JPH08109217A - Olefin polymer production catalyst and olefin polymer production method - Google Patents

Abstract

(57) [Summary] [Object] To provide a catalyst for producing an olefin polymer, which is capable of efficiently supporting a complex during catalyst preparation and suppressing the adhesion of scale on the reactor wall. [Structure] (a) An inorganic oxide characterized in that a compound having a hydrocarbon group having 8 or more carbon atoms, which may contain halogen, N, O, P, S or Si, is supported by a chemical bond. , (B) an organoaluminum oxy compound,
(C) A catalyst for producing an olefin polymer, which is obtained by contacting a transition metal compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the production of an olefin polymer comprising an inorganic oxide, an organic aluminum oxy compound, a transition metal compound, an olefin, and an organic metal compound, which are chemically bonded to a compound having a hydrocarbon group having 8 or more carbon atoms. And a method for polymerizing olefins using the catalyst.

[0002]

2. Description of the Related Art As a method for producing a polyolefin,
It is already known to use catalyst systems which consist of a combination of transition metal compounds and organometallic compounds. Also,
According to Kaminsky et al., A catalyst using metallocene and methylaluminoxane shows high activity in producing an olefin polymer containing propylene.
It is known from, for example, the 19309 publication.

However, in the catalyst system disclosed in the above publication, although the polymerization activity is excellent, the solution polymerization system is often used because the catalyst system is soluble in the reaction system, and the production process is limited. In addition, it is necessary to use a relatively large amount of relatively expensive methylaluminoxane in order to produce a polymer having industrially useful physical properties. Therefore, there are problems in terms of cost and a large amount of aluminum remaining in the polymer.

On the other hand, a catalyst system in which the aforementioned soluble catalyst system is supported on an inorganic oxide carrier such as silica is disclosed in JP-A-60-35.
JP-A-63-152608 discloses that the particle properties of the polymer produced by gas phase polymerization can be improved by using a catalyst component prepolymerized with an olefin. There is.
However, the polymerization activity per methylaluminoxane was not sufficient even when the olefin was polymerized according to the methods described therein.

As a method for improving these, for example, JP-A-4-8704, JP-A-4-11604,
JP-A-4-213305 discloses that a gas phase polymerization using a catalyst system prepolymerized with a small amount of methylaluminoxane gives a polymer having excellent polymerization activity and good particle properties. There is. However, although the amount of methylaluminoxane used was small, the polymerization activity was still unsatisfactory, and there was the problem that scale adhered to the reactor wall during prepolymerization.

[0006]

The present invention has been made in order to solve this problem, and suppresses scale deposition on the reactor wall in the preparation of catalysts, and further, in the gas phase polymerization or suspension polymerization, organoaluminum oxy An object of the present invention is to provide a catalyst for producing an olefin polymer having excellent particle activity and excellent polymerization activity while reducing the amount of the compound used.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have made contact with an inorganic oxide, an organic aluminum oxy compound, a transition metal compound, an olefin, and an organic metal compound. In the resulting catalyst, by using an inorganic oxide in which a compound having a hydrocarbon group having 8 or more carbon atoms is chemically bonded as the inorganic oxide, the complex can be efficiently supported in the preparation of the catalyst, and the reaction which becomes a problem during the preparation. It was found that adhesion of scale on the vessel wall can be suppressed. Furthermore, using this catalyst,
The inventors have found that a polyolefin having excellent physical properties and processability can be efficiently produced, and completed the present invention.

That is, the present invention provides (a) halogen, N,
(B) Organoaluminum oxy compound, (b) an inorganic oxide, wherein a compound having a hydrocarbon group having 8 or more carbon atoms, which may include O, P, S, and Si, is supported by a chemical bond. c) A catalyst for producing an olefin polymer, which is obtained by contacting a transition metal compound, (a)
An inorganic oxide characterized in that a compound having a hydrocarbon group having 8 or more carbon atoms, which may contain halogen, N, O, P, S or Si, is supported by a chemical bond, (b)
A catalyst for producing an olefin polymer obtained by contacting an organoaluminum oxy compound, (c) transition metal compound, (d) olefin, (e) organometallic compound,
And (a) an inorganic oxide characterized in that a compound having a hydrocarbon group having 8 or more carbon atoms, which may contain halogen, N, O, P, S or Si is supported by a chemical bond, (B) Organoaluminum oxy compound, (c)
An olefin polymer-producing catalyst obtained by contacting an olefin prepolymerization catalyst formed by prepolymerizing an olefin (d) with a catalyst component composed of a transition metal compound, and (e) an organometallic compound, and further, these A method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst.

The present invention will be described in detail below.

First, the catalyst for producing an olefin polymer of the present invention will be described. The inorganic oxide (a) used in the present invention has an average particle size of 1 to 300 μm, and particularly 10 to
Fine-grained porous particles in the range of 200 μm are preferable because they are easy to handle during catalyst preparation and polymerization processes. Specifically, inorganic oxides of typical elements such as silica, alumina and magnesia, inorganic oxides of transition metal elements such as titania and zirconia, and mixtures of silica-alumina, silica-magnesia and the like are used. These inorganic oxides usually contain Na ₂ O, K ₂ CO ₃ , Ba as impurities.
It contains salts of alkali metals such as SO ₄ and alkaline earth metals. The fine-particle inorganic oxide may be used in a state of containing these impurities, but it is preferable to use an inorganic oxide that has been previously subjected to an operation of removing these impurities. Such a porous fine-particle inorganic oxide has different properties depending on its type and production method,
In the present invention, the specific surface area is 10 to 1000 m ² /
g, especially 50 to 800 m ² / g, pore volume 0.1 to 3
The cc / g one can support a large amount of the catalyst component such as the transition metal compound (c), and is also suitable from the viewpoint of handling the catalyst preparation and polymerization.

The compound having a hydrocarbon group having 8 or more carbon atoms which is chemically bonded to these inorganic oxides is represented by the general formula (1)

[0012]

Embedded image

(Where M1 is the periodic table Ia, IIa, II
Is an element of Group Ia, IVa, Sn or Zn, and each R1 is independently an alkyl group having 8 or more carbon atoms, an alkenyl group, which may contain halogen, N, O, P, S or Si;
It is an arylalkyl group, and R2 is a hydrogen atom and has 1 carbon atom.
To an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group, and X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy having 6 to 20 carbon atoms. Group, arylalkoxy group, alkylaryloxy group, chemical formula (2)

[0014]

[Chemical 17]

(R3 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and some or all of hydrogen atoms may be substituted with halogen. .) Or a chemical formula (3).

[0016]

Embedded image

(R4 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and some or all of hydrogen atoms may be substituted with halogen. ) Is a sulfonyl group. n is equal to the oxidation number of M1, and l is 1 to n
And m is an integer from 0 to n. ), An organometallic compound represented by the general formula (4)

[0018]

[Chemical 19]

(Where M2 is the periodic table Ia, IIa, II
Is an element of Group Ia, IVa, Sn or Zn, and R5 is each independently an alkyl group having 8 or more carbon atoms, an alkenyl group, which may contain halogen, N, O, P, S or Si;
It is an arylalkyl group, and R6 and R7 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 to 2
0 is an aryl group, an arylalkyl group, or an alkylaryl group. p is an integer of 1 or more, q is an integer of 0 or more, and (p + q + 1) is equal to the oxidation number of M2. r is 1 to
It is an integer of 3. ) Or an amine represented by the general formula (5)

[0020]

Embedded image

(R8 is independently halogen, N,
It is an alkyl group having 8 or more carbon atoms, alkenyl group, or arylalkyl group which may contain O, P, S, and Si. ) Is an alcohol represented by.

Specific examples of these organometallic compounds include octyllithium, octadecyllithium, docosyllithium, triacontyllithium, 2-ethyloctyllithium, trioctylaluminum, trioctadecylaluminum, tridocosylaluminum, tritriacone. Cyl aluminum, tri (2-ethyloctyl) aluminum, trioctylborane, trioctadecylborane, tridocosylborane, tritriacontylborane, tri (2-ethyloctyl) borane, dimethyloctylchlorosilane, dimethyloctadecylchlorosilane, dimethyldocosyl Chlorosilane, dimethyltriacontylchlorosilane, dimethyl (2-ethyloctyl) chlorosilane, dimethyloctylsilane, dimethyloctadecylsilane, Methylnonacosanylsilane, dimethyldocosylsilane, dimethyltriacontylsilane, dimethyl (2-ethyloctyl) silane, dimethyloctylmethoxysilane, dimethyloctadecylmethoxysilane, dimethyldocosylmethoxysilane, dimethyltriacontylmethoxysilane, dimethyl (2-Ethyloctyl) methoxysilane, dimethyloctylethoxysilane, dimethyloctadecylethoxysilane, dimethyldocosylethoxysilane, dimethyltriacontylethoxysilane, dimethyl (2-ethyloctyl) ethoxysilane, dimethyloctyltrifluoroacetoxysilane, dimethyl Octadecyltrifluoroacetoxysilane, dimethyldocosyltrifluoroacetoxysilane, dimethyltriacontyltrifluoroa Toxysilane, dimethyl (2-ethyloctyl) trifluoroacetoxysilane, dimethyloctylsilyltrifluoromethanesulfonic acid, dimethyloctadecylsilyltrifluoromethanesulfonic acid, dimethyldocosylsilyltrifluoromethanesulfonic acid, dimethyltriacontylsilyltrifluoromethanesulfonic acid, dimethyl (2-ethyloctyl) silyltrifluoromethanesulfonic acid,
Diphenyloctylchlorosilane, diphenyloctadecylchlorosilane, diphenylnonacosanylchlorosilane, diphenyldocosylchlorosilane, diphenyltriacontylchlorosilane, diphenyl (2-ethyloctyl) chlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, docosyltrichlorosilane, triacontyltrichlorosilane Examples of chlorosilane and (2-ethyloctyl) trichlorosilane include amines such as 1,3-dioctyl-1,1,3,3-tetramethyldisilazane and 1,3-dioctadecyl-1,1,3.
3-tetramethyldisilazane, 1,3-dinonacosanyl-1,1,3,3-tetramethyldisilazane, 1,3-
Didocosyl-1,1,3,3-tetramethyldisilazane, 1,3-ditriacontyl-1,1,3,3-tetramethyldisilazane, 1,3-bis (2-ethyloctyl) -1,1, 3,3-Tetramethyldisilazane is exemplified, and as the alcohol, 1-octanol, 1-decanol, 1-docosilanol, 1-triacontanol and the like are exemplified, but are not limited thereto. Absent.

The method of chemically bonding the compound having a hydrocarbon group having 8 or more carbon atoms with an inorganic oxide is not particularly limited, but the inorganic oxide is insoluble and has a hydrocarbon group having 8 or more carbon atoms. A method in which a compound is contacted in a soluble organic solvent in a suspension state, a method in which these compounds having a hydrocarbon group having 8 or more carbon atoms are vaporized, and this is contacted with an inorganic oxide, or substantially a solvent A method of contacting with a ball mill or the like in the absence of such conditions is exemplified.

These inorganic oxides are dehydrated and O 2 before and after the reaction with the compound having a hydrocarbon group having 8 or more carbon atoms.
Heating temperature 100 to 1000 for the purpose of controlling the amount of H group
The heat treatment may be performed at ℃, under reduced pressure or under gas flow.

The inorganic oxide chemically bonded to the compound having a hydrocarbon group having 8 or more carbon atoms may be used for the same purpose as the heat treatment, prior to contact with other catalyst components, if necessary. The compound may be contacted. The metal compound used here is not particularly limited, but an organic metal compound is preferably used. The method of contacting the inorganic oxide with the metal compound is not particularly limited, but the inorganic oxide is insoluble, the metal compound is contacted in suspension in an organic solvent in which the metal compound is soluble, or substantially a solvent. A method of contacting with a ball mill or the like in the absence of such conditions is exemplified.

The organoaluminum oxy compound (b) used in the present invention is a conventionally known aluminoxane or an aluminoxane further reacted with water, and may be used as a mixture of two or more kinds. The aluminum substituent of aluminoxane is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, and preferably a methyl group. The degree of oligomer is 4 to 60. The production method of this kind of compound is known, for example, salts containing water of crystallization (copper sulfate hydrate,
An example is a method in which an aluminum compound is added to a hydrocarbon medium suspension of aluminum sulfate hydrate or the like) and reacted.

The transition metal compound (c) used in the present invention is represented by the following general formulas (6) and (7)

[0028]

[Chemical 21]

[0029]

[Chemical formula 22]

(In the formula, M3 is a titanium atom, a zirconium atom or a hafnium atom, Y is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
An aryl group, an arylalkyl group, and an alkylaryl group having 6 to 20 carbon atoms, wherein R9 and R10 are each independently the following general formula (8), (9), (10) or (11).

[0031]

[Chemical formula 23]

(In the formula, each R14 is independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group. ), The ligand forms a sandwich structure together with M3, and R12 and R13 each independently represent the following general formula (12), (13), (14) or ( 15)

[0033]

[Chemical formula 24]

(In the formula, each R15 is independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group. ), The ligand forms a sandwich structure with M3, and R11 is represented by the following general formula (1)
6) or (17)

[0035]

[Chemical 25]

(In the formula, R16 is independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group and an alkylaryl group, and M4 is a silicon atom, a germanium atom or a tin atom. ), Which acts to crosslink R12 and R13, and s is an integer of 1 to 5. Group IVb transition metal compound represented by the formula (1) or the following general formula (1
8), (19), (20) or (21)

[0037]

[Chemical formula 26]

(In the formula, M5 is independently a titanium atom,
A zirconium atom or a hafnium atom, Z is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, or an alkylaryl group, and L is Lewis base, w is 0 to 3, JR17 is a heteroatom ligand, J is a Va group element having a coordination number of 3 or an IVa group element having a coordination number of 2, R17 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group, an alkyl group. It is an aryloxy group, t is the coordination number of the element J, and R18 is the following general formula (22), (23), (24) or (25).

[0039]

[Chemical 27]

(In the formula, each R21 is independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group. ), R20 is a ligand represented by the following general formula (26), (27), (28) or (29)

[0041]

[Chemical 28]

(In the formula, each R22 is independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group. ), R19 is a ligand represented by the following general formula (30) or (31)

[0043]

[Chemical 29]

(In the formula, each R23 is independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group, and M6 is a silicon atom, a germanium atom, or a tin atom. ), Which acts to crosslink R20 and JR17, and u is an integer of 1 to 5. It is preferable that it is a group IVb transition metal compound represented by).

Examples of the compound represented by the general formula (6) or (7) include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride and bis (cyclopentadienyl). Hafnium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) hafnium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (butyl) Cyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (pentamethyl Cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (indenyl) titanium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) hafnium dichloride, methylenebis (cyclopentadienyl)
Titanium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) hafnium dichloride, methylenebis (methylcyclopentadienyl) titanium dichloride, methylenebis (methylcyclopentadienyl) zirconium dichloride, methylenebis (methylcyclopenta) Dienyl) hafnium dichloride, methylenebis (butylcyclopentadienyl) titanium dichloride, methylenebis (butylcyclopentadienyl) zirconium dichloride, methylenebis (butylcyclopentadienyl) hafnium dichloride, methylenebis (tetramethylcyclopentadienyl) titanium dichloride , Methylenebis (tetramethylcyclopentadienyl) Ruconium dichloride, methylenebis (tetramethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride, Ethylenebis (tetrahydroindenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) hafnium dichloride, ethylenebis (2-methyl-1-indenyl) titanium dichloride, ethylenebis (2-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (2-methyl-1-indenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-9-)
Fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Dimethyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Dimethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,
7-dimethyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,
7-di-t-butyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2, 7-di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopenta) Dienyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadiene) 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl -9
-Fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9) -Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-
2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, dimethylsilanediylbis (cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (cyclopenta) Dienyl) hafnium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) hafnium dichloride, dimethylsilane Diylbis (butylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) zirconium di Lolide, dimethylsilanediylbis (butylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) ) Titanium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (indenyl) titanium dichloride, dimethylsilanediylbis (2
-Methyl-indenyl) titanium dichloride, dimethylsilanediylbis (tetrahydroindenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-)
2,7-Dimethyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, dimethylsilanediylbis (2,2
4,5-Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-
Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl Bis (tetramethylcyclopentadienyl)
Zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-9- Fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) Zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis 2,4-Dimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride Dimethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, dimethylsilanediylbis (2-methyl-indenyl) hafnium dichloride, dimethylsilanediylbis (tetrahydroindenyl) hafnium Dichloride, dimethylsilanediyl (cyclopentadienyl-9
-Fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-)
t-Butyl-9-fluorenyl) hafnium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diethyl Silanediylbis (3-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride,
Diethylsilanediylbis (indenyl) titanium dichloride, diethylsilanediylbis (2-methyl-
Indenyl) titanium dichloride, diethylsilanediylbis (tetrahydroindenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9- Fluorenyl) titanium dichloride,
Diethylsilanediyl (cyclopentadienyl-2,7
-Di-t-butyl-9-fluorenyl) titanium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium Dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (tetramethylcyclopentadiene (Enyl) zirconium dichloride, diethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, diethylsilane Landiylbis (tetrahydroindenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (Cyclopentadienyl-2,7-di-t-butyl-9
-Fluorenyl) zirconium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride,
Diethylsilanediylbis (indenyl) hafnium dichloride, diethylsilanediylbis (2-methyl-
Indenyl) hafnium dichloride, diethylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9- Fluorenyl) hafnium dichloride,
Diethylsilanediyl (cyclopentadienyl-2,7
-Di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylsilanediylbis (2,4,5-
Trimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (4- t-Butyl-2-methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (indenyl) titanium dichloride, diphenylsilanediylbis (2-methyl-indenyl) ) Titanium dichloride, diphenylsilanediylbis (tetrahydroindenyl) titanium dichloride, diphenylsilanediyl (cyclopen Dienyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-) 9
-Fluorenyl) titanium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (3 -Methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, diphenylsilanediylbis (2-methyl-indenyl) Zirconium dichloride, diphenylsilanediyl bis (tetrahydroindenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-
9-fluorenyl) zirconium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl)
Hafnium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl)
Hafnium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (indenyl)
Hafnium dichloride, diphenylsilanediylbis (2-methyl-indenyl) hafnium dichloride,
Diphenylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, Diphenyl silanes such as diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, and dimethyl, diethyl, dihydro, diphenyl, dibenzyl of the above group IVb transition metal compounds. A body etc. can be illustrated.

The above general formulas (18), (19) and (20)
Or as the compound represented by (21), for example, pentamethylcyclopentadienyl-di-t-butylphosphinotitanium dichloride, pentamethylcyclopentadienyl-di-t-butylamido titanium dichloride, pentamethylcyclo Pentadienyl-n-butoxide titanium dichloride, pentamethylcyclopentadienyl-di-t-butylphosphino zirconium dichloride, pentamethylcyclopentadienyl-di-t-butylamide zirconium dichloride, pentamethylcyclopentadienyl- n-butoxide zirconium dichloride, pentamethylcyclopentadienyl-di-t-butylphosphinohafnium dichloride,
Pentamethylcyclopentadienyl-di-t-butylamido hafnium dichloride, pentamethylcyclopentadienyl-n-butoxide hafnium dichloride,
Dimethylsilanediyl tetramethylcyclopentadienyl-t-butylamido titanium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-
t-butylamido titanium dichloride, dimethylsilanediyltrimethylsilylcyclopentadienyl-t
-Butylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienylphenylamidotitanium dichloride, methylphenylsilanediyltetramethylcyclopentadienyl-t-butylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-p- n-Butylphenylamido titanium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl-p-methoxyphenylamido titanium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-2,5-
Di-t-butyl-phenylamido titanium dichloride, dimethylsilanediylindenyl-t-butylamido titanium dichloride, dimethylsilanediyl tetramethylcyclopentadienylcyclohexylamido titanium dichloride, dimethylsilanediylfluorenylcyclohexylamido titanium dichloride, dimethyl Silanediyltetramethylcyclopentadienylcyclododecylamide titanium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-t
-Butylamide zirconium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-t-
Butyramide zirconium dichloride, dimethylsilyltrimethylsilanediyl cyclopentadienyl-t-
Butylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl phenylamide zirconium dichloride, methylphenylsilanediyl tetramethylcyclopentadienyl-t-butylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl-pn -Butylphenylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl-p-methoxyphenylamide zirconium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-
2,5-di-t-butyl-phenylamide zirconium dichloride, dimethylsilanediylindenyl-t-
Butylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienylcyclohexylamide zirconium dichloride, dimethylsilanediylfluorenylcyclohexylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl cyclododecylamide zirconium dichloride, dimethylsilanediyl tetramethyl Cyclopentadienyl-t-butylamide hafnium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-t-butylamide hafnium dichloride, dimethylsilanediyltrimethylsilylcyclopentadienyl-t-butylamide hafnium dichloride, dimethylsilane Diyl tetramethyl cyclopentadienyl phenylamide Off pyridinium dichloride, methylphenyl silane diyl tetramethylcyclopentadienyl -t- butyl amide hafnium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl -p
-N-butylphenylamide hafnium dichloride,
Dimethylsilanediyl tetramethylcyclopentadienyl-p-methoxyphenylamide hafnium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-2,5-di-t-butyl-phenylamide hafnium dichloride, dimethylsilanediylindenyl -T-Butylamide hafnium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclohexylamide hafnium dichloride, dimethylsilanediylfluorenylcyclohexylamide hafnium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclododecylamide dichloride, etc. And the above group IVb transition metal compounds such as dimethyl, diethyl, dihydro, diphenyl and dibenzyl It can be exemplified, and the like.

As the olefin (d) used as a constituent component of the catalyst of the present invention, ethylene, propylene, butene-1, pentene-1,4-methyl-1-pentene,
Examples include α-olefins such as hexene-1 and octene-1, cyclic olefins such as norbornene and norbornadiene, and the like, but it is also possible to polymerize a mixed component of two or more thereof.

Further, the organometallic compound (e) used in the present invention is represented by the following general formula (32)

[0049]

Embedded image

(In the formula, M7 is the periodic table Ia, IIa, II.
It is an element of group Ia, Sn or Zn, and R24 is each independently a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group. , An arylalkoxy group, an alkylaryl group, and an alkylaryloxy group, and at least one R24 is an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 6 to 20 carbon atoms. x is equal to the oxidation number of M7. ) Is an organometallic compound.

Examples of the compound represented by the general formula (32) include trimethylaluminum, triethylaluminum, triisopropylaluminum and tri-n.
-Propyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, triamyl aluminum, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di-n-propyl aluminum ethoxide, diisobutyl aluminum ethoxide, di-
n-Butyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum hydride, di-n
-Propyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, di-n-propyl aluminum chloride, diisobutyl aluminum chloride, di-n-
Butyl aluminum chloride etc. can be illustrated.

In the olefin polymerization catalyst of the present invention, the amount of the transition metal compound (c) is not particularly limited with respect to 1 g of the inorganic oxide (a) in which the compound having a hydrocarbon group having 8 or more carbon atoms is supported by a chemical bond. However, the amount of transition metal atoms is 0.005-1 mmol, preferably 0.05-
It is 0.5 mmol, and the amount of Al atoms contained in the organoaluminum oxy compound (b) with respect to the transition metal compound (c) is preferably 10 to 200 mol based on 1 mol of the transition metal atom in the transition metal compound. It is preferable because the polymerization activity of is obtained. The amount of the olefin (d) is 0.01 with respect to 1 g of the inorganic oxide (a) in which the compound having a hydrocarbon group having 8 or more carbon atoms is supported by a chemical bond.
-100 g is preferable because good polymerization activity can be obtained. The amount of the organometallic compound (e) used here is not particularly limited.

In the present invention, the method of contacting the catalyst component is not particularly limited, but in the case of carrying out the prepolymerization, the inorganic oxide (a) in which the compound having a hydrocarbon group having 8 or more carbon atoms is supported by a chemical bond. Preferred is a method of contacting an olefin prepolymerization catalyst formed by prepolymerizing an olefin (d) with a catalyst component consisting of an organoaluminum oxy compound (b) and a transition metal compound (c) and an organometallic compound (e). . The conditions for contacting the olefin (d) in this prepolymerization are not particularly limited, but the prepolymerization is carried out without solvent or under an inert hydrocarbon solvent. Generally, this contact treatment is -50 to 100 ° C, preferably -20 to 60.
C., more preferably in the temperature range of 0 to 50.degree. C., and can be carried out under normal pressure or under increased pressure. When the treatment is carried out in the gas phase, it is carried out under the flow condition, and when the treatment is carried out in the liquid phase. It is preferable to make sufficient contact under stirring. The olefins used in the prepolymerization can be used alone or in combination of two or more kinds, and when prepolymerizing two or more kinds, they can be prepolymerized sequentially or simultaneously.

The catalyst for producing an olefin polymer of the present invention is obtained as described above, and a Lewis base compound may be added to this. Specific Lewis base compounds include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate. , Hexyl acetate, cyclohexyl acetate, benzyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 3-
Ethylhexyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl isovalerate, isokichi Isobutyl herbate, butyl stearate, pentyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate, ethyl cinnamate, diethyl oxalate, dibutyl oxalate, oxalic acid Esters such as dipentyl, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate and triacetin, methylacetate Amine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, diisopropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, allylamine, aniline, N -Methylaniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, cyclohexylamine, dicyclohexylamine, pyrrole, piperidine, pyridine, picoline, 2,4-lutidine, 2,6-lutidine, 2,6- Amines such as di (t-butyl) pyridine, quinoline and isoquinoline, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether Ether, anisole, phenetole, butyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, veratrole, 1,2-epoxypropane, dioxane, trioxane, furan,
Ethers such as 2,5-dimethylfuran, tetrahydrofuran, tetrahydropyran, 1,2-diethoxyethane, 1,2-dibutoxyethane and crown ether, acetone, methyl ethyl ketone, methyl propyl ketone,
Diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, dipropyl ketone,
Diisobutyl ketone, cyclohexanone, methylcyclohexanone, ketones such as acetophenone, dimethyl sulfide, diethyl sulfide, thioethers such as thiophene, tetrahydrothiophene, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, Tetraisopentoxysilane, tetrahexoxysilane, tetraphenoxysilane, tetrakis (2-ethylhexoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-methoxyethoxy) silane, methyltrimethoxysilane, ethyltrimethoxysilane , Propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane , Sec-butyltrimethoxysilane, t-butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, norbonyltrimethoxysilane, cyclohexyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorotrimethoxysilane, triethoxysilane, methyltriethoxysilane,
Ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, ethyltriisopropoxysilane, isopentyltributoxysilane, methyltrihexoxysilane , Methyldimethoxysilane, dimethyldimethoxysilane, propylmethyldimethoxysilane, propylethyldimethoxysilane, dipropyldimethoxysilane, isopropylmethyldimethoxysilane, diisopropyldimethoxysilane, propylisopropyldimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane, butylpropyl Dimethoxysilane, butylisopropyldimethoxysilane, dibutyldimethoxysilane, Seo-butyl methyl dimethoxy silane,
Diisobutyldimethoxysilane, sec-butylethyldimethoxysilane, di-sec-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylpropyldimethoxysilane, di-t-butyldimethoxysilane, t-butylhexyldimethoxysilane, diisoamyl Dimethoxysilane, hexylpropyldimethoxysilane, decylmethyldimethoxysilane, norbonylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diisopropyldiethoxysilane Ethoxysilane, sec-butylmethyldiethoxysilane, t-butylmethyldiethoxysilane, dimethyl Butoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, trimethylpropoxysilane, trimethyl-t-butoxysilane, trimethylisobutoxysilane, trimethylbutoxysilane, trimethylpentoxysilane, silyl ethers such as trimethylphenoxysilane, Methylphosphine, ethylphosphine, phenylphosphine, benzylphosphine, dimethylphosphine, diethylphosphine, diphenylphosphine, methylphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, tributylphosphine, Ethylbenzylphenylphosphine, ethylbenzylbutylphosphine, trimethoxyphosphine Phosphines such as diethylethoxyphosphine, triphenylphosphine oxide, dimethylethoxyphosphine oxide, phosphine oxides such as triethoxyphosphine oxide, acrylonitrile, cyclohexanedinitrile, nitriles such as benzonitrile, nitrobenzene, nitrotoluene, Nitro compounds such as dinitrobenzene, acetone dimethyl acetal, acetophenone dimethyl acetal, benzophenone dimethyl acetal, cyclohexanone dimethyl acetal, and other acetals, carbonic acid esters such as diethyl carbonate, diphenyl carbonate, ethylene carbonate, 1-ethoxy-1- (methylthio ) Examples include, but are not limited to, thioacetals such as cyclopentane and thioketones such as cyclohexanethione. It is not something that will be done.

When a Lewis base compound is added to obtain a catalyst, the transition metal compound (c) and the Lewis base compound are in mols.
The ratio is not particularly limited, but the molar ratio of the transition metal compound (c): Lewis base compound is preferably 1: 0.01 to.
It is in the range of 1: 1000, particularly preferably 1: 0.1
˜1: 100.

In addition, in preparing the catalyst, the method of adding the Lewis base compound is not limited, but it is preferable to add the Lewis base compound after contacting (a) to (e). In the present invention, in the presence of the catalyst for producing an olefin polymer prepared by the above method, the α-olefin or the cyclic olefin is melted, suspended or in a gas phase at a temperature of −60 to 280 ° C. 5-2000 bar
Can be polymerized or copolymerized under pressure to produce a polyolefin.

These olefins include ethylene,
Propylene, butene-1, pentene-1,4-methyl-
Examples thereof include α-olefins such as 1-pentene, hexene-1, and octene-1, and cyclic olefins such as norbornene and norbornadiene, but it is also possible to polymerize a mixed component of two or more kinds thereof.

When the polymerization is carried out in a solution state or a suspension state, the catalyst for producing an olefin polymer obtained by the above method may be used as it is or may be diluted with a polymerization solvent. The polymerization solvent may be any organic solvent commonly used, and specifically, halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride, and fats such as pentane, hexane, heptane, octane, nonane and decane. Examples thereof include aromatic hydrocarbons such as group hydrocarbons, benzene, toluene and xylene, or the olefin itself can be used as a solvent.

[0059]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The polymerization operation, reaction and solvent purification were all carried out under an inert gas atmosphere. Further, as the solvent and the like used in the reaction, those which were previously purified, dried and deoxidized by a known method were used. The compounds used in the reaction were those synthesized and identified by known methods. The melting index (MI) described in the examples was measured by a method according to ASTM D1238 condition E.

Example 1 [Treatment of silica with (C ₈ H ₁₇ ) Me ₂ SiCl] 30
To a 0 ml glass container, 3.3 g of silica (calcined at 200 ° C. for 5 hours) and 70 ml of a tetrahydrofuran solution (0.24 mol / l) of (C ₈ H ₁₇ ) Me ₂ SiCl were added,
It was suspended. The suspension was stirred under reflux for 10 hours.
After completion of the reaction, the solvent was removed and the residue was washed 4 times with 35 ml of a tetrahydrofuran solution.

[Polymerization] 1.0 g of the silica treated with the above (C ₈ H ₁₇ ) Me ₂ SiCl and 30 ml of hexane were added to a 1 liter glass electromagnetic stirring autoclave to form a suspension. 3.5 ml of a toluene solution of methylaluminoxane (2.39 mol / l) was added thereto, and the mixture was stirred at room temperature for 1 hour. Then, a toluene solution of bis (indenyl) zirconium dichloride (0.0024 mol /
l) 70 ml was added, and the mixture was stirred at room temperature for 1 hour. Then
40 ml of hexane was added, ethylene was introduced, and polymerization was carried out at 30 ° C. for 3 hours while continuously adding ethylene gas so that the internal pressure of the autoclave became 0.5 kg / cm ² G. After drying, 14 g of polymer was obtained. At this time, no polymer adhesion was observed on the wall of the reactor and the stirring blade.

Example 2 [Polymerization] The interior of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, a mixture of the polymer polymerized in Example 1 (containing zirconium corresponding to 2.5 μmol) and tri (i-butyl) aluminum (1.5 mmol) was inserted into an autoclave. Immediately introduce ethylene gas,
Polymerization was carried out at 80 ° C. for 30 minutes while continuously adding ethylene gas so that the internal pressure of the autoclave was 8 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI was 0.4 g / 10 minutes and bulk density was 0.32 g / cm.
44 g of the polymer of ³ were obtained.

Example 3 [Treatment of silica with (C ₁₈ H ₃₇ ) Me ₂ SiCl] In [Treatment of silica with (C ₈ H ₁₇ ) Me ₂ SiCl] of Example 1, (C ₈ H ₁₇ ) Me ₂ Silica was treated in the same manner as in Example 1 except that (C ₁₈ H ₃₇ ) Me ₂ SiCl was used instead of SiCl.

[Preparation of prepolymerization catalyst] In [Polymerization] of Example 1, silica treated with (C ₁₈ H ₃₇ ) Me ₂ SiCl was used instead of the silica treated with (C ₈ H ₁₇ ) Me ₂ SiCl. Polymerization was carried out in the same manner as in Example 1 except that was used to prepare a prepolymerized catalyst. As a result, 0.165 m of zirconium per 1 g of silica of the prepolymerization catalyst
A prepolymerized catalyst containing 1 mol of polyethylene and 16 g of polyethylene was obtained. At this time, no adhesion of the prepolymerization catalyst or polymer was observed on the wall of the reactor or the stirring blade.

[Polymerization] The interior of the stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Then, the prepolymerized catalyst prepared above (corresponding to 2.5 μmol of zirconium) and tri (i-butyl)
A mixture of 1.5 mmol of aluminum was inserted into the autoclave. Immediately, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 30 minutes while continuously adding ethylene gas so that the internal pressure of the autoclave became 8 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. as a result,
31 g of a polymer having an MI of 0.7 g / 10 minutes and a bulk density of 0.34 g / cm ³ was obtained.

Comparative Example 1 [Treatment of Silica with (Me ₃ Si) ₂ NH] In [Treatment of Silica with ((C ₈ H ₁₇ ) Me ₂ SiCl] of Example 1), (C ₈ H ₁₇ ) Me ₂ SiCl Instead (Me ₃ S
i) Silica was treated in the same manner as in Example 1 except that ₂ NH was used.

[Polymerization] In [Polymerization] of Example 1,
Polymerization was carried out in the same manner as in Example 1 except that the above (Me ₃ Si) ₂ NH-treated silica was used in place of the (C ₈ H ₁₇ ) Me ₂ SiCl-treated silica. At this time, adhesion of the polymer was observed on the wall of the reactor and the stirring blade.

Example 4 [Preparation of Preliminary Polymerization Catalyst] In Example 3, [Preparation of Preliminary Polymerization Catalyst], except that the amount of the methylaluminoxane toluene solution used was changed from 3.5 ml to 7.0 ml. A catalyst was prepared in the same manner as in. As a result, 0.094 of zirconium was added per 1 g of silica as the prepolymerization catalyst.
A prepolymerized catalyst containing 1 mmol of polyethylene and 12 g of polyethylene was obtained. At this time, only a small amount of polymer coating was observed on the liquid surface of the reactor wall.

[Polymerization] The interior of the stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a dispersion medium for the catalyst, and the internal temperature was adjusted to 75 ° C. Then, the prepolymerized catalyst prepared above (corresponding to 2.5 μmol of zirconium) and tri (i-butyl)
A mixture of 1.5 mmol of aluminum was inserted into the autoclave. Immediately, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 30 minutes while continuously adding ethylene gas so that the internal pressure of the autoclave became 8 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. as a result,
95 g of a polymer having an MI of 1.1 g / 10 minutes and a bulk density of 0.36 g / cm ³ was obtained.

Comparative Example 2 [Preparation of Preliminary Polymerization Catalyst] In [Preparation of Preliminary Polymerization Catalyst] of Example 4, instead of silica treated with (C ₁₈ H ₃₇ ) Me ₂ SiCl, silica only calcined at 200 ° C. A catalyst was prepared in the same manner as in Example 4 except that was used. As a result, a prepolymerized catalyst containing 0.087 mmol of zirconium and 10 g of polyethylene per 1 g of silica of the prepolymerized catalyst was obtained. At this time, a large amount of polymer was observed to adhere to the wall of the reactor and the stirring blade.

Example 5 [Polymerization] The interior of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, a mixture of the prepolymerized catalyst obtained in Example 4 (corresponding to 2.5 μmol of zirconium) and 1.5 mmol of tri (i-butyl) aluminum was inserted into an autoclave. Immediately, a mixed gas of ethylene / butene-1 (butene-1 content: 13 mol%) was introduced, and polymerization was carried out at 80 ° C. for 40 minutes while continuously adding the mixed gas so that the internal pressure of the autoclave was 8 kg / cm ² G. . After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI is 3.2g
/ 10 minutes, a melting point of 125 ° C., and a bulk density of 0.29 g / cm ³ of 36 g of a polymer were obtained.

[0073]

INDUSTRIAL APPLICABILITY The catalyst for producing an olefin polymer of the present invention can efficiently carry a complex in the preparation of the catalyst and can suppress the adhesion of scale on the reactor wall. Furthermore, in gas phase polymerization or suspension polymerization, an olefin polymer having excellent particle activity and excellent polymerization activity can be produced by using only a small amount of an organoaluminum oxy compound.

