JP2530624C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]   The present invention relates to a method for polymerizing an olefin. More specifically, in the present invention
When slurry polymerization, gas phase polymerization, and especially gas phase polymerization are adopted, the particle size distribution
Olefin polymerization method which is good, can produce spherical polymer and has excellent bulk specific gravity
About. It has a narrow molecular weight distribution and is suitable for copolymerization of two or more olefins.
When used, olefin copolymers with narrow molecular weight distribution and composition distribution
Polymerization with polymerization activity Related. [Conventional technology]   Conventional α-olefin polymers, especially ethylene polymers or ethylene-α-olefins
As a method for producing the vinyl copolymer, a titanium compound and an organoaluminum compound are used.
Titanium-based catalysts or vanadium compounds and organoaluminum compounds
Ethylene or ethylene and α-olefin are copolymerized in the presence of a nadium catalyst.
Methods of matching are known. In general, ethylene-α-O
Lefin copolymers generally have a broad molecular weight distribution and composition distribution, as well as transparency and surface
Non-stick and mechanical properties were inferior. In addition, the etchant obtained with vanadium catalysts
Len-α-olefin copolymers have a higher molecular weight than those obtained with titanium-based catalysts.
Quantitative distribution and composition distribution are narrow, and transparency, surface non-stickiness, and mechanical properties are considerable.
Although improved, it is still insufficient for applications where these performances are required.
Α-olefin polymers with improved performance, especially ethylene α-olefin
Copolymers are required.   On the other hand, zirconium compounds and zirconium compounds
Catalysts consisting of aluminum and aluminoxane have recently been proposed.   JP-A-58-19309 discloses the following formula:       (Cyclopentadienyl)_TwoMeRHal [Where R is cyclopentadienyl, C₁~ C₈-Alkyl, halogen,
Me is a transition metal, and Hal is a halogen.]
Compound and the following formula         Al_TwoOR_Four(Al (R) -O)_n Wherein R is methyl or ethyl and n is a number from 4 to 20. Linear aluminoxane represented by the following formula Wherein the definitions of R and n are the same as above.
Ethylene and C in the presence of a catalyst comprising_Three~ C₁₂Of α-olefins
Alternatively, a method of polymerizing two or more kinds at a temperature of -50 ° C to 200 ° C is described.
The publication discloses that to adjust the density of the resulting polyethylene, up to 10% by weight.
Of ethylene in the presence of small amounts of somewhat longer chain α-olefins or mixtures
It should be described.   JP-A-59-95292 discloses the following formula: [Where n is 2 to 40 and R is C₁~ C₈Is an alkyl]
Aluminoxane and the following formula [Wherein the definitions of n and R are the same as described above]
An invention relating to a method for producing sun is described. The publication states that
For example, methyl (aluminoxane) and titanium or zirconium bis (cyclo
(Pentadienyl) compound, and polymerization of olefin is performed.
It is stated that more than 25 million g of polyethylene can be obtained per metal and per hour.
ing.   JP-A-60-35005 discloses the following formula: [Where R¹Is C₁~ C_TenAlkyl, R⁰Is R¹Or is linked to -O
-Represents an aluminoxane compound represented by the formula
Reaction, then chlorinating the reaction product, and further adding a compound of Ti, V, Zr or Cr.
To produce a polymerization catalyst for olefins. In the gazette
Is that the catalyst is ethylene and C_Three~ C₁₂Particularly suitable for copolymerization of a mixture of α-olefins.
It is stated to be suitable.   JP-A-60-35006 discloses a catalyst system for producing a reactor blend polymer.
To obtain mono-, di- or tri-cyclopentadiazines of two or more different transition metals.
Combination of enyl or its derivative (a) and alumoxane (aluminoxane) (b)
Is disclosed. Example 1 of the publication discloses bis (pentamethylcyclopentadiamine).
(Enyl) zirconium dimethyl and alumoxane as catalysts
The polymer is polymerized to obtain a number average molecular weight of 15,300, a weight average molecular weight of 36,400 and
And that a polyethylene containing 3.4% of a propylene component was obtained.
