JP2709962B2 - Catalyst for polymerization of styrene compounds - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for polymerizing a styrenic compound.

2. Description of the Related Art A polymerization method of styrenes using a catalyst comprising a specific titanium compound and a contact product of an organoaluminum compound and a condensing agent has been attempted (JP-A-63-179906). However, the condensing agent described in this publication is substantially only water, and no mention is made of other condensing agents.

Also, a catalyst for olefin polymerization in which a reaction product of a trialkylaluminum and a compound containing one or more hydroxyl groups is combined with a specific transition metal compound has been proposed (JP-A-1-101303). ) Does not disclose that this catalyst is effective for the polymerization of styrene compounds.

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a catalyst for polymerizing a styrene compound in which a reaction product of a condensing agent other than water and an organoaluminum compound is combined with a transition metal compound.

Means for Solving the Problems The present inventors have conducted intensive studies, and as a result, a catalyst in which a reaction product of an organoaluminum compound and a condensing agent such as a diol compound is combined with a transition metal compound to polymerize a styrene compound. The inventors have found that the present invention is effective and completed the present invention.

SUMMARY OF THE INVENTION Namely, the present invention is (A) the general formula MX ¹ ₄ [where, M is titanium or zirconium atom, X ¹ is the same or different alkyl group having 1 to 20 carbon atoms,
It is a cycloalkadienyl group or an alkoxy group. A reaction product of a transition metal compound of formula (I) and (B) an organoaluminum compound (a) with at least one condensing agent (b) selected from the group consisting of the following: HO-R-OH [where R is carbon There are several to 20 divalent organic groups. A diol compound of the general formula H ₂ N—R ¹ —NH _{2 wherein} R ¹ is a divalent organic group having 2 to 20 carbon atoms. And the ammonia complex of copper.

Polymerization Catalyst The polymerization catalyst of the present invention comprises (A) a transition metal compound represented by the above general formula and (B) a reaction product of the organoaluminum compound (a) and the condensing agent (b).

(A) transition metal compound The transition metal compound is represented by the formula MX ¹ _4. In the formula, M is titanium or zirconium. X ¹ is the same or different and is an alkyl group having 1 to 20 carbon atoms, a cycloalkadienyl group or an alkoxy group.

Specific examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, etc., and the cycloalkadienyl group includes Cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, dimethylcyclopentadienyl, pentamethylcyclopentadienyl, indenyl, tetrahydroindenyl, and the like include methoxy, ethoxy, propoxy, isopropoxy as alkoxy groups. , Butoxy, isobutoxy, tertiary butoxy,
Pentyloxy, hexyloxy, octyloxy, 2
-Ethylhexyloxy, phenoxy, naphthyloxy and the like.

The following compounds can be exemplified as compounds of titanium. In the following, Me = methyl, Et = ethyl,
Pr = propyl, Bu = butyl, He = hexyl, Ph = phenyl, Cp = cyclopentadienyl, Bz = benzyl, respectively.

Ti (OME) ₄ , Ti (OEt) ₄ , Ti (Oi−Pr) ₄ , Ti (OBu) ₄ , T
i (Ot−Bu) ₄ , Ti (O2-Et · He) ₄ , TI (OPh) ₄ , Ti (OB
z) ₄ , Cp ₂ (OMe) ₂ Ti, Cp ₂ (OEt) ₂ Ti, Cp ₂ (OBu) ₂ Ti, Cp ₂
(O2-Et · He) ₂ Ti, Cp ₂ MeTi (OEt), Cp ₂ EtTi (OEt), Cp
₂ TiMe ₂ .

The following compounds can be exemplified as the zirconium compound.

Zr (OEt) ₄ , Zr (Oi-Pr) ₄ , Zr (OBu) ₄ , Zr (Ot-Bu)
_{4, Zr (O2-Et ·} He) 4, Zr (OPh) 4, Zr (OBz) 4, Cp 2 (OM
e) ₂ Zr, Cp ₂ (OEt) ₂ Zr, Cp ₂ (OBu) ₂ Zr, Cp ₂ (O2-Et.H
_{e) 2 Zr, Cp 2 MeZr} (OET), Cp 2 MeZr (OBu), Cp 2 EtZr (OE
t), Cp ₂ ZrMe ₂ .

Among the above transition metal compounds, compounds of titanium are desirable.

(B) (a) Organoaluminum Compound The organoaluminum compound is represented by the general formula R ² _n AlX ² _3-n
(However, R ² represents an alkyl group or an aryl group, X ² represents a halogen atom, an alkoxy group or a hydrogen atom, and n represents 1 ≦ n ≦
Any number in the range of 3. ),
For example, alkyl aluminum having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide and dialkyl aluminum monohydride. Compounds or mixtures or complex compounds thereof are particularly preferred. Specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trialkylaluminum such as trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride and the like Monoalkylaluminum dihalides such as dialkylaluminum monohalide, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, and alkylaluminum sesquichloride such as ethylaluminum sesquichloride , Dimethyl aluminum methoxide,
Diethylaluminum ethoxide, diethylaluminum phenoxide, dipropylaluminum ethoxide,
Examples thereof include dialkylaluminum monoalkoxides such as diisobutylaluminum ethoxide and diisobutylaluminum phenoxide, dimethylaluminum hydride, dialkylaluminum hydride, dialkylaluminum hydride, and dialkylaluminum hydride such as diisobutylaluminum hydride. Among these, trialkylaluminum, particularly trimethylaluminum, is desirable.

(B) (b) Diol compound The diol compound is represented by the general formula HO-R-OH.
In the formula, R is a divalent organic group having 1 to 20 carbon atoms.

R is -CR ³ R ⁴ · CR ⁵ R ^6- , CH _{2 n} , And the like. R ³ , R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, a methyl group or a phenyl group, R ⁷ and R ⁸ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an OR ⁹ group (R ⁹ represents a methyl group or an ethyl group), wherein n = 3 to 12.

Specific examples of the diol compound include ethylene glycol, propylene glycol, pinacol, hydrobenzoin, benzpinacol, trimethylene glycol,
4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,2-cyclopentanediol, 1,2-cyclohexanediol, 3-cyclohexanediol,
1,4-cyclohexanediol, catechol, resorcin, hydroquinone, 2,3-dioxytoluene, 3,4-dioxytoluene, cresorcin, orcin, β-orcin, m-xylorsin, 4-n-hexylresorcin,
Examples include 2-methylhydroquinone, 2,5-t-butylhydroquinone, 2,5-t-pentylhydroquinone, and 2,5-diethoxyhydroquinone. Among them, ethylene glycol, propylene glycol, pinacol, 1,2
-Cyclohexanediol, 1,4-cyclohexanediol and the like are desirable.

In addition to the diol compounds, monosaccharides having 3 to 6 carbon atoms such as sorbitol, glucose, and erythritol may be used.

Diamine compounds diamine compound is represented by the general formula ^{_{H 2 N-R 1 -NH 2}} . In the formula, R ¹ is a divalent organic group having 1 to 20 carbon atoms. R ¹ is CH _{2 n} , And the like. R ¹⁰ and R ¹¹ are a hydrogen atom, carbon number 1 to 6
Alkyl groups, where n = 2-12.

Specific examples of the diamine compound include ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane,
1,10-diaminodecane, o-phenylenediamine, m-
Examples include phenylenediamine, p-phenylenediamine and the like.

Ammonia complex of copper As an ammonia complex of copper, [Cu (NH ₃ ) ₄ ] (N
O ₃ ) ₂ and [Cu (NH ₃ ) ₄ ] (SO ₄ .H ₂ O).

The second component of the catalyst of the present invention is a reaction product of the organoaluminum compound (a) with the condensing agent (b).
The reaction between (a) and (b) is carried out by bringing the two into contact, preferably in the presence of an inert medium, for example, a hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene and xylene. The contact between the two
The reaction is performed at a temperature of -30 ° C to + 100 ° C for 4 to 50 hours. or,
The use ratio of both is “(b) / (a)” (molar ratio) = 0.
It is 1 to 10, preferably 0.5 to 2.0.

The catalyst of the present invention comprises a combination of a reaction product of a transition metal compound as a first component and an organoaluminum compound as a second component with a condensing agent. The first and second components, the transition metal of aluminum metal / first component of the second component (molar ratio) is generally 1 to 10 ^6, preferably used as a 10 to 10 ^5.

Specific examples of the styrene-based compound polymerized with the catalyst of the present invention include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
o, m-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-chlorostyrene, p-chlorostyrene and the like.

The polymerization reaction may be any of a gas phase and a liquid phase.When the polymerization is performed in a liquid phase, an inert carbon such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, or xylene is used. It can be carried out in hydrogen and in liquid monomers. As the inert hydrocarbon, benzene, toluene and xylene are particularly preferred. The polymerization temperature is usually −80 ° C.
+ 150 ° C, preferably in the range of 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atm. Adjustment of the molecular weight of the resulting polymer is carried out in the presence of hydrogen or other known molecular weight regulators. The polymerization of the styrene-based compound can be performed not only by homopolymerization but also by copolymerization (random polymerization, block polymerization) with another styrene-based compound. The polymerization reaction may be either continuous or batch type, and may be performed in one stage, or may be performed in two or more stages.

Effects of the Invention The catalyst of the present invention is effective for polymerizing styrene compounds.

Examples Hereinafter, the present invention will be described in detail with reference to examples.

Example 1 Reaction of trimethylaluminum with ethylene glycol A stirrer and a dropping funnel were provided, and the atmosphere was replaced with nitrogen gas in advance.
A 200 ml flask was charged with a solution of 15 ml of trimethylaluminum in 60 ml of toluene. On the other hand, a solution prepared by dissolving 0.19 mol of ethylene glycol in 30 ml of toluene was placed in the dropping funnel.

At 0 ° C., the above ethylene glycol solution was added dropwise from the dropping funnel over 1.5 hours with stirring.

Generation of methane was observed at the same time as the dropwise addition, and a white solid was obtained.

Polymerization of Styrene The reaction product obtained above (10 mg atom as aluminum metal), 0.17 mmol of tetrabutoxytitanium and 250 ml of toluene were placed in a 1-liter glass autoclave purged with nitrogen gas. Further, 30 g of styrene was added, and styrene was polymerized at 50 ° C. for 2 hours. Polystyrene was obtained with a catalytic activity of 300 g · polymer / g · titanium · hour.

Examples 2 to 7 Polymerization of styrene was carried out in the same manner as in Example 1, except that the diol compounds shown in Table 1 were used in place of ethylene glycol, and the reaction product obtained with trimethylaluminum was used. The results are shown in Table 1.

Examples 8 to 10 Styrene was polymerized in the same manner as in Example 1 except that the transition metal compounds shown in Table 1 were used instead of tetrabutoxytitanium, and the results are shown in Table 1.

Examples 11 and 12 A reaction product with trimethylaluminum was obtained by using the condensing agents shown in Table 1 instead of ethylene glycol.
Except that these reaction products were used, polymerization of styrene was carried out in the same manner as in Example 1, and the results are shown in Table 1.

[Brief description of the drawings]

FIG. 1 is a flowchart showing the preparation process of the catalyst of the present invention.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masafumi Imai 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. (56) References JP-A-60-212408 (JP, A) JP-A-61-138608 (JP, A) JP-A-63-132905 (JP, A)

Claims (1)

(57) [Claims] 1. A (A) the general formula MX ¹ ₄ [where, M is titanium or zirconium atom, X ¹ is the same or different alkyl group having 1 to 20 carbon atoms, cycloalkadienyl group or an alkoxy group. A reaction product of a transition metal compound of formula (I) and (B) an organoaluminum compound (a) with at least one condensing agent (b) selected from the group consisting of the following: HO-R-OH [where R is carbon There are several to 20 divalent organic groups. A diol compound of the general formula H ₂ N—R ¹ —NH _{2 wherein} R ¹ is a divalent organic group having 2 to 20 carbon atoms. ] A catalyst for polymerizing a styrene-based compound, comprising: