JPH08113604A - New carrier, its production and polymerization catalyst - Google Patents

Abstract

PURPOSE: To obtain a new carrier which can prevent problems encountered when a metallocene compound catalyst is used, such as the formation of a fine polymer particle having a low bulk density and the deposition of the formed polymer on the inside wall of the reactor and to provide a process for producing the carrier. CONSTITUTION: This carrier is prepared by reacting a solid having hydroxyl groups on the surface with a compound represented by the general formula: MR<1> R<2> R<3> (wherein M is an element of group 13 in the periodic table; and R<1> , R<2> and R<3> are each a 1-20C hydrocarbon group, an alkoxide group or a halogen) in such amounts that the equivalent ratio of the hydroxyl groups to the compound is unity or larger at a reaction temperature of -70 to 120 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel carrier for metallocene used for olefin polymerization, a method for producing the same, a metallocene catalyst for olefin polymerization using the novel carrier, and a method for producing polyolefin using the metallocene catalyst. is there.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a homogeneous polyolefin, a method for producing a polyolefin using a metallocene compound and methylaluminoxane as a catalyst is known. For example, in JP-A-58-19309, production of ethylene and a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms using biscyclopentadienyl zirconium dichloride as a catalyst with linear or cyclic methylaluminoxane is disclosed. A method is disclosed. Further, in JP-A-61-130314, a stereoregular polypropylene of a stereoregular polypropylene is prepared by using a catalyst composed of a zirconium compound whose ligand is a compound in which two indenyl groups are bonded via an ethylene group, and an aluminoxane. A manufacturing method is disclosed. Further, JP-A-2-41303 discloses a method for producing a poly-α-olefin having good syndiotacticity.

On the other hand, as a catalyst system which does not use aluminoxane as a cocatalyst, Taube et al., J. Organometall. Chem., 347 .C9.
(1988) [Cp ₂ TiMe (THF)] ⁺ [BPh
₄ ] ^- (Cp: cyclopentadienyl group, Me: methyl group, Ph: phenyl group, THF: tetrahydrofuran)
Polymerization of ethylene is carried out using the compound represented by. Jordan et al., J.Am.Chm.Soc., At 109 .4111 (1987) [C
It has been reported that a zirconium complex represented by p ₂ ZrR (L)] ⁺ (R: methyl group or benzyl group, L: Lewis base) polymerizes ethylene. In addition, special table 1
No. 501950 and Japanese Patent Publication No. 1-502036 disclose a method of polymerizing an olefin using a catalyst composed of a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. It is disclosed. Furthermore, Zambelli et al.
In ecules, 22 , 2186 (1989), it is reported that isotactic polypropylene can be produced by a catalyst in which a zirconium compound having a derivative of cyclopentadiene as a ligand is combined with trimethylaluminum and fluorodimethylaluminum. However, when the above catalyst system is used in a slurry process or a gas phase process, the resulting polymer particles become fine powder having a low bulk specific gravity, which makes it difficult to handle, and also causes problems such as adhesion of the produced polymer to a reactor. It was

In order to solve these problems, many studies have been carried out to support a metallocene compound or methylaluminoxane on a solid carrier. For example, JP
1-108610, JP-A-61-296008, JP-A-63-280703, JP-A-63-22804.
JP-A-63-51405, JP-A-63-5140
7, JP-A-63-55403, JP-A-63-610.
No. 10, JP-A No. 63-248803, and JP-A No. 4-10.
0808, JP-A-3-74412, and JP-A-3-70.
No. 9, JP-A No. 4-7306 and the like disclose an olefin polymerization method using a solid catalyst in which a metallocene compound and methylaluminoxane are supported on an inorganic metal oxide such as silica, alumina, or silica-alumina. There is.

JP-A-61-276805, JP-A-3-
Japanese Patent No. 74415 discloses a polymerization method in which a metallocene compound is used in combination with a metal oxide supporting only methylaluminoxane. JP-A-1-259004, JP-A-1-259005, JP-A-6-56928, and JP-A-6-56929 describe a metallocene compound having a special ligand as a porous metal oxide carrier such as silica. There is disclosed a method of using a catalyst supported on. JP-A-64
-6003, JP-A-64-6004, JP-A-64-
6005, JP-A-64-11104, JP-A-64-
Japanese Patent No. 11105 discloses a method using a catalyst in which a metallocene compound and an aluminoxane are supported on an organomagnesium compound.

