JP2586561B2 - Method for producing diene compound polymer - Google Patents

Description

The present invention relates to a method for producing a diene compound polymer using a diene compound polymerization catalyst.

More specifically, the present invention relates to a method for producing a diene compound polymer using a catalyst comprising a transition metal compound and an alumoxane.

<Prior Art> Conventionally, as a method for producing a diene compound polymer, various methods such as radical polymerization, cationic polymerization, anionic polymerization, and coordination anionic polymerization using a Ziegler-Natta catalyst are known. As the Siegler-Natta catalyst system, a catalyst system comprising a solid titanium compound based on titanium trichloride and an organic aluminum compound or a catalyst system comprising a solid supporting magnesium chloride titanium tetrachloride and an organic aluminum compound is generally known.

<Problems to be Solved by the Invention> Under such current situation, the problem to be solved by the present invention is that a diene compound polymer using a novel diene compound polymerization catalyst instead of the solid transition metal catalyst system is used. It is to provide a manufacturing method.

<Means for Solving the Problems> The present invention relates to a method for obtaining a diene compound polymer with high efficiency using a catalyst comprising a transition metal compound having a specific structure and an aluminoxane.

That is, the present invention provides: (1) a catalyst component (A): a general formula M (R) _l (OR ′) _m X
_{n (l + m)} (wherein, M is each atom of titanium, zirconium, hafnium or vanadium, R and R 'are hydrocarbon groups having 1 to 20 carbon atoms, X
Represents a halogen atom. l, m, n are l ≧ 0, m> 0, n
− (L + m) ≧ 0. n corresponds to the valence of the transition metal. ), A catalyst component (B): an aluminoxane obtained by reacting a trialkylaluminum with water, and (2) a catalyst component (A): a general formula M (R) _l (OR ' ) _M X
_{n (l + m)} (wherein, M represents each atom of titanium, zirconium, hafnium or vanadium, R and R 'represent a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom. l, m, n Is l ≧ 0, m>
0, n- (l + m) ≧ 0. n corresponds to the valence of the transition metal. ), A catalyst component (B): an aluminoxane obtained by reacting a trialkylaluminum with water, and a catalyst component (C): a general formula I, II, III, IV, V or VI HO-R ″-(Y) _n′- R-OH (I) (Wherein R ″, R is a hydrocarbon group having 1 to 20 carbon atoms, Y is a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —S—S—, (R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)
Represents Here, R ¹ , R ² , R ³ and R ⁴ represent a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a nitro group, a nitrile group, a hydrocarboxy group or a halogen atom. In this case, R ¹ , R ² ,
R ³ and R ⁴ may be the same or different. n '
Is an integer of 0 or 1 or more and represents the number of repetitions of the unit Y. Y, y ', y ", y, z, z', z" and z represent the number of substituents bonded to the aromatic ring. y, y ', z and z' represent 0 or an integer from 1 to 4, y ", z" represents 0 or an integer from 1 to 2, and y, z represents 0 or an integer from 1 to 3. The present invention relates to a method for producing a diene compound polymer using the catalyst system of (1) or (2) above.

 Hereinafter, the contents of the present invention will be described in detail.

General formula M used as catalyst component (A) in the present invention
In the transition metal compound represented by (R) _l (OR ′) _m X _{n- (l + m)} , specific examples of M include titanium, zirconium,
Examples include hafnium and vanadium, and titanium and zirconium give particularly favorable results.

R or R 'is a hydrocarbon group having 1 to 20 carbon atoms, and among them, an alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms can be preferably used.

Specific examples of R or R 'include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-heptyl, n
Alkyl groups such as -octyl, n-decyl and n-dodecyl; aryl groups such as phenyl and naphthyl; cycloalkyl groups such as cyclohexyl and cyclopentyl; allyl groups such as propenyl; and aralkyl groups such as benzyl.

Among them, R is preferably a methyl, ethyl, phenyl, benzyl group and the like, and R 'is preferably an alkyl group such as n-propyl, isopropyl, n-butyl and t-butyl and an aryl group such as phenyl. .

Examples of the halogen atom represented by X include chlorine, bromine and iodine. Particularly, chlorine is preferably used.

l, m, n are, for the above catalyst system (1), l ≧ 0, m> 0, n−
(L + m) ≧ 0.

On the other hand, in the case of the catalyst system (2), l ≧ 0, m> 0, n−
(L + m) ≧ 0. That is, the catalyst system (2)
In a system comprising a catalyst component (A) which is a transition metal compound of the following, a catalyst component (B) which is an aluminoxane, and a catalyst component (C) which is an organic compound having at least two hydroxyl groups, for example, m = 0 Titanium tetrachloride and zirconium tetrachloride can be used, but the catalyst component (A) of the catalyst system (1)
And a catalyst component (B), a hydrocarboxy group is essential.

Specific examples of the catalyst component (A) include titanium tetrachloride, zirconium tetrachloride, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, diphenoxy titanium dichloride, and dinaphthoxy titanium dichloride. , Tetraisopropoxyzirconium, tetra-n-butoxyzirconium or tetra-t
-Butoxyzirconium and the like.

Aluminoxane catalyst component (B) is a polymer of an aluminum compound of the general formula ^{R a (Al (R a)} O) nAlR a 2 ( linear compound) and / or ^{(Al (R a) O)} n ₊₁ (cyclic compound). In the formula, ^Ra is, for example, an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and the like, and particularly preferably a methyl and ethyl group. n is an integer of 1 or more,
Particularly, 1 to 20 is preferable.

Aluminoxane can be obtained by various general methods. For example, it can be synthesized by bringing a trialkylaluminum dissolved in an appropriate hydrocarbon solvent into contact with water. In this case, it is preferable that the water is brought into contact with the aluminum compound under mild conditions. Further, there are a method in which water vapor is brought into contact with the solution of the aluminum compound, and a method in which an organic solvent saturated with water is gradually dropped into the solution of the aluminum compound. Alternatively, copper sulfate hydrate (CuSO ₄ · 5H ₂ O) or aluminum sulfate hydrate _{(Al 2 (SO 4) 3} · 18H 2
There is also a method of reacting O) with an aluminum compound.

Usually, when synthesizing aluminoxane from trimethylaluminum and water, a linear compound and a cyclic compound are obtained at the same time. The reaction molar ratio is preferably selected such that water is equimolar to 1 mol of the aluminum compound.

General formula HO-R "-(Y) _n'- R-OH (I) used as a contact component (C) in the present invention In the compound represented by the formula, R ″, R is a hydrocarbon group having 1 to 20 carbon atoms, Y is a hydrocarbon group having 1 to 20 carbon atoms, —O
-, -S-, -SS-, (Where R ⁵ represents a hydrocarbon group having 1 to 6 carbon atoms). Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ″, R and Y include methylene, ethylene, trimethylene, propylene, diphenylmethylene, isopropylidene, ethylidene, n-propylidene, isopropylidene, n
-Butylidene, isobutylidene and the like. Among them, methylene, ethylene, ethylidene, isopropylidene and isobutylidene groups are preferably used.

Here, n 'is an integer of 0 or 1 or more, and represents the number of repetitions of the unit Y. In particular, 0 or 1 gives a preferable result.

R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group having 1 to 20 carbon atoms,
Represents a hydroxyl group, nitro group, nitrile group, hydrocarboxy group or halogen atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-heptyl, n-octyl, Examples thereof include alkyl groups such as n-decyl and n-dodecyl, aryl groups such as phenyl and naphthyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, allyl groups such as propenyl, and aralkyl groups such as benzyl. Among them, carbon number 1
Ten alkyl groups are preferably used.

y, y ', y ", y, z, z', z", z represents the number of substituents attached to the aromatic ring, and y, y ', z, z' represents 0 or 1 to 4
Integers up to y ″, z ″ are 0 or integers from 1 to 2, y, Z
Represents 0 or an integer from 1 to 3.

Specific examples of the catalyst component (C) include, for example, 2,4-dihydroxypentane, 2- (2-hydroxypropyl) phenol, catechol, resorcinol, 4-isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthalene. , 1,2-Dihydroxynaphthalene, 2,2'-biphenyldiol, 1,1'-bi-2-naphthol, 2,2'-dihydroxy-6,6'-dimethylbiphenyl, 4,4 ', 6,6 ′
-Tetra-t-butyl-2,2'-methylenediphenol,
4,4'-dimethyl-6,6'-di-tert-butyl-2,2'-methylenediphenol, 4,4 ', 6,6'-tetramethyl-2,
Examples thereof include 2'-isobutylidene diphenol, 2,2'-dihydroxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenyl sulfide and the like. Among them, 2,4'-dihydroxypentane, catechol, 2,2'-biphenyldiol, 1,1'-bi-2-naphthol, 4,4 ', 6,6'-tetra-t-butyl-2,2 '-Methylenediphenol, 4,4'-
Dimethyl-6,6'-di-tert-butyl-2,2'-methylenediphenol, 4,4 ', 6,6'-tetramethyl-2,2'-isobutylidenediphenol, 2,2'- Dihydroxy-3,3 '
-Di-tert-butyl-5,5'-dimethyldiphenyl sulfide gives favorable results.

When these catalyst systems are applied to the polymerization of diene compounds, it is possible to use only the catalyst components (A) and (B),
It is also possible to use (A), (B) and (C). The catalyst component (C) needs to be used after being reacted with the catalyst component (A) in advance before being subjected to polymerization.

The reaction can be carried out at a temperature of -20 ° C to 200 ° C in a hydrocarbon solvent or a polar solvent such as a halogenated hydrocarbon solvent or ether. The catalyst component (C) may be used directly in the reaction, but when the catalyst component (A) is a halogen-containing transition metal compound, ammonia is added to the reaction system in order to capture hydrogen halide generated during the reaction. , Pyridine or alkylamine can also be added.

In this case, it is preferable to remove the hydrogen halide-containing compound and then subject it to polymerization.

The catalyst component (C) is previously reacted with an alkali metal such as sodium metal or a hydride of an alkali metal such as lithium hydride to synthesize a metal alcoholate, a metal phenolate, a metal naphtholate, etc. Is also good. In this case, it is preferable to remove the alkali metal salt and then conduct the polymerization. Further, when the catalyst component (A) contains a hydrocarboxy group,
It is also possible to react the catalyst component (C) with a carboxylic acid such as acetic acid in advance and to provide this reaction as an ester compound.

In the reaction between the transition metal compound and the organic compound having at least two hydroxyl groups, it is considered that a compound having a form in which at least two hydroxyl groups of the organic compound are bonded to the same transition metal is generated.

As the addition amount of each catalyst component, the catalyst component (A) is 10 ^-10 to 10 ³ mmol /, preferably 10 ^-7 to 10 ³ as transition metal atoms.
Can be used in the range of ² mmol /. The catalyst component (B) can be used in an amount of 1 to 100,000, preferably 10 to 10,000 as aluminum atom / transition metal atom with respect to the catalyst component (A). The catalyst component (C) can be used at 0.01 to 4 (molar ratio) based on the transition metal atom of the catalyst component (A).

Specific examples of the diene compound applied in the present invention include butadienes such as 1,3-butadiene, isoprene and pentadienes such as 1,4-pentadiene and hexadienes such as 1,5-hexadiene and heptadiene. , For example, 1,6-heptadiene, octadienes, for example, 1,7
-Octadiene, 1,9-decadiene, cyclic dienes such as cyclohexadiene, norbornadiene and the like. These compounds can be used alone or in two or more copolymerizations, but the present invention is not limited to the above compounds.

The polymerization method is not particularly limited. For example, the solvent may be an aliphatic hydrocarbon solvent such as butane, pentane, hexane, heptane, octane, an aromatic hydrocarbon solvent such as benzene or toluene, or a halogen such as methylene chloride. A hydrocarbon solvent or a diene compound as a monomer can be used as the solvent. As a polymerization method, either a batch type or a continuous type polymerization is possible.

The polymerization temperature can range from -50 ° C to 200 ° C, but is particularly preferably between -20 ° C and 100 ° C.

<Examples> Next, the effects of the present invention will be specifically described with reference to examples and comparative examples of the present invention, but the present invention is not limited thereto.

The molecular weights in the examples are shown by weight average molecular weights calculated using gel permeation chromatography (GPC). GPC used Waters type 150C. Measurement is 140 ° C
And o-dichlorobenzene was used as a solvent. The column is
Three Shodex 80M / S columns were used. As polystyrene for preparing a calibration curve, 14 kinds of monodisperse polystyrene having a molecular weight range of 500 to 6.8 × 10 ⁻⁶ were used.

Example 1 (1) Reaction of catalyst components (A) and (C) 2,2'-dihydroxy-3,3'-di-tert-butyl-5,5'-in a 100-ml flask equipped with a stirrer. 0.9 mmol of dimethyldiphenyl sulfide was taken, and after substituting with argon, 50 ml of dried n-butyl ether was added thereto, followed by stirring and dissolving. 0.9 mmol of tetraisopropoxy titanium was added to this solution. The reaction was carried out at 25 ° C. with stirring for 2 hours. Thereafter, the mixture was allowed to stand, the supernatant was removed, and the precipitate was collected and washed. A part of the precipitate was dissolved in toluene to prepare a solution containing 0.001 mmol / ml Ti.

(2) Synthesis of catalyst component (B) A 500-ml flask equipped with a stirrer, a dropping funnel and a reflux condenser was purged with argon, and then 44 g (0.176 g) was added.
The CuSO ₄ · 5H ₂ O in mol) were suspended in toluene 300 ml, keeping the internal temperature at 5 ° C., dropwise While agitating, over a solution of 6 hours of toluene 70ml of trimethylaluminum 56 ml (0.58 mol) did. After dropping, stir for 40 hours while maintaining the temperature inside the flask at 5 ° C.
Stirring was continued for 20 hours. After removing the precipitate, the solvent was removed under reduced pressure to obtain 13.0 g of methylaluminoxane. For the polymerization, it was used after dilution with toluene (0.05 g / ml). In addition,
This aluminoxane solution was used in the following examples.

(3) Polymerization of butadiene After replacing the autoclave with an internal volume of 100 ml equipped with a stirrer with argon, 6 ml of toluene, 38 mg of the precipitate synthesized in (1) and 4 ml of the aluminoxane solution synthesized in (2) were charged. Stirred at room temperature for 10 minutes. Next, the autoclave was cooled to −50 ° C., and 30 g of 1,3-butadiene was charged to initiate polymerization. After polymerization at 60 ° C. for 5 hours with stirring, the residual pressure was purged, and then 10 ml of methanol was added, and the mixture was continued for 30 minutes. The polymer was filtered off, washed with 1N HCl / methanol and dried under reduced pressure at 60 ° C. for 2 hours. The obtained polybutadiene was 19.2 gr. This corresponds to 0.5 kg of polymer formed per gram catalyst.

The molecular weight of this polymer was 1,000,000 in terms of polystyrene.

Example 2 (1) Polymerization of 1,5 hexadiene After a three-necked flask having an internal volume of 1,000 ml equipped with a stirrer was purged with argon, 500 ml of toluene and Example 1 were added.
6 ml of the aluminoxane solution synthesized in (2) and 10 ml of the solution synthesized in Example 1- (1) were added. Stirred at room temperature for 10 minutes. Then, 70 ml of 1,5 hexadiene was charged to initiate polymerization. After polymerization at 60 ° C. for 60 minutes, 10 ml of methanol was added, and stirring was continued for 30 minutes. The polymer was filtered off, washed with 1N HCl / methanol and dried under reduced pressure at 60 ° C. for 2 hours. 2,6 g of poly-1,5 hexadiene obtained
Met. This corresponds to the formation of 260 g of polymer per Timol. The molecular weight of this polymer was 450,000 in terms of polystyrene.

(2) Polymerization of 1,5 hexadiene After a 100 ml three-necked flask equipped with a stirrer was purged with argon, 3 ml of the aluminoxane solution synthesized in Example 1- (2) and 8 mg of tetraisopropoxytitanium were added. Then, 5 ml of 1,5 hexadiene was charged to initiate polymerization. Polymerization was carried out at 40 ° C. for 30 minutes with stirring. Thereafter, the same operation as in the first embodiment is performed. 0.05 g of poly-1,5 hexadiene was recovered. The molecular weight of this polymer was 400,000 in terms of polystyrene.

Example 3 (1) Reaction of catalyst components (A) and (C) After a 100 ml three-necked flask equipped with a stirrer and a reflux condenser was purged with argon, 2,2'-dihydroxy-3,3'-di- was added. 0.9 mmol of t-butyl-5,5'-dimethyldiphenylsulfide was taken, 30 ml of dried n-butyl ether was added, and the mixture was stirred and dissolved. 0.9 mmol of titanium tetrachloride was gradually added to this solution with a syringe, and then at 25 ° C. for about 6 hours.
Stirring was continued for hours. After standing, the supernatant was removed and the precipitate was recovered. Further, 10 ml of n-butyl ether was added, and after stirring, the mixture was allowed to stand, the supernatant was removed, and the precipitate was dried and collected. Part of the precipitate was dissolved in toluene, and Ti was 0.001 mmol / ml.
The contained solution was prepared.

(2) Polymerization of 1,9-decadiene After replacing a 100-ml three-necked flask equipped with a stirrer with argon, 5 m of the solution synthesized in Example 1- (2) was used.
l was added and stirred at room temperature for 10 minutes. Then, 10 ml of 1,9 decadiene was charged to initiate polymerization. Polymerization was carried out at 40 ° C. for 4 hours with stirring. Thereafter, the same operation as in Example 1 was performed, and 1.5 g of poly 1,9-decadiene was recovered. This corresponds to 300 g of polymer formed per mmol of Ti.

The molecular weight of this polymer was 150,000 in terms of polystyrene.

Comparative Example 1 The procedure of Example 1 was repeated except that 250 mg of triethylaluminum was used instead of methylalumoxane as the catalyst component (B), and that the polymerization time was 1 hour. As a result, no polymer was recovered. Was.

<Effects of the Invention> According to the present invention, a novel catalyst for polymerizing a diene compound alone or copolymerizing two or more types can be obtained.
And the catalyst, that is, a catalyst system comprising an aluminoxane and a transition metal compound represented by the general formula M (R) _l (OR ') _m X _{n- (l + m)} or the general formula M (R) _l (OR') a transition metal compound that is _m X _{n- (l + m)} ,
By polymerizing or copolymerizing a diene compound using a catalyst system comprising an aluminoxane and an organic compound having at least two hydroxyl groups, a diene compound polymer could be produced in high yield.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Yoshiaki Seki, Inventor 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (56) References JP-A-62-167304 (JP, A) International Publication 87 / 2370 (WO, A)

Claims (6)

(57) [Claims] 1. A catalyst component (A) having the general formula M (R) _l (O
R ′) _m X _{n- (l + m)} (wherein, M represents each atom of titanium, zirconium, hafnium or vanadium, R and R ′ represent a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom. L, m, n are l ≧ 0, m
> 0, n- (l + m) ≧ 0. n corresponds to the valence of the transition metal. ) And a catalyst component (B): a process for producing a diene compound polymer using a catalyst system comprising an aluminoxane obtained by reacting a trialkylaluminum with water. 2. A catalyst component (A) having the general formula M (R) _l (O
R ′) _m X _{n- (l + m)} (wherein, M represents each atom of titanium, zirconium, hafnium or vanadium, R and R ′ represent a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom. .L, m,
n represents a number such that l ≧ 0, m> 0, and n− (l + m) ≧ 0. n corresponds to the valence of the transition metal. ), A catalyst component (B): an aluminoxane obtained by reacting a trialkylaluminum with water, and a catalyst component (C): a general formula I, II, III, IV, V or VI HO-R ″-(Y) _n′- R-OH (I) (Wherein, R ″, R is a hydrocarbon group having 1 to 20 carbon atoms, Y is a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —S—S
−, (R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)
Represents Here, R ¹ , R ² , R ³ and R ⁴ represent a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a nitro group, a nitrile group, a hydrocarboxy group or a halogen atom. In this case, R ¹ , R ² ,
R ³ and R ⁴ may be the same or different. n '
Is an integer of 0 or 1 or more, and represents the number of repetitions of the unit Y. Y, y ', y ", y, z, z', z" and z represent the number of substituents bonded to the aromatic ring. y, y ', z and z' represent 0 or an integer from 1 to 4, y ", z" represents 0 or an integer from 1 to 2, and y, Z represents 0 or an integer from 1 to 3. A) a process for producing a diene compound polymer using a catalyst system comprising: 3. The general formula M (R), which is a catalyst component (A).
3. The method according to claim 1, wherein M is titanium or zirconium in the transition metal compound represented by _l (OR ') _{mXn (l + m)} . 4. The method according to claim 1, wherein the trialkylammonium in the catalyst component (B) is trimethylaluminum or triethylaluminum. 5. A catalyst of the general formula I, II, V
5. The production method according to claim 1, wherein the compound represented by VI is used. 6. The method according to claim 1, wherein butadiene, isoprene or 1,5-hexadiene is used as the diene compound.