JPH03234709A - Solid catalyst for polymerization of olefin and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain the title catalyst which can give an olefin polymer having excellent particle properties and a narrow molecular weight distribution by mixing a particulate support with a specified transition metal compound. CONSTITUTION:The purpose catalyst is prepared by mixing a particulate support (e.g. silica) with a transition metal compound having cycloalkadienyl ligands and a boron-containing anion [e.g. a Zr catalyst component obtained from (n- butyl)ammonium tetra(p-tolyl) borate and bis(cyclopentadienyl) dimethylzirconium].

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a solid catalyst for olefin polymerization and a method for polymerizing olefins using this catalyst.

Specifically, the present invention makes it possible to produce a spherical olefin polymer with excellent bulk specific gravity and a narrow molecular weight distribution when a slurry polymerization method or a gas phase polymerization method, especially a gas phase polymerization method, is adopted. Moreover, the present invention relates to a solid catalyst for olefin polymerization that, when applied to the copolymerization of two or more types of olefins, provides an olefin polymer with a narrow molecular weight distribution and a narrow composition distribution.

Technical background of the invention and its problems Conventionally, titanium-based catalysts consisting of titanium compounds and organoaluminum or vanadium have been used as catalysts for producing α-olefin polymers, such as ethylene polymers or ethylene/thi-olefin copolymers. Vanadium-based catalysts comprising a compound and an organoaluminum compound are known.

In addition, as a new Ziegler type olefin polymerization catalyst,
Recently, a method for producing an ethylene/α-olefin copolymer using a catalyst consisting of a zirconium compound and an aluminoxane has been proposed.

An organoaluminum compound or aluminoxane is always used in the above-mentioned catalyst for olefin polymerization.

However, since these aluminum compounds are flammable and require great care in handling, it has been desired to develop a catalyst system that does not use these aluminum compounds.

On the other hand, Special Publication No. 1-501950, No. 1-5020
Publication No. 38 discloses a method for producing a transition metal compound catalyst containing a ligand having a cycloalkagenyl skeleton and an anion containing a boron element. It has been taught that it is active in olefin polymerization even without the use of olefins. However, the powder properties such as the bulk specific gravity of the produced polymer were insufficient.

Purpose of the Invention The present invention has been made in view of the prior art as described above, and it is possible to obtain an olefin polymer without using compounds such as organoaluminum compounds and aluminoxane, and further improves powder properties. The object of the present invention is to provide a solid catalyst for olefin polymerization that can provide an olefin polymer with excellent properties, and a method for polymerizing olefins using this catalyst.

Summary of the Invention The catalyst for olefin polymerization according to the present invention is formed from [A] a particulate carrier and [B] a transition metal compound containing a ligand having a cycloalkagenyl skeleton and an anion containing a boron element. It is characterized by being

In the olefin polymerization catalyst according to the present invention, the olefin may be prepolymerized.

Moreover, the method for polymerizing olefins according to the present invention is characterized in that olefins are polymerized or copolymerized in the presence of the above-described catalyst for olefin polymerization.

The olefin polymerization catalyst according to the present invention exhibits olefin polymerization activity without using an organoaluminum compound, aluminoxane, or the like, and can provide an olefin polymer with excellent powder properties.

The olefin polymerization catalyst and the olefin polymerization method using this catalyst according to the present invention will be specifically explained below.

In the present invention, the word "polymerization" is sometimes used to include not only homopolymerization but also copolymerization, and the word "polymer" is used to include not only homopolymers but also copolymers. Sometimes used in

FIG. 1 is an explanatory diagram of the olefin polymerization catalyst according to the present invention.

The olefin polymerization catalyst according to the present invention is formed from [A] a particulate carrier and [B] a transition metal compound containing a ligand having a cycloalkagenyl skeleton and an anion containing a boron element. .

In the present invention, the fine particulate carrier usually has an average particle diameter of 1 to 1.
A particulate inorganic carrier or a particulate organic carrier having a diameter of 300 μm, preferably 10 to 200 μm is used. The fine particulate inorganic carrier is preferably an oxide, specifically StO%A2flO, MgO1ZrO, TiO2 or
2 A mixture of these is used. Among these, SiO, A
A carrier containing as a main component at least one component selected from the group consisting of J2203 and MgO is preferred. Such an inorganic oxide support usually has a molecular weight of 150 to 1000
C., preferably 200 to 800.degree. C. for 2 to 20 hours.

Further, as the particulate organic carrier, particulate organic polymers such as polyethylene, polypropylene, poly-1
-Butene, a particulate polymer of polyolefin such as poly-4-methyl-1-pentene, a particulate polymer such as polystyrene, etc. are used.

[B] The transition metal compound containing a ligand having a cycloalkagenyl skeleton and containing an anion containing a boron element used in the present invention is a ligand having a [B-a] cycloalkagenyl skeleton. a transition metal compound containing [B-b] Brønsted acid or proton;
-c] It is a reaction product with an anion containing a boron element.

The transition metal compound containing a ligand having a [B-a] cycloalkagenyl skeleton used in the present invention has the formula MLx (where M is a transition metal and L is a coordination group that coordinates to the transition metal). At least one L is a ligand having a cycloalkagenyl skeleton, and when it contains at least two or more ligands having a cycloalkagenyl skeleton, at least two cycloalkagenyl The ligand having a cycloalkagenyl skeleton may be bonded via a bridging group such as an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group, and L other than the ligand having a cycloalkagenyl skeleton is carbon. 1 to 12 hydrocarbon groups or hydrogen, and X is the valence of the transition metal.

In the above formula, M is a transition metal, specifically,
Zirconium, titanium, nofnium or vanadium is preferred, and among these, zirconium and hafnium are particularly preferred.

Examples of the ligand having a cycloalkagenyl skeleton include a cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, an n-butylcyclopentagenyl group, a dimethylcyclopentagenyl group, Examples include alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl groups, indenyl groups, and fluorenyl groups.

Two or more of the above-mentioned ligands having a cycloalkagenyl skeleton may be coordinated to a transition metal, and in this case, the ligand having at least two cycloalkagenyl skeletons is They may be bonded via a bridging group such as an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group.

The ligand other than the ligand having a cycloalkagenyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen.

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, butyl group, etc.; cycloalkyl groups include cyclopentyl group, cyclohexyl group; aryl groups include phenyl group, tolyl group, etc.; aralkyl groups include benzyl group, Examples include a neophyll group.

Hereinafter, specific examples of transition metal compounds containing a ligand having a cycloalkagenyl skeleton in which M is zirconium will be exemplified.

Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis(cyclopentagenyl)phenylzirconium hydride, Bis(cyclopentagenyl)benzylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride Neopentyl zirconium hydride, Bis(methylcyclopentadienyl)dimethylzirconium, Bis(n-butylcyclopentadienyl)dimethylzirconium, Bis(indenyl)dimethylzirconium, (Pentamethylcyclopentadienyl)(Cyclopentagenyl) Genil)
Dimethylzirconium, bis(cyclopentagenyl)
Dimethylzirconium, Bis(pentamethylcyclopentagenyl)dimethylzirconium, Bis(cyclopentagenyl)zirconium diphenyl, Bis(cyclopentagenyl)zirconium dibenzyl, Bis(cyclopentagenyl)zirconium sibide, Bis(fluorenyl) ) dimethylzirconium, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)zirconium sibide, ethylenebis(4,5,8,7-tetrahydro-1-indenyl)dimethylzirconium, ethylene Bis(4-methyl-1-indenyl)dimethylzirconium, Ethylenebis(5-methyl-1-indenyl)dimethylzirconium, Ethylenebis(6-methyl-1-indenyl)dimethylzirconium, Ethylenebis(7-methyl-t- indenyl)dimethylzirconium, ethylenebis(5-methoxy-1-indenyl)dimethylzirconium, ethylenebis(2,3-dimethyl-1-indenyl)dimethylzirconium, ethylenebis(4,7-dimethyl-1-indenyl)dimethylzirconium , ethylenebis(4,7-simethoxy1-indenyl)
Dimethylzirconium, Methylenebis(cyclopentagenyl)zirconium cibide, Methylenebis(cyclopentagenyl)dimethylzirconium, Isopropylidene(cyclopentagenyl)zirconium cibide, Isopropylidene(cyclopentagenyl)dimethylzirconium, Isopropylidene( cyclopentadienyl-fluorenyl) zirconium sibide, isopropylidene (
cyclopentagenyl-fluorenyl) dimethylzirconium, silylenebis(cyclopentagenyl)zirconium cibide, silylenebis(cyclopentagenyl)dimethylzirconium, dimethylsilylene(cyclopentagenyl)zirconiumcibide, dimethylsilylene(cyclopentagenyl) ) Dimethylzirconium.

Furthermore, in the above zirconium compounds, transition metal compounds in which zirconium metal is replaced with titanium metal, hafnium metal, or vanadium metal can also be used.

The [B-b] Brønsted acid used in the present invention has the formula [M2R]" (wherein M2 is nitrogen or phosphorus, R is hydrogen or a hydrocarbon group, and at least one R is It is hydrogen.

).

In the above formula, examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of cycloalkyl groups include cyclopentyl and cyclohexyl groups; examples of aryl groups include phenyl and tolyl groups; examples of aralkyl groups include benzyl and neophyl groups. Examples include.

As the above [B-b] Brønsted acid,
Specifically, the following compounds are used.

Trimethylammonium, triethylammonium, tripropylammonium, tri(n-butyl)ammonium, N,N-dimethylfunirinium, N,N-diethylanilinium, N,N-2,4,5-pentamethylanilinium, Ji(
i-propyl)ammonium, dicyclohexylammonium, triphenylphosphonium, tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium.

Further, the anion containing the [B-c] boron element used in the present invention has the formula [BRl R''R3R' ] (wherein, B is boron, and R and R2 are aromatic or aromatic hydrocarbon groups). (wherein C and B are carbon and boron, respectively, and R5R6R7 is hydrogen , a hydrocarbon group or an organic metalloid group, X and x3 are integers of 0 or more, and a
is an integer of 11, x (an even number from + x 3+ a-2 to about 8, and Xl is an integer from 5 to about 22) or ) X21
0 n b (R)
and M are carbon, boron 9 or a transition metal, respectively, RR and R10 are hydrogen, halogen, hydrocarbon group or organic metalloid group, and
and X3 is an integer greater than or equal to 0, a is an integer of 2, an even number from x+x3+a-4 to about 8, and Xl
is an integer from 6 to about 12, n is an integer such that 2a-n-b, and b is an integer ≧1. ) or - formula [(CH) x (BH) Xl ]
(wherein C, B and H are each carbon, boron or hydrogen, Xl is 0 or 1, a is 2 or 1,
x, +a-2, and Xl is an integer from 10 to 12. ).

Specifically, the following compounds are used as the anion containing the [B-c] boron element as described above.

Tetraphenylborate, Tetra(p-tolyl)borate, Tetra(o-tolyl)borate, Tetra(Maro,-dimethylphenyltetra(O.S+-dimethylphenyl)borate, Tetra(pentafluorophenyl)borate, 7,8- Dicarbounde borate, tridecahydride-7-carboundecaborate, octadecaborate, bis(undecahydride-7,8-dicale borate) cobaltate (■), bis(7.8-dicale bounde borate) nickelate (m) Bis(7.8-dicarbaundecaborate) ferrate (■), dodecaborate, l-carbaundecaborate, l-carbadodecaborate.

In the present invention, when preparing the solid catalyst for olefin polymerization as described above, an organoaluminum compound or an aluminoxane may be used as necessary.

Examples of such organoaluminum compounds and aluminoxanes include organoaluminum compounds and aluminoxanes conventionally used in preparing catalysts for olefin polymerization.

Specifically, the solid catalyst for olefin polymerization in the present invention can be prepared as follows.

(1) In a hydrocarbon medium, [A] particulate carrier and [B]
A method of mixed contact with a transition metal compound.

At this time, the [BF-4 transition metal compound is usually used in an amount of 5 x 10 to 10-2 mol, preferably 10 to 10-3 mol, per 1 g of [A] particulate carrier, and the concentration of the transition metal compound is is about 10 to 5X10-2 mol/I, preferably 5X10-' to 10-2 mol/g. The reaction temperature is usually 0 to 150°C, preferably 20 to 8°C.
0°C, and the reaction time varies depending on the reaction temperature,
Usually about 0.2 to 50 hours, preferably about 0.5 to 20 hours.

<2> A method of evaporating the hydrocarbon solvent from the suspension obtained above.

(3) A method in which an olefin is brought into contact with the solid catalyst obtained by methods such as (1) and (2) for prepolymerization.

(4) A method in which an olefin is added and prepolymerized in a suspension containing [A] a particulate carrier and [B] a transition metal compound.

The olefin used in the prepolymerization is selected from the olefins used in the polymerization described later. Among these, ethylene is preferably used.

In prepolymerization, [A] for 1 g of particulate carrier [
B] It is desirable to use the transition metal compound in an amount of usually 10-5 to 5×3 10 mol, preferably 5×10-5 to 10-3 mol. [B] The transition metal compound is used in a range of approximately 10 to 5×10 −2 mol/g4 4 , preferably 5×10 to 10−2 mol/ρ. The prepolymerization temperature is usually in the range of -20 to 80°C, preferably 0 to 50°C, and the prepolymerization time is usually 0.25°C, although it varies depending on the prepolymerization temperature. It is about 5 to 100 hours, preferably about 1 to 50 hours.

The solid catalyst for olefin polymerization of the present invention obtained as described above has about 5×6−3 10 to 10 gram atoms, preferably 10−5 to 5×1 per 1 g of particulate carrier.
0-'gram atoms of transition metal atoms are supported. The amount of polymer produced by prepolymerization is about 0.61 to 500 g, preferably 0.3 to 3.0 g, per 1 g of particulate carrier.
00g, particularly preferably in the range of 1 to 100g.

Specifically, the inert hydrocarbon medium used in the preparation of the solid catalyst for olefin polymerization according to the present invention includes propane, butane, pentane, hexane, heptane, octane,
Aliphatic hydrocarbons such as decane, dodecane, and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride and chlorobenzenedichloromethane. Examples include hydrocarbons and mixtures thereof.

When polymerizing olefins using the catalyst for olefin polymerization according to the present invention as described above, the amount of the transition metal compound [B] is usually 10 to 10-3 grams in terms of transition metal atoms per 1 p of polymerization volume. It is desirable to use an amount of 7 atoms, preferably 10 to 10-4 gram atoms. At this time, an organic aluminum compound or aluminoxane may be used as necessary. Examples of such organoaluminum compounds and aluminoxanes include organoaluminum compounds and aluminoxanes conventionally used as olefin polymerization catalyst components.

Olefins that can be polymerized with such olefin polymerization catalysts include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-
Butene, l-hexene, 4-methyl-1-pentene, l
-Octene, l-decene, l-dodecene, 1-tetradecene, l-hexadecene, l-octadecene, l-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl -1,4,'5,8-dimethano-1,
Examples include 2,3,4,4a, 5,8,8a-octahydronaphthalene.

Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.

In the present invention, polymerization can be carried out by either liquid phase polymerization methods such as solution polymerization or suspension polymerization, or gas phase polymerization methods.

In the liquid phase polymerization method, the same inert hydrocarbon solvent used in the catalyst preparation method can be used, or the olefin itself can be used as the solvent.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually -50 to 200°C, preferably 0 to 200°C.
The temperature range is 150°C. Polymerization pressure is usually normal pressure to 11
00) c/cd, preferably under normal pressure to 50 kg/cd, and the polymerization reaction can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

The molecular weight of the resulting olefin polymer can be controlled by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

In addition, in the present invention, the olefin polymerization catalyst can contain other components useful for olefin polymerization in addition to the above-mentioned components.

Effects of the Invention The solid catalyst for olefin polymerization according to the present invention has excellent particle properties and a narrow molecular weight distribution, and when applied to the copolymerization of two or more types of olefins, it produces an olefin polymer with a narrow molecular weight distribution and composition distribution. can be given.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Preparation of zirconium catalyst] 0.65 g of tri(n-butyl)ammoniumtetra(p-tolyl)borate was suspended in 50 ml of toluene, and 0.32 g of bis(cyclopentadienyl)dimethylzirconium was suspended in 50 ml of toluene. and continued stirring at room temperature for 1 hour.

Next, a portion of toluene was distilled off, and the mixture was filtered to obtain a solid. The solid was washed with pentane and dried under reduced pressure to obtain a zirconium catalyst component.

[Preparation of solid catalyst] Silica (average particle size 70 μ, specific surface area 260 po/g) was placed in a 200 ml glass flask that was sufficiently purged with nitrogen.
, pore volume 1.65 knits/g) was calcined at 700 °C for 5 hours, 9.0 g of the zirconium catalyst prepared above was charged with 0.78 milligram atoms in terms of zirconium atoms, and 90 ml of toluene was charged. Heated at ℃ for 2 hours.

Thereafter, toluene was distilled off under reduced pressure using an evaporator to obtain a solid catalyst.

[Prepolymerization] Into a 400 ml glass flask that was sufficiently purged with nitrogen, 200 ml of hexane and 0.64 milligram atoms of the solid catalyst prepared above were charged in terms of zirconium atoms. After that, while supplying ethylene into the system,
Ethylene prepolymerization was carried out at .degree. C. for 6 hours.

After prepolymerization, remove hexane by decantation,
By further washing with hexane, a prepolymerized catalyst containing Sily-2, 7.9×10 to 10 gram atoms of zirconium and 2.3 g of polyethylene per gram of force was obtained.

[Polymerization] 150 g of sodium chloride (Wako Pure Chemicals special grade) was charged into a 2 g stainless steel autoclave that had been sufficiently purged with nitrogen.
It was dried under reduced pressure at 90°C for 1 hour.

Thereafter, the inside of the system was cooled to 65 DEG C., and 3.times.10@-2 milligram atoms of the prepolymerized catalyst prepared above was added in terms of zirconium atoms. Subsequently, 200 ml of hydrogen was introduced,
Furthermore, ethylene was introduced at 65°C to increase the total pressure to 8 kg/
Polymerization was initiated as cd-G. After that, the total pressure was maintained at 8 kg/cd-G while replenishing ethylene, and the
Polymerization was carried out at 0°C for 1 hour. After the polymerization was completed, sodium chloride was removed by washing with water, the remaining polymer was washed with methanol, and then dried under reduced pressure at 80° C. overnight. As a result, the bulk specific gravity was 0.39g/-, and the MFR was 0.55g/1.
0 minutes and Mv/Mn is 2.7 polyethylene 4
0 g was obtained.

Example 2 [Preparation of aluminoxane] AN (
So) - 1 g of 14H2037 and 133 ml of toluene were charged, and after cooling to -5°C, trimethylaluminum 47.
9 ml was added dropwise over 1 hour. After that, 1 at 0~=5℃
After reacting for 3 hours, the temperature was raised to 40℃ over 3 hours, and
The reaction was continued for an additional 72 hours at 0°C. After the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the filtrate to obtain white solid aluminoxane.

[Prepolymerization] 2.7 g of silica (same as that used in Example 1) was placed in a 400 ml glass flask that was sufficiently purged with nitrogen.
Converting aluminoxane to aluminum atoms: 13.
5 milligram atoms, II W L t in Example 1: 0.45 Si/I/conium catalyst in terms of zirconium atoms
Milligram atoms and 60 ml of hexane were charged and stirred at room temperature for 30 minutes. After that, 60 ml of hexane was added and ethylene was supplied into the system at 30°C under normal pressure.
A prepolymerization of ethylene is carried out for 22 8.7X10 -gram atoms of zirconium per gram of silica and 3.0 grams of polyethylene.
A prepolymerized catalyst containing 1 g was obtained.

[Polymerization] When polymerization was carried out in the same manner as in Example 1 using the prepolymerization catalyst as described above, the bulk specific gravity was 0.42 sr/d, the MFR was 0.47 g/10 min, and the 57 g of polyethylene with /Mn of 2.6 was obtained.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of the olefin polymerization catalyst according to the present invention.

Claims (1)

[Scope of Claims] 1) Formed from [A] a particulate carrier and [B] a transition metal compound containing a ligand having a cycloalkadienyl skeleton and an anion containing a boron element. Characteristic solid catalyst for olefin polymerization. 2) [A] A solid catalyst for olefin polymerization formed from a particulate carrier and [B] a transition metal compound containing a ligand having a cycloalkadienyl skeleton and an anion containing a boron element; A solid catalyst for olefin polymerization, which is obtained by prepolymerizing. 3) Prepolymerizing an olefin in a suspension containing [A] a particulate carrier and [B] a transition metal compound containing a ligand having a cycloalkadienyl skeleton and an anion containing a boron element. A solid catalyst for olefin polymerization, characterized in that it is formed by. 4) A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to claim 1. 5) A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to claim 2. 6) A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to claim 3.