[0006] JP-A-63-260903, JP-A-4-
No. 31403 and Japanese Patent Laid-Open No. 3-74411 disclose a method of using a catalyst in which a metallocene compound and an aluminoxane are supported on a polymer such as polyethylene or polystyrene. Japanese Unexamined Patent Publication No. 4-234405 discloses a method in which a complex is formed by using a cyclopentadienyl group bonded to poly (halogenated methylstyrene) to carry out solid catalysis. JP-A-3-234709
JP-A-5-247128 and JP-A-5-23913.
No. 8, JP-A-5-148316, JP-A-5-1483
16, JP-A-3-234709, and JP-A-5-155.
No. 926, JP-A-5-502906 and the like disclose a method of using a catalyst in which a cationic metallocene compound reacted with a non-coordinating boron compound is supported on an inorganic metal compound such as silica.

However, the above-mentioned catalyst in which a metallocene compound or methylaluminoxane is supported on a solid carrier has not been able to sufficiently solve the problem of preventing the polymer from adhering to the reactor wall in a slurry process or a gas phase process. The polymerization activity per complex in the catalyst is remarkably low, and as a result, the production method of the polyolefin using these catalysts increases the production cost of the polymer, so that the performance is not satisfactory.

[0008]

DISCLOSURE OF THE INVENTION The present invention, when a metallocene compound and a methylaluminoxane or a non-coordinating boron compound are used as a catalyst in the production of a polyolefin, the polymer particles produced become a fine powder having a low bulk specific gravity. There are no problems such as difficulty in handling and adhesion of the produced polymer to the reactor, and many catalyst systems in which the metatheron compound or methylaluminoxane is supported on the solid support examined for solving these problems are still present. A novel carrier for a metallocene catalyst which does not have the problem of unsolved polymer adhering to a reactor or a cost increase, a method for producing the same, an olefin polymerization catalyst using the new carrier, and an olefin polymerization catalyst The purpose is to develop a manufacturing method for polyolefins.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a group 13 element of the periodic table (inorganic chemical nomenclature 1990 Polymerization of an olefin using a novel carrier chemically bound to a compound containing (according to the year's rule) and an organic compound containing a transition metal of Group 4, 5 or 6 of the periodic table gives a highly active polymer. It was found that a high-molecular-weight polymer was obtained without adhesion of the above in the reactor. That is,
The present invention includes (1) a solid having a hydroxyl group on the surface and a compound represented by the following general formula (1): MR ¹ R ² R ³ (1) (wherein M is a group 13 group in the periodic table). Is an element, R ¹ , R
² , R ³ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxide group or halogen. ) A new carrier (A) obtained by reacting

(2) A solid having a hydroxyl group on the surface and a compound represented by the following general formula (1) MR ¹ R ² R ³ (1) (where M is an element of Group 13 of the periodic table) And R ¹ , R
² , R ³ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxide group or halogen. And a) in an organic solvent at a reaction temperature of −70 to 120 ° C. at a reaction rate of the compound represented by the general formula (1) with respect to a hydroxyl group in a ratio of at least equivalent. (3) (a) The above new carrier (A) (b) Organic compound containing a transition metal of Group 4, 5 or 6 of the periodic table (c) Hetero represented by the general formula (2) or (2 ') Atom-containing compound AL ¹ L ² (2) AL ¹ L ² L ³ (2 ') (In the formula, A is an element having a lone electron pair, L ¹ , L ² , L ³
May be the same or different and each is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or an alkoxide group. ) (D) Organoaluminum compound, wherein components (a), (b) and (d) or components (a), (b), (c) and (d) are blended for olefin polymerization catalyst. (4) The above object was achieved by developing a method for producing a polyolefin characterized by using the above-mentioned olefin polymerization catalyst.

The solid having a hydroxyl group on the surface in the present invention is an inorganic oxide, an inorganic chloride, an inorganic hydroxide or an organic polymer compound, and those having a hydroxyl group on the surface or the like can be used. Specifically, silica, alumina, silica-alumina, magnesia, titania, zirconia, inorganic oxide having a hydroxyl group on the surface such as calcia,
1 selected from the group of inorganic chlorides such as sodium chloride, magnesium chloride, potassium chloride and calcium chloride, or polymer compounds having a hydroxyl group such as polyvinyl alcohol 1
One kind or two or more kinds can be used. These compounds have an average particle size of 5 to 200 μm and a specific surface area of 10
The particles are preferably 0 to 1000 m ² / g.
Further, the adsorbed water is removed, and heat treatment is performed to control the number of hydroxyl groups. For example, the heat treatment time of silica is 2 to 24 hours,
Usually 4 to 8 hours. The hydroxyl group content depends on the heat treatment temperature, and when treated at 150 ° C, there are about 5 hydroxyl groups /
In the case of processing at nm ² and 600 ° C., the number is about 1 piece / nm ² . It is preferable to use one or more of silica, alumina, or the group of silica-alumina treated at 400 to 600 ° C.

The compound represented by the general formula (1) (hereinafter referred to as Group 13 compound) in the present invention is MR ¹ R ² R ³ (1), and M is an element of Group 13 of the periodic table. Of these, boron and aluminum are preferable, and boron is particularly preferable. R ¹ , R ² and R ³ may be the same or different and may be hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxide group or halogen.

Specific examples of the Group 13 compound include trimethylboron, triethylboron, tripropylboron,
Tributylboron, tripentylboron, trihexylboron, trioctylboron, tridecylboron, tricyclohexylboron, triphenylboron, tritolylboron, trixylylboron, tri (fluorophenyl) boron, tris (difluorophenyl) boron, tris (Pentafluorophenyl) boron, tris (chlorophenyl) boron, tris (trifluoromethyl) boron, dimethylethylboron, diethylbutylboron,
Diethylphenylboron, diphenylmethylboron, diphenylethylboron, methylethylphenylboron,
Dimethylchloroboron, diethylfluoroboron, diethylchloroboron, diethylbromoboron, dibutylchloroboron, diphenylchloroboron, di (pentafluorophenyl) chloroboron, diphenylphenoxyboron, diethylmethoxyboron, diethylethoxyboron, diethylpropoxyboron, diethyl Butoxyboron, diethylphenoxyboron, dibutylethoxyboron, dibutyl-2-ethylhexoxyboron, diphenylethoxyboron, diphenylphenoxyboron, diethylborohydride, dibutylboronhydride, diphenylborohydride, ethyldichloroboron, butyldichloroboron , Phenyldichloroboron, phenyldifluoroboron, phenyldibromoboron, ethyldimethoxyboron, ethyldie Kishihou arsenide, ethyl dibutoxyethoxyethyl judicial arsenide, ethyl di phenoxyborate arsenide, butyl diethoxy boron, butyl di phenoxyborate arsenide, phenyl dimethoxy boron, phenyl diethoxy boron, phenyl di phenoxyborate arsenide, ethyl borohydride, butyl borohydride,
Phenyl borohydride, tris (4-trifluoromethylphenyl) boron, tris [2,4,6-tris (trifluoromethyl) phenyl] boron, triphenylaluminum, tris [3,5-bis (trifluoromethyl) Phenyl] boron, trifluorophenylaluminum, tris (difluorophenyl) aluminum, tris (pentafluorophenyl) aluminum, tris (chlorophenyl) aluminum, tris (di-trifluoromethyl) aluminum and the like. Of these, triphenylboron and tris (pentafluorophenyl) boron are preferable.

The solid having a hydroxyl group in the present invention and the thirteenth
The reaction of the group compound can be carried out by various methods, and it is also possible to carry out the reaction in a non-solvent system, but it is generally carried out in an organic solvent. The organic solvent used is pentane,
Hexane, heptane, octane, nonane, decane and other aliphatic hydrocarbons, methylcyclopentane, cyclopentane, cyclooctane and other alicyclic hydrocarbons, benzene, toluene, xylene, cumene, cymene and other aromatic hydrocarbons, etc. Can be used. The conditions for reacting the solid having a hydroxyl group with the Group 13 compound are arbitrary as long as the effects of the present invention are observed, but the following conditions are generally preferable. The reaction temperature condition is usually -70 to 120 ° C, preferably 0 to 100 ° C. The reaction time cannot be specified unconditionally depending on the conditions such as concentration and temperature, but it is preferable to allow the reaction between the Group 13 compound and the solid hydroxyl group having a hydroxyl group to be sufficient, and at least 5 minutes or more is preferable. The reaction amount ratio between the solid having a hydroxyl group and the Group 13 compound in the present invention is not particularly limited, but it is preferable that the Group 13 compound is equivalent to or more than the number of hydroxyl groups.

The novel carrier (A), which is a reaction product, must be separated from the reaction solution, and the unreacted Group 13 compound must be removed by washing. As the washing solvent, the above organic solvent can be used. The washing temperature is −30 to 120 ° C., preferably 0 to 100 ° C. In washing, it is preferable that the Group 13 compound is not substantially detected in the washing liquid.
After washing, the novel carrier (A) can be dried or used in the presence of an organic solvent. Examples of the transition metal compound of Group 4, 5 or 6 of the periodic table in the present invention include those represented by the following general formula (3). In ^{_{(C 5 R 4 m) p}} R 6 s (C 5 R 5 n) MeQ 3-p or ^{_{(C 5 R 4 m) R}} 7 MeQ '...... (3) ( wherein, Me is the Periodic Table Group 4, 5, and 6 transition metals, (C ₅ R ⁴ _m ), (C ₅ R ⁵ _n ) are cyclopentadienyl or substituted cyclopentadienyl, and R ⁴ and R ⁵ are the same. They may be different, and are hydrogen, or an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a silylalkyl group, or two adjacent carbon atoms bonded to each other. R ⁶ may be a ring, R ⁶ is an alkylene group having 1 to 20 carbon atoms, —GeR ⁸ R ⁹ —, —S
^{iR 8 R 9 -, - O} -, - S -, - NR 8 -, - PR 8
-, R ⁷ is an alkylene group having 1 to 20 carbon atoms, -G
^{eR 8 R 9 -, - SiR} 8 R 9 -, - O -, - S -, -
NR ⁸ -, - PR ⁸ - or -OR ^8, -NR ⁸ R ^9,
—PR ⁸ R ⁹ (R ⁸ and R ⁹ are hydrogen or 1 to 20 carbon atoms.
Hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, alkylaryl groups, arylalkyl groups, or halogenated alkyl groups or halogenated aryl groups)
And R ⁶ is bonded to two (C ₅ R ⁴ _m ) rings,
R ⁷ is bonded to (C ₅ R ⁴ _m ) and Me. Q is selected from an aryl group, an alkyl group, an alkenyl group, an alkylaryl group, an arylalkyl group and an alkylsilyl group, and is a hydrocarbon group having 1 to 20 carbon atoms or halogen, which may be the same or different. Q'is an alkylidene radical having 1 to 20 carbon atoms, s is 0 or 1, p is 0, 1 or 2, s is 0 when p is 0,
m and n are 4 when s is 1 and 5 when s is 0. )

In the compounds represented by the general formula (3), specific examples of the transition metal compound in which Me is zirconium are shown below. (Cyclopentadienyl)
Zirconium trichloride, (pentamethylcyclopentadienyl) zirconium dimethyl monochloride, (cyclopentadienyl) titanium trimethoxide, (methylcyclopentadienyl) hafnium triethoxide, dimethylsilylene (cyclopentadienyl) (t −
Butylamino) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (t-butylamino) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (trimethylsilylamino) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (Ethyl) (trimethylsilylamino) titanium dimethyl, bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-
Butylcyclopentadienyl) zirconium monochloride monohydride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (t-butyl-)
Cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dibromide, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (indenyl) zirconium dichloride,

Ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibenzyl, ethylenebis (t -Butyl-indenyl) zirconium dichloride,
Dimethylsilylenebis (3-t-butyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dibromide, dimethylsilylenebis (4-methylindenyl) zirconium dimethyl, dimethylsilylenebis (2,3,5,2 ', 4) ', 5'-Hexamethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2,4,3', 5'-tetra-t-
Butylcyclopentadienyl) zirconium dimethyl,
Isopropylidene bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride,

Dimethylsilylene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (3,4-dimethylfluorenyl)
Zirconium dimethyl, isopropylidene (cyclopentadienyl) (7,8-dimethylfluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadiene) (3-t-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-t-butylcyclopentadienylzirconium) dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-neopentylcyclopentadienylzirconium) dichloride, dimethylsilylene (tetramethylcyclopentadienyl)
(3-Pentylcyclopentadienylzirconium) dichloride, dimethylsilylene (cyclopentadienyl)
(Indenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (tetrahydroindenyl) zirconium dibromide, methylmethylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride

Ethylene (4-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, ethylene (4-t-butyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, ethylene (4 -T-butyl-cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, ethylene (4-methyl-cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, ethylene (4-methyl) -Cyclopentadienyl) (3-trimethylsilyl-indenyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, isopropylidene (4-t-butyl-)
Cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, isopropylidene (4-t-butyl-cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, dimethylsilylene (4-methyl-cyclopenta) Dienyl) (3-methyl-
Indenyl) zirconium dichloride, dimethylsilylene (4-t-butyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, dimethylsilylene (4-t-butyl-cyclopentadienyl)
(3-t-Butyl-indenyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl) (1,2,3-trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (4-
Methyl-cyclopentadienyl) (1,2,3-trimethylcyclopentadienyl) zirconium dichloride,
Isopropylidene (4-t-butyl-cyclopentadienyl) (1,2,3-trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (4-
t-Butyl-cyclopentadienyl) (1,2,3-tri-t-butylcyclopentadienyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dimethyl, isopropyl Ridene (4-t-butyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dimethyl, isopropylidene (4-t-butyl-cyclopentadienyl) (3-t-butyl-indenyl) zirconium dimethyl,

Ethylene (4-methyl-cyclopentadienyl) (3-methyl-indenyl) hafnium dichloride, dimethylsilylene (3-t-butyl-cyclopentadienyl) (fluorenyl) zirconium dichloride,
Dimethylsilylene (3-t-butyl-cyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilylene (3-cyclohexylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-isopropylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylsilylene (3-((1,1-diethyl) butyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-phenylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethyl Silylene (3-mesityl cyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylsilylene (3- (o-tolyl) cyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylsilylene (3- (2,6-xylyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-benzylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3 -Tritylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-
Trimethylsilylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-t-butyl-cyclopentadienyl) (fluorenyl) zirconium dichloride,

Methylphenylsilylene (3-t-butyl-cyclopentadienyl) (fluorenyl) hafnium dichloride, methylphenylsilylene (3-cyclohexylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-isopropylcyclo) Pentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-
((1,1-diethyl) butyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-phenylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-mesitylcyclopentadienyl) Examples thereof include enyl) (fluorenyl) zirconium dichloride and methylphenylsilylene (3- (o-tolyl) cyclopentadienyl) (fluorenyl) zirconium dichloride. Examples of the zirconium compound as described above include transition metal compounds in which zirconium is replaced with titanium, hafnium, or vanadium. It is possible to use one type or two or more types from the group of these compounds.

The hetero atom-containing compound in the present invention is
It is represented by the following general formula (2) or (2 ′). AL ¹ L ² ………… (2) AL ¹ L ² L ³ …… (2 ′) (In the formula, A is an element having a lone pair of electrons, L ¹ , L ² , L
³ , may be the same or different, and have 1 to 2 carbon atoms.
It is a hydrocarbon group of 0, a silicon-containing hydrocarbon group such as a trimethylsilyl group or a trimethylsilylphenyl group, or an alkoxide group having 1 to 20 carbon atoms. ) Specific examples of A include nitrogen, oxygen, sulfur, phosphorus and the like. The compound containing a hetero atom may be supported on the novel carrier (A), or may be added at the time of polymerization. Specific examples of the hetero atom-containing compound include ethers; thioethers; trimethylamine, triethylamine, tributylamine, triisobutylamine, triphenylamine, aniline, pyridine, bipyridine, phenanthroline, N, N-dimethylamine, N, N. Amines such as diethylaniline; phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, and the like, and preferable ones are
N, N-dimethylaniline and N, N-diethylaniline.

Examples of the organoaluminum compound used in the present invention include compounds represented by the following general formula. AlR _n X _m (R is an alkyl group, X is a halogen, n and m are numbers, and n + m = 3.) Specifically, triethylaluminum, tripropylaluminum, tributylaluminum, trihexyl. Aluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride and the like can be mentioned, but triisobutylaluminum and triethylaluminum are preferred.

The olefin polymerization catalyst of the present invention comprises (a) the novel carrier (A), (b) a transition metal compound, and
It is prepared by contacting (d) the metal aluminum compound or further these compositions with (c) the compound containing a hetero atom in a solvent and / or in the presence of a liquid monomer. Of the components (a), (b), (c) and (d), only (a), (b) and (c) may be used, but high polymerization activity can be obtained by using the component (d). To be The contact method of each component is not particularly limited, for example, a method of mixing each component in an inert solvent. (A) Carrier (A) and component (c) are contacted in an inert solvent and washed with an inert solvent. After that, it can be performed by a method such as a method of mixing with the components (b) and (d).

The molar ratio of the organic compound having a transition metal of Group 4, 5 or 6 (transition metal compound) to the compound represented by the general formula (1) (Group 13 compound) is usually 1 to
The range is 0.1, preferably 1 to 0.5. If the molar ratio of the transition metal compound to the Group 13 compound exceeds 1, the transition metal compound that cannot be an active species remains, which is not preferable. Further, if this molar ratio is less than 0.1, a Group 13 compound unnecessary for active species formation will remain, and depending on the kind of the hetero atom-containing compound, the active site may be poisoned, which is unnecessary. It is desirable that the amount is as small as possible. It should be noted that the 13th
The amount of the group compound supported varies greatly depending on the firing conditions of the solid having a hydroxyl group. For example, in the case of silica, the amount of the group 13 compound acting is 0.06 to 3.3 mmol / g-silica, preferably 0.1 to 0.3 mmol / g-silica. 1.0 mmol / g-silica.

The polymerization method and the polymerization conditions using the catalyst of the present invention thus obtained are not particularly limited and include, for example, solution polymerization method, melt polymerization method, slurry polymerization method, suspension polymerization method,
A gas phase polymerization method or the like can be adopted. In particular, it is effective for processes in which the polymer is a heterogeneous system such as a slurry method and a gas phase method. The polymerization temperature is −100 to 300 ° C., preferably 0 to 150 ° C., and the polymerization pressure is atmospheric pressure to 100 k.
g / cm ² , preferably in the range of atmospheric pressure to 50 kg / cm ² . The polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. Furthermore, multistage polymerization can also be performed. The molecular weight of the obtained polymer can be controlled by the use of a chain transfer agent such as hydrogen and the polymerization temperature. Examples of the hydrocarbon medium used for polymerization using a medium such as a slurry polymerization method and a solution polymerization method include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, octane, nonane, and decane, and methyl. Alicyclic hydrocarbons such as cyclopentane, cyclopentane, cyclooctane, benzene, toluene, xylene, cumene,
Aromatic hydrocarbons such as cymene can be used. One kind or two or more kinds from the above group can be used.

As the olefins which can be polymerized, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene and tetracyclododecene. Further, styrene, vinylcyclohexane, vinylcyclohexene, vinylbenzene, diene and the like can be polymerized similarly to olefins.
In the present invention, not only homopolymerization of olefins,
For example, copolymers of ethylene and propylene, ethylene and 1-butene, etc. can be produced.

In the polymerization method of the present invention, preliminary polymerization can be carried out using the catalyst of the present invention. The prepolymerization method is not particularly limited and a known method can be used. The olefin used in the prepolymerization is not limited, and the above olefin can be used. The prepolymerization temperature is usually -20 to
The temperature is 300 ° C, preferably -10 to 200 ° C, more preferably 0 to 100 ° C. As the solvent, inert hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons, monomers and the like can be used. Aliphatic hydrocarbons are preferred. Further, the prepolymerization may be performed without a solvent. When the polymerization catalyst of the present invention is used for the polymerization of propylene, the polymerization activity per transition metal compound is about 15 to 30 × 10 ⁴ (g / g
It becomes a transition metal compound.h) and the activity per catalyst weight is about 1,000 to 30,000 (g / g complex.h).

[0029]

The reaction between the solid having a hydroxyl group on the surface and the compound represented by the general formula (1) is presumed to be the following reaction although no confirmation data has been obtained. That is, for example, silica and tris (pentafluorophenyl)
The following adduct (a) is formed in borane.

Embedded image When AL ¹ L ² L ³ acts on this, the hydrogen of the silanol group interacts with AL ¹ L ² L ³ and forms an adduct (b) when A is nitrogen (salt). .

Embedded image In contrast to (b), a transition metal compound (for example, Cp ₂ ZrR
_{It is considered that when 2} ) is used, the following active site is formed, the monomer is coordinated with the active site, the active site is inserted into the Zr-R bond, and the polymerization proceeds.

Embedded image

[0030]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example [Preparation of Boron-Supporting Inorganic Carrier] Silica was calcined at 600 ° C. for 4 hours in a nitrogen stream. The number of hydroxyl groups on the surface of the silica was 2 / nm ² . 30 ml of an isoparaffin solution of tris (tetrafluorophenyl) borane was added to 2 g of the silica and reacted at room temperature for 1 hour. The reaction product was washed with hexane and then dried. To the obtained solid, 30 ml of toluene and N, N-dimethylaniline of 0.
24 ml was added and it was made to react at room temperature for 3 hours. The reaction product was washed with toluene and then dried to prepare boron-supporting silica.

Example 1 [Polymerization of ethylene] The above boron-supporting inorganic carrier 10 was placed in a 1.5 L autoclave.
0 mg and 10 ml of a 0.5 M solution of triisobutylaluminum in toluene, 1 ml of a toluene solution of 2 mmol / 1 of ethylenebisindenylzirconium dichloride and 700 ml of isobutane were charged, and the mixture was heated to 50 ° C. and polymerized at an ethylene partial pressure of 10 kg / cm ² for 30 minutes. did. The results are shown in Table 2.

Example 2 [Copolymerization of ethylene-butene-1] The above-mentioned boron-supporting inorganic carrier 10 was placed in a 1.5 L autoclave.
0 mg and 10 ml of a 0.5 M solution of triisobutylaluminum in toluene, 1 ml of a 2 mmol / 1 solution of ethylenebisindenylzirconium dichloride in toluene, and 700 ml of isobutane were charged, and after heating to 50 ° C., 20 g of 1-butene was fed with ethylene to obtain ethylene. Partial pressure 10kg
Polymerization was carried out for 30 minutes at / cm ² . The results are shown in Table 2.

Examples 3 to 11 As components (a), (b), (c) and (d), the compounds shown in Table 1 were used and polymerization was carried out under the conditions of Table 2 in the same manner as in Examples 1 and 2. . The results are shown in Table 2.

Example 12 [Polymerization of propylene] Into a 1.5 L autoclave was charged 8 ml of 0.5 M toluene solution of triisobutylaluminum and 8 mol of propylene, the temperature was raised to 50 ° C, and 2 mmol of ethylenebisindenylzirconium dichloride was added thereto. 2.5 ml of a 1/1 toluene solution, 100 mg of the above boron-supporting inorganic carrier
And a mixture of 0.2 ml of a 0.5 M toluene solution of triisobutylaluminum were added and polymerization was carried out for 30 minutes. The results are shown in Table 2.

Examples 13 to 21 As components (a), (b), (c) and (d), the compounds shown in Table 1 were used and polymerization was carried out in the same manner as in Example 12 under the conditions of Table 2. The results are shown in Table 2.

Comparative Example [Preparation of Solid Catalyst] 1 g of silica, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 0.
20 ml of toluene solution of 5 mmol / 1, 0.5 mmol / of ethylenebisindenyl zirconium dichloride
20 ml of a toluene solution of 1 was mixed and reacted at room temperature for 1 hour. The mixed solution was dried up to obtain a solid catalyst.

Comparative Example 1 [Polymerization of ethylene] 100 mg of the above solid catalyst in a 1.5 L autoclave,
8 ml of a 0.5 M toluene solution of triisobutylaluminum and 700 ml of isobutane were charged, the temperature was raised to 70 ° C., and the polymerization was carried out at an ethylene partial pressure of 10 kg / cm ² for 30 minutes. The results are shown in Table 2.

Comparative Example 2 [Ethylene-butene-1 co-weight]
]] Into a 1.5 L autoclave, 100 mg of the above solid catalyst and
0.5M solution of triisobutylaluminum in toluene 8
ml, isobutane 700 ml were charged, and the temperature was raised to 70 ° C. 1
-Feed 50 g of butene with ethylene, ethylene partial pressure
10 kg / cm ² It was polymerized for 30 minutes. The results are shown in Table 2.
Was.

Comparative Example 3 [Polymerization of propylene] A 1.5 L autoclave was charged with 8 ml of a toluene solution of triisobutylaluminum and 8 mol of propylene, and 5
After the temperature was raised to 0 ° C., a mixture of 100 mg of the above solid catalyst, 10 ml of toluene, and 0.2 ml of a 0.5M toluene solution of triisobutylaluminum was added and polymerization was carried out for 30 minutes. The results are shown in Table 2.

Examples 22 to 24 Polymerization of propylene under the same conditions as in Example 12 except that the component (c) was replaced with N, N-dimethyltoluidine, N-methyldiphenylamine and N, N-dimethyl-1-naphthylamine. I went. The results are shown in Table 3.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

Industrial Applicability When an olefin is polymerized by a slurry process, a gas phase process or the like using the catalyst containing the novel carrier of the present invention, a polymer having high activity and good powder property is obtained, and the reactor of the polymer is obtained. Can be eliminated or significantly reduced.

Front page continuation (72) Inventor Shigenobu Miyake Oita-shi, Oita 2 Nakanosu, Oita Research Institute, Showa Denko Co., Ltd. (72) Inventor Shintaro Inazawa Oita-shi, Oita 2 Showa Denko Co., Ltd. Oita Research Institute

Claims (4)

[Claims] 1. A solid having a hydroxyl group on its surface and a compound represented by the following general formula (1) MR ¹ R ² R ³ (1) (wherein M is an element of Group 13 of the periodic table). Yes, R ¹ , R
² , R ³ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxide group or halogen. ) A new carrier (A) obtained by reacting 2. A solid having a hydroxyl group on the surface and a compound represented by the following general formula (1) MR ¹ R ² R ³ (1) (wherein M is an element of Group 13 of the periodic table). Yes, R ¹ , R
² , R ³ may be the same or different and each is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxide group or halogen. ) Are reacted in an organic solvent at a reaction temperature of -70 to 120 ° C at a ratio of the compound represented by the general formula (1) to the hydroxyl group in an equivalent amount or more. ) Manufacturing method. 3. A novel carrier (A) according to claim 1 (b) An organic compound containing a transition metal of Group 4, 5 or 6 of the periodic table (c) General formula (2) or (2 ′) heteroatom-containing compound represented ^{by) AL 1 L 2 ............ (2} ) AL 1 L 2 L 3 ...... (2 ') ( wherein, a is an element having a lone electron pair, L ^1, L ^2, L ³
May be the same or different and each is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or an alkoxide group. ) (D) Organoaluminum compound, wherein components (a), (b) and (d) or components (a), (b), (c) and (d) are blended for olefin polymerization catalyst. 4. A method for producing a polyolefin, which comprises using the catalyst for olefin polymerization according to claim 3.