JPH11130812A - Catalyst and production of conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new catalyst system of an iron compound and to provide a method for producing a controlled conjugated diene polymer with a high activity. SOLUTION: This catalyst is obtained from (A) an iron compound, (B) an ionic compound of a noncoordinating anion and a cation and (C) an organometallic compound of a group I to III element of the periodic table. The method for producing a conjugated diene polymer comprises polymerizing a conjugated diene compound by using the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel catalyst and a method for producing a conjugated diene polymer using a novel polymerization catalyst.

[0002]

2. Description of the Related Art Numerous proposals have been made on polymerization catalysts for conjugated dienes such as butadiene and isoprene, and polymers having various microstructures have been made possible, and some of them have been industrialized.

As a method for obtaining a conjugated diolefin polymer such as polybutadiene having a high cis-1,4 structure, a catalyst comprising a combination of a transition metal compound and an organic metal is known. Combination of compound and organoaluminum, nickel compound, 3
A catalyst composed of a combination of boron fluoride and an organoaluminum compound is often used.

On the other hand, as a butadiene polymerization catalyst using an iron compound, JP-B-35-9439 discloses FeB catalyst.
l ₃ catalyst system comprising -AlEt ₂ Cl, JP-B-38-94
No. 43 discloses a catalyst system comprising FeCl ₃ -AlCl ₃ -thiophene, and Japanese Patent Publication No. 44-2234 discloses a catalyst system comprising
Cl ₃ -AlRX ₂ - catalyst system such as is disclosed consisting of pyridine. In addition, Polymer Prepint
s, Japan 43, No. 6,1708 (199
4) reports a catalyst system comprising Fe (acac) ₃ -alumoxane.

However, these catalyst systems have insufficient polymerization activity.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel iron compound catalyst system and a method for producing a controlled conjugated diene polymer with high activity using the polymerization catalyst.

[0007]

The present invention provides (A) an iron compound, (B) an ionic compound of a non-coordinating anion and a cation, and (C) an ionic compound of a group I to III element of the periodic table. It relates to a catalyst obtained from an organometallic compound.

Further, the present invention relates to (A) an iron compound, (B)
The present invention relates to a catalyst comprising an ionic compound of a non-coordinating anion and a cation, and (C) an organometallic compound of an element from Groups I to III of the periodic table.

[0009] The present invention also relates to a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound using the above catalyst.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The iron compound as the component (A) of the catalyst system of the present invention includes iron metal carboxylate, alkoxide, β-diketone complex, phosphate and phosphite. Among them, carboxylate and phosphate are preferable,
Carboxylates are particularly preferred.

The carboxylate of iron metal has the general formula (RCO
₂ ) ₃ Fe (wherein, R is a hydrocarbon group having 1 to 20 carbon atoms).

R is a saturated or unsaturated alkyl group and is linear, branched or cyclic, and the carboxyl group CO ₂ is bonded to a primary, secondary or tertiary carbon atom. Specifically, octanoic acid, 2-ethyl-hexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid and versatic acid (trade names of shell chemistry, in which a carboxyl group is bonded to a tertiary carbon atom Carboxylic acid). Among them, 2-ethyl-hexanoic acid and versatic acid are preferred.

The alkoxide of iron metal has the general formula (R
O) ₃ Fe (wherein R is the same as described above). Examples of the alkoxy group represented by RO include 2-ethyl-hexylalkoxy, oleylalkoxy, stearylalkoxy, phenoxy and benzylalkoxy groups. Among them, 2-ethyl-hexylalkoxy and benzylalkoxy groups are preferred.

Examples of the iron metal β-diketone complexes include iron metal acetylacetone, benzoylacetone, propionitrileacetone, valerylacetone, and ethylacetylacetone complexes. Among them, acetylacetone and an ethylacetylacetone complex are preferred.

Examples of the iron metal phosphate or phosphite include iron metal bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, bis (p-nonylphenyl) phosphate and phosphorus Bis (polyethylene glycol-p-nonylphenyl) acid, (1-methylheptyl) phosphate (2-ethylhexyl), (2-ethylhexyl) phosphate (p-nonylphenyl), mono-2-ethylhexyl 2-ethylhexylphosphonate 2-Ethylhexylphosphonic acid mono-2-
Nonylphenyl, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-
Nonylphenyl) phosphinic acid, (1-methylheptyl)
Salts such as (2-ethylhexyl) phosphinic acid and (2-ethylhexyl) (p-nonylphenyl) phosphinic acid are exemplified. Of these, salts such as bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, and bis (2-ethylhexyl) phosphinic acid are preferred.

Of the above examples, particularly preferred are iron 2-ethylhexanoate, iron versatate, iron acetylacetonate, and bis (2-ethylhexyl) iron phosphate. Iron acid and iron acetylacetonate are most preferred.

The non-coordinating anion constituting the ionic compound of the non-coordinating anion and the cation of the component (B) of the catalyst system of the present invention includes, for example, tetra (phenyl) borate and tetra (fluorophenyl) ) Borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (Xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, and tridecahydride-7,8-dicarboundecaborate.

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

Specific examples of the carbenium cation include:
Examples include trisubstituted carbenium cations such as triphenylcarbenium cation and trisubstituted phenylcarbenium cation. Specific examples of the tri-substituted phenylcarbenium cation include tri (methylphenyl)
Carbenium cation and tri (dimethylphenyl) carbenium 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-diethylanilinium cation, N, N-2,4,
Examples thereof include N, N-dialkylanilinium cations such as 6-pentamethylanilinium cation, di (i-propyl) ammonium cation, and dialkylammonium cations such as dicyclohexylammonium cation.

Specific examples of the phosphonium cation include:
Examples include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

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

Among the ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) Phenyl) borate and the like are preferred. The ionic compounds may be used alone or in combination of two or more.

The periodic table of the component (C) of the catalyst system of the present invention
Group I to III elements include organoaluminum compounds,
Organic lithium compounds, organic magnesium compounds, organic zinc compounds, organic boron compounds and the like can be mentioned.

Specific compounds include methyllithium, butyllithium, phenyllithium, benzyllithium, neopentyllithium, trimethylsilylmethyllithium, bistrimethylsilylmethyllithium, dibutylmagnesium, dihexylmagnesium, diethylzinc, dimethylzinc, trimethylaluminum, Examples thereof include triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, boron trifluoride, and triphenylboron.

Further, ethyl magnesium chloride,
Organometallic halides such as butylmagnesium chloride, dimethylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, etc .; included. Further, two or more kinds of organometallic compounds can be used in combination.

Alumoxane may be used as the component (C). The alumoxane, be one obtained by contacting an organoaluminum compound and a condensing agent, the general formula (-Al (R ') chain aluminoxane represented by _O-n, or cyclic aluminoxanes and the like. ( R 'is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group. N is the degree of polymerization and is 5 or more, preferably 10 or more). Examples of R ′ include methyl, ethyl, propyl, and isobutyl groups, and among them, a methyl group is preferable, and examples of the organoaluminum compound used as a raw material for aluminoxane include trimethylaluminum, triethylaluminum, and triisobutylaluminum. Alkyl aluminum and mixtures thereof.

Alumoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used.

Examples of the condensing agent include water as a typical one, and any other condensing agent capable of subjecting the trialkylaluminum to a condensation reaction, for example, adsorbed water such as inorganic substances and diol.

The mixing ratio of each catalyst component varies depending on various conditions, but the molar ratio of component (A) to component (B) is preferably from 1: 0.1 to 1:10, and more preferably from 1: 0.2.
1: 5.

The molar ratio of component (A) to component (C) is preferably from 1: 0.1 to 1: 1000, more preferably from 1: 0.1.
It is 1 to 1: 500.

In the present invention, each catalyst component can be supported on an inorganic compound or an organic polymer compound.

The order of addition of the catalyst components is not particularly limited, but can be, for example, in the following order. The component (A) is added to the contact mixture in which the monomer to be polymerized, the component (B) and the component (C) are added in an arbitrary order.

The component (B) and then the component (A) are added to the contact mixture of the monomer to be polymerized and the component (C).

The component (A) and then the component (B) are added to the contact mixture of the monomer to be polymerized and the component (C).

A mixture of the components (A), (B) and (C) in any order is added to the monomer to be polymerized.

Further, each component may be aged in advance and used. Above all, it is preferable to ripen the components (A) and (C).

As the aging conditions, the components (A) and (B) are mixed in an inert solvent in the presence of a conjugated diene. The aging temperature is from 0 to 100 ° C., preferably from 10 to 60 ° C., and the aging time is not particularly limited, but usually 0.5 minutes or more is sufficient and stable for several days.

The monomer that can be polymerized using the catalyst in the present invention is not particularly limited, such as α-olefin, cyclic olefin, and conjugated diene, but conjugated diene compound monomers are particularly preferred.

As the conjugated diene compound monomer, 1,3-
Butadiene, isoprene, 1,3-pentadiene, 2-ethyl
Examples thereof include -1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene. These monomer components may be used alone or in a combination of two or more.

Among them, a conjugated diene compound monomer containing 1,3-butadiene as a main component is preferred.

Here, the conjugated diene compound monomer to be polymerized may be the whole or a part of the monomer. In the case of some of the monomers, the above contact mixture can be mixed with the remaining monomer or the remaining monomer solution. In addition to conjugated dienes, ethylene, propylene,
Acyclic monoolefins such as butene-1, butene-2, isobutene, pentene-1, 4-methylpentene-1, hexene-1, and octene-1, cyclic monoolefins such as cyclopentene, cyclohexene and norbornene, and / or styrene Vinyl compounds such as and α-methylstyrene, dicyclopentadiene, 5-ethylidene-2-norbornene, 1,5-
It may contain a small amount of non-conjugated diolefin such as hexadiene.

The polymerization method is not particularly limited, and bulk polymerization (bulk polymerization) using 1,3-butadiene itself as a polymerization solvent or solution polymerization can be applied. Examples of the solvent in the solution polymerization include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic hydrocarbons such as n-hexane, butane, heptane, and pentane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; -Butene, cis-2-butene,
Examples thereof include olefinic hydrocarbons such as trans-2-butene, hydrocarbon solvents such as mineral spirits, solvent naphtha, and kerosene, and halogenated hydrocarbon solvents such as methylene chloride.

Among them, toluene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene is preferably used.

The polymerization temperature is preferably in the range of -100 to 100 ° C, particularly preferably in the range of -50 to 60 ° C. Polymerization time is 10
A range of minutes to 12 hours is preferred, and 30 minutes to 6 hours is particularly preferred.

After the polymerization is carried out for a predetermined time, the pressure inside the polymerization tank is released as required, and post-treatments such as washing and drying steps are performed.

By using the polymerization method of the present invention, the 1,2-structure content is 4 to 30%, preferably 5 to 25%.
%, More preferably 5 to 20%, cis-1,4-structure content of 65 to 95%, preferably 70 to 95%, trans-1,4-structure content of 5% or less, preferably 4.5% The following polybutadiene can be produced.

[0048]

EXAMPLES In the examples, the term "catalytic activity" means that the polymerization time is 1 per 1 mmol of iron metal of the iron compound used in the polymerization reaction.
Polymer yield per hour (g).

The molecular weight distribution was evaluated by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained from GPC using polystyrene as a standard substance.

The microstructure was determined by infrared absorption spectroscopy. Cis 740cm ^-1 , transformer 967cm ^-1 ,
The microstructure was calculated from the absorption intensity ratio of 1,2-910 cm ^-1 .

Example 1 2.87 mol of butadiene (155
1.25 mmol of triethylaluminum (TEA) as component (C) in 750 mL of dehydrated cyclohexane solution containing g)
, Iron acetylacetonate (Fe (aca) as a component (A)
c) ₃ ) 0.025 mmol, and 0.05 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) as the component (B) were added as a toluene solution, and the polymerization temperature was increased to 40%. Polymerization was performed at 0.5 ° C. for 0.5 hour. After the polymerization, an unreacted part of 1,3-butadiene was released from the autoclave by adding an antioxidant. The polymerization solution is poured into ethanol, and the polymer is precipitated, washed, filtered,
Dried. Tables 1 and 2 show the polymerization conditions and the polymerization results.

(Examples 2 and 3) The same procedure as in Example 1 was performed except that the conditions shown in Table 1 were used. Tables 2 and 3 show the polymerization results.

Example 4 The same procedure as in Example 1 was carried out except that triethylaluminum was replaced with triisobutylaluminum (TIBA). Tables 1, 2 and 3 show the polymerization conditions and the polymerization results.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

According to the present invention, a novel iron compound catalyst system and a method for producing a controlled conjugated diene polymer with high activity using the polymerization catalyst can be provided.

Claims (3)

[Claims] 1. A catalyst obtained from (A) an iron compound, (B) an ionic compound of a non-coordinating anion and a cation, and (C) an organometallic compound of an element from Groups I to III of the periodic table. 2. A catalyst comprising (A) an iron compound, (B) an ionic compound of a non-coordinating anion and a cation, and (C) an organometallic compound of an element from Groups I to III of the periodic table. 3. A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene compound using the catalyst according to claim 1. Description: