cis content and molecular weight up to a certain molar ratio. The values are reduced. However, this molar ratio is not deeply related to the molecular weight distribution.

In this regard, the molar ratio of the bis (1,5-cyclooctadiene) nickel salt compound and the tris (pentafluorophenyl) borane compound is preferably 1: 2 to 1: 5, and more preferably the molar ratio is a nickel catalyst. It is a 2-4 molar ratio with respect to 1 mol. If the addition amount is less than 2 molar ratio with respect to 1 mole of nickel catalyst, catalyst activity will fall and polymerization yield will fall rapidly, and even if it adds more than 5 molar ratio, it may cause the fall of polymerization yield and molecular weight.

In addition, the content of the bis (1,5-cyclooctadiene) nickel salt compound as the main catalyst is usually 1.99 x 10 ^{-3 to} 6.66 x 10 ^-3 moles per 100 g of 1,3-butadiene as a monomer. If the amount is less than 1.99 x 10 ^-3 moles per 100 g of 1,3-butadiene, it may cause a decrease in the polymerization yield and the content of 1,4-cis, and if the amount exceeds 6.66 x 10 ^-3 moles, the excess It may be accompanied by an increase in production cost and formation of a gel by the use of a catalyst.

The polymerization solvent used with the catalyst of such a configuration should not be reactive with the catalyst, and preferably aromatic hydrocarbons and halogenated aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene and chlorobenzene. Cycloaliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane may be used, but in this case, the polymerization yield may be reduced.

In performing the polymerization reaction, the order of addition of each component is to sequentially administer a bis (1,5-cyclooctadiene) nickel compound, a tris (pentafluorophenyl) borane compound, a polymerization solvent, and 1,3-butadiene. However, in some cases, each component may be administered irrespective of these orders. The polymerization is carried out by mixing 1,3-butadiene and a catalyst together with a polymerization solvent. In this case, since the polymerization solvent affects the polymerization of the polymer, it is preferable to use one in which oxygen and water are removed.

On the other hand, the molecular weight distribution of the hysvial prepared according to the present invention has a deep relationship with the polymerization temperature, the lower the polymerization temperature shows a tendency to narrow the molecular weight distribution. This may be due to the uniformity of the catalytically active species at lower polymerization temperatures. The polymerization temperature also affects yield, 1,4-cis content and molecular weight. Specifically, as the polymerization temperature is raised to a certain temperature, the yield and molecular weight increase, but the yield and molecular weight decrease rather than a certain temperature. Show a tendency. In the case of 1,4-cis content, it increases as the polymerization temperature decreases, and when the polymerization temperature is 0 ° C, the 1,4-cis content is about 94%. However, when the polymerization temperature is lowered, the reaction may not be started. Therefore, the polymerization temperature is preferably from 0 ° C to 60 ° C, but even more preferred polymerization temperature is between 40 ° C and 60 ° C. If the reaction temperature is lower than 0 ℃ or higher than 60 ℃ can lead to a rapid decrease in the polymerization yield.

The polymerization is started in a high purity nitrogen atmosphere, the polymerization time is suitable for 2 to 5 hours under suitable catalytic conditions.

After completion of the reaction, 2,6-di- t -butyl paracresol was added as an antioxidant, and the reaction product was precipitated in methyl alcohol containing a small amount of HCl as a reaction terminator to obtain a product.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Example 1

After the polymerization reaction was sufficiently blown with a nitrogen pressure reactor, a bis (1,5-cyclooctadiene) nickel compound, a tris (pentafluorophenyl) borane compound, toluene (10ml), 1,3-butadiene (3g) It was added sequentially, followed by 2 hours at 40 ℃. At this time, the ratio of the polymerization solvent and the monomer is from about 2.9, bis (1,5-cyclooctadiene) nickel compound and the molar ratio of tris (pentafluorophenyl) borane compound is from 1: 2 was, monomer 6.42 × 10 per 3g ^{- 5} moles of bis (1,5-cyclooctadiene) nickel compound was used. After the reaction, 2,6-di-t-butyl-p-cresol and methanol containing a small amount of HCl were added to terminate the reaction.

Examples 2-5

1,4-cis polybutadiene was prepared in the same manner as in Example 1, except that the catalyst composition ratio or the concentration of the nickel salt catalyst was changed as shown in Table 1 below.