Claims (8)

[Claims] 1. An inorganic material characterized in that (a) a compound having a hydrocarbon group having 8 or more carbon atoms, which may contain halogen, N, O, P, S or Si, is supported by a chemical bond. Oxide, (b) organoaluminum oxy compound,
(C) A catalyst for producing an olefin polymer, which is obtained by contacting a transition metal compound. 2. An inorganic material characterized in that (a) a compound having a hydrocarbon group having 8 or more carbon atoms, which may contain halogen, N, O, P, S or Si, is supported by a chemical bond. Oxide, (b) organoaluminum oxy compound,
A catalyst for producing an olefin polymer, which is obtained by bringing (c) a transition metal compound, (d) an olefin, and (e) an organometallic compound into contact with each other. 3. An inorganic material characterized in that (a) a compound having a hydrocarbon group having 8 or more carbon atoms, which may contain halogen, N, O, P, S or Si, is supported by a chemical bond. Oxide, (b) organoaluminum oxy compound,
(C) An olefin polymer-producing catalyst obtained by contacting an olefin prepolymerization catalyst formed by prepolymerizing an olefin (d) with a catalyst component composed of a transition metal compound and (e) an organometallic compound. 4. A compound having a hydrocarbon group having 8 or more carbon atoms which is chemically bonded to an inorganic oxide is represented by the general formula (1): (In the formula, M1 is Periodic Table Ia, IIa, IIIa, IVa
Is a group, element of Sn or Zn, and R1 is each independently an alkyl group having 8 or more carbon atoms, alkenyl group or arylalkyl group which may contain halogen, N, O, P, S or Si, R2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, or an alkylaryl group, X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, 6-carbon
20 aryloxy group, arylalkoxy group, alkylaryloxy group, chemical formula (2): (R3 is an alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
In the aryl group, arylalkyl group, and alkylaryl group, a part or all of hydrogen atoms may be substituted with halogen. ) Or a carboxyl group represented by the chemical formula (3) (R4 is an alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
In the aryl group, arylalkyl group, and alkylaryl group, a part or all of hydrogen atoms may be substituted with halogen. ) Is a sulfonyl group. n is equal to the oxidation number of M1, l is an integer of 1 to n, m
Is an integer from 0 to n. ) An organometallic compound represented by
General formula (4) (In the formula, M2 is Periodic Table Ia, IIa, IIIa, IVa
R5 is an element of the group, Sn or Zn, and each R5 is independently an alkyl group having 8 or more carbon atoms, an alkenyl group or an arylalkyl group which may contain halogen, N, O, P, S or Si. R6 and R7 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, or an alkylaryl group.
p is an integer of 1 or more, q is an integer of 0 or more, and (p + q
+1) is equal to the oxidation number of M2. r is an integer of 1 to 3. ) Or an amine represented by the general formula (5): (R8 is independently halogen, N, O, P, S, S
It is an alkyl group having 8 or more carbon atoms, alkenyl group, or arylalkyl group which may contain i. 4. The catalyst for producing an olefin polymer according to claim 1, which is an alcohol represented by the formula (1). 5. A transition metal compound (c) is represented by the following general formula (6): Or the following general formula (7): (In the formula, M3 is a titanium atom, a zirconium atom, or a hafnium atom, and Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 to 2 carbon atoms.
Is an aryl group, an arylalkyl group or an alkylaryl group of 0, and R9 and R10 are each independently the following general formula (8), (9), (10) or (11): (In the formula, each R14 is independently a hydrogen atom and a carbon number of 1-2.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group. ), The ligand forms a sandwich structure together with M3, and R12 and R13 each independently represent the following general formula (12), (13), (14) or ( 15) [Chemical 9] (In the formula, each R15 is independently a hydrogen atom and a carbon number of 1-2.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group. ), The ligand forms a sandwich structure together with M3, and R11 is represented by the following general formula (16) or (1
7) (In the formula, each R16 independently represents a hydrogen atom or a carbon number of 1-2.
An alkyl group having 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group, and M4 is a silicon atom, a germanium atom or a tin atom. ), Which acts to crosslink R12 and R13, and s is an integer of 1 to 5. ) It is a group IVb transition metal compound represented by the formula (4), and the catalyst for producing an olefin polymer according to any one of claims 1 to 4. 6. The transition metal compound (c) has the following general formula (1)
8), (19), (20) or (21) (In the formula, M5 is each independently a titanium atom, a zirconium atom or a hafnium atom, and Z is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
An aryl group, an arylalkyl group, and an alkylaryl group having 6 to 20 carbon atoms, L is a Lewis base, w is 0 to 3, JR17 is a heteroatom ligand, and J is
Is a Va group element having a coordination number of 3 or an IVa group element having a coordination number of 2, and R17 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, An aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group, an alkylaryloxy group,
t is the coordination number of the element J, and R18 is the following general formula (2
2), (23), (24) or (25) (In the formula, each R21 independently represents a hydrogen atom or a carbon number of 1-2.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group. ), R20 is a ligand represented by the following general formula (26), (2
7), (28) or (29) (In the formula, each R22 independently represents a hydrogen atom and a carbon number of 1-2.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group. ), R19 is a ligand represented by the following general formula (30) or (31): (In the formula, each of R23 is independently a hydrogen atom or a carbon number of 1-2.
An alkyl group having 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, and an alkylaryl group, and M6 is a silicon atom, a germanium atom, or a tin atom. ), Which acts to crosslink R20 and JR17, and u is an integer of 1 to 5. ) It is a group IVb transition metal compound represented by the formula (4), and the catalyst for producing an olefin polymer according to any one of claims 1 to 4. 7. The organometallic compound (e) has the following general formula (3):
2) [Chemical 15] (In the formula, M7 is a periodic table Ia, IIa, IIIa group, Sn
Or an element of Zn, R24 is independently a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group. , An alkylaryl group, an alkylaryloxy group, and at least one R24 is an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 6 to 20 carbon atoms. x is equal to the oxidation number of M7. ) It is an organometallic compound represented by these, The catalyst for olefin polymer manufacture of any one of Claims 1-6 characterized by the above-mentioned. 8. An α-olefin or a cyclic olefin in a solution state, a suspension state or a gas phase state in the presence of the catalyst for producing an olefin polymer according to any one of claims 1 to -60 to 2
At a temperature of 80 ° C. and a pressure of 0.5 to 2000 bar,
A method for producing an olefin polymer, which comprises polymerizing or copolymerizing.