JPH072797B2 - Olefin Polymerization Method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for polymerizing an olefin using a Ziegler-based catalyst. More specifically, it relates to a polymerization method in which a stereoregular olefin polymer can be obtained in an extremely high yield by using a known three-component catalyst system comprising a compound containing a transition metal component and a highly active catalyst.

[Prior Art] Conventionally, when a catalyst having 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, see 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 and causes coloring, so that removal thereof is a major problem.

[Problems to be Solved by the Invention] An object of the present invention is to increase the 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 having high stereoregularity while maintaining the level. 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 ester has no 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. ] A magnesium compound represented by the following general formula [II]: Ti (OR ² ) _{4-m X'm} [II] [In the formula, 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 consisting of a complex obtained by contacting a titanium compound represented by the following, 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] [Wherein (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 They may be the same as 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 together with a ring having 4 to 6 carbon atoms. _{May be} formed, and R ⁴ has two (C ₅ ▲
R ³ _q ▼) is a group to be bonded, and is selected from an alkylene group having 1 to 4 carbon atoms, a dialkylgermanium, a dialkylsilicon, an alkylphosphine and an alkylamine group, and R ⁵ is a hydrocarbyl having 1 to 20 carbon atoms. A carbyl group, 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. ,
However, when P is 1, 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 1 to 1 carbon atoms. 18 is a hydrocarbyl group, provided that when Q is a methyl group, R ⁸ is a methyl group. ] It is a catalyst system containing the compound represented by this and the organic compound which has a Si-O bond.

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,
Trill, xylyl. X is a halogen atom, preferably a chlorine atom. n is an integer that satisfies 0 <n ≦ 2.

Specific examples of the above-mentioned magnesium compound include magnesium dihalide such as MgF ₂ , MgCl ₂ , MgBr ₂ , and MgI.
₂ , halohydrocarbyloxymagnesium, eg Mg
(OC ₂ H ₅ ) Cl, Mg (OC ₆ H ₅ ) Cl and the like. 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 . In the titanium compound represented by the general formula [II], alkyl, aryl or cycloalkyl having 1 to 10 carbon atoms which are the same as or different from R ² and R ¹ (among these,
[I] is the same as that 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 , Ti (OC ₄ H ₉ ) Cl ₃ , Ti (OC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₄ H ₉ ) 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) 2 Cl} 2, Ti (OC 3 H 7) 4 , and the like.

The contact between the magnesium compound represented by the general formula [I] and the titanium compound represented by the general formula [II] is generally
It may be carried out in the temperature range of -50 to 200 ° C. Contact time is usually 1
It is about 0 minutes to 48 hours. The two components can be brought into contact with each other by a mechanical pulverizing 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 hydrocarbons include hexane, heptane, benzene, toluene, cyclohexane, and the like, and specific examples of halogenated hydrocarbons include n-butyl chloride, n-butyl bromide, i-n-butyl iodide, and chlorobenzene. , N-octyl chloride, n-decyl chloride, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, benzyl chloride, iodobenzene and the like.

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] may be further represented by the general formula ▲ R ⁹ _3-r ▼ AlX ″ r or ▲ R ¹⁰ _3-s ▼ Al (O
An aluminum compound represented by R ¹¹ ) _s may be contacted. In these general formulas, R ⁹ , R ¹⁰ and R ¹¹ are hydrocarbon residues having 1 to 20 carbon atoms and may be the same or different, X ″ is a halogen atom, and r and s are 0 respectively. It is an integer satisfying ≦ r ≦ 2 and 0 ≦ s ≦ 1. Specific examples of such an aluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, trihexylaluminum, trioctylaluminum, and diethylaluminum monochloride. , Alkyl aluminum halides such as dimethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum butoxide, diethyl aluminum phenoxy Alkylaluminum alkoxides such as copper oxides, etc. Further, it is possible to use two or more of these aluminum compounds in combination.The contact with such aluminum compounds improves the sustainability of the polymerization activity during the polymerization of the catalyst. .

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 performed by stirring, 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, toluene, cyclohexane and the like. The amount of the aluminum compound used is preferably in the range of 0.01 to 200 (molar ratio) with respect to the magnesium compound [I], and more preferably in the range of 0.1 to 50 (molar ratio).

In the cyclopentadienyl compound 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 t at 1 at 4 o'clock and t is 0 at 5 o'clock. 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) methylchlorotitanium Cp ₂ TiMeCl Bis (cyclopentadienyl) dimethylzirconium Cp ₂ ZrMe ₂ Bis (indenyl) dimethyltitanium (Ind) ₂ TiMe ₂ Bis (indenyl) dimethylzirconium (Ind) ₂ ZrMe ₂ Ethylene bis (tetrahydroindenyl) dimethyl zirconium 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 compounds represented by the above general formulas [III], [IV] and [V] 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].

Further, the organic compound having a Si-O bond is represented by the general formula [VI] to [VI
II] is shown by the formula.

Si (OR ¹² ) _j ▲ R ¹³ _k ▼ [VI] R ¹⁴ (▲ R ¹⁵ ₂ ▼ SiO) _h Si ▲ R ¹⁶ ₃ ▼ [VII] (▲ R ¹⁷ ₂ ▼ SiO) _l [VIII] In the formula, R ¹² , R ¹³ and R ¹⁷ may be the same or different,
Hydrocarbon groups selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups having at most 20 carbon atoms (even if these are unsaturated, halogen atoms or at most 20 carbon atoms are present). R ¹³ may be a hydrogen atom or a halogen atom, and R ¹⁷ may be a hydrogen atom. R ¹⁴ , R ¹⁵
And R ¹⁶ may be the same or different, are the above hydrocarbon groups (these may be unsaturated or substituted) or halogen atoms, and j + k is 4 (provided that m ≠
0), h is an integer of 1 to 1000, and l is 2 to 10
It is an integer of 00.

Typical examples of the silicon compound represented by the formula (VI) include tetramethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, and tetrapropoxy. Silane, dipropoxypropylsilane, tetra-isopropoxysilane, di-isopropoxy-di-isopropylsilane, dimethoxydiethylsilane, diethoxydibutylsilane, tetra-n-butoxysilane, di-n-butoxy-di-n-butylsilane , Tetra-secondary-butoxysilane, tetrahexoxysilane, tetraoctoxysilane,
Tetraphenooxysilane, tetracresylsilane, trimethoxychlorosilane, dimethoxydichlorosilane,
Dimethoxydibromosilane, triethoxychlorosilane, diethoxydibromosilane, dibutoxychlorosilane, dicyclopentoxyethylsilane, diethoxydiphenylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane, 3, 5-dimethylphenoxytrimethylsilane, methylphenyl-bis (2-chloroethoxy) silane, dimethoxydibenzylsilane, tri-n-propylallyloxysilane, allyl
Tris (2-chloroethoxysilane and trimethoxy-
3-ethoxypropylsilane can be mentioned.

Further, typical examples of the silicon-based compound represented by the formula [VII] include hexamethyldicycloxane, octamethyltrisiloxane, tetracosamethylundecasiloxane, 3-hydroheptamethyltrisiloxane, and hexaphenyldisiloxane. , Hexacyclohexyldisiloxane, 1,3-dimethyldisiloxane, hexaethyldisiloxane, octaethyltrisiloxane, hexapropyldisiloxane, 1,3-dichlorotetramethyldisiloxane,
1,3- (bis-p-phenoxyphenyl) -1,3-dimethyl-1,
3-diphenyldisiloxane, 1,3-diallyl tetramethyldisiloxane, 1,3-dibenzyltetramethyldisiloxane, 2,2,4,4-tetraphenyl-2,4-disilane-1-oxa Included are cyclopentane, 1,1,3,3-tetramethyldisiloxane and hexachlorodisiloxane.

Furthermore, as typical ones of the silicon compounds represented by [VIII), 1,3,5-trimethylcyclotrisiloxane,
Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylchlorocyclotrisiloxane, 1,3,5-trimethyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,3,
5-tribenzyltrimethylcyclotrisiloxane and
An example is 1,3,5-triallyl trimethylcyclotrisiloxane.

Of these silicon compounds, R in the above formula [VI]
It is preferred that ¹² and R ¹³ are each represented by an alkyl group having at most 8 carbon atoms, a phenyl group or an aralkyl group. Further, in the formula [VII], it is preferable that R ¹⁴ , R ¹⁵ and R ¹⁶ are each represented by an alkyl group having at most 4 carbon atoms, a phenyl group or a halogen atom, and h is preferably 4 or less. . Further, in the above formula [VIII], it is desirable that R ¹⁷ is a hydrogen atom, an alkyl group having 4 or less carbon atoms, a phenyl group or a vinyl group, and further, 1 is preferably 10 or less. Examples of these suitable silicon compounds include diphenyldimethoxysilane and phenyltriethoxysilane. The amount of the above silicon compound used is 1 with respect to the cyclopentanedienyl compound represented by the formulas [III], [IV] and [V].
The following (molar ratio) is preferably in the range of 0.005 to 0.5. During the polymerization, the silicon compound may be mixed with the cyclopentadienyl compound in advance and used.

The olefin polymerized using the catalyst system of the present invention has a general formula R—CH═CH ₂ [wherein R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms and has a substituent group]. Also good]
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, or as a polymerization monomer. Polymerization temperature is -20
To 100 ° C, preferably 0 to 80 ° C, and the pressure is selected from atmospheric pressure to 100 atm.

EFFECTS OF THE INVENTION According to the polymerization method of the present invention, while maintaining the yield of the polymer per titanium in the catalyst component at a high level, an electron donor does not coexist in the polymerization system and high stereoregularity is achieved. An olefin polymer can be obtained. 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.

[Examples] 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 heated and dried under reduced pressure at a temperature of 300 ° C. for 2 hours. Then (4,6,
MgCl ₂ was pulverized for 2 hours by using a steel pulverizing 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 mechanism. The frequency was 8 Hz for a speed of 500 rpm.
Ethyl benzoate PhCO ₂ Et (5.5 mmol) was added to the crushed MgCl 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 was added and the suspension was reacted at a temperature of 60 ° C. for 2 hours. The concentration of TiCl ₄ was 60 mol /. After the reaction, the supernatant was removed, the mixture was 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 2.3% by weight of titanium.

Synthesis of bis (methylcyclopentadienyl) dimethyltitanium (MeCp) ₂ TiMe ₂ K. K.Clausset H. Bestion, Justus Liebig Ann. Chem., 65
4 , 8 (1962). ), 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 unstable to heat, light and oxygen,
In addition, considering the ease of use during polymerization, 0.3 m of heptane
It was diluted with ol / solution 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, 50 mg of the TiCl ₄ / PhCO ₂ Eh / MgCl ₂ catalyst prepared above was introduced, and the entire amount of heptane as a polymerization solvent (added later (MeCp) ₂ TiMe ₂ heptane solution and The amount of phenyltriethoxysilane in heptane solution is also included in the calculation].
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. Polymerization pressure is 1a
tm. Next, 4.0 mol of bis (methylcyclopentadienyl) dimethyltitanium (MeCp) ₂ TiMe ₂ in heptane (0.3 mol /) and phenyltriethoxysilane P
Polymerization was initiated by adding a mixed solution of 2.0 ml of a heptane solution of h (OEt) ₃ Si (0.03 mol /). Polymerization is 2
Polymerization was stopped by adding a hydrochloric acid-methanol solvent to the polymerization system for a period of time. The produced polymer was thoroughly washed with methanol and then vacuum dried. The polymerization activity (polymerization activity is an average value for 2 hours of polymerization, and is the same in the following Examples and Comparative Examples) was 900 g-PP / g-Tihr. The stereoregularity of the produced polymer is determined by boiling heptane extraction weight% (hereinafter, [I.
It is abbreviated as I]). In this example, II = 98%. 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 MeLi reacts with bis (cyclopentadienyl) dimethyltitanium Cp ₂ TiMe ₂
Was synthesized. Further, 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 / heptane solution and stored in the same manner.

Polymerization temperature was set to 25 ° C, using 4.0 ml of heptane solution of Cp ₂ TiMe ₂ (0.3 mol /) instead of 4.0 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 for the above. The polymerization activity was 260 g-PP / g-Ti · hr, and II was 97%. 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, GSReddy, J.Am.Chem.Soc., 11 , 3611 (1
978). ) (Bis (methylcyclopentadienyl) dimethyltitanium (MeCp) ₂ TiMe ₂ with trimethylaluminum AlMe ₃ to give (μ-methylene)
(Μ-methyl) bis (methylcyclopentadienyl)
(Dimethylaluminum) Titanium (MeCp) ₂ TiCH
₂ (CH ₃ ) Al (CH ₃ ) ₂ was synthesized. Without isolation, this was stored as a 0.3 mol / solution of heptane under a nitrogen gas atmosphere at -78 ° C in the dark.

Except for using the Polymerization (MeCp) ₂ TiMe ₂ solution in heptane (0.3 mol /) 4.0 ml instead of using the _{(MeCp) 2 TiCH 2 (CH} 3) AlMe 2 heptane solution (0.3 mol /) 4.0 ml at the time of polymerization Was polymerized with propylene in the same manner as in Example 1. The polymerization activity was 2050 g-PP / g-Tihr, and II was 96%. No coloration or odor problems were observed with the resulting polymer.

Comparative Example 1 TiCl ₄ / PhCO ₂ Et / MgCl to AlEt _{3 In} this example, AlEt ₃ commonly used for TiCl ₄ / PhCO ₂ Eh / 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,
Add all heptane as polymerization solvent (add later (AlEt) ₃
The amount of the heptane solution of was also included in the calculation) to be 100 ml. After stirring at a polymerization temperature of 40 ° C. for 5 minutes, nitrogen gas was evacuated and propylene gas was introduced to saturate for 20 minutes. The polymerization pressure was 1 atm. Next, heptane solution of AlEt (1.0 mol /
The polymerization was initiated by the addition of 1.0 ml). 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. Polymerization activity is 74
It was 90 g-PP / g-Tihr. The II of the produced polymer was 50%.

Comparative Example 2 TiCl ₄ / PhCO ₂ Et / MgCl 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 propylene 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-Ti
-Hr and II was 89%. PhC for the polymer produced
The odor due to O ₂ Et remained.

Example 4 Preparation of MgCl ₂ / TiCl ₄ solid catalyst 10.5 g (110.5 mmol) of anhydrous MgCl ₂ was heated and dried under reduced pressure at a temperature of 300 ° C. for 2 hours. Then various diameters (4,6,8,
12 mm) Steel crushing balls containing 50 g of steel balls were charged with 11.1 mmol of TiCl ₄ in the above dry-dried MgCl _{2 and} co-ground for 24 hours at room temperature in a nitrogen atmosphere. 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 obtained solid catalyst was found to contain 2.8 wt% titanium by colorimetric analysis.

Prepared above in place of 50 mg of combined TiCl ₄ / MgCl ₂ PhCO ₂ Et solid catalyst
When 62 mg of TiCl ₄ / MgCl ₂ solid catalyst was used, (MeC
p) ₂ TiMe ₂ in heptane solution (0.3mol /) 6.0ml and Ph (OE
t) Polymerization of propylene was carried out in the same manner as in Example 1 except that a mixed solution of 3.0 ml of a heptane solution of ₃ Si (0.03 mol /) 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 90 g-PP / g-Tihr. Polymer II
= 96%. No odor coloring was observed in the produced polymer.

Comparative Example 3 TiCl ₄ / MgCl _{2 to} AlEt _{3 As a} solid catalyst, 50 mg of the TiCl ₄ / MgCl ₂ catalyst prepared above in Example 4 was used, and a heptane solution of AlEt ₃ (1.0 mol / mol
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 0.6 mol of () was added. Polymerization activity is 3460g-PP / g-Ti
-Hr and II was 27%.

Synthesized in Example 3 in place of using a heptane solution (0.3 mol /) 6.0 ml Example 5 fold if _{(MeCp) 2 TiMe 2 (MeCp} ) 2 TiCH 2 (C
Polymerization of propylene was carried out in the same manner as in Example 4, except that 6.0 ml of a heptane solution of H ₃ ) AlMe ₂ (0.3 mol /) was used. The polymerization activity was 1000 g-PP / g-Ti · hr, and II was 96%. Neither odor nor coloring was observed in the produced polymer.

Example 6 Bis (cyclopentadienyl) dimethylzirconium Cp
₂ Synthesis of ZrMe ₂ . C. Method of PCWailes et al. (PCWailes, H.Wegold, APBell: J.Organomet.Chem., 3
4, in accordance with 155 (1972), bis (cyclopentadienyl) zirconium dichloride Cp ₂ ZrCl ₂ and methyllithium Me
Bis (cyclopentadienyl) dimethylzirconium Cp ₂ ZrMe ₂ was synthesized and isolated from the reaction with Li. Synthetic isolated Cp
₂ ZrMe ₂ is unstable to water, oxygen, etc., and considering the ease of use during polymerization, dilute it to 0.3 mol / solution of heptane and darken it in a nitrogen gas atmosphere at −78 ° C. in the dark. saved.

Same as Example 4 except that 6.0 ml of a heptane solution of ₂ Cp ₂ ZrMe ₂ (0.3 mol /) was used instead of 6.0 ml of a heptane solution of (MeCp) ₂ TiMe ₂ (0.3 mol /) at the time of polymerization. Polymerization was carried out by various methods. Polymerization activity is 75g-PP / g-Zr ・ hr
And II was 94%. 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 MCl ₂ was heated and dried under reduced pressure at a temperature of 300 ° C. for 2 hours. Then various diameters (4,6,8,
12 mm) Steel crushing balls containing 50 g of steel balls and having a capacity of 80 ml were charged with the above dry-dried MgCl ₂ , 11.1 mmol of Ti (OBu) ₄ and 170 mmol of heptane and 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 resulting solid was dried under vacuum at room temperature. The resulting solid catalyst was found by colorimetric analysis to contain 2.3% by weight of titanium.

When 75 mg of Ti (OBu) ₄ / MgCl ₂ / AlEt ₂ Cl solid catalyst prepared above was used instead of 50 mg of TiCl ₄ / PhCO ₂ Et / MgCl ₂ solid catalyst, heptane of (MeCp) ₂ TiMe ₂ was used during polymerization. Solution (0.3mol /
) 6.0 ml of Ph (OEt) ₃ Si in heptane (0.03 mol /
) Propylene was polymerized in the same manner as in Example 1 except that 3.0 ml of the mixed solution was used. The polymerization activity was 170 g-PP / g-Ti · hr. The resulting polymer II is
It was 97%. Neither smell nor coloring was observed.

Example 8 duplex if (MeCp) ₂ TiMe ₂ solution in heptane (0.3 mol /) instead _{(MeCp) 2 TiCH 2 (CH} 3) in 6.0 ml AlMe ₂ C heptane solution (0.3
Polymerization of propylene was carried out in the same manner as in Example 7 except that 6.0 ml of mol /) was used during the polymerization. The polymerization activity was 430 g-PP / g-Ti · hr, and II was 95%. 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 1900
It was g-PP / g-Ti · hr, and II was 48%.

Example 9 Preparation of Ti (OBu) ₄ / MgCl ₂ / AlEt ₂ Cl ₃ solid catalyst All were the same as in Example 7 except that 5.5 mmol of Al ₂ Et ₃ Cl ₃ was used instead of 11.1 mol of AlEt _2. The catalyst was prepared by the method. The titanium content in the solid catalyst obtained by the colorimetric analysis was 0.9% by weight.

Polymerized TiCl ₄ / PhCO ₂ Et / MgCl ₂ solid catalyst (50 mg) was replaced by Ti (OBu) ₄ / MgCl ₂ / Al ₂ Et ₃ Cl ₃ solid catalyst (192 mg) prepared during polymerization (MeCp) ₂ TiMe Heptane solution of ₂ (0.3mol /
) 6.0 ml and a solution of Ph (OEt) ₃ Si in heptane (0.03 mol /
) Polymerization of propylene was carried out in the same manner as in Example 1 except that 3.0 ml of the mixed solution was used. Polymerization activity is 90
g-PP / g-Ti · hr, II of the produced polymer was 97%. Neither smell nor 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 mol of a heptane solution of AlE ₃ was added during the polymerization. The polymerization activity was 2500 g-PP / g-Ti · hr, and II was 46%.

Example 10 Preparation of TiCl ₄ / n-BP / MgCl ₂ solid catalyst 10.5 g (110.5 mmol) of anhydrous MgCl ₂ was heated and dried under reduced pressure at a temperature of 300 ° C. for 2 hours. 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 above dry-dried MgCl ₂ and 2.1 ml of di-n-butyl phthalate (n-BP) were put therein and co-ground for 24 hours at room temperature under a nitrogen atmosphere. . 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 reacted with TiCl ₄ (50 ml) at 120 ° C. for 2 hours under a nitrogen atmosphere. The reaction product was thoroughly washed with toluene several times and the solid was dried under reduced pressure at room temperature. The resulting solid catalyst was found to contain 1.4 wt% titanium by colorimetric analysis.

124 mg of TiCl ₄ / n-BP / MgCl ₂ solid prepared above was used in place of 50 mg of polymerized TiCl ₄ / PhCO ₂ Et / MgCl ₂ solid catalyst, and (MeCp) ₂ TiMe ₂ in heptane solution (0.3 mol /) 6.0 ml
Polymerization of propylene was carried out in the same manner as in Example 1 except that a mixed solution of 3.0 ml of a heptane solution of Ph (OEt) ₃ Si (0.03 mol /) was used. Polymerization is carried out for 2 hours
Polymerization was stopped by adding a methanol solvent to the polymerization system. The polymerization activity was 85 g-PP / g-Ti · hr. The II of the produced polymer was 99%. Odor to the generated polymer,
No coloring was observed.

Example 11 fold if (MeCp) ₂ TiMe ₂ solution in heptane (0.3 mol /) to instead of using 6.0ml of _{(MeCp) 2 TiCH 2 (CE} 3) AlMe 2 heptane solution (0.3 mol /) at 6.0ml polymerization Polymerization of propylene was carried out in the same manner as in Example 10 except that the propylene was used. Polymerization activity was 2050 g-PP / g-Ti · hr, and II was 98%. Neither smell nor coloring was observed.

Example 12 (μ-methylene) (μ-methyl) bis (cyclopentadienyl) (dimethylaluminum) titanium Cp ₂ TiCH ₂
Synthesis of (CH ₃ ) AlMe ₂ F. N. Method of FNTebbe et al. (FNTebb
e, GWParshall, GSReddy, J.Am.Chem.Soc., 11 , 3611 (1
978). ), Bis (cyclopentadienyl) dimethyltitanium Cp ₂ TiMe ₂ and trimethylaluminum AlMe
By reaction with ₃ , (μ-methylene) (μ-methyl) bis (cyclopentadienyl) (dimethylaluminum)
Titanium Cp ₂ TiCH ₂ (CH ₃ ) AlMe ₂ was synthesized. Synthesized
Cp ₂ TiCH ₂ (CH ₃ ) AlMe ₂ was stored without isolation as a 0.3 mol / solution of heptane under a nitrogen gas atmosphere at −78 ° C. in the dark.

Instead of 6.0 ml of heptane solution of (MeCp) ₂ TiMe ₂ (0.3 mol /), 6.0 ml of heptane solution of Cp ₂ TiCH ₂ (CH ₃ ) AlMe ₂ (0.3 mol /) prepared above was used during polymerization. Polymerization of propylene was carried out in the same manner as in Example 11 except for the above.
The polymerization activity was 3600 g-PP / g-Ti · hr, and II was 98%. Neither smell nor coloring was observed.

Comparative Example 6 TiCl ₄ / n-BP / MgCl _{2 to} AlEt ₃ 124 mg of the TiCl ₄ / n-BP / MgCl ₂ catalyst prepared in Example 10 was used as a solid catalyst, and a heptane solution of AlEt ₃ (1.0 mol) was used during polymerization.
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 2.0 ml of /) was added. Polymerization activity is 4000g-PP / g-Ti
-Hr and II was 76%.

Comparative Example 7 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 8 TiCl ₃ to (MeCp) ₂ TiMe ₂ (CH ₃ ) AlMe ₂ Using 160 mg of Ti-reduced TiCl ₃ as a catalyst, (Me
Cp) ₂ TiCH ₂ (CH ₃ ) AlMe ₂ in heptane (0.3mol /)
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 3.4 ml of was used. The polymerization activity was 37 g-PP / g-Ti · hr. The II of the produced polymer was 93%.

Comparative Example _{9 MgCl 2 ~ (MeCp) 2} TiMe 2 solid component using a MgCl ₂ 500 mg for 2 hours Inuiku at 300 ° C. as 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.

Comparative Example 10 (MeCp) ₂ TiMe _{2 As a} solid component, nothing was added and (MeCp) ₂ TiMe ₂ was added during polymerization.
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 4.0 ml of the heptane solution (0.3 mol /) was used. There was no polymerization activity at all.

Comparative Example 11 MgCl ₂ to (MeCp) ₂ TiCH ₂ (CH ₃ ) AlMe _{2 As a} solid component, 500 mg of MgCl ₂ dried at 300 ° C. for 2 hours was used, and (MeCp) ₂ TiCH ₂ (CH ₃ ) AlMe ₂ was used during polymerization. Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 1.0 ml of the heptane solution was used. There was no polymerization activity at all.

Comparative Example 12 (MeCp) ₂ TiCH ₂ (CH ₃ ) AlMe _{2 No} solid component was added, and (MeCp) ₂ TiMe was added during polymerization.
Polymerization of propylene was carried out in the same manner as in Comparative Example 1 except that 4.0 ml of a heptane solution of ₂ (CH ₃ ) AlMe ₃ (0.3 mol /) was used. There was no polymerization activity at all.

Polymerization was carried out in the same manner as in Example 3, except that the silicon compounds shown in Table 1 were used instead of Examples 13, 14, 15, 16, 17 Ph (OEt) ₃ Si.

Polymerization was carried out in the same manner as in Example 5, except that the silicon compounds shown in Table 2 were used instead of Examples 18, 19, 20, 21, 22 Ph (OEt) ₃ Si.

Polymerization was carried out in the same manner as in Example 8 except that the silicon compounds shown in Table 3 were used instead of Examples 23, 24, 25, 26, 27 Ph (OEt) ₃ Si.

Polymerization was carried out in the same manner as in Example 12, except that the silicon compounds shown in Table 4 were used instead of Examples 28, 29, 30, _31, 32 Ph (OEt) ₃ Si.

Example 33 (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). ) Bis (cyclopentadienyl) dichlorotitanium Cp ₂ TiCl ₂ and trimethylaluminum Al according to
By reaction with (CH _{3) 3,} was synthesized (.mu.-methylene) (.mu.-chloro) bis (cyclopentadienyl) (dimethyl aluminum) titanium _{Cp 2 TiCH 2 (Cl) Al} (CH 3) 2. Without isolation, this was stored as a 0.3 mol / solution of heptane under a nitrogen gas atmosphere at -78 ° C in the dark.

Other than using 4.0 ml of a heptane solution (0.3 mol /) of poly (MeCp) ₂ TiMe _{2 in} the polymerization, 4.0 ml of a Cp ₂ TiCH ₂ (Cl) Al (CH ₃ ) ₂ heptane solution (0.3 mol /) was used. Was polymerized with propylene in the same manner as in Example 1. The polymerization activity was 680 g-PP / g-Ti · hr, and II was 97%. No coloring or odor problem was observed in the produced polymer.

Example 34 Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) dimethyl zirconium _{(C 2 H 4 (4,5,6,7-} tetrahydr
Synthesis of o-1-indenyl) ₂ Z- (CH ₃ ) ₂ ) The method of Walter Kaminsky et al. (Walter Kaminsky, Klauus Klper, Hans H. Brintzing)
er, Ferdinand RwPWild, Angew.Chem.Ed.Engl., 24 , 507
(1987), zirconium tetrachloride ZrCl ₄ was reacted with bis (indenyl) ethazilithium salt to synthesize ethylenebis (indenyl) dichlorozirconium, which was reacted with hydrogen in the presence of platinum oxide PtO ₂ to give ethylenebis (4 , 5,6,7-Tetrahydro-1-indenyl) dichlorozirconium was obtained. Ethylene bis (4,5,6,7−
Tetrahydro-1-indenyl) dimethyl zirconium (C ₂ H ₄ (4,5,6,7-tetrahydro-1-indenyl) ₂ Zr (C
H ₃ ) ₂ is ethylene bis (4,5,6,7-tetrahydro-1
- indenyl) were isolated synthetic single by reacting dichloro zirconium and CH ₃ Li. This was stored in a dark place at −78 ° C. under a nitrogen gas atmosphere as a toluene 0.3 mol / solution.

Instead of using 4.0 ml of heptane solution of (MeCp) ₂ TiMe ₂ (0.3 mol /), (C ₂ H ₄ (4,5,6,7-tetrahydro-1-inden
yl) ₂ Zr (CH ₃ ) ₂ ) in toluene (0.3mol /) 4.0ml
Polymerization of propylene was carried out in the same manner as in Example 1 except that was used during the polymerization.

The polymerization activity was 530 g-PP / g-Ti · hr, and II was 94%. No coloring or odor problem was observed in the produced polymer.

[Brief description of drawings]

FIG. 1 shows a flowchart of the olefin polymerization method of the present invention.

Claims (1)

[Claims] 1. The following general formula [I]: Mg (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] (In the formula, 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. )
And a metallocene comprising a cyclopentadienyl metal compound part 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. May be the same as 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 to form a ring having 4 to 6 carbon atoms. R ⁴ may be formed into two (C ₅ R ³
_q ) is a group which is bonded to C1 and is selected from an alkylene group having 1 to 4 carbon atoms, a dialkylgermanium, a dialkylsilicon, an alkylphosphine and an alkylamine group, and R ⁵ is a hydrocarbyl group having 1 to 20 carbon atoms. And 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, and p is 1, 2 or 3, provided that
When p is 1, t is 0, and q is 4:00 when t is 1, t
Is 5 when is 0, 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 a methyl group. Polymerization method of an olefin, which comprises polymerizing using a catalyst system containing a compound represented by the formula (4) and an organic compound having a Si-O bond.