Catalyst In order ^(weeks) Molar ratio Polymerization temperature (℃) Ni content (× 10 ^-5 mol) / 3 g of 1,3-butadiene Example 1 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 2 40 6.42 Example 2 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 40 6.42 Example 3 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 5 40 6.42 Example 4 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 40 5.98 Example 5 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 40 20.00 Ni (COD) ₂ : bis (1,5-cyclooctadiene) nickel B (C ₆ F ₅ ) ₃ : tris (pentafluorophenyl) borane

Examples 6-8

1,4-cis polybutadiene was prepared in the same manner as in Example 1, except that the polymerization temperature was performed as shown in Table 2 below.

Catalyst In order ^(weeks) Molar ratio Polymerization temperature (℃) Nickel content (× 10 ^-5 mol) / 3 g of 1,3-butadiene Example 6 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 0 6.42 Example 7 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 20 6.42 Example 8 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 60 6.42 Ni (COD) ₂ : bis (1,5-cyclooctadiene) nickel B (C ₆ F ₅ ) ₃ : tris (pentafluorophenyl) borane

Examples 9-11

1,4-cis polybutadiene was prepared in the same manner as in Example 1, except that the polymerization solvent was performed as shown in Table 3 below.

Catalyst In order ^(weeks) Molar ratio Polymerization Solvent Nickel content (× 10 ^-5 mol) / 3 g of 1,3-butadiene Example 9 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 benzene 6.42 Example 10 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 Chlorobenzene 6.42 Example 11 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 Cyclohexane 6.42 Ni (COD) ₂ : bis (1,5-cyclooctadiene) nickel B (C ₆ F ₅ ) ₃ : tris (pentafluorophenyl) borane

Comparative Examples 1 to 8

1,4-cis polybutadiene was prepared in the same manner as in Example 1, except that another organic nickel salt compound was used instead of a bis (1,5-cyclooctadiene) nickel compound (Comparative Examples 1-3), or a catalyst. When another organic borane compound was used instead of the active compound tris (pentafluorophenyl) borane compound (Comparative Example 4-6), and the bis (1,5-cyclooctadiene) nickel compound and the tris (pentafluorophenyl) borane compound The molar ratio of (Comparative Example 7) and polymerization temperature (Comparative Example 8) are shown in Table 4 below.

Catalyst input sequence Molar ratio Polymerization temperature (℃) Polymerization Solvent Nickel content (× 10 ^-5 mol) / 3 g of 1,3-butadiene Comparative Example 1 Ni (2-EHN) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 40 toluene 6.42 Comparative Example 2 (BAB-2,6-DIPI) NiBr ₂ / B (C ₆ F ₅ ) ₃ 1: 3 40 toluene 6.42 Comparative Example 3 (BAB-2,6-DIPI) (1,3-BD) Ni / B (C ₆ F ₅ ) ₃ 1: 3 40 toluene 6.42 Comparative Example 4 Ni (COD) ₂ / BEt ₃ 1: 3 40 toluene 6.42 Comparative Example 5 Ni (COD) ₂ / B (C ₆ H ₅ ) ₃ 1: 3 40 toluene 6.42 Comparative Example 6 Ni (COD) ₂ / BF ₃ OBu ₂ 1: 3 40 toluene 6.42 Comparative Example 7 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 1 40 toluene 6.42 Comparative Example 8 Ni (COD) ₂ / B (C ₆ F ₅ ) ₃ 1: 3 -20 toluene 6.42 Ni (2-EHN) ₂ : Nickel (2-ethylhexanoate) (BAB-2,6-DIPI) NiBr ₂ : Biacetylbis (2,6-diisopropylphenylimmine) NiBr ₂ (BAB-2,6-DIPI) ) (1,3-BD) Ni: Biacetylbis- (2,6-diisopropylphenylimmine) (1,3-butadiene) nickelNi (COD) ₂ : Bis (1,5-cyclooctadiene) nickel B (C ₆ F ₅ ) ₃ : tris (pentafluorophenyl) borane

Experimental Example 1

The 1,4-cis polybutadiene prepared in Examples 1 to 11 and Comparative Examples 1 to 8 was measured for 1,4-cis content, yield, molecular weight (Mw) and molecular weight distribution (MWD). It is shown in Table 5 below. At this time, the 1,4-cis content was measured according to the Morero method (Chim. Indust., Vol 41, p758, 1959).

From the results of Table 5, other organic nickel compounds are used without using bis (1,5-cyclooctadiene) nickel compounds acting as main catalysts according to the present invention (Comparative Examples 1-3), or as catalyst activators. When 1,3-butadiene was polymerized in solution using another organic borane compound instead of a functional tris (pentafluorophenyl) borane compound (Comparative Example 4-6), the polymerization activity was not shown (Comparative Example 1-5). ) Even if the polymerization activity is shown, it can be observed that the resulting molecular weight of the resulting cisis vial is greatly reduced (Comparative Example 6). In addition, even when the molar ratio (comparative example 7) and polymerization temperature (comparative example 8) of the bis (1,5-cyclooctadiene) nickel compound and the tris (pentafluorophenyl) borane compound were carried out differently from the present invention, the yield was obtained. It can be seen that the 1,4-cis content and molecular weight are greatly reduced. However, according to the present invention, a mixture produced by mixing a bis (1,5-cyclooctadiene) nickel compound and a tris (pentafluorophenyl) borane compound is used as a catalyst and 1,3-butadiene in the presence of a suitable polymerization solvent. It can be seen that the polybutadiene having a high 1,4-cis content and a high molecular weight (Mw> 40,000 or more) when the polybutadiene is prepared using the monomer as a monomer.

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In addition, the effect of the catalyst molar ratio on the polymerization reaction can be seen from the results of Examples 1-3 and Comparative Example 7, the molar ratio of the nickel catalyst and the tris (pentafluorophenyl) borane compound from 1: 1 to 1: It can be seen that as the increase to 3, the 1,4-cis content, yield and molecular weight increase significantly, and when the molar ratio is 1: 5 (Example 3), the values are slightly decreased.

In addition, the effect of the polymerization temperature on the polymerization reaction can be seen from the results of Examples 2, 6-8, and Comparative Example 8. As the polymerization temperature is increased from 0 ° C to 40 ° C, the polymerization yield and molecular weight increase. (Example 2 and Example 6-7), and when the temperature was increased to 60 ℃ (Example 8) it can be seen that both values decrease slightly. In conclusion, in order to control the molecular weight of the hysisvial while maintaining a certain level of yield, it is more effective to control the molecular weight by changing the polymerization temperature to control the molecular weight by controlling the molar ratio of the two components constituting the catalyst. It can be seen that. Meanwhile, the 1,4-cis content was constantly increased as the polymerization temperature was decreased from 60 ° C to 0 ° C. When the polymerization temperature is too low, the difficulty of initiating the reaction can be seen from the results of Comparative Example 8.

The effect of the polymerization solvent on the reaction can be seen from the results of Examples 2 and 9-11, when the polymerization solvent is an aromatic hydrocarbon such as toluene, benzene, or chlorobenzene (Examples 2 and 9-10). Cyclohexane, a cyclo aliphatic hydrocarbon, showed better polymerization yield. However, when cyclohexane is used as the polymerization solvent, the yield is considered to be satisfactory when mixed with toluene, benzene, or chlorobenzene without using a single polymerization solvent.

As described in detail above, when the tris (pentafluorophenyl) borane compound is added as a catalyst activator to the bis (1,5-cyclooctadiene) nickel salt compound as the main catalyst according to the present invention, the catalyst is present. Polybutadiene having a high 1,4-cis content of 80% or more can be prepared by polymerizing 1,3-butadiene monomers without using an organoaluminum compound that acts as an alkylating agent in the manufacture of a hysvial, and tris (pentafluoro By changing the amount of the phenyl) borane compound added, the molecular weight affecting the processability and physical properties of the rubber can be easily controlled.

Claims (5)

In preparing 1,4-cis polybutadiene via 1,3-butadiene polymerization, In the presence of an inert organic solvent, a bis (1,5-cyclooctadiene) nickel salt compound as a polymerization catalyst and a tris (pentafluorophenyl) borane compound as a catalyst activator are mixed and used in a ratio of 1: 2 to 1: 5. A process for producing 1,4-cis polybutadiene, characterized in that the polymerization is carried out at 0 to 60 ° C with, 3-butadiene. The method for producing 1,4-cis polybutadiene according to claim 1, wherein the inert organic solvent is selected from one or two or more compounds among aromatic hydrocarbons, halogenated aromatic hydrocarbons and cycloaliphatic hydrocarbons. The 1,4-cis polybutadiene according to claim 1 or 2, wherein the inert organic solvent is one or two or more selected from benzene, toluene, ethylbenzene, chlorobenzene, and cyclohexane. Manufacturing method. The 1,4-cis according to claim 1, wherein the bis (1,5-cyclooctadiene) nickel salt compound is used in an amount of 1.99 × 10 ^{−3 to} 6.66 × 10 ⁻³ mole per 100 g of 1,3-butadiene. Method for producing polybutadiene. The method for producing 1,4-cis polybutadiene according to claim 1, wherein the 1,4-cis content is 80% or more.