You. In Example 2, bis (pentamethylcyclopentadienyl) zirco
Dichloride, bis (methylcyclopentadienyl) zirconium dichloride
Polymerizes ethylene and propylene using alide and alumoxane as catalysts
Propylene component having a molecular weight of 2,200, a weight average molecular weight of 11,900 and 30 mol%
Containing toluene and a number average molecular weight of 3.0 And a toluene containing a propylene component having a weight average molecular weight of 7,400 and 4.8 mol%.
Number average molecular weight of 2,000, weight average molecular weight of 8,300 and 7.
Polyethylene and ethylene-propylene copolymer containing 1 mol% of propylene component
The blend is obtained. Example in the same way % Soluble part and molecular weight distribution 3.04 and propylene component 2.9 mol% insolubility
A blend of two-part LLDPE and an ethylene-propylene copolymer is described.
Have been.   JP-A-60-35007 discloses that ethylene alone or α-α having 3 or more carbon atoms can be used.
Metallocene with olefin and the following formula [Where R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to about 20]
A cyclic alumoxane represented by the following formula: [Wherein the definitions of R and n are the same as above]
A method for polymerizing in the presence of a catalyst system comprising Obtained by the same method
According to the publication, the obtained polymer has a weight average molecular weight of about 500 to about 1.4 million.
And has a molecular weight distribution of 1.5 to 4.0.   Also, Japanese Patent Application Laid-Open No. Sho 60-35008 discloses that at least two types of metallo- Has a broad molecular weight distribution by using a catalyst system containing
Polyethylene or ethylene and C_Three~ C_TenΑ-olefin copolymer is produced
It is described. The publication discloses the above copolymer.   Is the catalyst formed from these transition metal compounds and aluminoxane conventional?
Polymerization activity is remarkably superior to known catalyst systems.
The system is soluble in the reaction system, the bulk specific gravity of the produced polymer is small, and the weight is excellent in powder properties.
It was difficult to obtain a coalescence.   On the other hand, the transition metal compound is made of silica, silica-alumina, alumina or the like.
Formed from aluminoxane and a solid catalyst component supported on a conductive inorganic oxide carrier
The method using a catalyst is also described in JP-A-60-35006 and JP-A-60-350.
No. 07, JP-A-60-35008 and the like.
JP-A-61-31404, JP-A-61-108610 and JP-A-61-108610
Japanese Patent No. 60-106808 discloses a solid supported on a similar porous inorganic oxide carrier.
A method using a catalyst component has been proposed. The methods described in these prior arts
The use of a supported solid component reduces the polymerization activity or
In many cases, powder properties such as bulk specific gravity of the body were insufficient. [Problems to be solved by the invention]   The present inventors have found that the powder properties are excellent, the molecular weight distribution is narrow, and two or more olefins are used.
Olefin copolymer with narrow molecular weight distribution and composition distribution when applied to copolymerization of olefins
Ethylene with good coalescence, especially excellent powder properties and narrow molecular weight distribution and / or composition distribution
For producing polymers or ethylene / α-olefin copolymers with excellent polymerization activity
As a result of studying the method, It was found that the above-mentioned object was achieved by using a solid catalyst component.
The invention has been reached. [Means to solve the problem] and [Action]   According to the present invention,   (1) [A] Organoaluminum (however, aluminoxane and halogen
Excluding aluminoxane fluoride), organic boron, organic zinc and organic lithium
The porous inorganic oxide carrier treated with the organometallic compound to be [B] A solid catalyst supporting a zirconium compound having a cycloalkadienyl group
Medium, wherein zirconium is 3 × 10 5 per gram of the porous inorganic oxide carrier.^-3
From 3 to 3 milligram atoms of the solid catalyst component, and [C] aluminoxane, (Wherein (A) the following formula (I) treated with an organometallic compound)       R¹ _kR^Two _lR^Three _mR^Four _nM (I) (Where R¹Represents a cycloalkadienyl group;^Two, R^ThreeAnd R^FourIs cycloal
Cadenyl, aryl, alkyl, aralkyl, alkoxy, halogen
Is k ≧ 1, k + 1 + m + n = 4, and M is zirconium.
