JPH0749445B2 - Olefin Polymerization Method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for polymerizing olefins using a Ziegler-based catalyst. More specifically, the present invention relates to a polymerization method in which a stereoregular olefin polymer can be obtained in an extremely high yield by using a known two-component catalyst system composed of a compound containing a high activity catalyst and a transition metal component.

[Conventional technology]

Conventionally, when a catalyst having a low polymerization activity is used, the deashing step for removing the catalyst residue has been unavoidable because the yield of the polymer per titanium in the catalyst component is low. Since a large amount of alcohol or chelating agent is used in this deashing step, a complicated operation of recovery or regeneration is required. Therefore, many proposals have been made and put to practical use in order to enhance the polymerization activity of the catalyst component. Of these, the most practical method is a method using a catalyst system in which a transition metal compound such as a titanium halide is supported on a carrier material such as magnesium chloride. Although this magnesium chloride-supported titanium catalyst exhibits high polymerization activity, it has a drawback in that the polymer produced has very low stereoregularity.

In order to solve such a problem, a technique has been proposed in which an electron donating compound such as an aromatic carboxylic acid ester is allowed to coexist in a polymerization system together with a magnesium chloride-supporting titanium catalyst (see, for example, Japanese Patent Application Laid-Open Publication No. Sho. 54-132494, JP-A-54-4294). However, although the aromatic carboxylic acid ester improves the stereoregularity of the produced polymer, it imparts an ester odor peculiar to the polymer or causes coloring, and thus its removal is a major problem.

[Problems to be solved by the invention]

The object of the present invention is to achieve a high stereoregularity while maintaining a high yield of the polymer per titanium in the catalyst component without making an electron donor such as an aromatic carboxylic acid ester coexist in the polymerization system. Another object of the present invention is to provide a polymerization method capable of obtaining an olefin polymer. According to the method of the present invention, since the aromatic carboxylic acid ester is not allowed to coexist in the polymerization system, the produced polymer has no ester odor and is not colored.

[Means for solving problems]

The above object is achieved by polymerizing an olefin using the following catalyst. That is, the catalyst used is represented by the following general formula [I]: Mg (OR ¹ ) _2-n X _n [I] (In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, and 4 to 10 carbon atoms.
Is a cycloalkyl group or an aryl group, X is a halogen atom, and n is an integer satisfying 0 <n ≦ 2. ) And a magnesium compound represented by the following general formula [II]: Ti (OR ² ) _4-m X ′ _m [II] (wherein R ² is an alkyl group having 1 to 10 carbon atoms, and 4 to 10 carbon atoms).
Is a cycloalkyl group or an aryl group, X ′ is a halogen atom, and m is an integer of 0 <m ≦ 4. )
A metallocene comprising a complex obtained by contacting a titanium compound represented by: and a cyclopentadienyl metal compound part, represented by the following general formula (III) or (IV): (C ₅ R ▲ ³ _q ▼) _p R ⁴ _t MR ⁵ R ▲ ⁶ _3-p ▼ (III) (In the formula, (C ₅ R ▲ ³ _q ▼) is a cyclopentadienyl group or a substituted cyclopentadienyl group, R ³ is hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and R ³ May be the same or different from each other, and two adjacent carbon atoms forming a cyclopentadienyl group or a substituted cyclopentadienyl group may be bonded to R ^{3 and} each of them may have 4 to 6 carbon atoms. may form a ring, R ⁴ is a group bonding the two _{^{(C 5 R ▲ 3 q ▼}} ), an alkylene group having 1 to 4 carbon atoms, a dialkyl germanium, dialkyl silicon, alkyl phosphine and an alkyl amine R ⁵ is a hydrocarbyl group having 1 to 20 carbon atoms, R ⁶ is a hydrocarbyl group having 1 to 20 carbon atoms or a halogen atom, M is titanium or zirconium, t is 0 or Is 1, P is 1, 2 or 3, provided that, P is 0 when t is the 1, q when t is 1 4
And when t is 0, 5 is, Q is a methyl group or a chlorine atom, R ⁸ is a hydrocarbyl group having 1 to 18 carbon atoms, provided that when Q is a methyl group, R ⁸ is It is a methyl group. And a compound represented by the formula (1).

In the magnesium compound represented by the general formula [I], R ¹ is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, preferably 5 to 8 carbon atoms. Or an aryl group, preferably phenyl, tolyl, xylyl. X is a halogen atom, preferably a chlorine atom. n is an integer that satisfies 0 <n ≦ 2.

Specific examples of the magnesium compound as described above include magnesium dihalides such as MgF ₂ , MgCl ₂ , MgBr ₂ ,
MgI ₂ , halohydrocarbyloxymagnesium, for example
Examples thereof include Mg (OC ₂ H ₅ ) Cl and Mg (OC ₆ H ₅ ) Cl. These magnesium compounds may be used as a mixture of two or more. For example, a mixture of MgCl ₂ and Mg (OC ₂ H ₅ ) ₂ is included in the magnesium compound in the present invention. A particularly preferred magnesium compound is MgCl ₂ . General formula (II)
In the titanium compound represented by, R ² is the same or different from R ¹ and is an alkyl, aryl or cycloalkyl having 1 to 10 carbon atoms (each of these is preferably
[I] is the same as described for R ¹ in the formula). X ′ is a halogen atom, preferably a chlorine atom, and n is an integer of 0 <n ≦ 4. Specific examples of the titanium compound include TiCl ₄ , TiBr ₄ , TiI ₄ , and Ti (OC ₄ H ₉ ) C.
l ₃ , Ti (OC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₄ H ₈ ) Cl ₃ , Ti (OC
₄ H ₉ ) ₄ , Ti (OC ₃ H ₇ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₃ H
₇ ) Cl ₃ , Ti (OC ₆ H ₅ ) Cl ₃ , Ti (OC ₆ H ₅ ) Cl ₂ , Ti (OC
₄ H ₉ ) ₄ , Ti (OC ₃ H ₇ ) _{4 and the} like.

The contact between the component A and the component B may be generally performed in the temperature range of -50 to 200 ° C. The contact time is usually about 10 minutes to 48 hours. The two components can be brought into contact with each other by a mechanical pulverization method using a ball mill, a vibration mill or the like, or under stirring.

The contact of both components can also be performed in the presence of a dispersion medium. In that case, the dispersion medium used may be hydrocarbon, halogenated hydrocarbon, or the like. Specific examples of the hydrocarbon include hexane, heptane, benzene, toluene and cyclohexane, and specific examples of the halogenated hydrocarbon include n-chloride.
Butyl, n-butyl bromide, -n-butyl iodide, chlorobenzene, n-octyl chloride, n-decyl chloride, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, benzyl chloride, iodobenzene, etc. is there.

When the magnesium compound [I] and the titanium compound [II] are brought into contact with each other to prepare a complex thereof, an electron donor such as a commonly used aromatic carboxylic acid derivative may be brought into contact at any stage. . Contacting such an electron donor generally increases the polymerization activity of the catalyst. In addition, in the polymerization, if the aromatic carboxylic acid ester is added to the polymerization system together with the catalyst to carry out the polymerization, the problems of odor and coloring occur as described above, which must be avoided, but the preparation of the catalyst system as described above. It does not matter to take in it from time to time.

The titanium compound [II] is preferably used in an amount of 0.01 to 200 (molar ratio) with respect to the magnesium compound [I].
More preferably, it is in the range of 0.1 to 50 (molar ratio). When the electron donor is added, the amount used is preferably in the range of 0.001 to 100 (molar ratio) with respect to the magnesium compound [I],
More preferably, it is in the range of 0.01 to 30 (molar ratio).

If desired, the product obtained by contacting the magnesium compound [I] with the titanium compound [II] can be further represented by the general formula ▲ R ⁹ _3-r ▼ Al ▲ X ^″ _r ▼ or ▲ R ¹⁰ _3-s ▼. Al (OR ¹¹ )
An aluminum compound represented by _s may be contacted. In these general formulas, R ⁹ , R ¹⁰ and R ¹¹ are hydrocarbon residues having 1 to 20 carbon atoms, which may be the same or different from each other, X ″ is a halogen atom, r and s are respectively It is an integer satisfying 0 ≦ r ≦ 2 and 0 ≦ s ≦ 1. Specific examples of such an aluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, trihexylaluminum, trioctylaluminum, and diethylaluminum monochrome. Alkyl aluminum halides such as chloride, dimethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum butoxide,
Examples thereof include alkyl aluminum alkoxides such as diethyl aluminum phenoxide. Furthermore, two or more of these aluminum compounds can be used in combination.
Contact with such an aluminum compound improves the sustainability of polymerization activity of the catalyst during polymerization.

The contact between the aluminum compound and the contact product of the magnesium compound [I] and the titanium compound [II] is generally
It may be carried out in the temperature range of 50 to 200 ° C. Contact time is 10 minutes to 2
It takes about 4 hours. The contacting method is usually such that stirring is performed, but a ball mill, a vibration mill or the like may be used. Further, hydrocarbon or the like can be used as the dispersion medium. Specific examples of the dispersion medium include hexane, heptane, benzene,
Examples include toluene and cyclohexane. The amount of aluminum compound used is based on magnesium compound [I]
It is preferably in the range of 0.01 to 200 (molar ratio), more preferably
It is in the range of 0.1 to 50 (molar ratio).

