JPH10298224A - Titanium complex compound, solid catalyst component for olefin polymerization prepared by using the same, olefin polymerization catalyst, and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid catalyst component for olefin polymn. which, when used in the polymn. of a 3C or higher α-olefin, can give a very highly stereoregular olefin polymer and to provide an olefin polymn. catalyst and a process for producing an olefin polymer. SOLUTION: This solid catalyst component is formed by bringing a titanium complex compd. represented by the formula: TiCl4 .AE [TiCl4 is titanium tetrachloride; and AE is an alkoxy ester compd. represented by the formula (2) (R1 and R2 are each independently a hydrocarbon group; and R3 and R4 are each independently H or a hydrocarbon group)] into contact with a magnesium compd. The olefin polymn. catalyst is prepd. from the solid catalyst component, an organoaluminum compd., and an electron-donating compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a titanium complex compound,
The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same. In particular, when the present invention is applied to the polymerization of olefins, high-performance catalysts, particularly olefins having 3 or more carbon atoms, a solid catalyst component for olefin polymerization capable of obtaining an olefin polymer having extremely high stereoregularity, olefin polymerization The present invention relates to a catalyst for use and a method for producing an olefin polymer.

[0002]

2. Description of the Related Art Heretofore, many solid catalyst components have been proposed which comprise a magnesium compound, a titanium compound, a halogen compound and an electron donating compound as essential components as a catalyst component used in the polymerization of olefins. These catalysts have high activity in the polymerization of olefins and
It is well known that olefins exhibit high stereospecificity in polymerization.

[0003] In particular, it is well known that when an aromatic ester such as a phthalic acid ester compound is used as an electron-donating compound in preparing the solid catalyst component, excellent performance is exhibited. (For example, JP-A-57-63310). In recent years, a catalyst system using a compound having two ether bonds existing through a plurality of atoms as the above-mentioned electron donating compound (JP-A-3-294)
304) has also been proposed.

The present inventors have also proposed that an excellent catalytic performance is exhibited when an alkoxyester compound is used as the electron-donating compound (Japanese Patent Laid-Open No. 2-28).
9604, JP-A-4-178406, JP-A-4-149
217, JP-A-4-185612, JP-A-4-1856
13, JP-A-7-133310, JP-A-8-14361
9). However, in recent years, in the field of industrial materials such as automobile parts and electric / electronic parts, olefin polymers having higher stereoregularity have been demanded, and even if these catalyst systems are used, they are satisfactory in terms of stereoregularity. Things are no longer available. For this reason, there has been a demand for the development of a catalyst that exhibits even higher stereospecific performance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst system which provides an olefin polymer having a very high stereoregularity, which was insufficient with the above prior art.

[0006]

Means for Solving the Problems The present inventors have conducted various studies to obtain a solid catalyst component for olefin polymerization which has solved these problems. As a result, a titanium complex compound represented by the following general formula (1) was obtained. By using an olefin polymerization solid catalyst component formed by contacting with a magnesium compound, by polymerizing or copolymerizing an olefin,
The inventors have found that an olefin polymer having extremely high stereoregularity can be obtained, and have reached the present invention.

Hereinafter, the titanium complex compound, the solid catalyst component for olefin polymerization, the catalyst for olefin polymerization, and the method for producing the olefin polymer according to the present invention will be specifically described. The titanium complex compound according to the present invention has the following general formula (1)
It is represented by TiCl ₄ .AE (1) (where TiCl ₄ is titanium tetrachloride and AE is an alkoxyester compound represented by the following general formula (2))

[0008]

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(Wherein R ¹ and R ² are hydrocarbon groups, which may be the same or different from each other. R ³ and R ⁴ are hydrocarbon groups or hydrogen atoms, and they are the same or different from each other. May be.)

In the present invention, the titanium complex compound represented by the general formula (1) is a complex compound of titanium tetrachloride and an alkoxyester compound (AE) represented by the general formula (2). This complex compound is obtained by contacting titanium tetrachloride with an alkoxyester compound (AE) represented by the general formula (2). The method of contacting the two is not particularly limited, and examples thereof include a method of contacting the two in an organic solvent. As the organic solvent, a hydrocarbon solvent such as hexane, heptane, and decane or an aromatic hydrocarbon solvent such as toluene can be used.

The molar ratio of the two when they are brought into contact with each other is as follows: 1 titanium tetrachloride and 1 alkoxy ester compound (AE).
10, usually in the range of 1-2. The temperature and time for contacting both are -100 to 150 ° C, 1 second to
24 hours. The temperature is preferably from -78 ° C to 100 ° C for 5 minutes to 2 hours, and in this case, it is preferable to perform the reaction in an inert gas atmosphere. After contacting both, unreacted compound by performing purification operations such as filtration, washing, distillation and recrystallization,
By-products and decomposition products can be removed. Thereby, a titanium complex compound represented by the general formula (1) is obtained.

The alkoxyester compound (AE) used in the present invention is a compound represented by the following general formula (2).

[0013]

Embedded image

In the formula, R ¹ and R ² are hydrocarbon groups, which may be the same or different from each other. The hydrocarbon group is preferably a straight chain having 1 to 20 carbon atoms or a branched hydrocarbon group having 3 to 20 carbon atoms. Particularly preferably,
It is a straight-chain or branched-chain hydrocarbon group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a tert- group. There are alkyl groups such as a butyl group and a 2-ethylhexyl group.

R ³ and R ⁴ are a hydrocarbon group or a hydrogen atom, which may be the same or different from each other. Among the hydrocarbon groups, preferably a straight chain having 1 to 20 carbon atoms,
It is a branched hydrocarbon group having 3 to 20 carbon atoms or a cyclic hydrocarbon group having 3 to 20 carbon atoms. Particularly preferably, it is linear having 1 to 8 carbon atoms,
A branched or cyclic hydrocarbon group having 3 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group Groups, a linear or branched alkyl group such as an isopentyl group, an isohexyl group and a 2-ethylhexyl group, and a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.

The above alkoxy ester compound (A
Specific examples of E) include methyl 3-methoxy-propionate, ethyl 3-methoxy-propionate, normal propyl 3-methoxy-propionate, isopropyl 3-methoxy-propionate, normal butyl 3-methoxy-propionate, Isobutyl 3-methoxy-propionate, tert-butyl 3-methoxy-propionate, 3
2-ethylhexyl methoxy-propionate, methyl 3-ethoxy-propionate, ethyl 3-ethoxypropionate, normal propyl 3-ethoxy-propionate, isopropyl 3-ethoxy-propionate, normal butyl 3-ethoxy-propionate, 3-ethoxy-
Isobutyl propionate, tert-butyl 3-ethoxy-propionate, 2-ethylhexyl 3-ethoxy-propionate, methyl 3-isopropoxy-propionate, ethyl 3-isopropoxy-ethyl propionate, normal propyl 3-isopropoxy-propionate, 3 -Isopropoxy-isopropylpropionate, 3-isopropoxy-normal butyl propionate, 3-isopropoxy-isobutyl propionate, 3-isopropoxy-
Tert-butyl propionate, 3-isopropoxy-
2-ethylhexyl propionate, 2-isopropyl-
Methyl 3-methoxy-propionate, ethyl 2-isopropyl-3-methoxy-propionate, normal propyl 2-isopropyl-3-methoxy-propionate, 2
Isopropyl-3-isopropyl-3-methoxy-propionate, normal butyl 2-isopropyl-3-methoxy-propionate, isobutyl 2-isopropyl-3-methoxy-propionate,

Tert-Butyl 2-isopropyl-3-methoxy-propionate, 2-ethylhexyl 2-isopropyl-3-methoxy-propionate, methyl 2-isopropyl-3-ethoxy-propionate, 2-isopropyl-3-ethoxy -Ethyl propionate, normal propyl 2-isopropyl-3-ethoxy-propionate, isopropyl 2-isopropyl-3-ethoxy-propionate, normal butyl 2-isopropyl-3-ethoxy-propionate, 2-isopropyl-3-ethoxy -Isobutyl propionate, 2-isopropyl-3-
Tert-butyl ethoxy-propionate, 2-ethylhexyl 2-isopropyl-3-ethoxy-propionate, methyl 2-isopropyl-3-isopropoxy-propionate, 2-isopropyl-3-isopropoxy-
Ethyl propionate, 2-isopropyl-3-isopropoxy-normal propionate, 2-isopropyl-3-isopropoxy-isopropyl propionate, 2-isopropyl-3-isopropoxy-normal propionate, 2-butyl-3-isopropoxy-propionate Isobutyl propionate, 2-isopropyl-
Tert-butyl 3-isopropoxy-propionate,
2-isopropyl-3-isopropoxy-2-ethylhexyl propionate, 2-isobutyl-3-methoxy-
Methyl propionate, 2-isobutyl-3-methoxy-
Ethyl propionate, 2-isobutyl-3-methoxy-
Normal propyl propionate, 2-isobutyl-3-
Isopropyl methoxy-propionate, normal butyl 2-isobutyl-3-methoxy-propionate, isobutyl 2-isobutyl-3-methoxy-propionate, 2
-Isobutyl-3-methoxy-propionic acid tert-
Butyl, 2-ethylhexyl 2-isobutyl-3-methoxy-propionate, 2-isobutyl-3-ethoxy-
Methyl propionate, 2-isobutyl-3-ethoxy-
Ethyl propionate, 2-isobutyl-3-ethoxy-
Normal propyl propionate, 2-isobutyl-3-
Isopropyl ethoxy-propionate, normal butyl 2-isobutyl-3-ethoxy-propionate, isobutyl 2-isobutyl-3-ethoxy-propionate, 2
-Tert-isobutyl-3-ethoxy-propionic acid-
Butyl, 2-ethylhexyl 2-isobutyl-3-ethoxy-propionate, methyl 2-isobutyl-3-isopropoxy-propionate, ethyl 2-isobutyl-3-isopropoxy-propionate,

