JP2000017013A - Preparation of conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having an excellent stereoregularity in a high activity by using a catalyst obtained from a cobalt compound other than phosphine complexes, a specific ionic compound, an organometallic compound and water in which the molar ratio of the organometallic compound to water is specified. SOLUTION: (A) An organometallic compound of an element of Groups I to III in the Periodic table and (B) water are mixed in a molar ratio of component A to component B of 1:0.01-1:2 in an inert solvent at -50 to 80 deg.C for 0.01-24 hours. (C) A cobalt compound other than phosphine complexes and (D) an ionic compound of a non-coordinating anion and a cation are added to this mixture such that the molar ratio of component C to component D is 1:0.1-1:10 and the molar ratio of component C to component A is 1:0.1-1:1000 to obtain a catalyst. In the presence of this catalyst, a conjugated diene compound is polymerized at -30 to 150 deg.C, preferably at 30 to 100 deg.C for 1 minute to 12 hours to obtain a conjugated diene polymer having a cis structure content of 98 wt.% or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a conjugated diene polymer using a polymerization catalyst comprising a cobalt compound.

[0002]

2. Description of the Related Art Numerous proposals have been made on polymerization catalysts for conjugated dienes such as 1,3-butadiene and isoprene, and some of them have been industrialized. For example, as a method for producing a conjugated diene polymer having a high cis-1,4 structure, a combination of a compound such as titanium, cobalt, nickel, neodymium and an organic aluminum is often used.

As a method for producing a conjugated diene polymer having a high cis-1,4 structure using a cobalt compound, Japanese Patent Publication No.
No. 243 discloses a process for producing high cis-1,4 polybutadiene using a catalyst comprising a compound of cobalt and / or nickel, an acidic metal halide, an organoaluminum compound, and 2 to 50 parts of water per million parts of the reaction mixture. ing. Also, Polym. Commun., Vol. 32, 514 (199
1) discloses a method for polymerizing 1,3-butadiene using a catalyst comprising cobalt acetylacetonate and methylalumoxane.

On the other hand, as a method for producing a conjugated diene polymer using a boron compound, JP-A-7-268013 discloses a method for preparing a rare earth salt, a metal compound belonging to Groups 1 to 3 of the periodic table, and a trivalent boron organometallic derivative compound. A catalyst for producing a polydiolefin is disclosed. Also, Japanese Patent Application Laid-Open No. 7-766
05 is a cobalt phosphine compound, an organoaluminum compound modified with alumoxane or water, and trivalent and
A method for producing a butadiene-based polymer having a high vinyl bond content (a vinyl content of about 70% or more) using a catalyst comprising a tetravalent boron compound is disclosed. The above prior arts have problems such as low polymerization activity or high gel content in the resulting conjugated diene polymer.

[0005]

SUMMARY OF THE INVENTION The present invention provides a method for producing a conjugated diene polymer having excellent stereoregularity with high activity using a novel cobalt-based catalyst.

[0006]

The present invention provides (A) a cobalt compound (excluding a phosphine complex), (B) an ionic compound of a non-coordinating anion and a cation, and (C) a first compound of the periodic table. An organometallic compound of an element of group III to III, and (D) water (provided that (C) :( D) = 1: 0.01 to 2 (molar ratio)
It is. The present invention relates to a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound using a catalyst obtained from the above.

Further, the present invention provides (A) a cobalt compound (excluding a phosphine complex), (B) an ionic compound of a non-coordinating anion and a cation, and (C) a first compound of the periodic table.
(D) water (however,
(C) :( D) = 1: 0.01 to 2 (molar ratio). The present invention relates to a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound using a catalyst comprising

As the cobalt compound as the component (A) of the catalyst system of the present invention, a cobalt salt or complex is preferably used. Particularly preferred are cobalt salts such as cobalt chloride, cobalt bromide, cobalt nitrate, cobalt octylate, cobalt naphthenate, cobalt acetate, cobalt malonate, and bisacetylacetonate, trisacetylacetonate, and ethyl acetoacetate of cobalt. Organic base complexes such as ester cobalt, pyridine complexes and picoline complexes,
Alternatively, an ethyl alcohol complex may be used.

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 (fluoro) Phenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ Tris (pentafluorophenyl), phenyl] borate, torideca hydride 7,8-dicarboxylic Bowne Deca Bole -
And the like.

On the other hand, examples of the cation include a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl 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-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 the ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and 1,1′-dimethylferrocenium Tetrakis (pentafluorophenyl) borate and the like are preferred.

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

As the organometallic compound of the Group 1 to 3 elements of the Periodic Table as the component (C) of the catalyst system of the present invention, organolithium, organomagnesium, organoaluminum and the like are used. Preferred among these compounds are trialkylaluminum, dialkylaluminum chloride, dialkylaluminum bromide, alkylaluminum sesquichloride, alkylaluminum sesquibromide and the like. Specific compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum.

Further, organic aluminum halides such as dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, etc .; Also included are organoaluminum hydride compounds. Two or more of these organoaluminum compounds can be used in combination.

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 10, more preferably from 1: 0.2. ~ 5
It is.

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

The molar ratio of component (C) to component (D) is
1: 0.01 to 2, preferably 1: 0.01 to
1.5, particularly preferably 1: 0.1 to 1.5.

The order of addition of the catalyst components is not particularly limited, but may be, for example, in the following order.

In an inert organic solvent, the component (D) is added in the presence or absence of the conjugated diene compound monomer to be polymerized, the component (C) is added, and then the components (A) and (B) are added. Are added in any order.

After adding the components (D) and (C) in an inert organic solvent in the presence or absence of the conjugated diene compound monomer to be polymerized, the components (A) and (B) are optionally added. Add in order.

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

As the aging conditions, the components (C) and (D) are mixed in an inert solvent in the presence or absence of the conjugated diene compound monomer to be polymerized. Aging temperature is -50
To 80 ° C, preferably -10 to 50 ° C, and the aging time is 0.01 to 24 hours, preferably 0.05 to 5 hours.

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

The conjugated diene compound monomers include 1,1
3-butadiene, isoprene, 1,3-pentadiene,
Examples thereof include 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene. Among them, a conjugated diene compound monomer containing 1,3-butadiene as a main component is preferable.

These monomer components may be used alone or in combination of two or more.

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,
Butene-1, butene-2, isobutene, pentene-1,
4-methylpentene-1, hexene-1, octene-1
Acyclic monoolefins such as cyclopentene, cyclohexene, norbornene, and / or the like; and / or
Alternatively, a small amount of an aromatic vinyl compound such as styrene or α-methylstyrene, a non-conjugated diolefin such as dicyclopentadiene, 5-ethylidene-2-norbornene, and 1,5-hexadiene may be contained.

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. Solvents for solution polymerization include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; Olefinic hydrocarbons such as -butene, cis-2-butene, trans-2-butene,
Examples include hydrocarbon solvents such as mineral spirits, solvent naphtha, and kerosene, and halogenated hydrocarbon solvents such as methylene chloride.

Among them, toluene, cyclohexane, a mixture of cis-2-butene and trans-2-butene, and the like are preferably used.

The polymerization temperature is preferably in the range of -30 to 150 ° C, particularly preferably in the range of 30 to 100 ° C. The polymerization time is preferably in the range of 1 minute to 12 hours, particularly preferably 5 minutes to 5 hours.

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.

When a conjugated diene is polymerized by using the catalyst of the present invention, the microstructure of the obtained polymer varies depending on the catalyst and polymerization conditions, but in particular, the ratio of component (C) to component (D) is changed. As a result, a conjugated diene polymer having a cis structure content of preferably 98% by weight or more can be obtained with high activity.

[0036]

EXAMPLES In the examples, 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 determined by GPC using polystyrene as a standard substance.

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

Example 1 The inside of an autoclave having an internal volume of 1.5 L was replaced with nitrogen, and 500 ml of cyclohexane and 155 g of butadiene were charged and stirred at 700 rpm. The water content of the solution measured by Karl Fischer was 4 ppm (0.12 mmol). After adjusting the temperature of the solution to 25 ° C., 0.75 ml of a toluene solution of triethylaluminum (TEA) (0.15 mol / l) was added.
After 5 minutes, a solution of cobalt octenoate (Co (Oct) ₂ ) in toluene
(0.004 mol / l) 1.5 ml was added. After 5 minutes, raise the solution temperature to 65
At a temperature of ° C., 2.4 ml of a toluene solution (0.005 mol / l) of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) was added to initiate polymerization. 30
Minutes later, an ethanol / heptane (1/1) solution containing an antioxidant
5.0 ml was added to stop the polymerization. After releasing the pressure inside the autoclave, the polymerization liquid was poured into ethanol to recover polybutadiene. Then, the recovered polybutadiene was added to 50
Vacuum dried at ℃ for 6 hours. Table 1 shows the polymerization conditions, and Tables 2 and 3 show the results of polymerization and the results of analysis of the obtained polybutadiene.

(Examples 2 and 3) The same procedure as in Example 1 was carried out except that the amount of TEA added was changed as shown in Table 1. Tables 2 and 3 show the results of polymerization and the results of analysis of the obtained polybutadiene.

(Examples 4 to 9) The same procedure as in Example 1 was carried out except that TEA was triisobutylaluminum (TIBA) and the amount of TIBA added was as shown in Table 1. Tables 2 and 3 show the results of polymerization and the results of analysis of the obtained polybutadiene.

Examples 10-12 TEA was diisobutylaluminum hydride (DIBALH), and the amount of DIBALH added was
The procedure was performed in the same manner as in Example 1 except that the conditions shown in 1 were used. Tables 2 and 3 show the results of polymerization and the results of analysis of the obtained polybutadiene.

Example 13 The inside of an autoclave having an internal volume of 1.5 L was replaced with nitrogen, 500 ml of cyclohexane and 155 g of butadiene were charged, and the mixture was stirred at 700 rpm. Then water (H ₂ O) 1.98
μl was added. The water content of the solution measured by Karl Fischer was 7.5 ppm (0.23 mmol). Solution temperature 25
After the temperature was raised to 3.0 ° C., 3.0 ml of a toluene solution of TIBA (0.15 mol / l) was added. Five minutes later, 1.5 ml of a solution of cobalt octenoate (Co (Oct) ₂ ) in toluene (0.004 mol / l) was added. After 5 minutes, the temperature of the solution was set to 65 ° C., and a toluene solution of Ph ₃ CB (C ₆ F ₅ ) ₄ (0.005 mol
(l / l) 2.4 ml was added to initiate polymerization. After 30 minutes, 5.0 ml of an ethanol / heptane (1/1) solution containing an antioxidant was added to terminate the polymerization. After releasing the pressure inside the autoclave, the polymerization liquid was poured into ethanol to recover polybutadiene. Next, the recovered polybutadiene was vacuum dried at 50 ° C. for 6 hours. Table 1 shows the polymerization conditions, and Tables 2 and 3 show the results of polymerization and the results of analysis of the obtained polybutadiene.

(Examples 14 to 16) The same procedures as in Example 13 were carried out except that the amount of H ₂ O added was changed to the conditions shown in Table 1. Tables 2 and 3 show the results of polymerization and the results of analysis of the obtained polybutadiene.

(Comparative Example 1) The inside of a 1.5 L autoclave was replaced with nitrogen, and 500 ml of cyclohexane and 155 g of butadiene were charged and stirred at 700 rpm. The water content of the solution measured by Karl Fischer was 5 ppm (0.15 mmol). After the temperature of the solution was adjusted to 10 ° C., 1.5 ml of a toluene solution (1.0 mol / l) of triethylaluminum (TEA) was added. Five
After a minute, 3.75 ml of a toluene solution (0.02 mol / l) of dibromobis (triphenylphosphine) cobalt (CoBr _2. (PPh ₃ ) ₂ ) was added. After 5 minutes, a solution of Ph ₃ CB (C ₆ F ₅ ) ₄ in toluene (0.005mo
(l / l) 30 ml was added to initiate polymerization. 30 minutes later, 5.0 ml of an ethanol / heptane (1/1) solution containing an antioxidant was added,
The polymerization was stopped. 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. Table 1 shows the polymerization conditions, and Tables 2 and 3 show the results of polymerization and the results of analysis of the obtained polybutadiene.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

According to the present invention, a controlled conjugated diene polymer can be produced with high activity using a novel cobalt compound-based polymerization catalyst.

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Claims (2)

[Claims] (A) a cobalt compound (excluding a phosphine complex); (B) an ionic compound of a non-coordinating anion and a cation; and (C) an organic metal of a Group 1 to 3 element of the periodic table. Compound and (D) water (provided that (C): (D)
= 1: 0.01 to 2 (molar ratio). ). A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene compound using the catalyst obtained from the above). (A) a cobalt compound (excluding a phosphine complex), (B) an ionic compound of a non-coordinating anion and a cation, and (C) an organic metal of an element belonging to Groups 1 to 3 of the periodic table. Compound and (D) water (provided that (C): (D)
= 1: 0.01 to 2 (molar ratio). A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene compound using a catalyst comprising