In the cyclopentadienyl compounds represented by the general formulas (III) and (IV), R ³ is hydrogen or alkyl,
A hydrocarbyl group having 1 to 20 carbon atoms such as alkenyl, aryl, alkylaryl and arylalkyl, wherein R ^{3 s} may be the same or different from each other, and are cyclopentadienyl group or substituted cyclo Two adjacent carbon atoms forming a pentadienyl group may form a ring having 4 to 6 carbon atoms together with R ³ bonded to each. R ⁴
Is a group for connecting two (C ₅ ∑R ³ _q ), and is selected from an alkylene group having 1 to 4 carbon atoms, a dialkylgermanium, a dialkylsilicon, an alkylphosphine and an alkylamine group. R ⁵ is a hydrocarbyl group having 1 to 20 carbon atoms such as alkyl, aryl, alkenyl, alkylaryl, and arylalkyl group, and R ⁶ is C 1 to 20 alkyl, aryl, alkenyl, alkylaryl, aryl It is a hydrocarbyl group such as an alkyl group or a halogen atom, and M is titanium or zirconium. t is 0 or 1, P is 1,
2 or 3. However, when P is 1, t is 0, and q
Is 4 when t is 1 and 5 when t is 0. Q is a methyl group or a chlorine atom, and R ⁸ is a hydrocarbyl group having 1 to 18 carbon atoms such as alkyl, aryl, alkenyl, alkylaryl and arylalkyl groups. However, when Q is a methyl group, R ⁸ is a methyl group.

Specific examples of the hydrocarbyl group in R ³ , R ⁵ , R ⁶ and R ⁸ include methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl,
Mention may be made of such things as octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl.

Specific examples of the alkylene group for R ⁴ include methylene, ethylene, propylene and the like. Examples of the halogen in R ⁵ include chlorine, bromine and iodine, with chlorine being preferred. Among the above M, titanium is preferable.

Specific examples of the compounds represented by the general formulas (III) and (IV) include the following compounds (Cp = cyclopentadienyl, Ind = indenyl).

Bis (cyclopentadienyl) dimethyltitanium Cp
₂ TiMe ₂ bis (methylcyclopentadienyl) dimethyltitanium (MeCp) ₂ TiMe ₂ ) bis (pentamethylcyclopentadienyl) dimethyltitanium ((Me) ₅ Cp) ₂ TiMe ₂ bis (cyclopentadienyl) methylchloro Titanium
Cp ₂ TiMeCl Bis (cyclopentadienyl) dimethyl zirconium
Cp ₂ ZrMe ₂ Bis (indenyl) dimethyltitanium (Ind) ₂ TiMe
₂ Bis (indenyl) dimethyl zirconium (Ind) ₂ Zr
Me ₂ Ethylenebis (tetrahydroindenyl) dimethylzirconium Et [H ₄ Ind] ₂ ZrMe ₂ (μ-chloro) (μ-methylene) bis (cyclopentadienyl) (dimethylaluminum) titanium (Μ-Methylene) (μ-methyl) bis (cyclopentadienyl) (dimethylaluminum) titanium (Μ-Methylene) (μ-methyl) bis (methylcyclopentadienyl) (dimethylaluminum) titanium Bis (methylcyclopentadienyl) diphenyltitanium (MeCp) ₂ TiPh ₂ Dimethylsilyldicyclopentadienyldiphenyltitanium Methylphosphine dicyclopentadienyl diphenyl titanium Methylenedicyclopentadienyldimethyltitanium The amount of the catalyst component [III] containing the above transition metal compound component used is preferably within the range of 0.1 to 1000 in terms of molar ratio to the titanium component of the titanium compound [II].

Polymerize using the catalyst system of the present invention. Olefins, (wherein, R represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, which may have a substituent) formula R-CH = CH ₂ is represented by. Specific examples include olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1. Ethylene and propylene are preferable, and propylene is particularly preferable.

The operation method itself for polymerizing an olefin using the catalyst of the present invention is not particularly limited, and a known polymerization method can be used. For example, a slurry polymerization method can be mentioned. As a polymerization solvent in the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, pentane, cyclohexane, benzene, or toluene is used alone or as a mixture. The polymerization temperature is selected from the range of -20 ° C to 100 ° C, preferably 0 to 80 ° C, and the pressure is atmospheric pressure to 100 ° C.
It is selected from the range of atmospheric pressure.

〔The invention's effect〕

According to the polymerization method of the present invention, an olefin polymer having high stereoregularity can be obtained while maintaining a high yield of the polymer per titanium in the catalyst component without allowing an electron donor to coexist in the polymerization system. be able to. Since no electron donor such as aromatic carboxylic acid ester is added to the polymerization system, odor and coloration problems do not occur in the resulting polymer.

〔Example〕

 Hereinafter, the present invention will be specifically described with reference to Examples.

Example 1 Preparation of MgCl ₂ / PhCO ₂ Et / TiCl ₄ solid catalyst 10.5 g (110.5 mmol) of anhydrous MgCl ₂ was dried by heating at a temperature of 300 ° C. for 2 hours under reduced pressure. Then various diameters (4,6,8,
12 mm) MgCl ₂ was crushed for 2 hours using a steel crushing ball having a capacity of 80 ml containing 50 g of steel balls. The ball was moved by the reciprocating vertical movement transmitted from the motor by the eccentric rod mechanism. The frequency was 8 Hz for a speed of 500 rpm. MgCl crushed with ethyl benzoate PhCO ₂ Et (5.5 mmol)
Added to ₂ . Auxiliary pulverization was performed again for 6 hours in the same manner as above under an inert atmosphere. The co-ground product was suspended in heptane.
10 ml TiCl ₄ were added and the suspension was reacted at a temperature of 60 ° C. for 2 hours. The temperature of TiCl ₄ was 6 mol /. After the reaction, the supernatant was removed and the solid was washed several times with heptane, and the solid was dried under reduced pressure at room temperature. The resulting solid catalyst was found by colorimetric analysis to contain 2.3% by weight of titanium.

Synthesis of bis (methylcyclopentadienyl) dimethyltitanium (MeCp) ₂ TiMe ₂ K. Method of K.Clauss et al. (K.Clausset HB
estion, Justus Liebig Ann. Chem., 654, 8 (1962). )
Then, bis (methylcyclopentadienyl) dichlorotitanium (MeCp) ₂ TiCl ₂ was reacted with methyllithium MeLi to synthesize and isolate bis (methylcyclopentadienyl) dimethyltitanium (MeCP) ₂ TiMe ₂ . The synthetically isolated (MeCp) ₂ TiMe ₂ was an orange needle crystal and was identified by elemental analysis. (MeCp) ₂ TiMe ₂ is indefinite with respect to heat, light and oxygen, and considering the ease of use during polymerization,
It was diluted with 0.3 mol / solution of heptane and stored under a nitrogen gas atmosphere at -78 ° C in the dark.

A 200 ml glass flask was used as the polymerization vessel. The reaction vessel was previously placed under a nitrogen atmosphere, 100 mg of the TiCl ₄ / PhCO ₂ Et / MgCl ₂ catalyst prepared above was introduced, and the entire amount of heptane as a polymerization solvent (added later (MeCp) ₂ TiMe ₂ of a heptane solution (The amount is also included in the calculation) was added to 100 ml. After stirring at a polymerization temperature of 40 ° C. for 5 minutes, nitrogen gas was exhausted and propylene gas was introduced to saturate for 20 minutes. The polymerization pressure was 1 atm. Then, the polymerization was initiated by adding 1.7 ml of a solution of (MeCp) ₂ TiMe ₂ in heptane (0.3 mol /). The polymerization was carried out for 2 hours, and the polymerization was stopped by adding a hydrochloric acid-methanol solvent to the polymerization system. The produced polymer was thoroughly washed with methanol and then vacuum dried. The polymerization activity (polymerization activity is an average value of polymerization for 2 hours, and is the same in the following Examples and Examples) was 920 g-PP / g-Ti · hr. The stereoregularity of the produced polymer was evaluated by boiling peptane extraction residue (hereinafter abbreviated as "II"). Of this example
II = 96%. No coloration or odor problems were observed with the resulting polymer.

Example 2 Synthesis of bis (cyclopentadienyl) dimethyltitanium A case similar to (MeCp) ₂ TiMe _{2 of} Example 1 was used. Claus (K.
Bis (cyclopentadienyl) by the method of Clauss)
Dichlorotitanium Cp ₂ TiCl ₂ by reaction with MeLi bis (cyclopentadienyl) dimethyltitanium Cp ₂ TiMe ₂
Was synthesized. Also, similar to (MeCp) ₂ TiMe _2, considering the chemical properties of the compound and the ease of use during polymerization,
It was diluted to 0.3 mol / solution of heptane and stored in the same manner.

Polymerization (MeCp) ₂ TiMe ₂ heptane solution (0.3 mol /) 1.7 ml was used instead of Cp ₂ TiMe ₂ heptane solution (0.3 mol /) 1.0 ml during the polymerization, and the polymerization temperature was 25 ° C. Polymerization of propylene was carried out in the same manner as in Example 1 except for the above. The polymerization activity was 280 g-PP / g-Ti · hr, and II was 95%. No coloration or odor problems were observed with the resulting polymer.

Example 3 Synthesis of (μ-methylene) (μ-methyl) bis (methylcyclopentadienyl) (dimethylaluminum) titanium (MeCp) ₂ TiCH ₂ (CH ₃ ) Al (CH ₃ ) ₂ F. N. Method of FNTebbe et al. (FNTebb
e, GWParshall, GSReday, J.Am.Chom.Soc., 11 , 3611 (1
978). ) (Methylcyclopentadienyl) dimethyltitanium (MeCp) ₂ TiMe ₂ and trimethylaluminum AlMe _{3 according} to
(Μ-methyl) bis (methylcyclopentadienyl)
(Dimethylaluminum) Titanium (MeCp) ₂ TiCH
₂ (CH ₃ ) Al (CH ₃ ) ₂ was synthesized. Synthesized (MeCp) ₂ Ti
Without isolation, CH ₂ (CH ₃ ) Al (CH ₃ ) ₂ was stored in the dark at −78 ° C. under a nitrogen gas atmosphere as a 0.3 mol / solution of heptane.

Polymerization of 1.0 ml of (MeCP) ₂ TiCH ₂ (CH ₃ ) Al (CH ₃ ) ₂ in heptane (0.3 mol /) instead of using 1.0 ml of heptane solution of (MeCp) ₂ TiMe ₂ (0.3 mol /) Polymerization of propylene was carried out in the same manner as in Example 1 except that it was used at that time. Polymerization activity is 1850g-PP / g-Ti · hr, II = 93
%Met. No coloration or odor problems were observed with the resulting polymer.

Comparative Example 1 TiCl ₄ / PhCO ₂ Et / MgCl _{2 to} AlEt _{3 In} this example, AlEt ₃ commonly used for TiCl ₄ / PhCO ₂ Et / MgCl ₂ catalyst.
Was used as a cocatalyst.

A 200 ml glass flask was used as a polymerization vessel. The reaction vessel was previously placed under a nitrogen atmosphere, and 42 mg of the TiCl ₄ / PhCO ₂ Et / MgCl ₂ catalyst prepared in Example 1 was introduced,
Heptane was added as a polymerization solvent so that the total amount (including the amount of a heptane solution of AlEt ₃ added later) was 100 ml. The polymerization temperature was 40 ° C., and the mixture was stirred for 5 minutes, then nitrogen gas was exhausted and propylene gas was introduced to saturate for 20 minutes. The polymerization pressure was 1 atm. Then, a solution of AlEt ₃ in heptane (1.
Polymerization was initiated by adding 1.0 ml of 0 mol /). The polymerization was carried out for 2 hours, and the polymerization was stopped by adding a hydrochloric acid-methanol solvent to the polymerization system. The produced polymer was thoroughly washed with methanol and then vacuum dried. The polymerization activity was 7490 g-PP / g-Ti · hr. I. of the resulting polymer
I. was 50%.

Comparative Example 2 TiCl ₄ / PhCO ₂ Et / MgCl _{2 to} AlEt ₃ .PhCO ₂ Et In this example, the same catalyst system as in Comparative Example 1 was used, and Ph
CO ₂ Et electron donor was added.

During the polymerization, 0.3 mmol of PhCO ₂ Et and a solution of AlEt ₃ in heptane (1mo
Polymerization of pyropyrene was carried out in the same manner as in Comparative Example 1 except that 1.0 ml of l /) was added. Polymerization activity is 3540g-PP / g-T
i · hr and II was 89%. P for the produced polymer
The odor due to hCO ₂ Et remained.

Example 4 Preparation of MgCl ₂ / TiCl ₄ solid catalyst 10.5 g (110.5 mmol) of anhydrous MgCl ₂ was dried by heating at a temperature of 300 ° C. for 2 hours under reduced pressure. Then various diameters (4,6,8,
12mm) The above dried MgCl ₂ and 11.1mmol TiCl ₄ were put into a steel crushing ball having a capacity of 80ml containing 50g of steel balls, and the mixture was placed under a nitrogen atmosphere.
Co-ground for 24 hours at room temperature. The ball was moved by the reciprocating vertical movement transmitted from the motor by the eccentric rod mechanism. The frequency was 8 Hz for a speed of 500 rpm. The co-ground product was thoroughly washed with heptane several times, and the solid was dried under reduced pressure at room temperature. The resulting solid catalyst was found by colorimetric analysis to contain 2.8 wt% titanium.

Using 100 mg of the TiCl ₄ / MgCl ₂ solid catalyst prepared above in place of 100 mg of the combined TiCl ₄ / PhCO ₂ Et / MgCl ₂ solid catalyst, (MeCp) ₂ TiMe ₂ in heptane solution (0.3 mol /) 2.0 Polymerization of propylene was carried out in the same manner as in Example 1 except that ml was used. The polymerization was carried out for 2 hours, and the polymerization was stopped by adding a hydrochloric acid-methanol solvent to the polymerization system. The polymerization activity was 120 g-PP / g-Ti · hr. I. of the resulting polymer
I. was 91%. Neither odor nor coloring was observed in the produced polymer.

Comparative Example 3 TiCl ₄ / MgCl ₂ -AlEt ₃ TiCl ₄ / MgCl ₂ catalyst prepared in Example 4 as a solid catalyst 50 m
g, using a solution of AlEt ₃ in heptane (1.0 mol /) during polymerization
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 0.6 ml of was added. Polymerization activity is 3460g-PP / g-Ti ・ h
r and II was 27%.

Example 5 Instead of using 2.0 ml of a heptane solution (0.3 mol /) of poly (MeCp) ₂ TiMe ₂ in Example 3, it is desired to synthesize (MeCp) ₂ TiCH ₂ (C
2.0 ml of a heptane solution (0.3 mol /) of H ₃ ) Al (CH ₃ ) ₂
Propylene was polymerized in the same manner as in Example 4 except that it was used during the polymerization. Polymerization activity is 950g-PP / g-Ti
-Hr and II = 90%. Neither odor nor coloring was observed in the produced polymer.

Example 6 Bis (cyclopentadienyl) dimethyl zirconium Cp
₂ Synthesis of ZrMe ₂ . C. Method of PCWailes et al. (PCWail
es, H.Weigold, APBell: J.Organomet.Chem., 34 , 155 (19
72)), bis (cyclopentadienyl) dimethylzirconium Cp ₂ ZrMe ₂ was synthesized and isolated from the reaction of bis (cyclopentadienyl) dichlorozirconium Cp ₂ ZrCl ₂ with methyllithium MeLi. The synthetically isolated Cp ₂ ZrMe ₂ is unstable to water, oxygen, etc., and in consideration of the ease of use during polymerization, it was diluted with 0.3 mol / solution of heptane under a nitrogen gas atmosphere-- Stored in the dark at 78 ° C.

A solution of poly (MeCp) ₂ TiMe ₂ in heptane 2.0 ml instead of Cp ₂ ZrMe ₂
Polymerization of propylene was carried out in the same manner as in Example 4 except that 2.0 ml of the heptane solution of 1 was used during the polymerization.
The polymerization activity was 100 g-PP / g-Ti · hr, and II = 79%. Neither odor nor coloring was observed in the produced polymer.

Example 7 Preparation of Ti (OBu) ₄ / MgCl ₂ / AlEt ₂ Cl solid catalyst 10.5 g (110.5 mmol) of anhydrous MgCl ₂ was dried by heating at a temperature of 300 ° C. for 2 hours under reduced pressure. Then various diameters (4,6,8,
(12 mm) 50 g of steel balls were placed in a steel crushing ball having a capacity of 80 ml, and the dry MgCl ₂ , 11.1 mmol of Ti (OBu) ₄ and 170 mmol of heptane were added, and the mixture was co-ground for 24 hours at room temperature under a nitrogen gas atmosphere. The ball was moved by the reciprocating vertical movement transmitted from the motor by the eccentric rod mechanism. Frequency is 500 rpm
It was 8Hz for the speed of. The co-ground product was washed several times with heptane. The obtained solid was reacted with 11.1 mmol of AlEt ₂ Cl in 170 mmol of heptane solvent under a nitrogen atmosphere at room temperature for 60 minutes. The reaction was washed several times with heptane and the solid obtained was dried under reduced pressure at room temperature. The solid catalyst obtained was found by colorimetric analysis to contain 2.3% by weight of titanium.

When 170 mg of Ti (OBu) ₄ / MgCl ₂ / AlEt ₂ Cl solid catalyst prepared above was used instead of 100 mg of TiCl ₄ / PhCO ₂ Et / MgCl ₂ solid catalyst, heptane of (MeCp) ₂ TiMe ₂ was used during polymerization. Solution (0.3mol /
) Polymerization of propylene was carried out in the same manner as in Example 1 except that 2.3 ml was used. Polymerization activity is 180g-PP / g
It was Ti · hr. The II of the produced polymer was 92%. Neither smell nor coloring was observed.

Example 8 Instead of 2.3 ml of heptane solution of poly (MeCp) ₂ TiMe ₂ (MeCp) ₂
Polymerization of propylene was carried out in the same manner as in Example 7 except that 2.3 ml of a heptane solution of TiMe ₂ (CH ₃ ) Al (CH ₃ ) ₂ was used during the polymerization. Polymerization activity is 410g-PP / g-Ti ・ hr
And II was 90%. Neither smell nor coloring was observed.

Comparative Example 4 Ti (OBu) ₄ / MgCl ₂ / AlEt ₂ Cl to AlEt ₃ Ti (OBu) ₄ / MgCl ₂ / A prepared in Example 7 as a solid catalyst.
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 50 mg of 1Et ₂ Cl catalyst was used and 0.5 ml of a heptane solution of AlEt ₃ (1.0 mol /) was added during the polymerization. Polymerization activity is 1900g
-PP / g-Ti * hr, and II was 48%.

Example _{9 Ti (OBu) 4 / MgCl} 2 / Al 2 Et 2 Cl 3 of the solid catalyst of Preparation 11.1mmol
A catalyst was prepared in the same manner as in Example 7, except that 5.5 mmol of Al ₂ Et ₃ Cl _{3 was} used instead of AlEt ₂ Cl. The titanium content in the solid catalyst obtained by the colorimetric analysis was 0.
It was 9% by weight.

When 250 mg of Ti (OBu) ₄ / MgCl ₂ / Al ₂ Et ₂ Cl solid catalyst prepared above was used in place of 100 mg of TiCl ₄ / PhCO ₂ Et / MgCl ₂ solid catalyst, (MeCp) ₂ TiMe ₂ Solution of heptane (0.3mol /
) Propylene was polymerized in the same manner as in Example 1 except that 3.1 ml was used. Polymerization activity is 100g-PP / g-Ti
hr and the polymer II was 93%. smell,
No coloring was observed.

Comparative Example 5 Ti (OBu) ₄ / MgCl ₂ / Al ₂ Et ₃ Cl _{3 to} AlEt ₃ Ti (OBu) ₄ / MgCl ₂ / A prepared in Example 9 as a solid catalyst.
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 125 mg of l ₂ Et ₃ Cl ₃ catalyst was used and 1.0 ml of a heptane solution of AlEt ₃ (1.0 mol /) was added during the polymerization. Polymerization activity is 2500
It was g-PP / g-Ti · hr, and II was 46%.

Comparative Example 6 TiCl ₃ to (MeCp) ₂ TiMe _{2 As} catalyst, 160 mg of Ti reduced TiCl ₃ was used, and (Me
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 3.4 ml of a heptane solution of Cp) ₂ TiMe ₂ (0.3 mol /) was used. The polymerization activity was 47 g-PP / g-Ti · hr. The II of the produced polymer was 95%.

Comparative Example _{7 MgCl 2 ~ (MeCp) 2} TiMe 2 solid component, using a MgCl ₂ 500 mg of dried 2 hours at 300 ° C., during the polymerization (MeCp) ₂ TiMe ₂ solution in heptane (0.3 mol
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 1.0 ml of /) was used. There was no polymerization activity at all.

What Comparative Example 8 (MeCp) ₂ TiMe ₂ solid component without adding any polymerization during (MeCp) ₂ TiMe ₂ solution in heptane (0.3 mol /) 4.0 ml propylene at all Comparative Example 1 The same method except for using Was polymerized. There was no polymerization activity at all.

Example 10 (μ-methylene) (μ-chloro) bis (cyclopentadienyl) (dimethylaluminum) titanium Cp ₂ TiCH ₂
Synthesis of (Cl) Al (CH ₃ ) ₂ F. N. Method of FNTebbe et al. (FNTebb
e, GWParshall, GSReddy, J.Am.Chem.Soc., 11 , 3611 (1
978). ) According to bis (cyclopentadienyl)
Dichlorotitanium Cp ₂ TiCl ₂ and trimethylaluminum
By reaction with Al (CH ₃ ) ₃ , (μ-methylene) (μ-
Chloro) bis (cyclopentadienyl) (dimethylaluminum) titanium Cp ₂ TiCH ₂ (Cl) Al (CH ₃ ) ₂ was synthesized. Without isolation, 0.3 mol / l of heptane
The solution was stored under a nitrogen gas atmosphere at -78 ° C in the dark.

Polymerization (MeCp) ₂ TiMe ₂ solution of heptane (0.3mol / l) 4.0ml is used instead of Cp ₂ TiCH ₂ (Cl) Al (CH ₃ ) ₂ heptane solution (0.3mol / l) 4.0ml. Polymerization of propylene was carried out in the same manner as in Example 1 except that The polymerization activity was 560 g-PP / g-Ti · hr, and II was 94%.
No coloring or odor problem was observed in the produced polymer.

Example 11 Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) dimethyl zirconium (C ₂ H ₄ (4,5,6,7-Tetrahydy
o-1-indenvl) ₂ Zr (CH ₃ ) ₂ ) Synthesis of Walter Kaminsky et al. (Walter Kaminsky, Klauus Klper, Hans H. Brintzin)
ger, Ferdinand RWPWild, Angew.Chem.Ed.Engl., 24 , 5
07 (1985)), zirconium tetrachloride ZrCl ₄
Ethylenebis (indenyl) dichlorozirconium was synthesized by the reaction of bis (indenyl) ethanedilithium salt with ethylene bis (4,5,6,7-tetrahydro), which was hydrogenated in the presence of platinum oxide PtO _2. -1-Indenyl) dichlorozirconium was obtained. Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) dimethyl zirconium C ₂ H ₄ (4,5,6,7-Tetrahydyo-1-indeny
l) ₂ Zr (CH ₃ ) ₂ ) is ethylene bis (4,5,6,7-tetrahydro-1-indenyl) dichlorozirconium and CH ₃ L
Synthesized and isolated by reaction i. 0.3 mol of toluene
The solution was stored in the dark at −78 ° C. under a nitrogen gas atmosphere.

Polymerization (MeCp) ₂ TiMe ₂ solution of 4.0 ml of heptane solution (0.3 mol / l) was used instead of C ₂ H ₄ (4,5,6,7-Tetrahydyo-1-indenv
l) Propylene polymerization was carried out in the same manner as in Example 1, except that 4.0 ml of a toluene solution (0.3 mol / l) of ₂ Zr (CH ₃ ) ₂ ) was used during the polymerization. The polymerization activity was 300 g-PP / g-Ti · hr, and II was 95%. No problem of coloring or smell was found in the produced polymer.

[Brief description of drawings]

FIG. 1 is a flow chart showing the components and preparation steps of the catalyst system used in the method of the present invention.

Claims (1)

[Claims] 1. A compound represented by the following general formula [I]: M _g (OR ¹ ) _2-n X _n [I] (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and 4 to 10 carbon atoms).
Is a cycloalkyl group or an aryl group, X is a halogen atom, and n is an integer satisfying 0 <n ≦ 2. ) And a magnesium compound represented by the following general formula [II]: Ti (OR ² ) _4-m X'm [II] (wherein R ² is an alkyl group having 1 to 10 carbon atoms, and 4 to 10 carbon atoms).
Is a cycloalkyl group or an aryl group, X ′ is a halogen atom, and m is an integer of 0 <n ≦ 4. )
And a metallocene comprising a cyclopentadienyl metal compound moiety obtained by contacting a titanium compound represented by the following general formula (III) or (IV) (C ₅ R ³ _q ) _p R ⁴ _t MR ⁵ R ⁶ _3-p (III) (In the formula, (C ₅ R ³ _q ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, R ³ is hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and R ³ is a mutual group. Which may be the same or different from each other, and two adjacent carbon atoms forming a cyclopentadienyl group or a substituted cyclopentadienyl group can be bonded to R ^{3 and} a ring having 4 to 6 carbon atoms. R ⁴ may form two (C ₅
R ³ _q ) is a group to be bonded, which is an alkylene group having 1 to 4 carbon atoms, dialkylgermanium, dialkylsilicon,
Selected from alkylphosphine and alkylamine groups, R ⁵ is a hydrocarbyl group having 1 to 20 carbon atoms,
R ⁶ is a hydrocarbyl group having 1 to 20 carbon atoms or a halogen atom, M is titanium or zirconium, t is 0 or 1, P is 1, 2 or 3, and P is 1 When t is 0, q is 4 when t is 1, 5 is when t is 0, Q is a methyl group or a chlorine atom, and R ⁸ is hydrocarbyl having 1 to 18 carbon atoms. Provided that R ⁸ is a methyl group when Q is a methyl group. The method for polymerizing olphin, which comprises polymerizing using a catalyst system containing a compound represented by the formula (1).