Normal propyl 2-isobutyl-3-isopropoxy-propionate, isopropyl 2-isobutyl-3-isopropoxy-propionate, normal butyl 2-isobutyl-3-isopropoxy-propionate, 2-isobutyl-3-isopropoxy-propionate Acid isobutyl, 2-isobutyl-3-isopropoxy-
Tert-butyl propionate, 2-isobutyl-3-
2-ethylhexyl isopropoxy-propionate, 2
Methyl sec-butyl-3-methoxy-propionate, ethyl 2-sec-butyl-3-methoxy-propionate, normal propyl 2-sec-butyl-3-methoxy-propionate, 2-sec-butyl-3- Isopropyl methoxy-propionate, normal butyl 2-sec-butyl-3-methoxy-propionate, 2-s
ec-butyl-3-methoxy-propionate isobutyl, 2-sec-butyl-3-methoxy-propionate tert-butyl, 2-sec-butyl-3-methoxy-propionate 2-ethylhexyl, 2-sec-butyl- 3-ethoxy-methyl propionate, 2-sec-
Ethyl butyl-3-ethoxy-propionate, 2-se
n-propyl c-butyl-3-ethoxy-propionate, isopropyl 2-sec-butyl-3-ethoxy-propionate, 2-sec-butyl-3-ethoxy-
Normal butyl propionate, 2-sec-butyl-3
-Isobutyl ethoxy-propionate, tert-butyl 2-sec-butyl-3-ethoxy-propionate,
2-sec-butyl-3-ethoxy-propionic acid 2-
Ethylhexyl, methyl 2-sec-butyl-3-isopropoxy-propionate, 2-sec-butyl-3-
Ethyl isopropoxy-propionate, normal propyl 2-sec-butyl-3-isopropoxy-propionate, isopropyl 2-sec-butyl-3-isopropoxy-propionate, normal butyl 2-sec-butyl-3-isopropoxy-propionate, 2-sec
-Butyl-3-isopropoxy-isopropionate, tert-butyl 2-sec-butyl-3-isopropoxy-propionate, 2-ethylhexyl 2-sec-butyl-3-isopropoxy-propionate, 2-ethylhexyl
methyl tert-butyl-3-methoxy-propionate, ethyl 2-tert-butyl-3-methoxy-propionate, normal propyl 2-tert-butyl-3-methoxy-propionate,

Isopropyl 2-tert-butyl-3-methoxy-propionate, 2-tert-butyl-3-
Normal butyl methoxy-propionate, 2-tert
Isobutyl -butyl-3-methoxy-propionate, 2
-Tert-butyl-3-methoxy-propionic acid
rt-butyl, 2-tert-butyl-3-methoxy-
2-ethylhexyl propionate, methyl 2-tert-butyl-3-ethoxy-propionate, 2-tert
-Butyl-3-ethoxy-ethyl propionate, 2-t
n-propyl tert-butyl-3-ethoxy-propionate, isopropyl 2-tert-butyl-3-ethoxy-propionate, n-butyl 2-tert-butyl-3-ethoxy-propionate, 2-tert-
Isobutyl butyl-3-ethoxy-propionate, 2-
tert-butyl-3-ethoxy-propionic acid ter
t-butyl, 2-ethylhexyl 2-tert-butyl-3-ethoxy-propionate, methyl 2-tert-butyl-3-isopropoxy-propionate, 2-te
ethyl tert-butyl-3-isopropoxy-propionate, normal propyl 2-tert-butyl-3-isopropoxy-propionate, 2-tert-butyl-3
-Isopropoxy-isopropylpropionate, 2-t
n-butyl tert-butyl-3-isopropoxy-propionate, isobutyl 2-tert-butyl-3-isopropoxy-propionate, tert-butyl 2-tert-butyl-3-isopropoxy-propionate, 2-tert-butyl-3 -2-ethylhexyl isopropoxy-propionate, 2-isopentyl-3-
Methyl methoxy-propionate, 2-isopentyl-3
-Ethyl methoxy-propionate, 2-isopentyl-
Normal propyl 3-methoxy-propionate, isopropyl 2-isopentyl-3-methoxy-propionate, normal butyl 2-isopentyl-3-methoxy-propionate, isobutyl 2-isopentyl-3-methoxy-propionate, 2-isopentyl- Tert-butyl 3-methoxy-propionate, 2-isopentyl-
2-ethylhexyl 3-methoxy-propionate, 2-
Methyl isopentyl-3-ethoxy-propionate, 2
-Ethyl isopentyl-3-ethoxy-propionate,
2-isopentyl-3-ethoxy-propionate normal propyl, 2-isopentyl-3-ethoxy-propionate isopropyl, 2-isopentyl-3-ethoxy-propionate normal butyl,

2-Isopentyl-3-ethoxy-isopropionate isobutyl, 2-isopentyl-3-ethoxy-
Tert-butyl propionate, 2-isopentyl-3
2-ethylhexyl ethoxy-propionate, methyl 2-isopentyl-3-isopropoxy-propionate, ethyl 2-isopentyl-3-isopropoxy-ethyl propionate, 2-isopentyl-3-isopropoxy-
Normal propyl propionate, 2-isopentyl-3
Isopropyl isopropoxy-propionate, normal butyl 2-isopentyl-3-isopropoxy-propionate, isobutyl 2-isopentyl-3-isopropoxy-propionate, tert-butyl 2-isopentyl-3-isopropoxy-propionate, 2-isopentyl- 2-ethylhexyl 3-isopropoxy-propionate, methyl 2-isohexyl-3-methoxy-propionate, ethyl 2-isohexyl-3-methoxy-propionate, normal propyl 2-isohexyl-3-methoxy-propionate, 2-isohexyl Isopropyl-3-methoxy-propionate, normal butyl 2-isohexyl-3-methoxy-propionate, isobutyl 2-isohexyl-3-methoxy-propionate,
2-isohexyl-3-methoxy-propionic acid ter
t-butyl, 2-ethylhexyl 2-isohexyl-3-methoxy-propionate, methyl 2-isohexyl-3-ethoxy-propionate, 2-isohexyl-3-
Ethoxy-ethyl propionate, 2-isohexyl-3
-Normal propyl ethoxy-propionate, isopropyl 2-isohexyl-3-ethoxy-propionate,
Normal butyl 2-isohexyl-3-ethoxy-propionate, isobutyl 2-isohexyl-3-ethoxy-propionate, tert-butyl 2-isohexyl-3-ethoxy-propionate, 2-isohexyl-3-
2-ethylhexyl ethoxy-propionate, methyl 2-isohexyl-3-isopropoxy-propionate,
Ethyl 2-isohexyl-3-isopropoxy-propionate, normal propyl 2-isohexyl-3-isopropoxy-propionate, isopropyl 2-isohexyl-3-isopropoxy-propionate, normal butyl 2-isohexyl-3-isopropoxy-propionate, Isobutyl 2-isohexyl-3-isopropoxy-propionate, tert-butyl 2-isohexyl-3-isopropoxy-propionate,

2-isohexyl-3-isopropoxy-
2-ethylhexyl propionate, methyl 2- (2-ethylhexyl) -3-methoxy-propionate, 2-
Ethyl (2-ethylhexyl) -3-methoxy-propionate, 2- (2-ethylhexyl) -3-methoxy-
Normal propyl propionate, isopropyl 2- (2-ethylhexyl) -3-methoxy-propionate, 2
-(2-ethylhexyl) -3-methoxy-propionate normal butyl, 2- (2-ethylhexyl) -3-
Isobutyl methoxy-propionate, tert-butyl 2- (2-ethylhexyl) -3-methoxy-propionate, 2-ethylhexyl 2- (2-ethylhexyl) -3-methoxy-propionate, 2- (2-ethylhexyl)- Methyl 3-ethoxy-propionate, 2- (2
Ethyl-ethylhexyl) -3-ethoxy-propionate, normal propyl 2- (2-ethylhexyl) -3-ethoxy-propionate, isopropyl 2- (2-ethylhexyl) -3-ethoxy-propionate, 2-
N-butyl (2-ethylhexyl) -3-ethoxy-propionate, isobutyl 2- (2-ethylhexyl) -3-ethoxy-propionate, tert-butyl 2- (2-ethylhexyl) -3-ethoxy-propionate, 2 2- (2-ethylhexyl) -3-ethoxy-propionate 2-ethylhexyl, 2- (2-ethylhexyl) -3-isopropoxy-methyl propionate, 2-
Ethyl (2-ethylhexyl) -3-isopropoxy-propionate, normal propyl 2- (2-ethylhexyl) -3-isopropoxy-propionate, 2- (2
-Ethylhexyl) -3-isopropoxy-propionate isopropyl, 2- (2-ethylhexyl) -3-isopropoxy-propionate normal butyl, 2- (2
-Ethylhexyl) -3-isopropoxy-propionate isobutyl, 2- (2-ethylhexyl) -3-isopropoxy-propionate tert-butyl, 2- (2
2-ethylhexyl) -3-isopropoxy-propionate, methyl 2-cyclopentyl-3-methoxy-propionate, 2-cyclopentyl-3-
Methoxy-ethyl propionate, 2-cyclopentyl-
Normal propyl 3-methoxy-propionate, isopropyl 2-cyclopentyl-3-methoxy-propionate, normal butyl 2-cyclopentyl-3-methoxy-propionate, 2-cyclopentyl-3-methoxy-
Isobutyl propionate,

Tert-butyl 2-cyclopentyl-3-methoxy-propionate, 2-cyclopentyl-3-
2-ethylhexyl methoxy-propionate, methyl 2-cyclopentyl-3-ethoxy-propionate, 2-
Ethyl cyclopentyl-3-ethoxy-propionate,
Normal propyl 2-cyclopentyl-3-ethoxy-propionate, isopropyl 2-cyclopentyl-3-ethoxy-propionate, normal butyl 2-cyclopentyl-3-ethoxy-propionate, isobutyl 2-cyclopentyl-3-ethoxy-propionate, 2-cyclopentyl-3-ethoxy-propionic acid tert-
Butyl, 2-ethylhexyl 2-cyclopentyl-3-ethoxy-propionate, methyl 2-cyclopentyl-3-isopropoxy-propionate, ethyl 2-cyclopentyl-3-isopropoxy-propionate, 2-cyclopentyl-3-isopropoxy-propionate Normal propyl, 2-cyclopentyl-3-isopropoxy-isopropylate, 2-cyclopentyl-
3-isopropoxy-normal butyl propionate, 2
-Cyclopentyl-3-isopropoxy-propionate isobutyl, 2-cyclopentyl-3-isopropoxy-propionate tert-butyl, 2-cyclopentyl-3-isopropoxy-propionate 2-ethylhexyl, 2-cyclohexyl-3-methoxy-propionate methyl Ethyl 2-cyclohexyl-3-methoxy-propionate, normal propyl 2-cyclohexyl-3-methoxy-propionate, 2-cyclohexyl-3-
Isopropyl methoxy-propionate, normal butyl 2-cyclohexyl-3-methoxy-propionate, 2
Isobutyl cyclohexyl-3-methoxy-propionate, tert-butyl 2-cyclohexyl-3-methoxy-propionate, 2-ethylhexyl 2-cyclohexyl-3-methoxy-propionate, methyl 2-cyclohexyl-3-ethoxy-propionate Ethyl 2-cyclohexyl-3-ethoxy-propionate, normal propyl 2-cyclohexyl-3-ethoxy-propionate, isopropyl 2-cyclohexyl-3-ethoxy-propionate, normal butyl 2-cyclohexyl-3-ethoxy-propionate , 2-cyclohexyl-
Isobutyl 3-ethoxy-propionate, tert-butyl 2-cyclohexyl-3-ethoxy-propionate, 2-ethylhexyl 2-cyclohexyl-3-ethoxy-propionate,

Methyl 2-cyclohexyl-3-isopropoxy-propionate, ethyl 2-cyclohexyl-3-isopropoxy-propionate, normal propyl 2-cyclohexyl-3-isopropoxy-propionate, 2-cyclohexyl-3-isopropoxy-propionate Isopropyl, normal butyl 2-cyclohexyl-3-isopropoxy-propionate, isobutyl 2-cyclohexyl-3-isopropoxy-propionate, tert-butyl 2-cyclohexyl-3-isopropoxy-propionate, 2-cyclohexyl-3-isopropoxy-propionate 2-ethylhexyl acid, 2,
Methyl 2-diisopropyl-3-methoxy-propionate, ethyl 2,2-diisopropyl-3-methoxy-propionate, 2,2-diisopropyl-3-methoxy-
Normal propyl propionate, 2,2-diisopropyl-3-methoxy-isopropyl propionate, 2,2
-Normal butyl diisopropyl-3-methoxy-propionate, isobutyl 2,2-diisopropyl-3-methoxy-propionate, 2,2-diisopropyl-3-
Tert-butyl methoxy-propionate, 2-ethylhexyl 2,2-diisopropyl-3-methoxy-propionate, methyl 2,2-diisopropyl-3-ethoxy-propionate, 2,2-diisopropyl-3-ethoxy-propionic acid Ethyl, 2,2-diisopropyl-
Normal propyl 3-ethoxy-propionate, 2,2
-Isopropyl diisopropyl-3-ethoxy-propionate, normal butyl 2,2-diisopropyl-3-ethoxy-propionate, 2,2-diisopropyl-3
-Isobutyl ethoxy-propionate, tert-butyl 2,2-diisopropyl-3-ethoxy-propionate, 2-ethylhexyl 2,2-diisopropyl-3-ethoxy-propionate, 2,2-diisopropyl-3
Methyl isopropoxy-propionate, ethyl 2,2-diisopropyl-3-isopropoxy-propionate, normal propyl 2,2-diisopropyl-3-isopropoxy-propionate, isopropyl 2,2-diisopropyl-3-isopropoxy-propionate,
Normal butyl 2,2-diisopropyl-3-isopropoxy-propionate, 2,2-diisopropyl-3-
Isobutyl isopropoxy-propionate, 2,2-diisopropyl-3-isopropoxy-propionic acid
rt-butyl, 2-ethylhexyl 2,2-diisopropyl-3-isopropoxy-propionate,

Methyl 2,2-diisobutyl-3-methoxy-propionate, ethyl 2,2-diisobutyl-3-methoxy-propionate, 2,2-diisobutyl-3-
Normal propyl methoxy-propionate, isopropyl 2,2-diisobutyl-3-methoxy-propionate, normal butyl 2,2-diisobutyl-3-methoxy-propionate, isobutyl 2,2-diisobutyl-3-methoxy-propionate, 2,2-diisobutyl-
Tert-butyl 3-methoxy-propionate, 2,2
2-ethylhexyl diisobutyl-3-methoxy-propionate, methyl 2,2-diisobutyl-3-ethoxy-propionate, ethyl 2,2-diisobutyl-3-ethoxy-propionate, 2,2-diisobutyl-3-
Normal propyl ethoxy-propionate, isopropyl 2,2-diisobutyl-3-ethoxy-propionate, normal butyl 2,2-diisobutyl-3-ethoxy-propionate, isobutyl 2,2-diisobutyl-3-ethoxy-propionate, 2,2-diisobutyl-
Tert-butyl 3-ethoxy-propionate, 2,2
-2-ethylhexyl diisobutyl-3-ethoxy-propionate, methyl 2,2-diisobutyl-3-isopropoxy-propionate, 2,2-diisobutyl-3-
Ethyl isopropoxy-propionate, 2,2-diisobutyl-3-isopropoxy-normal propyl propionate, 2,2-diisobutyl-3-isopropoxy-
Isopropyl propionate, 2,2-diisobutyl-3
-Isopropoxy-normal butyl propionate, 2,
2-diisobutyl-3-isopropoxy-isopropionate, tert-butyl 2,2-diisobutyl-3-isopropoxy-propionate, 2-ethylhexyl 2,2-diisobutyl-3-isopropoxy-propionate, 2,2-diethyl methyl tert-butyl-3-methoxy-propionate, 2,2-ditert-butyl-
Ethyl 3-methoxy-propionate, 2,2-diter
normal propyl t-butyl-3-methoxy-propionate, isopropyl 2,2-ditert-butyl-3-methoxy-propionate, normal butyl 2,2-ditert-butyl-3-methoxy-propionate, 2, 2
Isobutyl di-tert-butyl-3-methoxy-propionate, tert-butyl 2,2-ditert-butyl-3-methoxy-propionate, 2,2-ditert
2-ethylhexyl-butyl-3-methoxy-propionate,

Methyl 2,2-ditert-butyl-3-ethoxy-propionate, ethyl 2,2-ditert-butyl-3-ethoxy-propionate, 2,2-dite
rt-butyl-3-ethoxy-n-propylpropionate, 2,2-ditert-butyl-3-ethoxy-
Isopropyl propionate, normal butyl 2,2-ditert-butyl-3-ethoxy-propionate, 2,2
Tert-butyl 2-di-tert-butyl-3-ethoxy-propionate, tert-butyl 2,2-di-tert-butyl-3-ethoxy-propionate, 2,2-di ter
2-ethylhexyl t-butyl-3-ethoxy-propionate, methyl 2,2-ditert-butyl-3-isopropoxy-propionate, ethyl 2,2-ditert-butyl-3-isopropoxy-propionate, 2, 2
-Ditert-butyl-3-isopropoxy-n-propylpropionate, 2,2-ditert-butyl-
3-isopropoxy-isopropyl propionate, 2,
2-ditert-butyl-3-isopropoxy-n-butylpropionate, 2,2-ditert-butyl-
3-isopropoxy-isobutyl propionate, 2,2
Di-tert-butyl-3-isopropoxy-propionate tert-butyl, 2,2-ditert-butyl-
2-ethylhexyl 3-isopropoxy-propionate, methyl 2,2-dicyclopentyl-3-methoxy-propionate, ethyl 2,2-dicyclopentyl-3-methoxy-propionate, 2,2-dicyclopentyl-
Normal propyl 3-methoxy-propionate, 2,2
Isopropyl dicyclopentyl-3-methoxy-propionate, 2,2-dicyclopentyl-3-methoxy-
Normal butyl propionate, 2,2-dicyclopentyl-3-methoxy-isobutyl propionate, 2,2-
Dicyclopentyl-3-methoxy-propionic acid ter
t-butyl, 2-ethylhexyl 2,2-dicyclopentyl-3-methoxy-propionate, methyl 2,2-dicyclopentyl-3-ethoxy-propionate, 2,2
-Ethyl dicyclopentyl-3-ethoxy-propionate, normal propyl 2,2-dicyclopentyl-3-ethoxy-propionate, 2,2-dicyclopentyl-
Isopropyl 3-ethoxy-propionate, normal butyl 2,2-dicyclopentyl-3-ethoxy-propionate, isobutyl 2,2-dicyclopentyl-3-ethoxy-propionate,

Tert-Butyl 2,2-dicyclopentyl-3-ethoxy-propionate, 2-ethylhexyl 2,2-dicyclopentyl-3-ethoxy-propionate, 2,2-dicyclopentyl-3-isopropoxy-
Methyl propionate, 2,2-dicyclopentyl-3-
Ethyl isopropoxy-propionate, normal propyl 2,2-dicyclopentyl-3-isopropoxy-propionate, isopropyl 2,2-dicyclopentyl-3-isopropoxy-propionate, isopropyl 2,2-dicyclopentyl-3-isopropoxy-propionate Normal butyl, isobutyl 2,2-dicyclopentyl-3-isopropoxy-propionate, tert-butyl 2,2-dicyclopentyl-3-isopropoxy-propionate, 2,2-dicyclopentyl-3-isopropoxy-
2-ethylhexyl propionate, 2-isopropyl-
Methyl 2-isopentyl-3-methoxy-propionate, ethyl 2-isopropyl-2-isopentyl-3-methoxy-propionate, normal propyl 2-isopropyl-2-isopentyl-3-methoxy-propionate, 2-isopropyl-2 Isopropyl isopentyl-3-methoxy-propionate, 2-isopropyl-2
-Normal butyl isopentyl-3-methoxy-propionate, isobutyl 2-isopropyl-2-isopentyl-3-methoxy-propionate, 2-isopropyl-
2-isopentyl-3-methoxy-propionic acid ter
t-butyl, 2-isopropyl-2-isopentyl-3
2-ethylhexyl methoxy-propionate, methyl 2-isopropyl-2-isopentyl-3-ethoxy-propionate, 2-isopropyl-2-isopentyl-
Ethyl 3-ethoxy-propionate, 2-isopropyl-2-isopentyl-3-ethoxy-propionate, 2-isopropyl-2-isopentyl-
Isopropyl 3-ethoxy-propionate, n-butyl 2-isopropyl-2-isopentyl-3-ethoxy-propionate, isobutyl 2-isopropyl-2-isopentyl-3-ethoxy-propionate, 2-isopropyl-2-isopentyl-3 Tert-butyl ethoxy-propionate, 2-ethylhexyl 2-isopropyl-2-isopentyl-3-ethoxy-propionate, methyl 2-isopropyl-2-isopentyl-3-isopropoxy-methyl propionate, 2-isopropyl-2
-Isopentyl-3-isopropoxy-ethyl propionate,

2-isopropyl-2-isopentyl-3
-Isopropoxy-normal propyl propionate, 2
-Isopropyl-2-isopentyl-3-isopropoxy-isopropylate, 2-isopropyl-2
-Isopentyl-3-isopropoxy-n-butyl propionate, 2-isopropyl-2-isopentyl-
3-isopropoxy-isobutyl propionate, 2-isopropyl-2-isopentyl-3-isopropoxy
Tert-butyl propionate, 2-isopropyl-2
-Isopentyl-3-isopropoxy-propionic acid 2
-Ethylhexyl, methyl 2-isopropyl-2-cyclopentyl-3-methoxy-propionate, ethyl 2-isopropyl-2-cyclopentyl-3-methoxy-propionate, 2-isopropyl-2-cyclopentyl-
Normal propyl 3-methoxy-propionate, 2-isopropyl-2-cyclopentyl-3-methoxy-propionate, normal butyl 2-isopropyl-2-cyclopentyl-3-methoxy-propionate, 2-isopropyl-2-cyclopentyl- 3-Methoxy-isopropionate, 2-isopropyl-2
-Cyclopentyl-3-methoxy-propionic acid ter
t-butyl, 2-isopropyl-2-cyclopentyl-
2-ethylhexyl 3-methoxy-propionate, 2-
Methyl isopropyl-2-cyclopentyl-3-ethoxy-propionate, ethyl 2-isopropyl-2-cyclopentyl-3-ethoxy-propionate, normal propyl 2-isopropyl-2-cyclopentyl-3-ethoxy-propionate, 2-isopropyl -2-cyclopentyl-3-ethoxy-isopropyl propionate,
Normal butyl 2-isopropyl-2-cyclopentyl-3-ethoxy-propionate, 2-isopropyl-2
Isobutyl cyclopentyl-3-ethoxy-propionate, tert-butyl 2-isopropyl-2-cyclopentyl-3-ethoxy-propionate, 2-ethylhexyl 2-isopropyl-2-cyclopentyl-3-ethoxy-propionate, 2-isopropyl -2-cyclopentyl-3-isopropoxy-methyl propionate,
Ethyl 2-isopropyl-2-cyclopentyl-3-isopropoxy-propionate, 2-isopropyl-2-
Normal propyl cyclopentyl-3-isopropoxy-propionate, isopropyl 2-isopropyl-2-cyclopentyl-3-isopropoxy-propionate,

2-isopropyl-2-cyclopentyl-
3-isopropoxy-normal butyl propionate, 2
-Isopropyl-2-cyclopentyl-3-isopropoxy-isopropionate, 2-isopropyl-2
-Tert-butyl cyclopentyl-3-isopropoxy-propionate, 2-ethylhexyl 2-isopropyl-2-cyclopentyl-3-isopropoxy-propionate, methyl 2-methyl-2-tert-butyl-3-methoxy-propionate, 2 -Methyl-2-tert
Ethyl-butyl-3-methoxy-propionate, n-propyl-2-methyl-2-tert-butyl-3-methoxy-propionate, isopropyl 2-methyl-2-tert-butyl-3-methoxy-propionate, 2-
Normal butyl methyl-2-tert-butyl-3-methoxy-propionate, isobutyl 2-methyl-2-tert-butyl-3-methoxy-propionate, 2-methyl-2-tert-butyl-3-methoxy-propionate Tert-butyl acid, 2-ethylhexyl 2-methyl-2-tert-butyl-3-methoxy-propionate, methyl 2-methyl-2-tert-butyl-3-ethoxy-propionate, 2-methyl-2-tert Ethyl-butyl-3-ethoxy-propionate, normal propyl 2-methyl-2-tert-butyl-3-ethoxy-propionate, isopropyl 2-methyl-2-tert-butyl-3-ethoxy-propionate, 2- Normal butyl methyl-2-tert-butyl-3-ethoxy-propionate, -Methyl-2-tert-butyl-3-ethoxy-propionate isobutyl, 2-methyl-2-tert-butyl-3-ethoxy-tert-butyl propionate, 2-methyl-2-tert-butyl-3-ethoxy -2-ethylhexyl propionate, 2
Methyl-methyl-2-tert-butyl-3-isopropoxy-propionate, ethyl 2-methyl-2-tert-butyl-3-isopropoxy-propionate, 2-
Methyl-2-tert-butyl-3-isopropoxy-
Normal propyl propionate, 2-methyl-2-te
isopropyl tert-butyl-3-isopropoxy-propionate, normal butyl 2-methyl-2-tert-butyl-3-isopropoxy-propionate, isobutyl 2-methyl-2-tert-butyl-3-isopropoxy-propionate, 2 Tert-butyl-methyl-2-tert-butyl-3-isopropoxy-propionate,

2-methyl-2-tert-butyl-3-
2-ethylhexyl isopropoxy-propionate, 2
Methyl-ethyl-2-cyclohexyl-3-methoxy-propionate, 2-ethyl-2-cyclohexyl-3-
Ethyl methoxy-propionate, n-propyl 2-ethyl-2-cyclohexyl-3-methoxy-propionate, isopropyl 2-ethyl-2-cyclohexyl-3-methoxy-propionate, 2-ethyl-2-cyclohexyl-3-methoxy -Normal butyl propionate, 2-ethyl-2-cyclohexyl-3-methoxy-
Isobutyl propionate, tert-butyl 2-ethyl-2-cyclohexyl-3-methoxy-propionate,
2-ethylhexyl 2-ethyl-2-cyclohexyl-3-methoxy-propionate, methyl 2-ethyl-2-cyclohexyl-3-ethoxy-propionate, ethyl 2-ethyl-2-cyclohexyl-3-ethoxy-propionate, Normal propyl 2-ethyl-2-cyclohexyl-3-ethoxy-propionate, 2-ethyl-2
-Isopropyl cyclohexyl-3-ethoxy-propionate, normal butyl 2-ethyl-2-cyclohexyl-3-ethoxy-propionate, isobutyl 2-ethyl-2-cyclohexyl-3-ethoxy-propionate, 2-ethyl-2- Cyclohexyl-3-ethoxy-
Tert-butyl propionate, 2-ethyl-2-cyclohexyl-3-ethoxy-propionate 2-ethylhexyl, 2-ethyl-2-cyclohexyl-3-isopropoxy-methyl propionate, 2-ethyl-2-cyclohexyl-3- Ethyl isopropoxy-propionate, 2-ethyl-2-cyclohexyl-3-isopropoxy-propionate normal propyl, 2-ethyl-2
-Cyclohexyl-3-isopropoxy-isopropylate, 2-ethyl-2-cyclohexyl-3-
Normal butyl isopropoxy-propionate, isobutyl 2-ethyl-2-cyclohexyl-3-isopropoxy-propionate, tert-butyl 2-ethyl-2-cyclohexyl-3-isopropoxy-propionate, 2-ethyl-2-cyclohexyl-3 2-ethylhexyl isopropoxy-propionate and the like.

The solid catalyst component for olefin polymerization according to the present invention is formed by bringing a titanium complex compound represented by the general formula (1) into contact with a magnesium compound. The magnesium compound used in the present invention includes magnesium halides such as magnesium chloride and magnesium bromide: ethoxymagnesium, alkoxymagnesiums such as isopropoxymagnesium: magnesium carboxylates such as magnesium laurate and magnesium stearate. Acid salts: alkylmagnesium such as butylethylmagnesium can be exemplified. Also, a mixture of two or more of these compounds may be used. Preferably, a magnesium halide is used, and more preferably, the halogen is chlorine. Alcohol compounds, ether compounds,
A magnesium halide to which an oxygen-containing organic compound such as an ester compound is added may be used. Examples of the alcohol compound include ethanol, butanol, 2-ethylhexanol and the like, examples of the ether compound include tetrahydrofuran, diethers and alkoxysilanes, and examples of the ester compound include formate, benzoate and phthalate.

The method of contacting the titanium complex compound represented by the general formula (1) with the magnesium compound is not particularly limited, but a specific method is to use a vibrating ball mill or the like to convert the two. A method of co-milling can be exemplified. Further, a method of contacting both by dispersing and dissolving in a solvent can also be exemplified. At this time, any of a method of dispersing and contacting the two, a method of dispersing one and dissolving the other to make contact with each other, and a method of dissolving and contacting both may be used, and a combination of a precipitation operation and the like is also possible. Among these, the preferred method is
This is a method in which a titanium complex compound represented by the general formula (1) is dissolved in a solvent to form a uniform solution, and then a magnesium compound is brought into contact. The solvent used is not particularly limited, but examples thereof include a hydrocarbon solvent such as hexane, heptane or decane, and an aromatic hydrocarbon solvent such as toluene, and these may be used in combination.

The molar ratio when the two are brought into contact with each other is arbitrary as long as the effect of the present invention is recognized, but the following range is generally preferred. Within the range of 0.001-1000 titanium complex compound, preferably 0.0
It is in the range of 1-100.

The temperature and the time when the two are brought into contact with each other vary depending on the contact method, but are generally -100 to 200.
° C, 1 minute to 72 hours, preferably -78 ° C to 150 ° C,
It is 30 minutes to 48 hours, and in this case, it is preferable to carry out in an inert gas atmosphere. The solid catalyst component for olefin polymerization thus obtained may be used as it is for the production of an olefin polymer, but may be used after removing unreacted products and by-products by operations such as filtration and washing. I can do it.

The solid catalyst component for olefin polymerization of the present invention can also be obtained by contacting the solid catalyst component for olefin polymerization with a Lewis acid compound and / or a Lewis base compound.

As the Lewis acid compound used in the present invention, phosphorus chloride compounds such as phosphorus trichloride and phosphorus pentachloride: silicon tetrachloride: titanium trichloride compounds such as titanium trichloride and titanium tetrachloride: triethylaluminum; Organic aluminum compounds such as tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diethylaluminum bromide and ethylaluminum sesquichloride are exemplified.

The amount of the Lewis acid compound to be brought into contact is arbitrary as long as the effects of the present invention are recognized, but the following range is generally preferred. The molar ratio of the Lewis acid compound to the magnesium compound 1 is in the range of 0.001 to 1000, preferably 0.01 to 100.

The Lewis base compound used in the present invention includes an oxygen-containing compound and a nitrogen-containing compound. As the oxygen-containing compound, alcohols, phenols, ketones, aldehydes, ethers, ketoethers, organic acid esters, inorganic acid esters, alkoxyesters, ketoesters, acid anhydrides, thiols, thioethers, Sulfuric esters, sulfonic acids, and alkoxysilanes, and nitrogen-containing compounds include amines, amides, and nitriles. Of these, alcohols, ethers, ketoethers, organic acid esters, alkoxyesters, ketoesters, and alkoxysilanes are preferred.

Specific examples of alcohols include methanol, ethanol, propanol, butanol, heptanol, hexanol, octanol, dodecanol, octadecyl alcohol, 2-ethylhexanol, benzyl alcohol, cumyl alcohol, diphenylmethanol, triphenylmethanol and the like. Alcohols having 1 to 20 carbon atoms are exemplified.

Specific examples of ethers include methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofurananisole, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether,
Ethers having 2 to 25 carbon atoms such as 2,2-dimethoxypropane, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-1 , 3-Dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2
-Cumyl-1,3-dimethoxypropane, 2- (phenylethyl) -1,3-dimethoxypropane, 2- (2-
Cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1, 3-dimethoxypropane, 2- (2-fluorophenyl) -1,3
-Dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (p-ter
t-butylphenyl) -1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,
2,2-diisopropyl-1,3-dimethoxypropane, 2,2-ditert-butyl-1,3-dimethoxypropane, 2-methyl-2-normalpropyl-1,3
-Dimethoxypropane, 2-methyl-2-benzyl-
1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxy Propane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2
-Cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl)-
1,3-dimethoxypropane, 2,2-diisobutyl-
1,3-dimethoxypropane, 2,2-diphenyl-
1,3-dimethoxypropane, 2,2-dibenzyl-
Examples thereof include diethers such as 1,3-dimethoxypropane and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane.

As the ketoethers, specifically, (1-
Isopropyl-2-methoxyethyl) methylketone,
(1-methyl-1-isopropyl-2-methoxyethyl) methylketone, (1,1-diisopropyl-2-methoxyethyl) methylketone, (1-isopropyl-1
-Normal butyl-2-methoxyethyl) methyl ketone, (1-isopropyl-1-isobutyl-2-methoxyethyl) methyl ketone, (1-isobutyl-2-methoxyethyl) methyl ketone, (1,1-diisobutyl-
2-methoxyethyl) methylketone, (1-tert-
Butyl-2-methoxyethyl) methylketone, (1-t
tert-butyl-2-ethoxyethyl) methylketone,
(1-methyl-1-tert-butyl-2-methoxyethyl) methylketone, (1-isopentyl-2-methoxyethyl) methylketone, (1-methyl-1-isopentyl-2-methoxyethyl) methylketone, (1-isopropyl -1-Isopentyl-2-methoxyethyl) methylketone, (1-tert-butyl-1-isopentyl-2-methoxyethyl) methylketone, (1-isopentyl-2-ethoxyethyl) methylketone, (1-methyl-1-isopentyl) -2-ethoxyethyl) methylketone, (1-isopropyl-1-isopentyl-2-)
(Ethoxyethyl) methylketone, (1-tert-butyl-1-isopentyl-2-ethoxyethyl) methylketone, (1-cyclohexyl-2-methoxyethyl) methylketone, (1-methyl-1-cyclohexyl-2-)
(Methoxyethyl) methyl ketone, (1-isopropyl-
1-cyclohexyl-2-methoxyethyl) methyl ketone, (1-tert-butyl-1-cyclohexyl-2)
-Methoxyethyl) methyl ketone, (1-isopropyl-2-methoxyethyl) phenyl ketone, (1-methyl-1-isopropyl-2-methoxyethyl) phenyl ketone, (1,1-diisopropyl-2-methoxyethyl) phenyl ketone , (1-isopropyl-1-normalbutyl-2-methoxyethyl) phenyl ketone, (1
-Isopropyl-1-isobutyl-2-methoxyethyl) phenyl ketone, (1-isobutyl-2-methoxyethyl) phenyl ketone, (1,1-diisobutyl-2)
-Methoxyethyl) phenyl ketone, (1-tert-
Butyl-2-methoxyethyl) phenylketone, (1-
(tert-butyl-2-ethoxyethyl) phenylketone, (1-methyl-1-tert-butyl-2-methoxyethyl) phenylketone, (1-isopentyl-2-)
(Methoxyethyl) phenylketone, (1-methyl-1-)
Isopentyl-2-methoxyethyl) phenyl ketone,
(1-Isopropyl-1-isopentyl-2-methoxyethyl) phenylketone, (1-tert-butyl-1)
-Isopentyl-2-methoxyethyl) phenylketone, (1-isopentyl-2-ethoxyethyl) phenylketone, (1-methyl-1-isopentyl-2-ethoxyethyl) phenylketone, (1-isopropyl-1)
-Isopentyl-2-ethoxyethyl) phenylketone, (1-isopropyl-2-methoxyethyl) isopropylketone, (1-methyl-1-isopropyl-2-)
(Methoxyethyl) isopropylketone, (1,1-diisopropyl-2-methoxyethyl) isopropylketone, (1-isopropyl-1-normalbutyl-2-methoxyethyl) isopropylketone, (1-isopropyl-1-isobutyl-2-) (Methoxyethyl) isopropylketone, (1-isobutyl-2-methoxyethyl) isopropylketone, (1,1-diisobutyl-2-methoxyethyl) isopropylketone, (1-tert-butyl-2-methoxyethyl) isopropylketone, ( 1
-Tert-butyl-2-ethoxyethyl) isopropylketone, (1-methyl-1-tert-butyl-2-)
(Methoxyethyl) isopropyl ketone, (1-isopentyl-2-methoxyethyl) isopropyl ketone, (1
-Methyl-1-isopentyl-2-methoxyethyl) isopropyl ketone, (1-isopropyl-1-isopentyl-2-methoxyethyl) isopropyl ketone, (1
-Tert-butyl-1-isopentyl-2-methoxyethyl) isopropylketone, (1-isopentyl-2)
-Ethoxyethyl) isopropylketone, (1-methyl-1-isopentyl-2-ethoxyethyl) isopropylketone, (1-isopropyl-1-isopentyl-2)
And ketoesters such as (ethoxyethyl) isopropylketone.

Specific examples of the organic acid esters include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl propionate,
Methyl normal butyrate, methyl isobutyrate, ethyl isobutyrate, isopropyl isobutyrate, ethyl valerate, butyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl methacrylate, ethyl crotonate, cyclohexanecarbon Ethyl acetate, methyl phenylacetate, methyl phenylbutyrate, propyl phenylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate,
Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, Diisobutyl phthalate, diheptyl phthalate, dineopentyl phthalate, γ
Organic acid esters having 2 to 20 carbon atoms, such as -butyrolactone, [gamma] -palerolactone, coumarin, phthalide, diethyl carbonate, methyl orthoformate and ethyl orthoformate.

As the alkoxyesters, specifically,
The alkoxy ester compound (AE) represented by the general formula (2) described above is exemplified. Specific examples of ketoesters include methyl acetyl acetate, ethyl acetyl acetate, butyl acetyl acetate, methyl propionyl acetate, phenyl acetyl acetate, ethyl propionyl acetate, butyl propionyl acetate, phenyl propionyl acetate, butyl propionyl acetate, ethyl butyryl acetate, and isobutanoyl acetate. Ethyl, ethyl pentanoyl acetate, methyl 3-acetylpropionate, ethyl 3-acetylpropionate, butyl 3-acetylpropionate, ethyl 3-propionylpropionate, butyl 3-propionylpropionate, normal octyl 3-propionylpropionate, Dodecyl 3-propionylpropionate, pentamethylphenyl 3-propionylpropionate,
Ethyl (isopropionyl) propionate, butyl 3- (isopropionyl) propionate, allyl 3- (isopropionyl) propionate, cyclohexyl 3- (isopropionyl) propionate, ethyl 3-neopentanoylpropionate, 3-normal Butyl lauryl propionate, methyl 3- (2,6-dimethylhexanoyl) propionate, ethyl 4-propionyl butyrate, 4-
Cyclohexyl propionyl butyrate, octyl 5-butyryl valerate, ethyl 12-butyryl laurate, methyl 3-acetyl acrylate, methyl 2-acetyl acrylate, ethyl 3-benzoyl propionate, methyl 3-benzoyl propionate, 3-methyl Ethyl benzoylpropionate, butyl 3-toluylbutyrate, ethyl o-benzoylbenzoate, ethyl m-benzoylbenzoate, p-
Ethyl benzoylbenzoate, butyl o-toluylbenzoate, ethyl o-toluylbenzoate, ethyl m-toluylbenzoate, ethyl p-toluylbenzoate, o- (2,
4,6-Trimethylbenzoyl) ethyl benzoate, m-
Ethyl (2,4,6-trimethylbenzoyl) benzoate, ethyl p- (2,4,6-trimethylbenzoyl) benzoate, ethyl o-ethylbenzoylbenzoate, o-
Ketoesters such as ethyl acetylbenzoate, ethyl o-propionylbenzoate, ethyl o-laurylbenzoate, ethyl o-cyclohexanoylbenzoate and ethyl o-dodecylbenzoate are exemplified.

Specific examples of the alkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, vinyltriethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane,
Containing silicon having 2 to 24 carbon atoms such as triphenylmethoxysilane, hexamethyldisiloxane, octamethyltrisiloxane, trimethylsilanol, phenyldimethylsilanol, triphenylsilanol, diphenylsilanediol, and lower alkyl silicate (especially ethyl silicate) Compounds are exemplified.

The amount of the Lewis base compound to be brought into contact is arbitrary as long as the effect of the present invention is recognized, but the following range is generally preferred. The molar ratio of the Lewis base compound to the magnesium compound 1 is in the range of 0.001 to 1000, preferably 0.01 to 100.

The contact method and conditions are not particularly limited, but the methods and conditions described in the item of contact between the titanium complex compound represented by the general formula (1) and the magnesium compound are exemplified. Can be done. The order of contacting both the Lewis acid compound and the Lewis base compound is not particularly limited, either. Either the method or the method of contacting both simultaneously may be used. The solid catalyst component for olefin polymerization thus obtained may be used as it is for the production of an olefin polymer, but may be used after removing unreacted products and by-products by operations such as filtration and washing. I can do it.

The olefin polymerization catalyst according to the present invention comprises:
It consists of a solid catalyst component for olefin polymerization and an organoaluminum compound. In addition, an electron-donating compound can also be used as the third component.

Representative examples of the organoaluminum compound in the present invention are represented by the following general formulas (3) to (5).

[0048]

Embedded image

In equations (3), (4) and (5), R
⁸, R⁹, R^TenMay be the same or different and have many carbon atoms
With 12 hydrocarbon groups, halogen atoms or hydrogen atoms
But at least one of them is a hydrocarbon group
R¹¹, R¹², R¹³And R ¹⁴May be the same or different
And a hydrocarbon group having at most 12 carbon atoms. Also
R^FifteenIs a hydrocarbon group having at most 12 carbon atoms,
n is an integer of 1 or more.

Representative examples of the organoaluminum compound represented by the formula (3) include trialkylaluminums such as triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum. Furthermore, alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, and alkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride can be mentioned.

Representative examples of the organoaluminum compound represented by the formula (4) include alkyldialuminoxanes such as tetraethyldialuminoxane and tetrabutyldialuminoxane.

Formula (5) represents aluminoxane, which is a polymer of an aluminum compound. R ¹⁵ includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and is preferably a methyl group or an ethyl group. The value of n is preferably 1 to 10.

Of these organoaluminum compounds,
Trialkylaluminums, alkylaluminum halides and alkylaluminoxanes are preferred, and trialkylaluminums are particularly preferred because they give favorable results.

In the production of the olefin polymer, the amount of the organoaluminum compound used in the polymerization system is generally at least 10 ^-4 mmol / l, preferably at least 10 ^-2 mmol / l. The molar ratio of the solid catalyst component for olefin polymerization to titanium atom is generally 0.5 or more, preferably 2 or more, and more preferably 10 or more. If the amount of the organoaluminum compound is too small, the polymerization activity is significantly reduced. When the amount of the organoaluminum compound used in the polymerization system is 20 mmol / l or more and the ratio to the titanium atom is 1000 or more in molar ratio, the catalyst performance is further improved even if these values are further increased. I will not do it.

In the olefin polymerization catalyst according to the present invention, an electron donating compound is used as the third component in addition to the solid catalyst component for olefin polymerization and the organic aluminum compound. As the electron donating compound, it is preferable to use at least one compound selected from an organic silicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound and an oxygen-containing compound. Among them, it is particularly preferable to use an organosilicon compound having an alkoxy group. The amount of the electron-donating compound used as the third component is such that the molar ratio to the organoaluminum compound is 0.0
It is in the range of 01-5, preferably 0.01-1.

Specific examples of the organosilicon compound having an alkoxy group include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and triethylethoxysilane. , Ethyl isopropyl dimethoxy silane, propyl isopropyl dimethoxy silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silane, isopropyl isobutyl dimethoxy silane, di te
rt-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylnormalpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylnormalbutyldimethoxysilane, tert-butylisobutyldimethoxysilane, t
tert-butyl (sec-butyl) dimethoxysilane,
tert-butylamyldimethoxysilane, tert-
Butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, tert-butyldecyldimethoxysilane, te
rt-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, tert-butyl (cyclopentyl) dimethoxysilane, tert-butyl (cyclohexyl) dimethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane , Bis (2,3-dimethylcyclopentyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, mesityltrimethoxysilane, ethyltrimethoxysilane, normal propyltrimethoxysilane,
Isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornane Trimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl (tert-butoxy) dimethoxysilane, isopropyl (tert-butoxy) dimethoxysilane, ter
t-butyl (isobutoxy) dimethoxysilane, ter
t-butyl (tert-butoxy) dimethoxysilane,
Texyltrimethoxysilane, texyl (isopropoxy) dimethoxysilane, texyl (tert-butoxy) dimethoxysilane, and the like.

As the nitrogen-containing compound, specifically,
2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl-2,2,
2,6-substituted piperidines such as 6,6-tetramethylpiperidine, 2,5-diisopropylazolidine, N-
2,5-substituted azolidines such as methyl-2,2,5,5-tetramethylazolidine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethyl Substituted methylene diamines such as methylene diamine; and substituted imidazolines such as 1,3-dibenzyl imidazolidine and 1,3-dibenzyl-2-phenyl imidazolidine.

Specific examples of the phosphorus-containing compound include triethyl phosphite, trinormal propyl phosphite, triisopropyl phosphite, trinormal butyl phosphite, triisobutyl phosphite, diethyl normal butyl phosphite, and diethyl phenyl phosphite. And the like.

As the oxygen-containing compound, specifically,
2,2,6,6-tetramethyltetrahydrofuran,
2,6-substituted tetrahydrofurans such as 2,2,6,6-tetraethyltetrahydrofuran, 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, diphenyldimethoxymethane and the like And the like.

The method for producing an olefin polymer according to the present invention is a method for polymerizing or copolymerizing an olefin using the above-mentioned catalyst for olefin polymerization. The olefin used for the polymerization is generally an olefin having at most 12 carbon atoms, and typical examples thereof include ethylene,
Examples include propylene, butene-1, 4-methylpentene-1, hexene-1, and octene-1. In carrying out the polymerization, these olefins may be homopolymerized, or two or more olefins may be copolymerized.
Particularly, it is advantageous for stereospecific polymerization of olefin having 3 or more carbon atoms, and propylene polymerization is most preferable.

In carrying out the polymerization, the solid catalyst component for olefin polymerization of the present invention, the organoaluminum compound or these and the third component, the electron-donating compound, may be individually introduced into a polymerization vessel. May be mixed in advance. Typically, an inert solvent, an organoaluminum compound and an electron-donating compound as a third component, which will be described later, are added to a dropping funnel replaced with nitrogen, and mixed. After a lapse of at least one hour (about one minute or more), the mixture is preferably brought into contact with a solid catalyst component for olefin polymerization, and further reacted for a certain time or more (about one minute or more), and then added to the polymerization reaction vessel. The inert solvent used in this case includes alkane and cycloalkane such as pentane, hexane, heptane, normal octane, isooctane, cyclohexane and methylcyclohexane; toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, normal propylbenzene Alkylaromatic hydrocarbons such as benzene, diethylbenzene and mono- or dialkylnaphthalene; halogenated and hydrogenated aromatic hydrocarbons such as chlorobenzene, chloronaphthalene, orthodichlorobenzene, tetrahydronaphthalene, decahydronaphthalene; high molecular weight liquid paraffin or Can be used.

The polymerization of the olefins according to the invention is carried out at atmospheric pressure or at monomer pressures above atmospheric pressure. In the gas phase polymerization, the monomer pressure must not be lower than the vapor pressure at the polymerization temperature of the olefin to be polymerized, but generally the monomer pressure is in the range of normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . is there. The polymerization can be carried out in an inert solvent, in a liquid monomer (olefin) or in the gas phase. In addition, polymerization, batch type,
It can be carried out in any of a semi-continuous method and a continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions. To obtain a polymer with a practical melt flow, a molecular weight regulator (generally hydrogen)
May coexist. The polymerization time is, in the case of the batch method,
It is generally from 30 minutes to several hours, with a corresponding average residence time in the case of a continuous process. About 1 in autoclave type reaction
Polymerization times ranging from hours to 6 hours are typical.

In the slurry method, the polymerization time is preferably from 30 minutes to several hours. Suitable diluent solvents for use in slurry polymerization include alkanes and cycloalkanes such as pentane, hexane, heptane, normal octane, isooctane, cyclohexane and methylcyclohexane; toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, normalpropyl Alkylaromatic hydrocarbons such as benzene, diethylbenzene and mono- or dialkylnaphthalene; halogenated and hydrogenated aromatic hydrocarbons such as chlorobenzene, chloronaphthalene, orthodichlorobenzene, tetrahydronaphthalene, decahydronaphthalene; high molecular weight liquid paraffin or There are mixtures thereof, and other well-known diluent solvents.

In the gas phase polymerization method in which the present invention is useful, a stirred bed reactor, a fluidized bed reactor system and the like can be used. A typical gas-phase olefin polymerization reactor system can include an olefin monomer and a catalyst component, and comprises a reaction vessel equipped with a stirrer, wherein the catalyst components are reacted together or separately from one or more valving ports. Added to the container. The olefin monomer is a method in which unreacted monomer and fresh feed monomer which are typically removed as exhaust gas are mixed, pressed into a reaction vessel, and supplied to the reactor through a recycle gas system.

Although not generally required, when the polymerization is complete or when the polymerization is terminated or deactivated according to the present invention, water, alcohol, acetone or other suitable catalyst deactivators known as catalyst poisons are used. This is possible by contacting with an agent.

The polymerization temperature is generally from -10 ° C to 180 ° C.
However, from the viewpoint of obtaining good catalytic performance and a high production rate, 20 ° C to 100 ° C is preferable, and more preferably 5 ° C to 5 ° C.
It is in the range of 0 ° C to 80 ° C.

Although pre-polymerization is not always necessary, it is preferable to carry out pre-polymerization. The olefin used in the prepolymerization may be the same as or different from the olefin used in the above-mentioned polymerization, but it is preferable to use propylene. The reaction temperature during the prepolymerization is
The range is -20 to 100C, preferably -20 to 60C. The prepolymerization is performed in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, per 1 g of the solid catalyst for olefin polymerization.
Particularly preferably, the reaction is carried out so as to produce 1 to 200 g of a polymer. In the prepolymerization, a molecular weight regulator such as hydrogen may be used. The prepolymerization can be performed in a batch system or a continuous system.

In addition, there are no particular restrictions inherent in the olefin polymerization catalyst of the present invention as to the polymerization control method, post-treatment method and the like, and all known methods can be applied.

[0069]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to these examples. In each Example, each compound (organic solvent, titanium tetrachloride, alkoxyester compound, magnesium chloride, propylene, hydrogen, organosilicon compound, etc.) used in the production and polymerization of the titanium complex compound and the solid catalyst component for olefin polymerization was All are substantially water-removed. The production of the titanium complex compound and the solid catalyst component for olefin polymerization and the polymerization were carried out in a nitrogen-free atmosphere substantially without water. In the composition analysis of the titanium complex compound, the sample was decomposed with dilute hydrochloric acid, and organic substances were extracted with hexane. Then, the content of titanium atoms was determined by an ICP emission spectrometer, and the content of an alkoxyester compound was determined by gas chromatography. The NMR spectrum of the titanium complex compound was measured using EX400 manufactured by JEOL Ltd. The solvent used was heavy chloroform (CDCl ₃ ).
Polymer melt flow rate (ie, MFR)
Was measured according to JIS K-6758-1995. The stereoregularity of the polymer was evaluated by the amount of xylene-insoluble matter (XI%) at 25 ° C of the polymer. That is,
After dissolving 2.5 g of the polymer in 250 ml of xylene at 135 ° C., the amount of the polymer (wt%) precipitated by cooling the solution to 25 ° C. was measured and defined as the xylene-insoluble content (XI%).

Example 1 [Synthesis of titanium complex compound]
200 ml of purified hexane and 3.79 g of titanium tetrachloride were added to a 00 ml three-necked flask (with a condenser tube), mixed with stirring, and then mixed with 2-tert-butyl-3-ethoxy-.
A mixture of 4.24 g of ethyl propionate and 5 ml of purified hexane was added dropwise over 5 minutes. Thereafter, the contents of the flask were heated and reacted under reflux for 30 minutes. After completion of the reaction, the contents of the flask were cooled to room temperature, and the precipitated solid was separated by filtration and washed three times with 200 ml of purified hexane.
After washing, dry-up was performed to remove the yellow solid substance to 7.59.
g was obtained. From the results of composition analysis and NMR measurement, this yellow solid substance was found to be composed of titanium tetrachloride and 2-tert-butyl-3-.
It was found to be a complex compound of ethoxy-ethyl propionate. Titanium content = 12.0 wt% (theoretical 12.2 wt%)
%), Ethyl 2-tert-butyl-3-ethoxy-propionate content = 51.1 wt% (theoretical value 51.6 wt%)
%). ^{1 H-NMR (400MHz, CDCl} 3); 4.9
8 (t, 1H), 4.73 (q, 2H), 4.41
(M, 2H), 3.50 (dd, 2H), 1.50
(T, 3H), 1.48 (t, 3H), 1.15 (s,
^{9H) ppm 13 C-NMR (} 100MHz, CDCl 3); 18
4.72, 75.19, 70.22, 68.03, 5
2.59, 34.03, 28.49, 13.90, 1
3.15 ppm

[Preparation of solid catalyst component for olefin polymerization]
Under a nitrogen stream, 100 g of anhydrous magnesium chloride was put into a sufficiently dried vibrating ball mill container (stainless steel cylindrical type, inner volume: 1 L, magnetic ball mill having a diameter of 10 mm, filled with an apparent volume of about 50%). This was mounted on a vibrating ball mill having an amplitude of 6 mm and pulverized for 10 hours.
In a nitrogen stream, 1.50 g of anhydrous magnesium chloride and 20 ml of toluene after the pulverization treatment were added to a sufficiently dried 300 ml three-necked flask (flask A), and the contents of flask A were heated with stirring to obtain a 90 ° C. slurry state. Kept.
The above titanium complex compound 3. was placed in another 300 ml three-necked flask (flask B) sufficiently dried under a nitrogen stream.
09 g and 80 ml of toluene were added, and the content of Flask B was heated with stirring to dissolve the titanium complex compound, thereby obtaining a uniform solution at 90 ° C. Next, the entire amount of the homogeneous solution in the flask B was dropped into the slurry in the flask A over 5 minutes. The contents of Flask A were further heated under stirring and heated to 110 ° C., and then stirring was continued at the same temperature for 2 hours. Thereafter, the contents of the flask A were cooled to 90 ° C., the solid substance was separated by filtration at the same temperature, and washed three times with 100 ml of toluene. It was further cooled to room temperature and washed three times with 100 ml of purified hexane. After the washing, the solid was dried up to obtain a solid catalyst component for olefin polymerization.

[Polymerization Polymerization] In a 1.5 L internal volume stainless steel autoclave sufficiently dried under a nitrogen stream, 30 mg of the solid catalyst component for olefin polymerization produced above, 205 mg of triethylaluminum and 205 mg of t
-Butyltrimethoxysilane 91 mg, then 3
36 g of propylene and 0.1 g of hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was kept at 70 ° C. After one hour, the content gas was released to terminate the polymerization. as a result,
71 g of powdered polypropylene were obtained. The MFR of the obtained polypropylene was 8.5 g / 10 min, and the XI was 99.3%.

Comparative Example 1 [Preparation of a solid catalyst component for olefin polymerization]
1.50 g of anhydrous magnesium chloride and 20 ml of toluene after the pulverization treatment described in Example 1 were added to a sufficiently dried 300 ml three-necked flask (flask A), and the content of flask A was heated to 90 ° C. while stirring. The slurry was kept. Two other 300 ml three-necked flasks each having been sufficiently dried were prepared (flask B and flask C), and 1.50 g of titanium tetrachloride and 40 ml of toluene were added to the flask B under a nitrogen gas stream. -Butyl-
1.59 g of ethyl 3-ethoxy-propionate and 40 ml of toluene were added. The contents of Flask B and Flask C were heated with stirring to form uniform solutions at 90 ° C. Next, the entire amount of the homogeneous solution in the flask B and the uniform solution in the flask C were simultaneously dripped into the slurry in the flask A from separate inlets over 5 minutes. The contents of Flask A were further heated under stirring and heated to 110 ° C., and then stirring was continued at the same temperature for 2 hours. Thereafter, the contents of the flask A were cooled to 90 ° C., the solid substance was separated by filtration at the same temperature, and washed three times with 100 ml of toluene. Cool to room temperature and purify hexane 1
Washing was performed three times with 00 ml. After the washing, the solid was dried up to obtain a solid catalyst component for olefin polymerization.

[Polymerization of propylene] Polymerization was carried out in the same manner as in Example 1 using the above-mentioned solid catalyst component for olefin polymerization. As a result, 63 g of powdery polypropylene was obtained. The MFR of the obtained polypropylene was 10.
4 g / 10 min, XI was 96.1%.

Comparative Example 2 [Preparation of a solid catalyst component for olefin polymerization]
To a sufficiently dried 300 ml three-necked flask (flask A) was added 1.50 g of the anhydrous magnesium chloride obtained after the pulverization treatment described in Example 1 and 20 ml of toluene, and the contents of Flask A were heated with stirring to obtain a slurry at 90 ° C. Kept in condition. Two other 300 ml three-necked flasks each having been sufficiently dried were prepared (flask B and flask C), and 1.50 g of titanium tetrachloride and 40 ml of toluene were added to the flask B under a nitrogen gas stream. -Butyl-
1.59 g of ethyl 3-ethoxy-propionate and 40 ml of toluene were added. The contents of Flask B and Flask C were heated with stirring to form uniform solutions at 90 ° C. Next, the entire amount of the homogeneous solution in the flask B was dropped into the slurry in the flask A over 5 minutes, and the content of the flask A was stirred at 90 ° C. for 1 hour. The whole amount of the homogeneous solution in the flask C was dropped over 5 minutes. The contents of Flask A were further heated under stirring and heated to 110 ° C., and then stirring was continued at the same temperature for 2 hours. Thereafter, the content of Flask A was cooled to 90 ° C,
At the same temperature, a solid substance was separated by filtration and washed three times with 100 ml of toluene. Cool to room temperature and purify hexane 100m
Washing was performed three times with l. After the washing, the solid was dried up to obtain a solid catalyst component for olefin polymerization.

[Polymerization of Propylene] Polymerization was carried out in the same manner as in Example 1 using the solid catalyst component for olefin polymerization described above. As a result, 55 g of powdery polypropylene was obtained. The MFR of the obtained polypropylene is 12.
4 g / 10 min, XI was 94.8%.

Comparative Example 3 [Preparation of Solid Catalyst Component for Olefin Polymerization]
To a sufficiently dried 300 ml three-necked flask (flask A) was added 1.50 g of the anhydrous magnesium chloride obtained after the pulverization treatment described in Example 1 and 20 ml of toluene, and the contents of Flask A were heated with stirring to obtain a slurry at 90 ° C. Kept in condition. Another 300ml of 3
To a one-necked flask (flask B), 15 g of titanium tetrachloride and 75 ml of toluene were added, and while stirring, the content of the flask B was mixed with 1.59 g of ethyl 2-tert-butyl-3-ethoxy-propionate and 5 ml of toluene. 5
It was added dropwise over a period of minutes. Thereafter, the contents of this flask B were heated with stirring to obtain a uniform solution at 90 ° C. Next, the entire amount of the homogeneous solution in the flask B was dropped into the slurry in the flask A over 5 minutes. The contents of Flask A were further heated under stirring and heated to 110 ° C., and then stirring was continued at the same temperature for 2 hours. Thereafter, the content of Flask A was cooled to 90 ° C,
At the same temperature, a solid substance was separated by filtration and washed three times with 100 ml of toluene. Cool to room temperature and purify hexane 100m
Washing was performed three times with l. After the washing, the solid was dried up to obtain a solid catalyst component for olefin polymerization.

[Polymerization of Propylene] Polymerization was carried out in the same manner as in Example 1 using the solid catalyst component for olefin polymerization described above. As a result, 70 g of powdery polypropylene was obtained. The MFR of the obtained polypropylene was 15.
7 g / 10 min, XI was 95.5%.

Example 2 [Polymerization polymerization] Propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component for olefin polymerization of Example 1 was not used and t-butyltrimethoxysilane was not used. Was. The polymerization results are shown in Table 1.

Comparative Examples 4 to 6 Using the solid catalyst components for olefin polymerization of Comparative Examples 1 to 3,
Propylene was polymerized in the same manner as in Example 1 except that t-butyltrimethoxysilane was not used. The polymerization results are shown in Table 1.

Examples 3 to 6 In Example 1, ethyl 2-tert-butyl-3-methoxy-propionate, isopropyl 2-tert-butyl-3-methoxy-propionate were used as the alkoxyester compound (AE). Ethyl 2-cyclopentyl-3-ethoxy-propionate, 2,2-diisobutyl-3
A titanium complex compound was synthesized, a solid catalyst component for olefin polymerization was prepared, and propylene was polymerized in the same manner as in Example 1 except that ethyl methoxy-propionate was used. Table 2 shows the results of the composition analysis of the titanium complex compound and the results of the polymerization evaluation.

Example 7 [Preparation of Solid Catalyst Component for Olefin Polymerization]
To a sufficiently dried 300 ml three-necked flask (flask A), 1.50 g of anhydrous magnesium chloride and 20 ml of toluene after the pulverization treatment described in Example 1 were added, and the contents of flask A were heated with stirring to obtain a slurry at 90 ° C. Kept in condition. Another 300ml of 3
To a one-necked flask (flask B), 3.09 g of the above titanium complex compound and 80 ml of toluene were added, and the content of flask B was heated with stirring to dissolve the titanium complex compound.
A homogeneous solution at a temperature of .degree. Next, to the slurry in flask A,
The whole amount of the homogeneous solution in the flask B was dropped over 5 minutes, and the content of the flask A was further heated with stirring and heated to 110 ° C., and then stirring was continued at the same temperature for 2 hours. Thereafter, the contents of the flask A were cooled to 90 ° C., the solid substance was separated by filtration at the same temperature, and washed three times with 100 ml of toluene. 25 ml of toluene was newly added to the solid matter in the flask A, and the content was maintained in a slurry state at 90 ° C. with stirring. Then, a mixture of 1.50 g of titanium tetrachloride and 25 ml of toluene was added to the slurry over 5 minutes. The whole amount was dropped. The contents of Flask A were further heated under stirring and heated to 110 ° C., and then stirring was continued at the same temperature for 2 hours. Thereafter, the contents of the flask A were cooled to 90 ° C., the solid substance was separated by filtration at the same temperature, and washed three times with 100 ml of toluene. It was further cooled to room temperature and washed three times with 100 ml of purified hexane. After the washing, the solid was dried up to obtain a solid catalyst component for olefin polymerization.

[Polymerization of Propylene] Using the above-mentioned solid catalyst component for olefin polymerization, polymerization was carried out in the same manner as in Example 1. As a result, 92 g of powdery polypropylene was obtained. 13. The MFR of the obtained polypropylene is 14.
9 g / 10 min, XI was 99.0%.

Example 8 [Preparation of solid catalyst component for olefin polymerization] In Example 6, 2-tert-butyl-3 was used instead of titanium tetrachloride.
The same preparation as in Example 5 was carried out except that 1.59 g of ethyl-ethoxy-propionate was used to obtain a solid catalyst component for olefin polymerization.

[Polymerization of Propylene] Polymerization was carried out in the same manner as in Example 1 using the solid catalyst component for olefin polymerization described above. As a result, 69 g of powdery polypropylene was obtained. The MFR of the obtained polypropylene was 4.3.
g / 10 min, XI was 99.5%.

Example 9 [Preparation of a solid catalyst component for olefin polymerization]
To a sufficiently dried 300 ml three-necked flask (flask A), 1.50 g of anhydrous magnesium chloride and 20 ml of toluene after the pulverization treatment described in Example 1 were added, and the contents of flask A were heated with stirring to obtain a slurry at 90 ° C. Kept in condition. Another 300ml of 3
To a one-necked flask (flask B), 3.09 g of the above titanium complex compound and 80 ml of toluene were added, and the content of flask B was heated with stirring to dissolve the titanium complex compound.
A homogeneous solution at a temperature of .degree. Next, to the slurry in flask A,
The whole amount of the homogeneous solution in the flask B was dropped over 5 minutes, and the content of the flask A was further heated with stirring and heated to 110 ° C., and then stirring was continued at the same temperature for 2 hours. Thereafter, the contents of the flask A were cooled to 90 ° C., the solid substance was separated by filtration at the same temperature, and washed three times with 100 ml of toluene. 25 ml of toluene was newly added to the solid matter in the flask A, and the contents were maintained in a slurry state at 90 ° C. with stirring. The mixture with 25 ml was added dropwise over 5 minutes. The contents of Flask A were further heated under stirring and heated to 110 ° C., and then stirring was continued at the same temperature for 2 hours. After that, the content of the flask A was cooled to 90 ° C., and a solid substance was separated by filtration at the same temperature.
Washing was performed three times with l. To the solid substance in flask A, 25 ml of fresh toluene was added, and the content was maintained in a slurry state at 90 ° C. with stirring.
A mixture of 50 g and 25 ml of toluene was added dropwise over 5 minutes. The contents of Flask A were further heated while stirring
After the temperature was raised to 10 ° C., stirring was continued at the same temperature for 2 hours. Thereafter, the contents of the flask A were cooled to 90 ° C., the solid substance was separated by filtration at the same temperature, and washed three times with 100 ml of toluene. Cool to room temperature and purify hexane 100ml
Was performed three times. After cleaning, dry up,
A solid catalyst component for olefin polymerization was obtained.

[Polymerization Polymerization] Polymerization was carried out in the same manner as in Example 1 using the above-mentioned solid catalyst component for olefin polymerization. As a result, 85 g of powdery polypropylene was obtained. The MFR of the obtained polypropylene was 9.6.
g / 10 min, XI was 99.3%.

[0088]

As described above, the use of the solid catalyst component for olefin polymerization obtained by the present invention makes it possible to produce an olefin polymer having extremely high stereoregularity.

[0089]

[Table 1]

[0090]

[Table 2]

Continuation of the front page (72) Inventor Shintaro Inazawa Oita City, Oita City, Oita Prefecture

Claims (8)

[Claims] 1. A titanium complex compound represented by the following general formula (1). TiCl ₄ .AE (1) (where TiCl ₄ is titanium tetrachloride and AE is an alkoxyester compound represented by the following general formula (2)) (Where R ¹ and R ² are hydrocarbon groups, which may be the same or different from each other; R ³ and R ⁴ are hydrocarbon groups or hydrogen atoms, which may be the same or different from each other Good.) 2. An alkoxyester compound (AE) represented by the general formula (2), wherein R ¹ and R ² are a straight-chain hydrocarbon group having 1 to 20 carbon atoms and a branched hydrocarbon group having 3 to 20 carbon atoms. The same or different substituents selected from the group
³ and R ⁴ are the same selected from a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, a cyclic hydrocarbon group having 3 to 20 carbon atoms, and a hydrogen atom The titanium complex compound according to claim 1, wherein the titanium complex compound is a different substituent. 3. A solid catalyst component for olefin polymerization, which is formed by contacting a titanium complex compound represented by the general formula (1) according to claim 1 with a magnesium compound. 4. A solid catalyst component for olefin polymerization, which is formed by bringing a Lewis acid compound and / or a Lewis base compound into contact with the solid catalyst component for olefin polymerization according to claim 3. 5. An olefin polymerization catalyst comprising the solid catalyst component for olefin polymerization according to claim 3 or 4 and an organoaluminum compound. 6. An olefin polymerization catalyst comprising the solid catalyst component for olefin polymerization according to claim 3 or 4, an organoaluminum compound, and an electron-donating compound as a third component. 7. The method according to claim 1, wherein at least one compound selected from the group consisting of an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound is used as the third component. The olefin polymerization catalyst according to claim 6. 8. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin using the olefin polymerization catalyst according to claim 5. Description: