JP2000226409A - A method for producing trans-1,4-polybutadiene. - Google Patents

Abstract

(57) [Problem] To provide a method for producing trans-1,4-polybutadiene using a supported catalyst. SOLUTION: (A) a vanadium compound, (B) an organic metal compound belonging to Group 1 to 3 of the periodic table, and a carrier produced by contact-treating an inorganic oxide and an alkylaluminum compound.
And (C) a process for producing trans-1,4-polybutadiene, which comprises polymerizing butadiene using a catalyst carrying a mixture of butadiene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing trans-1,4-polybutadiene using a supported catalyst.

[0002]

2. Description of the Related Art It is known that a polymer having various microstructures can be obtained from polybutadiene by a polymerization catalyst. In particular, as described in JP-A-9-268208 and JP-A-9-272861, polybutadiene having a trans-1,4-structure as a main structure is a catalyst system comprising a vanadium compound and an organometallic compound. The polymer produced by polymerization has a large latent heat due to crystal transition, and is expected to be applied to heat storage materials and the like. The method using a supported catalyst as a polymerization catalyst can be applied to a gas phase polymerization method using no solvent. The gas phase polymerization method has an advantage that the solvent does not need to be removed from the produced polymer as compared with the solution polymerization method, and post-treatment such as drainage is simplified. Gas phase polymerization has already been industrialized as a method for producing various polyolefins such as polyethylene and polypropylene.

Further, elastomers such as polybutadiene are also disclosed in, for example, JP-A-3-217402,
JP-A-3-106911, JP-A-7-16581
No. 1 discloses a production method by gas phase polymerization. When a homogeneous catalyst typified by a metallocene catalyst is used in a gas phase polymerization process, a catalyst supported on some carrier is usually used. As a method of supporting a metallocene-based compound component and a catalyst system using methylalumoxane as a co-catalyst on silica gel, JP-A-2-170805, JP-A-2-503687, and JP-A-3-501.
No. 869, JP-A-3-502207 and the like.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing trans-1,4-polybutadiene using a supported catalyst.

[0005]

According to the present invention, a carrier produced by contacting an inorganic oxide and an alkylaluminum compound is provided with (A) a vanadium compound, and (B) a first compound of the periodic table.
The present invention relates to a method for producing trans-1,4-polybutadiene, which comprises polymerizing butadiene using a catalyst supporting a mixture comprising a group III-III organometallic compound and (C) butadiene.

[0006] The present invention also relates to the method for producing trans-1,4-polybutadiene according to claim 1, wherein butadiene is subjected to gas phase polymerization using the catalyst.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The inorganic oxide used in the present invention includes silica, alumina, magnesia, titania, zirconia, calcia and the like. These inorganic oxides have an average particle diameter of 5 to 150 μm and a specific surface area of 2 μm.
８００800 m ² / g of porous fine particles are preferable.
It can be used after heat treatment at 0 to 800 ° C.

[0008] The above-mentioned inorganic oxide is contact-treated with alkylaluminum to produce a carrier.

The above treatment is preferably carried out in a substantially anhydrous state. For example, a method of suspending an inorganic oxide which has been heated and dried in an inert gas stream, for example, at 150 to 250 ° C. for 2 to 10 hours, in a dehydrated inert solvent, adding alkyl aluminum, and subjecting it to a contact reaction for a predetermined time. No.

[0010] Examples of the inert gas include nitrogen and argon. Examples of the inert solvent include aromatic hydrocarbons such as toluene and benzene, and linear or cyclic aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, and cyclohexane.

Examples of the above-mentioned alkyl aluminum include alkyl aluminum halide compounds, alkyl aluminum hydride compounds, and trialkyl aluminum compounds. Examples of the alkylaluminum halide compound include dimethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride, and ethylaluminum dichloride. Examples of the hydrogenated organometallic compound include diethyl aluminum hydride and sesquiethyl aluminum hydride. Examples of the trialkylaluminum compound include trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum.

The amount of the aluminum alkyl used is as follows:
The content is preferably in the range of 0.1 to 100 mmol per 1 g of the inorganic oxide.

In the present invention, a catalyst comprising (A) a vanadium compound, (B) an organometallic compound belonging to Groups 1 to 3 of the periodic table, and (C) butadiene is supported on the above-mentioned carrier to form a polymerization catalyst. Is obtained.

The vanadium compound (A) in the above mixture includes vanadium triacetylacetonate, vanadium trichloride THF complex, vanadium oxytrichloride, vanadium naphthenate and the like.

(B) The organometallic compounds of Groups 1 to 3 of the periodic table include organometallic compounds, organometallic halogen compounds,
Hydrogenated organometallic compounds, alumoxanes and the like can be mentioned.

Examples of the organometallic compound include organic lithium compounds such as methyllithium, butyllithium, and phenyllithium; organic magnesium compounds such as dibutylmagnesium; trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. And other organic aluminum compounds.

Examples of the organometallic halogen compound include a Grignard compound such as ethyl magnesium chloride and butyl magnesium chloride, and a halogenated organoaluminum compound such as dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride and ethyl aluminum dichloride. Is mentioned. Examples of the hydrogenated organometallic compound include diethyl aluminum hydride and sesquiethyl aluminum hydride.

Alumoxane is represented by the general formula (-Al (R)
O-) is a linear or cyclic polymer represented by _m (R is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with halogen atoms and / or RO groups. Is the degree of polymerization and is 5 or more, preferably 10 or more). R is methyl,
Ethyl, propyl and isobutyl groups are mentioned, but a methyl group is preferred.

As the component (B), among the above, an organoaluminum compound is preferred, an organoaluminum halide compound is more preferred, and sesquiethylaluminum chloride is more particularly preferred.

The butadiene of the component (C) may contain a small amount of a monomer other than butadiene. Monomers other than butadiene include conjugated dienes such as isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene. ,ethylene,
Acyclic monoolefins such as propylene, butene-1, butene-2, isobutene, pentene-1, 4-methylpentene-1, hexene-1, octene-1, cyclopentene,
Examples include cyclic monoolefins such as cyclohexene and norbornene, aromatic vinyl compounds such as styrene and α-methylstyrene, and non-conjugated diolefins such as dicyclopentadiene, 5-ethylidene-2-norbornene and 1,5-hexadiene.

The amount of each component used in the above mixture is (A)
The component (B) is present in an amount of 1 to 100 per 1 mol of the compound as the component.
It is preferably in the range of 0 mol. Further, the amount of the component (C) is 1 to 100 m per 1 mol of the compound of the component (A).
It is preferably in the range of ol.

The catalyst for polymerization is obtained by supporting the mixture on the above-mentioned carrier. As a supporting method, for example, the above mixture solution dissolved in an inert solvent is brought into contact with a carrier in an inert gas atmosphere, and after stirring for a predetermined time,
By separating and drying, a supported catalyst powder having good fluidity can be obtained.

The polymerization catalyst of the present invention comprises trans-1,4
-It can be suitably used for production of polybutadiene.
As the polymerization method, a gas phase method, a slurry method, a solution method and the like can be adopted. Among them, it can be suitably used in a gas phase polymerization method.

The gas phase polymerization method can be applied to continuous gas phase polymerization, semi-batch type gas phase polymerization, batch type gas phase polymerization and the like. As the gas phase polymerization tank, a stirring reaction tank, a paddle type reaction tank, a rotary reaction tank, a fluidized bed reaction tank, or the like, or a combination thereof can be used.

In the case of production by continuous gas-phase fluidized-bed polymerization, a catalyst component, a monomer, an inert gas, an additive and the like are continuously introduced into a fluidized-bed reactor, and catalyst particles and polymer particles are dispersed by a gas-phase component. The polymerization is carried out while flowing. In continuous polymerization, the resulting polymer is continuously or intermittently withdrawn from the reactor, and unreacted monomer gas is continuously discharged from the fluidized bed reactor. The unreacted monomer gas is supplied to the fluidized bed reactor through a heat exchanger and a compressor through a circulation line, where the monomer and the like are appropriately replenished.

The circulating gas may contain an inert gas such as hydrogen or nitrogen as a molecular weight regulator.

In the gas-phase polymerization method of the present invention, the gas-phase reactant may contain a saturated hydrocarbon, preferably a saturated hydrocarbon having 4 to 6 carbon atoms. Specific compounds include n-butane, i-butane, n-pentane, i-pentane, hexanes and mixtures thereof.

In the gas phase polymerization, a polymerization bed may be used to assist dispersion of the catalyst. The polymerization bed is not particularly limited as long as it does not cause catalyst poisoning, but a spherical polymer having good fluidity is preferably used. The polymerization bed is preferably preliminarily subjected to preliminary treatment such as dehydration and drying, deoxygenation, and organic aluminum treatment.

The gas phase polymerization is usually carried out at a temperature of -100 to 10
0 ° C., preferably −50 to 80 ° C.

[0030]

The catalyst obtained by supporting the catalyst component on the catalyst carrier obtained in the present invention exhibits high polymerization activity in the production of trans-1,4-polybutadiene.

[0031]

Example 1 (Preparation of carrier) Porous silica (CariACT P-1 manufactured by Fuji Silysia) previously dehydrated and dried at 200 ° C. for 6 hours under a nitrogen stream.
0) 10 g was placed in a flask purged with nitrogen, 87.5 mL of a dehydrated toluene solution was added thereto, and 12.5 mL of a 2M toluene solution of sesquiethylaluminum chloride was further added thereto, followed by reaction at 50 ° C. for 1 hour. After the reaction, the suspension was returned to room temperature, filtered, and dried under reduced pressure at room temperature for 2 hours.

Example 2 (Preparation of catalyst) To a flask equipped with a three-way cock and a stirring device and purged with nitrogen, 65 mL of toluene, 8.6 mL of a 0.29 mM toluene solution of butadiene (2.5 mL of butadiene), and vanadium triacetylacetonate were used. -(V (acac) ₃ ) 0.03
7.58 mL of a toluene solution of mM (vanadium 0.25
mmol) and 8.75 mL (37.5 mmol of aluminum) of a 2M toluene solution of sesquiethylaluminum chloride was added to the flask charged with the carrier obtained above under a nitrogen stream.
After stirring at room temperature for 1 hour, the solution was separated by filtration and dried under reduced pressure to obtain a catalyst solid. The vanadium metal content in this catalyst was 0.039 wt%, 0.0076 mmol / g
-Cat. Met. The aluminum metal content in this catalyst was 6.7 wt%, and 2.48007
6 mmol / g-cat. Met.

(Polymerization of butadiene) A catalyst injector having an upper part closed by a three-way stopcock and a lower part closed by a two-way stopcock, an introduction pipe for sending the catalyst to the flask, and a three-way stopcock for introducing gaseous butadiene are provided. A rotary evaporator flask connected to a gas butadiene line, a nitrogen line, and a vacuum line was used. After replacing the inside of the rotary evaporator with nitrogen, the above-mentioned supported catalyst is placed under a nitrogen stream,
It was introduced into the flask by injection with nitrogen. 1 mm device
The flask was rotated while cooling in an ice bath while evacuating to -Hg. At this time, the temperature of the ice bath was 2 ° C. After sufficiently reducing the pressure, the pressure reducing line is closed and the butadiene flask line is opened to open gaseous dry butadiene (dew point -4.4 ° C).
Was introduced. The polymerization was carried out at 2 ° C. for 120 minutes at normal pressure. The micro content of 3.4 g of the polybutadiene obtained is 95.8.
% And a vinyl content of 4.2%.

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Claims (2)

[Claims] 1. A support prepared by contacting an inorganic oxide with an alkylaluminum compound, comprising: (A) a vanadium compound, (B) an organometallic compound of Groups 1 to 3 of the periodic table, and (C) butadiene. A method for producing trans-1,4-polybutadiene, comprising polymerizing butadiene using a catalyst carrying a mixture of the following. 2. The trans-polymer according to claim 1, wherein butadiene is subjected to gas-phase polymerization using the catalyst.
A method for producing 1,4-polybutadiene.