Or hafnium. ) A solid catalyst component in which the compound represented by is supported on a particulate carrier, and (B) aluminoxane, Olefins are polymerized or copolymerized in the presence of a catalyst formed from
A method for polymerizing an olefin is provided.   Hereinafter, the present invention will be described in detail.   In the present invention, the term polymerization is used to mean not only homopolymerization but also copolymerization.
The term polymer includes not only homopolymers but also copolymers
It may be used for the purpose.   The catalyst used in the present invention comprises three catalyst components [A], [B] and [C].
Formed from   The catalyst component [A] is an organoaluminum (provided that aluminoxane and halo
Excluding aluminoxane gen), organic boron, organic zinc and organic lithium
It is a porous inorganic oxide carrier treated with a selected organometallic compound. With the above carrier
Specifically, SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, TiO_Two, B_TwoO_Three, C
aO, ZnO, BaO, ThO_TwoOr a mixture thereof, for example, SiO 2_Two-M
gO, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two-C
r_TwoO_Three, SiO_Two-TiO_Two-MgO and the like can be exemplified. S in these
iO_TwoAnd Al_TwoO_ThreeAt least one component selected from the group consisting of
Is preferred. The inorganic oxide contains a small amount of Na_TwoCO_Three,
K_TwoCO_Three, CaCO_Three, MgCO_Three, Na_TwoSO_Four, Al_Two(SO_Four)_Three, BaSO_Four, K
NO_Three, Mg (NO_Three)_Two, Al (NO_Three)_Three, Na_TwoO, K_TwoO, Li_TwoCarbonate such as O, sulfuric acid
It may contain acid salts, nitrates and oxide components. The type of the carrier
Although the properties differ depending on the production method, the carrier preferably used in the present invention has a particle size of
10 to 300μ, preferably 20 to 200μ, specific surface area of 50 to 1
000m^Two/ G, preferably 100 to 700 m^Two/ G, no pore volume of 0.3
3.0cm^Three/ G, preferably 0.5 to 2.5 cm^Three/ G. The carrier is
Through Baking at 150 to 1000 ° C, preferably 200 to 800 ° C
.   In the catalyst component [A], the above-mentioned carrier is an organic gold before loading the catalyst component [B].
Treated with a genus compound. Organometallic compounds include organoaluminum (however,
Excluding luminoxane and halogenated aluminoxane), organic boron, organic
Zinc, organic lithium and the like can be mentioned. Organic aluminum among these
Compounds are preferred, specifically, trimethyl aluminum, triethyl aluminum
Aluminum, trialkyl aluminum such as tributyl aluminum, isobrenyl alcohol
Alkenyl aluminum such as ruminium, dimethyl aluminum methoxide
Diethylaluminum ethoxide, dibutylaluminum butoxide
Alkyl aluminum alkoxide, methyl aluminum sesquimethoxide, d
Alkyl aluminum sesquialkoxides such as chill aluminum sesquiethoxide
In addition to Cid, R¹ _2.5Al (OR^Two)_0.5Partial with an average composition represented by
Alkyl aluminum, dimethyl aluminum chloride,
Dials such as diethylaluminum chloride and dimethylaluminum bromide
Kill aluminum halide, methyl aluminum sesquichloride, ethyl aluminum
Alkyl aluminum sesquihalides such as ammonium sesquichloride,
Alkyl aluminum such as luminium dichloride, ethyl aluminum dichloride
Partially halogenated alkylaluminums such as ammonium dihalide, etc.
Can be exemplified.   Trialkylaluminum, dialkyla
Luminium dichloride is preferred, trimethylaluminum, Triethylaluminum, dimethylaluminum chloride and diethylaluminum
Um chloride is particularly preferred.   The mixing ratio of the organoaluminum compound and the carrier in the above treatment was
From 0.5 to 50, preferably from 50 to 50, preferably
It is in the range of 1 to 30, more preferably 1.5 to 20.   Porous inorganic oxide carrier with organoaluminum compound in catalyst component [A]
After dispersing this carrier in an inert solvent, the treatment of the organoaluminum compound
One or more kinds are added, and 0 to 120 ° C, preferably 10 to 100 ° C,
More preferably at a temperature of 20 to 90 ° C. for 10 minutes to 10 hours, preferably 2 minutes.
0 minutes to 5 hours, more preferably 30 minutes to 3 hours under normal pressure, reduced pressure or increased pressure
This can be done by processing.   Examples of inert solvents include aromatic hydrocarbons such as benzene, toluene, and xylene;
Aliphatic hydrocarbons such as tan, hexane and isooctane, and alicyclic rings such as cyclohexane
Formula hydrocarbons can be mentioned.   Zirconium compound having cycloalkadienyl group in catalyst component [B]
Is, for example, the following formula (I)         R¹ _kR^Two _lR^Three _mR^Four _nZr (I) [Where R¹Represents a cycloalkadienyl group;^Two, R^ThreeAnd R^FourIs cycloa
Lucadienyl group, aryl group, alkyl group, aralkyl group, alkoxy group, halo
A gen atom or hydrogen, and k ≧ 1, k + 1 + m + n = 4].
It is a compound.   Cycloalkadienyl groups include, for example, cyclopentadienyl group, methyl Cyclopentadienyl group, ethylcyclopentadienyl group, dimethylcyclopen
A tadienyl group, an indenyl group, a tetrahydroindenyl group and the like. R^Two, R^ThreeYou
And R^FourExamples of the alkyl group include a methyl group, an ethyl group, a propyl group,
Examples thereof include a propyl group and a butyl group.
And an aralkyl group such as benzyl group or tolyl group.
Group, neophyl group, etc., and the alkoxy group is a methoxy group
, Ethoxy, propoxy, butoxy, 2-ethylhexoxy, etc.
Examples of halogen atoms include fluorine, chlorine, and bromine.
Can be. The following compounds can be exemplified as the zirconium compound.   Bis (cyclopentadienyl) zirconium monochloride monohydride,   Bis (cyclopentadienyl) zirconium monobromide monohydride,   Bis (cyclopentadienyl) methyl zirconium hydride,   Bis (cyclopentadienyl) ethyl zirconium hydride,   Bis (cyclopentadienyl) cyclohexylzirconium hydride,   Bis (cyclopentadienyl) phenyl zirconium hydride,   Bis (cyclopentadienyl) benzylzirconium hydride,   Bis (cyclopentadienyl) neopentyl zirconium hydride,   Bis (methylcyclopentadienyl) zirconium monochloride mono Hydride,   Bis (indenyl) zirconium monochloride monohydride,   Bis (cyclopentadienyl) zirconium dichloride,   Bis (cyclopentadienyl) zirconium dibromide,   Bis (cyclopentadienyl) methyl zirconium monochloride,   Bis (cyclopentadienyl) ethyl zirconium monochloride,   Bis (cyclopentadienyl) cyclohexylzirconium monochloride,   Bis (cyclopentadienyl) phenyl zirconium monochloride,   Bis (cyclopentadienyl) benzylzirconium monochloride,   Bis (methylcyclopentadienyl) zirconium dichloride,   Bis (indenyl) zirconium dichloride,   Bis (indenyl) zirconium dibromide,   Bis (cyclopentadienyl) zirconium dimethyl,   Bis (cyclopentadienyl) zirconium phenyl,   Bis (cyclopentadienyl) zirconium dibenzyl,   Bis (cyclopentadienyl) methyxizirconium chloride,   Bis (cyclopentadienyl) ethoxyzirconium chloride,   Bis (cyclopentadienyl) butoxyzirconium chloride,   Bis (cyclopentadienyl) 2-ethylhexoxyzirconium chloride,   Bis (cyclopentadienyl) methylzirconium ethoxide,   Bis (cyclopentadienyl) methyl zirconium butoxide,   Bis (cyclopentadienyl) ethyl zirconium ethoxide,   Bis (cyclopentadienyl) phenyl zirconium ethoxide,   Bis (cyclopentadienyl) benzylzirconium ethoxide,   Bis (methylcyclopentadienyl) ethoxyzirconium chloride,   Bis (indenyl) ethoxyzirconium chloride,   Bis (cyclopentadienyl) ethoxyzirconium,   Bis (cyclopentadienyl) butoxyzirconium,   Bis (cyclopentadienyl) 2-ethylhexoxy zirconium.   In the method of the present invention, the catalyst component [B] is supported on the catalyst component [A].   In the supporting reaction, organoaluminum (however, aluminoxane and ha
Excluding aluminoxane), organic boron, organic zinc and organic lithium
Catalyst component which is a porous inorganic oxide carrier treated with an organometallic compound selected from the group consisting of:
A] 1 g of a zirconium compound having a cycloalkajenyl group
The medium component [B] is 3 × 10 in terms of zirconium atoms.^-3Or 3 milligram atoms
, Preferably 5 × 10^-3To 2 milligram atoms, more preferably 1 × 10^-2What
One milligram atom is carried. Loading amount is 3 × 10^-3Lower than milligram atoms
If a large amount of carrier remains in the resulting polymer,
If it causes eyes and is higher than 3 milligram atoms, the unit zirconium
This is not preferred because the activity per atom is reduced.   The supporting method comprises adding a catalyst component [A] to an inert hydrocarbon medium, and adding the catalyst component to the catalyst component [A].
Add [B]. The reaction temperature is generally 0 to 100 ° C, preferably 20 to 90 ° C.
° C, and the reaction time is usually 5 minutes to 5 hours, preferably 10 minutes to 2 hours.
is there. After the loading reaction, the inert hydrocarbon medium is filtered. Obtain solid catalyst component by removing by filtration or evaporating under normal pressure or reduced pressure
be able to.   The catalyst component [C] is an aluminoxane.   The aluminoxane used as the catalyst component [C] is represented by the general formula (II):
General formula (III) The organic aluminum compound represented by these can be illustrated. The aluminoki
In the sun, R is a hydrocarbon such as methyl, ethyl, propyl, butyl, etc.
Group, preferably a methyl group, an ethyl group, particularly preferably a methyl group,
m is an integer of 2 or more, preferably 5 or more. The method for producing the aluminoxane is as follows.
Then, for example, the following method can be exemplified. (1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride
Hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, salt
Trialkylaluminum in a suspension of a hydrocarbon medium such as cerium iodide hydrate
A method of adding and reacting. (2) Medium such as benzene, toluene, ethyl ether, and tetrahydrofuran
Method in which water acts directly on trialkylaluminum in water. Among these methods, it is preferable to adopt the method (1). The aluminum
Nooxane may contain a small amount of an organic metal component.   The present invention relates to olefin polymers, especially ethylene polymers and ethylene and α-olefin.
It is effective for the production of a copolymer of quinone.   Examples of α-olefins that can be used in the present invention include ethylene and
And α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene,
1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-de
Decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eico
Sen etc. can be mentioned.   In the method of the present invention, the polymerization of the olefin is usually performed in a gas phase or a liquid phase,
For example, the reaction is carried out in a slurry state, but a gas phase polymerization method is particularly preferred. Performed by gas phase polymerization
The polymerization temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C.
Range.   When the method of the present invention is carried out by a gas phase polymerization method, the proportion of the zirconium compound used is
, The concentration of zirconium metal atoms in the polymerization reaction system is usually 10^-8Or 10
^-2Gram atoms / l, preferably 10^-7Or 10^-3In the range of gram atoms / l
.   The proportion of aluminoxane used depends on the concentration of aluminum atoms in the polymerization reaction system.
Usually 10 degrees^-FourOr 10^-1Gram atoms / l, preferably 10^-3Or 5
× 10^-2Gram atom / l, and zirconium metal source in the polymerization reaction system.
The ratio of aluminum metal atoms to atoms is usually 25 to 10^Five, Preferably
Is 10^TwoOr 10^FourRange. Aluminoxane may be added during polymerization
And zircon prior to polymerization It may be used in a form in which it is carried on a carrier on which nickel is carried.   The molecular weight of the polymer can be adjusted by hydrogen and / or polymerization temperature.   The polymerization pressure is usually from normal pressure to 100 kg / cm^Two, Preferably 2 to 50k
g / cm^TwoIt is preferably carried out under the pressurized condition of Batch polymerization, semi-continuous, continuous
Can be performed by any of the methods described above. Further, the polymerization is performed under different reaction conditions.
It is also possible to carry out by dividing into stages or more. [The invention's effect]   Olefin polymerization in the present invention, particularly ethylene polymerization or ethylene and α-ole
Slurry polymerization or gas phase polymerization, especially when gas phase polymerization is used for fin copolymerization
In this case, the polymer does not adhere to the reactor, the powder properties are excellent, and the molecular weight distribution is narrow.
Molecular weight distribution and composition when applied to copolymerization of two or more olefins
An olefin copolymer with a narrow cloth can be obtained. [Example]   Next, the method of the present invention will be specifically described with reference to examples. Examples and
In the comparative example, the MFR has a temperature of 190 ° C. and a load of 2.16 kg. Chromatography "as follows. (1) Standard polystyrene of known molecular weight (Toyo Soda (manufactured by) monodisperse polystyrene)
) Using the molecular weight M and its GPC (Gel Permeation Chromatograph) counter
Then, a calibration curve for the correlation between the molecular weight M and the EV (Elution Volume) is created.
At this time, the concentration is 0.02% by weight. (2) Take a GPC chromatograph of the sample by GPC measurement, The conditions and GPC measurement conditions are as follows. [Sample preparation] (A) The sample was added together with the o-dichlorobenzene solvent to a concentration of 0.1 wt%.
Dispense into a square flask. (B) Heat the Erlenmeyer flask to 140 ° C., stir for about 30 minutes, and dissolve. (C) The filtrate is subjected to GPC. [GPC measurement conditions]   The test was performed under the following conditions. (B) Equipment Waters (150C-ALC / GPC) (B) Caram Toyo soda (GMH type) (C) Sample volume 400μl (D) Temperature 140 ° C (E) Flow speed 1ml / min   Amount of n-decane soluble part in the copolymer (the smaller the soluble part, the narrower the composition distribution)
Is measured by adding about 3 g of the copolymer to 450 ml of n-decane and dissolving at 145 ° C.
The mixture was gradually cooled to 23 ° C., and the n-decane-insoluble portion was removed by filtration.
Was collected. Example 1 [Preparation of catalyst component [C]]   In a 400 ml flask sufficiently purged with nitrogen, add Al_Two(SO_Four)_Three・ 14 H_Two37 g of O and 125 ml of toluene were charged, and cooled to 0 ° C.
500 mmol of trimethylaluminum diluted with 1 were added dropwise. Next, at 40 ° C
The reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation is performed by filtration.
And then remove toluene from the filtrate to obtain a white solid aluminum oxide.
13 g of sun were obtained. The molecular weight determined by freezing point depression in benzene is 930.
And the m value shown in the catalyst component (B) was 14. [Preparation of solid catalyst component (zirconium catalyst)]   Silica (average particle size 70μ, specific surface
260m^Two/ G, pore volume 1.65 cm^Three/ G) was calcined at 700 ° C for 5 hours.
5.2 g of dimethylaluminum monochloride in toluene solution (Al 1 mol
/ L) 26 ml and toluene 50 ml were added and heated at 80 ° C. for 2 hours. Then filter
The catalyst component [A] was obtained by performing solid-liquid separation by filtration. This catalyst component [A]
Was transferred into 50 ml of toluene, and bis (cyclope) as a catalyst component [B] was further added thereto.
(Tantadienyl) zirconium dichloride in toluene solution (Zr 0.04 mol /
l) Add 43 ml and heat at 80 ° C. for 1 hour. Again, perform solid-liquid separation by filtration
, 1 g of silica, 0.012 mg atom of Zr and 1.12 mg atom of Al
As a result, a solid component carrying the atom was obtained. This solid component is converted to zirconium atom in an amount of 0.5.
015 mg atom, toluene solution of aluminoxane as catalyst component [C]
(Al 1.03 mol / l) 4.9 ml and toluene 20 ml were added, and the mixture was added at room temperature.
Stirred for 0 minutes. Then, remove the toluene at room temperature using an evaporator.
As a result, a solid component of 0.08 wt% of Zr and 10 wt% of Al was obtained. [polymerization]   Sodium chloride was added to a 2 l stainless steel autoclave, which had been sufficiently purged with nitrogen.
And then dried under reduced pressure at 90 ° C. for 1 hour. Then system
The inside was replaced with ethylene, and the temperature was set to 75 ° C. Subsequently, the entire amount of the catalyst prepared above was loaded.
And further introduce ethylene to bring the total pressure to 8 kg / cm^Two・ Start polymerization as a gauge
Was. After that, only ethylene was replenished and the total pressure was 8 kg / cm^Two・ Keep the gauge, 80
The polymerization was carried out at a temperature of 1 hour. After polymerization, remove sodium chloride by washing with water
The polymer thus obtained was washed with hexane and then dried under reduced pressure at 80 ° C. overnight. MFR 0.07
g / 10 2 g were obtained.   No adhesion of the polymer to the autoclave wall was observed. Example 2 [Preparation of solid catalyst component (zirconium catalyst)]   Alumina (average particle size 60μ, ratio table)
Area 270m^Two/ G, pore volume 1.05 ml / g) was calcined at 500 ° C for 5 hours.
5.8 g of dimethylaluminum monochloride in toluene solution (Al 1 mol
/ L) 17 ml and toluene 50 ml were added and heated at 80 ° C. for 2 hours. Then filter
Solid-liquid separation is performed by filtration, the solid part is transferred into 50 ml of toluene, and
(Cyclopentadienyl) zirconium dichloride in toluene solution (Zr 0.
(036 mol / l) and heated at 80 ° C. for 1 hour. The solid-liquid content is again filtered.
Separation was performed to obtain a solid component of 0.25 wt% of Zr. This solid component and aluminoki
The reaction with sun was carried out in the same manner as in Example 1, and the solid catalyst was 0.16 wt% of Zr. The components were obtained. [polymerization]   The above solid catalyst was used in an amount of 0.015 milligram atoms in terms of zirconium atoms.
The polymerization was carried out in exactly the same manner as in Example 1, and as a result, the MFR was 0.09 g / 10 2 g were obtained.   No adhesion of the polymer to the autoclave wall was observed. Example 3 [Preparation of solid catalyst component (zirconium catalyst)]   Silica (average particle size 70μ, specific surface
260m^Two/ G, pore volume 1.65 cm^Three/ G) was calcined at 300 ° C for 4 hours.
2.3 g of dimethylaluminum monochloride in toluene (Al 1 mol
/ L) 15 ml and toluene 50 ml were added and heated at 80 ° C. for 2 hours. afterwards,
Solid-liquid separation is performed by filtration, and the solid part is transferred into 50 ml of toluene.
Solution of bis (cyclopentadienyl) zirconium dichloride in toluene (Zr
 (0.01 mol / l), and the mixture was stirred at room temperature for 2 hours. Next, in Example 1,
31 ml of synthesized aluminoxane toluene solution (Al 1.03 mol / l)
Was added and stirred at room temperature for 30 minutes. Subsequent operations were performed in the same manner as in Example 1, and Zr
A solid catalyst component of 0.14 wt% and 22 wt% of Al was obtained. [polymerization]   Example using the above solid catalyst in 0.015 milligram atoms in terms of zirconium atoms
Was. No adhesion of the polymer to the autoclave wall was observed. Comparative Example 1   In Example 1, the silica was not treated with dimethyl aluminum monochloride.
Otherwise, the catalyst was prepared and polymerized in the same manner as in Example 1, and the MFR was adjusted to 0.2. 2.1 g of polymer were obtained.   The solid catalyst components used in the polymerization were 0.35 wt% of Zr and 35 wt% of Al.
Was included. Example 4 [Preparation of solid catalyst component (zirconium catalyst)]   In Example 1, dimethyl alcohol was added to 1 g of silica calcined at 800 ° C. for 12 hours.
Add 6 mmol of triethylaluminum instead of minium monochloride and add 50
C. for 2 hours and biscyclopentadiene per 1 g of silica.
0.042 mmol of ruzirconium dichloride was added and reacted at room temperature for 2 hours.
Except for this, the same procedure was performed as in Example 1 and zirconium was added in an amount of 6.7 × 1 to 1 g of silica.
0^-3A solid catalyst component carrying milligram atoms was obtained. [polymerization]   In Example 1, 15 mg of aluminoxane was converted to aluminum atoms.
Atom, the solid catalyst component prepared above was 0.015 mg in terms of zirconium atom.
Except that ram atom was charged and 50 ml of hydrogen was introduced. 0, bulk specific gravity 0.31 g / cm^Three69 g of a polymer were obtained.   Little adhesion of polymer to autoclave wall was observed Was. Example 5 [Preparation of solid catalyst component (zirconium catalyst)]   In Example 4, diethyl aluminum was used instead of triethyl aluminum.
Except for using nochloride, the same procedure as in Example 4 was carried out.
5.7 × 10^-3A solid catalyst component carrying milligram atoms was obtained. [polymerization] 59, 0.34 g / cm bulk specific gravity^Three71 g of a polymer were obtained. Note that the polymer
Almost no adhesion to the toclave wall was observed. Example 6 [polymerization]   In Example 1, 10 ml of hexene-1 was added and polymerized at 70 ° C. for 0.5 hour.
Was performed in the same manner as in Example 1 except that the MFR was 2.05 g / 1. 26g / cm^Three42 g of a polymer having a soluble fraction by weight of decane at room temperature of 0.15 wt% was obtained.
Was.   In addition, adhesion of the polymer to the autoclave wall was hardly obtained.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing one example of the preparation of a catalyst in the polymerization of an olefin of the present invention.

Claims (1)

Claims (1) [A] Porous treated with an organometallic compound selected from organoaluminum (excluding aluminoxane and halogenated aluminoxane), organoboron, organozinc and organolithium A solid catalyst in which [B] a zirconium compound having a cycloalkadienyl group is supported on an inorganic oxide carrier, wherein zirconium is contained in an amount of 3 × 10 ⁻³ per gram of the porous inorganic oxide carrier.
(A) a catalyst formed from a solid catalyst component carrying 3 to 3 milligrams of atoms and [C] aluminoxane, wherein (A) the following formula (I) treated with an organometallic compound: R ¹ _k R ² _l R ³ _m R ⁴ _n M (I) wherein R ¹ represents a cycloalkadienyl group, and R ² , R ³ and R ⁴ represent a cycloalkadienyl group, an aryl group, an alkyl group, an aralkyl group, an alkoxy group, a halogen An atom or hydrogen, k ≧ 1, k + 1 + m + n = 4, and M is zirconium or hafnium.] A solid catalyst component in which a compound represented by the following formula is supported on a particulate support, and (B) aluminoxane: Olefin polymerization or polymerization in the presence of a catalyst formed). (2) The polymerization method according to claim 1, wherein [A] the organometallic compound is organoaluminum (however, excluding aluminoxane and halogenated aluminoxane). (3) A zirconium compound having a cycloalkadienyl group is represented by the following formula (I)
R ¹ _k R ² _l R ³ _m R ⁴ _n Zr (I) wherein R ¹ represents a cycloalkadienyl group, and R ² , R ³ and R ⁴ represent a cycloalkadienyl group, an aryl group, An alkyl group, an aralkyl group, an alkoxy group, a halogen atom or hydrogen, k ≧ 1, k + 1 + m + n = 4, and a cycloalkadienyl group is a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadiyl group. Enyl group, dimethylcyclopentadienyl group,
And the compound is an indenyl group or a tetrahydroindenyl group].