JP2000327721A - Polybutadiene and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polybutadiene comprising a specific high mol.wt. polybutadiene and a specific low mol.wt. polybutadiene, and to provide a method for producing the polybutadiene in which polymerization activity. SOLUTION: This polybutadiene comprises the following components (A) and (B): (A) the polybutadiene which is produced in the presence of the compound of a rate earth metal having the atomic number of 57 to 71 as a catalyst and has a weight-average mol.wt. (Mw) of 700,000 to 3,000,000 measured by gel permeation chromatograph(GPC); and (B) the polybutadiene which is produced in the presence of the compound of a rare earth metal having the atomic number of 57 to 71 as a catalyst and has a weight-average mol.wt. (Mw) of 5,000 to 70,000 measured by gel permeation chromatograph(GPC).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a bimodal polybutadiene rubber composition comprising a mixture of a high molecular weight polybutadiene component and a low molecular weight polybutadiene component.

[0002]

2. Description of the Related Art As a polybutadiene for impact-resistant polystyrene compositions, a bimodal polybutadiene rubber composition comprising a mixture of a high molecular weight polybutadiene component and a low molecular weight polybutadiene component is known.

Japanese Patent Application Laid-Open No. 62-179542 discloses that a high molecular weight polybutadiene having an intrinsic viscosity [η] of 3.0 to 6.0 and cis-1,4-polybutadiene as a main component is 70 to 30% by weight. Polybutadiene rubber composition suitable as a rubber component of an impact-resistant polystyrene resin comprising a low-molecular-weight polybutadiene having a viscosity [η] of 0.6 to 1.4 and a low molecular weight polybutadiene having a cis-1,4-polybutadiene as a main component, Is disclosed. Production methods include a cobalt compound,
A method is disclosed in which cyclooctadiene is added as a molecular weight regulator to a catalyst comprising an organoaluminum halide and water to produce a low molecular weight polybutadiene alone and then blended with a separately polymerized high molecular weight polybutadiene.

Japanese Patent Application Laid-Open No. Hei 4-100810 discloses a high molecular weight polybutadiene having an intrinsic viscosity [η] of 3.0 to 7.0 and a polybutadiene having a cis-1,4-structure ratio of 80% or more as a main component. Impact resistant polystyrene comprising 30% by weight and 30 to 70% by weight of a low molecular weight polybutadiene containing polybutadiene as a main component and having an intrinsic viscosity [η] of 0.5 to 1.4 and a cis-1,4-structure ratio of less than 80%. A polybutadiene rubber composition suitable as a rubber component of a base resin is disclosed. As a production method, a high-molecular-weight polybutadiene is produced using cyclooctadiene as a chain transfer agent in a catalyst composed of cobalt octanoate, diethylaluminum chloride, and water, and a low-molecular-weight polybutadiene is produced using n-butyllithium as a catalyst. And a method of solution blending them.

Japanese Patent Application Laid-Open No. 10-60174 discloses that 98 to 30% by weight of a high molecular weight polybutadiene having a peak top molecular weight of 100,000 to 1.5 million in a molecular weight distribution curve measured by GPC,
The peak top molecular weight of the molecular weight distribution curve measured by PC
A polybutadiene rubber composition suitable as a rubber component of an impact-resistant polystyrene resin comprising 2 to 70% by weight of low molecular weight polybutadiene of 10,000 to 50,000 is disclosed. As a production method, a high molecular weight polybutadiene is produced using a catalyst consisting of cobalt octenoate, diethylaluminum chloride, trimethyl orthoformate and water, and a low molecular weight polybutadiene is produced by using a catalyst consisting of nickel naphthenate, diethylaluminum chloride and water. And a method of solution blending them.
However, the molecular weight distribution is as narrow as 4.5 to 14.5.

Japanese Patent Publication No. 42-9017 discloses 70-95% by weight of a high molecular weight polybutadiene having an intrinsic viscosity [η] of 1.5 to 20 and a cis-1,4-structure ratio of 85% or more. Low molecular weight polybutadiene having an [η] of 0.35 to 0.75 30 to 5
A rubber composition comprising by weight percent is disclosed. As a production method, a method is described in which a low molecular weight polybutadiene is produced by homopolymerization using a cobalt compound-sesquialuminum catalyst, and a separately polymerized high molecular weight polybutadiene is blended.

Further, Japanese Patent Publication No. 3-22887, Japanese Patent Publication No. 4-260
No. 1, JP-A-8-73515 and JP-A-10-158316 disclose a method for polymerizing butadiene using a combination of a rare earth metal compound and an organoaluminum compound. In addition, Journal of Polymer Science: Part A:
Polymer Chemistry 36 (1998), pp. 1707 and 2283, discloses a method for polymerizing and copolymerizing a conjugated diene compound using a combination of a rare earth metal compound and an organoaluminum compound. JP-A-10-3247
07 discloses a polymerization catalyst for a conjugated diene compound using an ionic compound of an organic rare earth metal compound.

However, a method of producing a polybutadiene comprising a specific high molecular weight polybutadiene and a specific low molecular weight polybutadiene using a rare earth metal compound has not been known so far.

SUMMARY OF THE INVENTION The present invention provides a polybutadiene comprising a specific high molecular weight polybutadiene and a specific low molecular weight polybutadiene, and a method for producing the polybutadiene with a high polymerization activity using a rare earth metal compound. The purpose is to:

[0009]

The present invention relates to a polybutadiene having a cis-1,4-structure content of 75% or more and comprising the following components (A) and (B), and a method for producing the polybutadiene. In the first polymerization step, atomic number 57
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using a catalyst system consisting of a rare earth metal compound, a cobalt compound, a nickel compound, an organoaluminum compound, and water of 71 or less. 700,000 to 3,000,000 polybutadiene (A)
Then, in the second polymerization step, atomic number 57 or more 71
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using a catalyst system consisting of the following rare earth metal compounds, cobalt compounds, nickel compounds, organoaluminum compounds, and water is 5,000. The present invention relates to a method for producing polybutadiene, comprising producing up to 70,000 polybutadiene (B).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polybutadiene obtained in the present invention has a weight average molecular weight (Mw) of 700,000 as measured by gel permeation chromatography (GPC) of the component (A).
3,000,000, preferably 1,000,000 to 2,000,000.

The polybutadiene (B) obtained by the present invention
Gel Permeation Chromatograph (GPC)
Is from 5,000 to 70,000, preferably from 5,000 to 60,000, particularly preferably from 5,000 to less than 30,000, and still more preferably from 5,000 to 2.5,000.
And more preferably 10,000 to 25,000.

The molecular weight distribution of the polybutadiene of the present invention comprising the components (A) and (B) represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 15 -100, preferably 20-100.

The polybutadiene of the present invention comprising the above components (A) and (B) has a cis-1,4-structure content of 70%.
Or more, preferably 80% or more, more preferably 90% or more.

The polybutadiene as the component (A) has a cis-1,4-structural unit content of 70% or more;
It is preferably at least 90%, particularly preferably at least 95%.

The content of the cis-1,4-structural unit of the polybutadiene as the component (B) is from 40 to 95%, particularly preferably from 50 to 92%, and particularly preferably from 50 to 90%. is there. The content of trans-1,4-structural unit is 60% or less, particularly preferably 3%.
~ 45%. 1,2-structural unit content is 10%
Or less, particularly preferably 0.5 to 7%.

The ratio between the high molecular weight polybutadiene of the component (A) and the low molecular weight polybutadiene of the component (B) is as follows:
(A) component is 30% by weight or more and less than 70% by weight, preferably 40% by weight or less.
(B) is more than 30% by weight and less than 70% by weight, preferably more than 30% by weight and less than 70% by weight.
% By weight or less. If the proportion of the component (A) is larger than the above range, the processability is reduced. If the proportion of the component (A) is smaller than the above range, the viscosity of the polybutadiene rubber composition is too small, which is not preferable.

In the present invention, the method for producing the polybutadiene comprising the above components (A) and (B) is not particularly limited, but (1) two-stage tandem polymerization, for example,
A method of producing the component (A) in the first tank and producing the component (B) in the final tank, or a method of producing the component (B) in the first tank and producing the component (A) in the final tank, (2) ) One-stage polymerization, for example
A method of producing the component (A) and subsequently producing the component (B) in a single tank, or a method of producing the component (B) and subsequently producing the component (A)
A method of producing the components in one tank, (3) two-stage parallel polymerization, for example, after producing the components (A) and (B) in separate tanks,
Mixing method (4) A method of separately preparing the component (A) and the component (B) and then mixing them by solution blending, melt blending, or the like.

In the present invention, the polybutadiene comprising the above-mentioned components (A) and (B) comprises the component (A),
The component (B) can be produced using a rare earth metal compound having an atomic number of 57 or more and 71 or less as a catalyst.

That is, in the present invention, in the first polymerization step, the above component (A) is produced using a catalyst system comprising a rare earth metal compound having an atomic number of 57 to 71, an organoaluminum compound, and water, Next, in the second polymerization step, the above component (B) can be produced using a catalyst system comprising a rare earth metal compound having an atomic number of 57 or more and 71 or less, an organoaluminum compound, and water.

In the above-mentioned production method, it is preferable that the atomic number is 57 or more.
When a rare earth metal compound of 71 or less is used, the above component (A) or component (B) can be produced by using an ionic compound composed of a non-coordinating anion and a cation in combination.

In the above-mentioned production method, in the second polymerization step, at least one component selected from the group consisting of a component constituting the catalyst system, water and butadiene monomer is additionally added, and the above-mentioned component (A) or (B) is added. The components can be manufactured.

The catalyst system and the polymerization conditions in the first polymerization step include the following.

As the rare earth metal compound having an atomic number of 57 or more and 71 or less, a salt or a complex thereof is preferably used. Particularly preferred are chloride, bromide, nitrate, versatic acid (trade name of Shell Chemical, a carboxylic acid having a carboxyl group mainly bonded to a tertiary carbon atom), octylate, 2-ethyl Hexanoate, naphthenate,
Fatty acid salts such as acetate, trifluoroacetate and malonate, monoacetylacetonate, bisacetylacetonate, trisacetylacetonate, ethylacetoacetate complex, triarylphosphine complex of halide, and trialkylphosphonate Examples include an organic base complex such as a fin complex, a pyridine complex and a picoline complex, an ether complex such as a diethyl ether complex, a tetrahydrofuran complex, and a dioxane complex, and an ethyl alcohol complex.

Among them, fatty acid salts such as versatate, octylate, naphthenate and trifluoroacetate are preferred.

The rare earth metal having an atomic number of 57 or more and 71 or less is preferably neodymium, praseodymium, cerium,
Lanthanum, gadolinium, samarium or a mixture thereof, particularly preferably neodymium.

Examples of the organoaluminum compound include a halogen-containing aluminum compound, an alkylaluminum hydride, a trialkylaluminum, and a reaction product of the above compound with water.

As the halogen-containing aluminum compound,
Examples thereof include dialkylaluminum halides such as dialkylaluminum chloride and dialkylaluminum bromide, alkylaluminum sesquichlorides such as alkylaluminum sesquibromide, and alkylaluminum dihalides such as alkylaluminum dichloride and alkylaluminum dibromide.

Specific compounds include diethylaluminum monochloride, diethylaluminum monobromide, dibutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, dicyclohexylaluminum monochloride, diphenylaluminum monochloride and the like.

Examples of the alkyl aluminum hydride include dialkyl aluminum hydride, alkyl aluminum sesquihydride, and alkyl aluminum dihydride.

Specific examples of the compound include diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum sesquihydride, ethylaluminum dihydride, dicyclohexylaluminum hydride, diphenylaluminum hydride and the like.

Examples of the trialkylaluminum compound include triethylaluminum, trimethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like.

The reaction product of the organoaluminum compound and water includes alumoxane obtained by reacting trimethylaluminum, triethylaluminum, diethylaluminum monochloride, diethylaluminum monobromide, ethylaluminum sesquichloride and ethylaluminum dichloride with water, respectively. Is mentioned.

The above-mentioned organoaluminum compounds may be used alone or in combination of two or more.

In the ionic compound comprising a non-coordinating anion and a cation, which is used when a rare earth metal compound having an atomic number of 57 to 71 is used, the non-coordinating anion may be, for example, tetra (phenyl) borane. , Tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl)
Borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate
, Tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tridecahydride-7,8-dicarboundecaborate, tetra Fluoroborate, hexafluorophosphate and the like can be mentioned.

On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

Specific examples of the carbonium cation include:
Examples include trisubstituted carbonium cations such as triphenylcarbonium cation and tris (substituted phenyl) carbonium cation. Specific examples of the tris (substituted phenyl) carbonium cation include a tri (tolyl) carbonium cation and a tris (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include:
Trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation, N, N-dimethylanilinium cation;
N-diethylanilinium cation, N, N-2,4,
N, N- such as 6-pentamethylanilinium cation
Dialkylanilinium cation, di (i-propyl)
Examples thereof include a dialkylammonium cation such as an ammonium cation and a dicyclohexylammonium cation.

Specific examples of the phosphonium cation include:
Triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation can be mentioned.

As the ionic compound, those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.

Among them, ionic compounds include triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (fluorophenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) )
And 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate are preferred. Of these, triphenylcarbonium tetrakis (pentafluorophenyl) borate is particularly preferred.

The ionic compounds may be used alone or in combination of two or more.

The amount of atomic number 57 or 71 or less of a rare earth metal compound, with respect to mole butadiene, usually, rare earth metal compound is ^{5 × 10 - 7 ~1 × 10} -3 mol, preferably 1 × 10 ^-6 ５5 × 10 ^-4 mol.

The amount of the organoaluminum compound to be used is usually in the range of 1 to 1,000 mol, preferably 5 to 500 mol, per 1 mol of the rare earth metal compound having an atomic number of 57 to 71.

The amount of water to be used is
It is usually 0.001 to 2 mol, preferably 0.002 to 1.5 mol, per mol.

The order of addition of the catalyst components is not particularly limited.
In the first polymerization step, it is preferable that water and organic aluminum are added in this order, and then the rare earth metal compound having an atomic number of 57 or more and 71 or less, and then, if necessary, an ionic compound or organic aluminum are added in that order.

In the first polymerization step, if necessary, the components constituting the catalyst system may be brought into contact with each other for a certain period of time before being added to the monomer or the monomer solution.

The polymerization method is not particularly limited.
Bulk polymerization using 1,3-butadiene itself as a polymerization solvent can be applied. Solvents for solution polymerization include toluene,
Aromatic hydrocarbons such as benzene and xylene, aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane;
Alicyclic hydrocarbons such as cyclopentane and cyclohexane,
Olefinic hydrocarbons such as 1-butene, cis-2-butene, and trans-2-butene; mineral spirits, solvent naphtha, hydrocarbon solvents such as kerosene, and halogenated hydrocarbon solvents such as methylene chloride. Can be

The catalyst system and the polymerization conditions in the second polymerization step include the following.

As the rare earth metal compound having an atomic number of 57 to 71, the same compounds as those used in the first polymerization step can be used.

As the organoaluminum compound, the same compounds as those used in the first polymerization step can be used.

The amount of atomic number 57 or 71 or less of a rare earth metal compound, with respect to mole butadiene, usually, the metal compound is ^{5 × 10 - 7 ~1 × 10} -3 mol, preferably 1 × 1
The range is 0 ^{-6 to} 5 × 10 ^-4 mol.

The amount of the organoaluminum compound to be used is generally in the range of 5 to 5000 mol, preferably 10 to 1000 mol, per 1 mol of the rare earth metal compound having an atomic number of 57 to 71.

The amount of water used depends on the amount of the organoaluminum compound 1
It is usually 0.001 to 2 mol, preferably 0.002 to 1.5 mol, per mol.

The order of addition of the catalyst components is not particularly limited.
After the addition of the organic aluminum, it is preferable to add the rare earth metal compound having an atomic number of 57 or more and 71 or less, and then, if necessary, an ionic compound or organic aluminum in order.

In the second polymerization step, if necessary, a component constituting the catalyst system, an organoaluminum compound,
At least one component selected from water and a butadiene monomer may be additionally added. When these components are used in combination, they may be brought into contact with each other for a certain period of time before additional addition.

The polymerization method is not particularly limited.
Bulk polymerization using 1,3-butadiene itself as a polymerization solvent can be applied. Solvents for solution polymerization include toluene,
Aromatic hydrocarbons such as benzene and xylene, aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane;
Alicyclic hydrocarbons such as cyclopentane and cyclohexane,
Olefinic hydrocarbons such as 1-butene, cis-2-butene, and trans-2-butene; mineral spirits, solvent naphtha, hydrocarbon solvents such as kerosene, and halogenated hydrocarbon solvents such as methylene chloride. Can be

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

EXAMPLES Microstructure was performed by infrared absorption spectroscopy. Cis-1,4 structure 740 cm ^-1, trans 1,4 structure 967 cm ^-1, 1,2-structure 910 cm ^-1
The microstructure was calculated from the ratio of absorption intensities. Intrinsic viscosity [η]
Was measured at 30 ° C. using a toluene solution. The weight average molecular weight Mw, number average molecular weight Mn, and their ratio Mw / Mn were determined by GPC using polystyrene as a standard substance.
The ratio of the component (A) to the component (B) was calculated from the area ratio of the high molecular weight polybutadiene to the low molecular weight polybutadiene in the GPC chart.

[Example 1] Production of component (A) (high molecular weight polybutadiene) (first polymerization step) The inside of a 1.5 L autoclave was purged with nitrogen.
700 mL of a solution in which 33.3 wt% of butadiene and 66.7 wt% of cyclohexane are mixed in advance is added, and added at room temperature so that the concentration of water (H ₂ O) becomes 0.4 mmol / L, and vigorously stirred at 700 rpm for 30 minutes. did.
8.4 ml of a cyclohexane solution (1 mol / L) of triethylaluminum (TEA) was added, and the mixture was stirred at room temperature for 2 minutes. Further, neodymium versatate (Nd (Ve
r) ₃ ) n-heptane solution (0.1 mol / L)
4 ml was added and stirred for 2 minutes. The mixture was heated to 50 ° C, polymerization was started by adding 0.42 ml of a cyclohexane solution (1 mol / L) of diethyl aluminum chloride (DEAC), and the mixture was polymerized at 50 ° C for 40 minutes. The polymerization was stopped by adding 5 mL of an ethanol / heptane (1/1) solution containing an antioxidant. After releasing the pressure inside the autoclave, the polymerization solution was poured into ethanol to recover polybutadiene. Next, the recovered polybutadiene was treated at 50 ° C. for 6 hours.
Vacuum dried for hours. Table 3 shows the polymerization results.

Example 2 Production of Component (A) (High Molecular Weight Polybutadiene) (First Polymerization Step) In Example 1, diisobutylaluminum hydride (DIBAH) was used in place of TEA. The polymerization was carried out in the same manner, except that the polymerization was changed as shown in Table 1. Table 3 shows the polymerization results.

Example 3 Production of Component (A) (High Molecular Weight Polybutadiene) (First Polymerization Step) In Example 1, triphenylcarbenium tetrakis (pentafluorophenyl) borate (Borate) was used instead of DEAC. Polymerization was carried out in the same manner except that the amount of the catalyst component used was changed as shown in Table 1. Table 3 shows the polymerization results.

Example 4 Production of Component (B) (Low Molecular Weight Polybutadiene) (Second Polymerization Step) A 1.5 L autoclave was purged with nitrogen.
700 mL of a solution in which 33.3 wt% of butadiene and 66.7 wt% of cyclohexane are mixed is added in advance, and added at room temperature so that the concentration of water (H ₂ O) becomes 0.4 mmol / L, and vigorously stirred at 700 rpm for 30 minutes. did.
Diisobutyl aluminum hydride (DIBAH)
Of cyclohexane (5 mol / L) was added, and the mixture was stirred at room temperature for 2 minutes. Further, 2.1 ml of an n-heptane solution (0.1 mol / L) of neodymium versatate (Nd (Ver) ₃ ) was added, and the mixture was stirred at room temperature for 2 minutes. The mixture was heated to 50 ° C., and a solution of diethyl aluminum chloride (DEAC) in cyclohexane (1 mol) was added.
(L) 0.32 ml was added to start polymerization, and polymerization was carried out at 50 ° C. for 40 minutes. The polymerization was stopped by adding 5 mL of an ethanol / heptane (1/1) solution containing an antioxidant. After releasing the pressure inside the autoclave, the polymerization liquid was recovered, the solvent was recovered by an evaporator, and the remaining low molecular weight polybutadiene was recovered. Next, the recovered polybutadiene was vacuum dried at 50 ° C. for 6 hours. Table of polymerization results
3 is shown.

Example 5 Production of Component (B) (Low Molecular Weight Polybutadiene) (Second Polymerization Step) In Example 4, triphenylcarbenium tetrakis (pentafluorophenyl) borate (Borate) was used instead of DEAC. Polymerization was carried out in the same manner except that the amount of the catalyst component used was changed as shown in Table 2. Table 4 shows the polymerization results.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[Examples 6 to 9] 10 g of the high molecular weight component obtained in Examples 1 to 3 and 10 g of the low molecular weight component obtained in Examples 4 to 5 were dissolved by stirring in cyclohexane, and then added to ethanol. And polybutadiene. Next, the recovered polybutadiene was vacuum dried at 50 ° C. for 6 hours. Table 5 shows the area ratio, molecular weight, and molecular weight distribution of the high molecular weight polybutadiene and the low molecular weight polybutadiene in the GPC chart of the obtained bimodal polybutadiene.

[0068]

[Table 5]

Example 10 Production of Component (A) (High Molecular Weight Polybutadiene) (First Polymerization Step) A 1.5 L autoclave was purged with nitrogen.
700 mL of a solution prepared by mixing 33.3 wt% of butadiene and 66.6 wt% of cyclohexane is prepared in advance, and adjusted at room temperature so that the concentration of water (H ₂ O) becomes 0.4 mmol / L, and vigorously stirred at 700 rpm for 30 minutes. did.
9 ml of a cyclohexane solution (1 mol / L) of triethylaluminum (TEA) was added, and the mixture was stirred at room temperature for 2 minutes. In addition, neodymium versatate (Nd (Ver)
₃ ) n-heptane solution (0.1 mol / L) 1.4 m
was added and stirred for 2 minutes. After heating to 50 ° C., 0.46 ml of a cyclohexane solution (1 mol / L) of diethylaluminum chloride (DEAC) was added to initiate polymerization, and polymerization was performed at 50 ° C. for 30 minutes.

Production of Component (B) (Low Molecular Weight Polybutadiene) (Second Polymerization Step) Following the production of Component (A), 28 ml of a cyclohexane solution (1 mol / L) of diisobutylaluminum hydride (DIBAL-H) was added at 50 ° C. Was added and polymerized for an additional 30 minutes. The polymerization was stopped by adding 5 mL of an ethanol / heptane (1/1) solution containing an antioxidant. After releasing the pressure inside the autoclave, the polymerization solution was poured into ethanol to recover polybutadiene. Next, the recovered polybutadiene was vacuum dried at 50 ° C. for 6 hours.
The polymerization results are shown in Tables 8-9.

[Example 11] In the production of the component (A), a cyclohexane solution of TEA (1 mol / L) 7.7 was used.
The polymerization was carried out for 40 minutes with the use of DIBAL-H in a cyclohexane solution (1 mol
(l / L), and the same operation as in Example 10 was performed except that polymerization was performed for 40 minutes using 25.2 ml. Table 8-
The results are shown in FIG.

Example 12 Production of Component (A) (High Molecular Weight Polybutadiene) (First Polymerization Step) The inside of a 1.5 L autoclave was purged with nitrogen.
700 mL of a solution prepared by mixing 33.3 wt% of butadiene and 66.6 wt% of cyclohexane is prepared in advance, and adjusted at room temperature so that the concentration of water (H ₂ O) becomes 0.4 mmol / L, and vigorously stirred at 700 rpm for 30 minutes. did.
Diisobutylaluminum hydride (DIBAL-
H) cyclohexane solution (1 mol / L) 1.1 ml
Was added and stirred at room temperature for 2 minutes. Further, 0.7 ml of an n-heptane solution (0.1 mol / L) of neodymium versatate (Nd (Ver) ₃ ) was added, and the mixture was stirred at room temperature for 2 minutes. The mixture was heated to 50 ° C., and a solution of diethyl aluminum chloride (DEAC) in cyclohexane (1 mol) was added.
/ L) 0.21 ml was added to start polymerization, and polymerization was carried out at 50 ° C. for 40 minutes.

Production of Component (B) (Low Molecular Weight Polybutadiene) (Second Polymerization Step) Following the production of component (A), 40 ml of a cyclohexane solution (1 mol / L) of diisobutylaluminum hydride (DIBAL-H) was added at 50 ° C. And neodymium versatate (Nd (Ver) ₃ )
-0.8 ml of a heptane solution (0.1 mol / L) and 0.12 ml of a diethylaluminum chloride (DEAC) cyclohexane solution (1 mol / L) are added thereto, and 50
Polymerized for minutes. The polymerization was stopped by adding 5 mL of an ethanol / heptane (1/1) solution containing an antioxidant. After releasing the pressure inside the autoclave, the polymerization solution was poured into ethanol to recover polybutadiene. Next, the recovered polybutadiene was vacuum dried at 50 ° C. for 6 hours. The polymerization results are shown in Tables 8-9.

Example 13 Production of Component (A) (High Molecular Weight Polybutadiene) (First Polymerization Step) A 1.5 L autoclave was purged with nitrogen.
700 mL of a solution prepared by mixing 33.3 wt% of butadiene and 66.6 wt% of cyclohexane is prepared in advance, and adjusted at room temperature so that the concentration of water (H ₂ O) becomes 0.4 mmol / L, and vigorously stirred at 700 rpm for 30 minutes. did.
1.75 ml of a cyclohexane solution (1 mol / L) of triethylaluminum (TEA) was added, and the mixture was stirred at room temperature for 2 minutes. Further, neodymium versatate (Nd (V
er) ₃ ) n-heptane solution (0.1 mol / L)
0.35 ml was added and stirred at room temperature for 2 minutes. 50 ℃
Then, 14 ml of a toluene solution (5 mmol / L) of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Borate) was added to initiate polymerization, and polymerization was performed at 50 ° C. for 25 minutes.

(B) Production of Component (Low Molecular Weight Polybutadiene) (Second Polymerization Step) Following the production of component (A), cyclohexane solution (1 mol / L) of diisobutylaluminum hydride (DIBAL-H) at 50 ° C. 5 ml, 0.72 ml of n-heptane solution (0.1 mol / L) of neodymium versatate (Nd (Ver) ₃ ), cyclohexane solution (1 mol / L) of triethylaluminum (TEA)
3.5 ml of triphenylcarbenium tetrakis (pentafluorophenyl) borate (B
orate) toluene solution (5 mmol / L) 20 m
1 was added and polymerized for 10 minutes. The polymerization was stopped by adding 5 mL of an ethanol / heptane (1/1) solution containing an antioxidant. After releasing the pressure inside the autoclave, the polymerization solution was poured into ethanol to recover polybutadiene.
Next, the recovered polybutadiene was vacuum dried at 50 ° C. for 6 hours. The polymerization results are shown in Tables 8-9.

[0076]

[Table 6]

[0077]

[Table 7]

[0078]

[Table 8]

[0079]

[Table 9]

According to the present invention, polybutadiene comprising a specific high molecular weight polybutadiene and a specific low molecular weight polybutadiene can be obtained with high activity using a rare earth metal compound as a catalyst.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J002 AC03W AC03X 4J015 DA04 DA05 DA14 4J028 AA02A AB00A AC49A BA00A BA02B BB00A BB02B BC15B BC16B BC17B BC19B BC27B CA32C CB65C CB86C CB87C CB94 EC02 GA01 GA03 FA02 FA08 FA09

Claims (5)

[Claims] 1. A polybutadiene comprising the following components (A) and (B). (A) A weight average molecular weight (Mw) of 70 produced by using a rare earth metal compound having an atomic number of 57 or more and 71 or less as measured by gel permeation chromatography (GPC).
Polybutadiene of 10,000 to 3 million. (B) a weight average molecular weight (Mw) of 5 produced by using a rare earth metal compound having an atomic number of 57 or more and 71 or less as a catalyst and measured by gel permeation chromatography (GPC);
Polybutadiene of 1,000 to 70,000. 2. The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of all the polymers is 15 to 100. Polybutadiene. 3. The component (A) according to claim 1, wherein a catalyst system comprising a rare earth metal compound having an atomic number of 57 to 71, an organoaluminum compound, and water is used in the first polymerization step. And then, in the second polymerization step, producing the component (B) according to claim 1 using a catalyst system mainly comprising a rare earth metal compound having an atomic number of 57 to 71, an organoaluminum compound, and water. The method for producing polybutadiene according to claim 1 or 2, 4. The method for producing polybutadiene according to claim 3, wherein an ionic compound comprising a non-coordinating anion and a cation is used in combination in the catalyst system. 5. A component constituting a catalyst system in the second polymerization step,
The method for producing polybutadiene according to claim 3, wherein at least one component selected from water and a butadiene monomer is additionally added.