JP2752964B2 - Olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION The present invention relates to an olefin polymerization method.
About. For details, use less aluminoxane.
Of olefin polymerization with excellent polymerization activity
I do. More specifically, in the present invention, the slurry polymerization method
Good particle size distribution and spherical shape when using gas-phase polymerization method
Oleide that can produce polymers and has excellent bulk specific gravity
The present invention relates to a fin polymerization method. In addition, the molecular weight distribution is narrow,
Moreover, when applied to copolymerization of two or more olefins,
Is an olefin copolymer with narrow molecular weight distribution and composition distribution
The present invention relates to a method for polymerizing a polymer with excellent polymerization activity. [0002] 2. Description of the Related Art Conventionally, α-olefin polymers, especially
Tylene polymer or ethylene / α-olefin copolymer
The production method of the titanium compound and the organic aluminum
A titanium-based catalyst or a vanadium compound comprising a compound
Existence of vanadium-based catalysts composed of organoaluminum compounds
In the presence of ethylene or ethylene and α-olefin
Are known. Generally titanium catalyst
The ethylene / α-olefin copolymer obtained in
Wide distribution of amount and composition, transparency, non-stick surface
Properties and mechanical properties were inferior. In addition, vanadium-based
The ethylene / α-olefin copolymer obtained in the medium is
Molecular weight distribution and
Composition distribution is narrow, transparency, surface non-stickiness, dynamics
Physical properties are considerably improved, but these performances are required
Still inadequate for applications, and further improved their performance
Α-olefin polymers, especially ethylene-α-ole
There is a need for fin copolymers. On the other hand, a new Ziegler-type olefin polymerization
As catalysts, zirconium compounds and aluminoxas
Catalysts consisting of benzene have recently been proposed. JP-A-58-1
No. 9309 discloses the following formula: (Cyclopentadienyl)_TwoMe R Hal [Where R is cyclopentadienyl, C₁~ C₆Al
Kill, halogen, Me is a transition metal, Hal
Is a halogen]
And the following equation Al_TwoOR_Four(Al (R) -O)_n [Where R is methyl or ethyl and n is 4 to 2]
A linear aluminoxane represented by the formula:
Is the following formula [0004] Embedded image [Where the definitions of R and n are the same as above
And a cyclic aluminoxane represented by
Ethylene and C in the presence of a catalyst_Three~ C₁₂Α-Olefi
One or two or more of the components at a temperature of -50C to 200C.
A method for polymerizing is described. The publication also states that
10% by weight to adjust the density of polyethylene
Small amounts of somewhat longer chain α-olefins or mixtures up to
It states that ethylene polymerization should be carried out in the presence of
You. JP-A-59-95292 discloses the following formula: [0006] Embedded image [Where n is 2 to 40 and R is C₁
~ C₆And a linear aluminoxane represented by the following formula: [0008] Embedded image [Where the definitions of n and R are the same as above
The production method of the cyclic aluminoxane represented by
Related inventions are described. The gazette states that the manufacturing method
Made from, for example, methylaluminoxane and titanium
Or zirconium bis (cyclopentadienyl)
When the compound is mixed and the olefin is polymerized, 1 g
25 million g or more per transition metal and per hour
It is stated that polyethylene is obtained. JP 60
Japanese Patent No. 35005 discloses the following formula: [0010] Embedded image [Where R¹Is C₁~ C_TenAlkyl
R⁰Is R¹Or bonded to represent -O-]
The aluminoxane compound represented by
Reaction product and then chlorinate the reaction product,
And then treated with a compound of Ti, V, Zr or Cr,
A method for producing a polymerization catalyst for refins is disclosed.
The publication states that the catalyst is ethylene and C_Three-C₁₂α-Oleph
It is stated to be particularly suitable for the copolymerization of mixtures of
You. JP-A-60-35006 discloses a reaction.
Two or more different catalyst systems
The above transition metal mono-, di- or tri-cyclopenes
Tadienyl or its derivative (a) and alumoxane (A
Combinations of luminoxane) (b) are disclosed. same
In Example 1 of the publication, bis (pentamethylcyclopenta
Dienyl) catalyzed by zirconium dimethyl and alumoxane
Polymerized ethylene and propylene as
Molecular weight 15,300, weight average molecular weight 36,400 and
Polyethylene containing 3.4% of propylene component was obtained.
It is disclosed. In the second embodiment, the screws
(Pentamethylcyclopentadienyl) zirconium di
Chloride, bis (methylcyclopentadienyl) silyl
Conium dichloride and alumoxane as catalysts
Polymerizes ethylene and propylene to obtain a number average molecular weight of 2,20
0, weight average molecular weight of 11,900 and 30 mole%
Toluene-soluble part containing ropylene component and number average molecular weight
3,000, weight average molecular weight 7,400 and 4.8 mol
Number consisting of toluene-insoluble part containing propylene component
Average molecular weight 2,000, weight average molecular weight 8,300 and
Polyethylene containing 7.1 mol% of propylene component
A blend of a Tylene / propylene copolymer is obtained.
Similarly, in Example 3, the molecular weight distribution (Mw / Mn) was 4.
57 and a soluble portion of 20.6 mol% of the propylene component
And a molecular weight distribution of 3.04 and a propylene component of 2.9 mol%
Consisting of an insoluble part of ethylene and ethylene-propylene
Blends of copolymers are described. Japanese Unexamined Patent Publication No. 60-35007 discloses an etchant.
Is used alone or in combination with α-olefins having 3 or more carbon atoms.
And the following formula [0014] Embedded image [Where R is an alkyl group having 1 to 5 carbon atoms]
And n is an integer from 1 to about 20].
Alumoxane or the following formula [0016] Embedded image [Where the definitions of R and n are the same as above
And a linear alumoxane represented by the formula:
A method for polymerizing in the presence of is described. In the same way
According to the description of the publication, the obtained polymer is about 50
It has a weight average molecular weight of 0 to about 1.4 million and 1.5 to 4.5.
It has a molecular weight distribution of zero. Further, Japanese Patent Application Laid-Open No. 60-35008 discloses
Contains at least two metallocenes and alumoxanes
Has a broad molecular weight distribution by using a catalyst system
Polyethylene or ethylene and C_Three~ C_TenΑ-Olefi
It is described that a copolymer of olefins is produced. Same prince
It is reported that the copolymer has a molecular weight distribution (Mw / Mn) of 2 to 5
It is stated to have 0. These transition metal compounds and alumino
Catalysts formed from xanes are known catalysts.
The polymerization activity is remarkably superior to that of the solvent system.
Is soluble in the reaction system and the bulk specific gravity of the polymer produced
And it is difficult to obtain a polymer with excellent powder properties.
Was. On the other hand, the transition metal compound is silica,
For porous inorganic oxide carriers such as alumina and alumina
Formed from the supported solid catalyst component and aluminoxane
The method using a catalyst to be used is also disclosed in JP-A-60-35006.
JP-A-60-35007, JP-A-60-35007
No. 35008, etc.
JP-A-61-31404, JP-A-61-10861
No. 0 and JP-A-60-106808
Solid catalyst component supported on a similar porous inorganic oxide support
A method of using is proposed. With these prior art
The method described employs a supported solid component.
The polymerization activity is reduced or the bulk specific gravity of the polymer obtained is
Many powder properties were insufficient. Further, a transition metal compound and an aluminoki
Mixed organic alcohols composed of sun and organoaluminum compounds
Olefins using catalysts formed from minium compounds
JP-A-60-260602 discloses a method for polymerizing
And Japanese Patent Application Laid-Open No. 60-130604.
By adding an organoaluminum compound.
It is described that polymerization activity per transition metal is improved.
ing. However, all of these methods use aluminium
High usage of xane, activity per aluminoxane
Was still low. [0022] DISCLOSURE OF THE INVENTION The present inventors have proposed a powder
Excellent properties, narrow molecular weight distribution, and two or more types
When applied to fin copolymerization, the molecular weight distribution and
Olefin copolymer with narrow composition distribution, especially in powder form
Excellent ethylene polymer with narrow molecular weight distribution and composition distribution
Or low ethylene / α-olefin copolymer
Even with the use of minoxane, it can be produced with excellent polymerization activity.
As a result of studying the method, [A]
[B] Solid in which aluminoxane is supported on an inorganic carrier
Catalyst component and [C] specific organoaluminum compound
Using a catalyst formed from the above [A],
A solid catalyst in which [B] and [C] are supported on an inorganic carrier;
It is expected that their use will achieve the above objectives.
And arrived at the present invention. [0023] Means and action for solving the problems
If [A] R¹ _kR^Two _lR^Three _mR^Four _nM (I) [Where M is titanium, zirconium or hafnium
And R¹Is a cycloalkadienyl group;^Two, R
^ThreeAnd R^FourIs a cycloalkadienyl group, an aryl group,
Alkyl group, aralkyl group, alkoxy group, halogen atom
Or a hydrogen atom. However, the cycloalkadieni
Groups include indenyl and tetrahydroindenyl groups.
And the cycloalkadienyl group, the aryl group and
And aralkyl groups may have a substituent.
Ndenyl group, substituted indenyl group and partially hydrides thereof
At least two groups selected from the group consisting of
It may be bonded via a kylene group. k ≧ 1, l ≠
0, k + 1 + m + n = 4. Periodic table
Group IVB transition metal compound and [B] aluminoxane
And a solid catalyst component supported on an inorganic carrier, and [C]
Organic aluminum containing hydrocarbon groups other than n-alkyl groups
Olefin in the presence of a catalyst formed from
Characterized in that olefin is polymerized or copolymerized
Is provided. In the present invention, the catalyst component [A] and
[C] supported on an inorganic carrier together with [B] and [B]
A medium component may be formed. Hereinafter, the present invention will be described in detail. Book
In the invention, the term polymerization means not only homopolymerization but also copolymerization
May be used to include
The term is used to include not only homopolymers but also copolymers.
May be included. In the present invention, a transition metal of Group IVB of the periodic table is used.
Compound [A], aluminoxane [B], and n-alkyl
Organoaluminum compounds having a hydrocarbon group other than
And [C] are used as catalyst components.
And a solid catalyst component having [B] supported on an inorganic carrier; and
[C] to form a catalyst or [A], [B]
And [C] from a solid catalyst component supported on an inorganic carrier.
A medium is formed and used. Used in the method of the invention
The catalyst component [A] has a periodic rule represented by the following formula (I).
Table IVB transition metal compounds. R¹ _kR^Two _lR^Three _mR^Four _nM (I) [Where M is titanium, zirconium or hafnium
And R¹Is a cycloalkadienyl group;^Two, R
^ThreeAnd R^FourIs a cycloalkadienyl group, an aryl group,
Alkyl group, aralkyl group, alkoxy group, halogen atom
Or a hydrogen atom. However, the cycloalkadieni
Phenyl groups include indenyl and tetrahydroindenyl groups.
And the cycloalkadienyl group, the aryl group and
And aralkyl groups may have a substituent.
Ndenyl group, substituted indenyl group and partially hydrides thereof
At least two groups selected from the group consisting of
You may couple | bond together through a kylene group. k ≧ 1, 1 ≠ 0, k
+ L + m + n = 4. ] Wherein the cycloalkadienyl group is, for example, cyclopentane
Dienyl group, methylcyclopentadienyl group, ethyl
Clopentadienyl group, dimethylcyclopentadienyl
Group, indenyl group, tetrahydroindenyl group, etc.
You. R^Two, R^ThreeAnd R^FourExamples of the alkyl group of
Methyl, ethyl, propyl, isopropyl, butyl
Examples of the aryl group include a tyl group and the like.
Represents, for example, a phenyl group, a tolyl group, etc.
Aralkyl groups such as benzyl and neophyl
And the like. Examples of the halogen atom include:
Examples include fluorine, chlorine, and bromine. The di
The following compounds should be exemplified as ruconium compounds.
Can be. Bis (cyclopentadienyl) zirconium
Mumonochloride monohydride, bis (cyclopentane
Dienyl) zirconium monobromide monohydrate
De, bis (cyclopentadienyl) methyl zirconium
Hydride, bis (cyclopentadienyl) ethyldi
Ruconium hydride, bis (cyclopentadienyl
Le) phenyl zirconium hydride, bis (cyclo
Pentadienyl) benzyl zirconium hydride,
Bis (cyclopentadienyl) neopentyl zirconium
Muhydride, bis (methylcyclopentadienyl)
Zirconium monochloride hydride, bis (indene
Nyl) zirconium monochloride monohydride, bi
(Cyclopentadienyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dibromine
De, bis (cyclopentadienyl) methyl zirconium
Monochloride, bis (cyclopentadienyl) ethyldi
Ruconium monochloride, bis (cyclopentadienyl
G) cyclohexyl zirconium monochloride, bis
(Cyclopentadienyl) phenyl zirconium monoc
Loride, bis (cyclopentadienyl) benzylzirco
Ium monochloride, bis (methylcyclopentadieni
G) zirconium dichloride, bis (indenyl) zyl
Conium dichloride, bis (indenyl) zirconium
Dibromide, bis (cyclopentadienyl) zirconium
Mudiphenyl, bis (cyclopentadienyl) zirconi
Umdibenzyl, bis (cyclopentadienyl) methoxy
Sidylconium chloride, bis (cyclopentadienyl)
Le) butoxyzirconium chloride, bis (cyclopentene)
Tadienyl) 2-ethylhexoxy zirconium chloride
De, bis (cyclopentadienyl) methyl zirconium
Ethoxide, bis (cyclopentadienyl) methylzyl
Conium butoxide, bis (cyclopentadienyl) e
Tylzirconium ethoxide, bis (cyclopentadie
Nil) phenylzirconium ethoxide, bis (cyclo
Pentadienyl) benzylzirconium ethoxide,
(Methylcyclopentadienyl) ethoxyzirconium
Muchloride, bis (indenyl) ethoxyzirconium
Chloride, bis (cyclopentadienyl) ethoxydyl
Conium, bis (cyclopentadienyl) butoxydil
Conium, bis (cyclopentadienyl) 2-ethylhexyl
Sil zirconium. Further, an indenyl group and a substituted indenyl group
And at least one selected from the group consisting of
Polydentate in which two groups are bonded via a lower alkylene group
Zirconium compounds having coordinating compounds as ligands
Can be As the zirconium compound, the following
Compounds can be exemplified. Ethylene bis (indenyl) dimethylzyl
Conium, ethylene bis (indenyl) diethyl zircon
, Ethylenebis (indenyl) diphenylzirco
, Ethylenebis (indenyl) methylzirconium
Mumonochloride, ethylenebis (indenyl) ethyldi
Ruconium monochloride, ethylene bis (indenyl)
Methyl zirconium monobromide, ethylene bis (in
Denenyl) zirconium dichloride, ethylenebis (in
Denenyl) zirconium dibromide, ethylenebis (4,5,
6,7-tetrahydro-1-indenyl) dimethylzirconium
, Ethylenebis (4,5,6,7-tetrahydro-1-indene
Le) Methyl zirconium monochloride, ethylene bis
(4,5,6,7-tetrahydro-1-indenyl) zirconium
Dichloride, ethylenebis (4,5,6,7-tetrahydro-1-
Indenyl) zirconium dibromide, ethylene bis
(4-methyl-1-indenyl) zirconium dichloride,
Ethylene bis (5-methyl-1-indenyl) zirconium
Dichloride, ethylene bis (6-methyl-1-indenyl)
Zirconium dichloride, ethylene bis (7-methyl-1-
Indenyl) zirconium dichloride, ethylene bis
(5-methoxy-1-indenyl) zirconium dichloride
, Ethylenebis (2,3-dimethyl-1-indenyl) zyl
Conium dichloride, ethylene bis (4,7-dimethyl-1-
Indenyl) zirconium dichloride, ethylene bis
(4,7-dimethoxy-1-indenyl) zirconium dichloride
Lido. Transition metal compound of group IVB of the periodic table
[A] is trimethylaluminum before loading on an inorganic carrier.
Aluminum, dimethyl aluminum chloride, methyl aluminum
Treated with organoaluminum compounds such as
It may be. In the present invention, a transition metal compound of Group IV of the periodic table is used.
The product [A] may be used together with a catalyst component [B] described later or
Together with catalyst component [B] and catalyst component [C]
Although supported on the body, as the inorganic carrier, inorganic oxides
Preferably, specifically, SiO 2 _Two, Al_TwoO_Three, MgO, Z
rO_Two, TiO_Two, B_TwoO_Three, CaO, ZnO, BaO, T
hO_TwoOr mixtures thereof, such as SiO_Two-Mg
O, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two−
V_TwoO_Five, SiO_Two−Cr_TwoO_Three, SiO_Two-TiO_Two-Mg
O and the like can be exemplified. Of these, SiO_Two
And Al_TwoO_ThreeAt least one selected from the group consisting of
Is preferred. In addition,
The inorganic oxide contains a small amount of Na_TwoCO_Three, K_TwoCO_Three, Ca
CO_Three, MgCO_Three, Na_TwoSO_Four, Al_Two(SO_Four)_Three, B
aSO_Four, KNO_Three, Mg (NO_Three)_Two, Al (NO_Three)_Three,
Na_TwoO, K_TwoO, Li_TwoCarbonate such as O, sulfate, nitric acid
It may contain salts and oxide components. The nature of the carrier depends on its type and production method.
Although different, the carrier preferably used in the present invention has a particle size
10-300μ, preferably 20-200μ,
Specific surface area 50 to 1000m^Two/ G, preferably 1
00 to 700m^Two/ G, pore volume of 0.3 to 3.
0cm^Three/ G, preferably 0.5 to 2.5 cm^Three/ G
You. The carrier is usually at 150 to 1000 ° C., preferably
Is used after firing at 200 to 800 ° C. In the supported reaction of the present invention, the periodic table IVB
As a transition metal atom of group IV transition metal compound [A]
The mixing ratio (transition metal / support) is 0.5 to 15
% By weight, preferably 0.8 to 10% by weight, preferably
Is 1 to 7% by weight. The catalyst components [A] and [B]
Catalyst components [A], [B] and [C] supported on inorganic carrier
Before the transition, the transition metal compound [A] or inorganic
The carrier may be treated as described below. (1) The carrier is previously prepared with trimethylaluminum, dimethyl
Organic aluminum such as aluminum chloride
Halogen such as minoxane or trichlorosilane
After treatment with a silicon-containing compound, the above in the presence of an inert solvent
It is mixed with the Group IVB transition metal compound [A] of the periodic table. (2) The transition metal group IVB transition metal compound [A]
Methyl aluminum, dimethyl aluminum chloride
After treatment with any organoaluminum, in the presence of an inert solvent
Mixed with the carrier. (3) In the presence of an inert solvent, the carrier, the periodic table IV
Al of the Group B transition metal compound [A] and the catalyst component [B]
After mixing the minoxane, cool it at room temperature or
Warm and use evaporator under normal pressure or reduced pressure
To remove the solvent. The solid catalyst component thus obtained includes
The transition metal of Group IVB transition metal compound [A] in the periodic table is 0.0
1 to 3% by weight, preferably 0.03 to 1% by weight
It is carried. Catalyst component used in the method of the present invention
[B] is an aluminoxane;
As sun, general formula (II) and general formula (III) [0037] Embedded imageAn example is an organoaluminum compound represented by
Can be shown. In the aluminoxane, R
Is a carbon such as methyl, ethyl, propyl, butyl, etc.
A hydrogen group, preferably a methyl group, an ethyl group,
Is preferably a methyl group, and m is 2 or more, preferably
It is an integer of 5 or more. The method for producing the aluminoxane is as follows.
Then, for example, the following method can be exemplified. (1) Compound containing adsorbed water, salt containing water of crystallization
, For example, magnesium chloride hydrate, copper sulfate hydrate, sulfuric acid
Aluminum hydrate, nickel sulfate hydrate, chloride 1
Trialkyl is added to a hydrocarbon medium suspension such as cerium hydrate.
A method of adding aluminum and reacting. (2) benzene, toluene, ethyl ether, tetrahi
Trialkyl aluminum in media such as drofuran
A method of applying water directly. Among these methods, the method (1) is
It is preferable to employ it. The aluminoxane has
It does not matter even if it contains a small amount of organometallic components.
Used as a catalyst component in the process of the present invention.
Aluminum compound [C] is a coal other than n-alkyl group.
An organoaluminum compound having a hydride group. n-a
Examples of hydrocarbon groups other than alkyl groups include isoalkyl
Alkyl or cycloalkyl groups having a branched chain of
And the like. The organic aluminum
Specifically, triisopropylaluminum
, Triisobutylaluminum, tri-2-methylbuty
Aluminum, tri-methylbutylaluminum,
Li 2-methylpentyl aluminum, tri-3-methyl pliers
Aluminum, tri-4-methylpentyl aluminum,
Tri 2-methylhexyl aluminum, tri 3-methyl hex
Sil aluminum, tri-2-ethylhexyl aluminum
Such as trialkylaluminum, tricyclohexyl
Tricycloalkyl aluminum such as aluminum,
Triphenyl aluminum, tolyl aluminum
Which triaryl aluminum, diisobutyl aluminum
Dialkyl aluminum, such as aluminum hydride
Hydride, isobutylaluminum methoxide,
Sobutyl aluminum ethoxide, isobutyl aluminum
Alkyl aluminum alloys such as aluminum isopropoxide
Cooxide and the like can be exemplified. These organic
Among the luminium compounds, there are branched alkyl groups.
Organoaluminum compounds are preferred, especially tria
It is preferably a rutile aluminum compound. Ma
General formula (I-C_FourH₉)_xAl_y(C_FiveH_Ten)_z (X, y, z are positive numbers and z ≧ 2x)
Isoprenyl aluminum is also preferred. In addition, heavy
As the above-mentioned organoaluminum compound is formed in the combined system
Compounds such as aluminum halide and alkyl
Lithium or aluminum halide and alkyl mag
It does not matter even if nesium is added. In the method of the present invention, the polymerization of olefin
The reaction can be performed in a liquid phase such as a slurry polymerization method or a solution polymerization method.
Or in any of the gas phase polymerization processes. Also,
Using a small amount of olefin prior to olefin polymerization
Pre-polymerization can be performed. The prepolymerization can be carried out in (1) without solvent or (2)
It is performed in an active hydrocarbon medium. Of these methods
Is preferably the method of (1). At this time, load the inorganic carrier in advance.
First, the catalyst components [A] and [B] are inertly carbonized.
After mixing in a hydrogen medium, raise the temperature to room temperature or
Alternatively, the solvent is removed under reduced pressure using, for example, an evaporator.
By leaving, it becomes a solid catalyst component. For pre-polymerization treatment
Component for transition metal atom of catalyst component [A]
Molar ratio of aluminum atom (B) (Al / transition metal source)
20) to 5000, preferably 25 to 20
00, more preferably in the range of 30 to 1000
You. The prepolymerization temperature is from -20 ° C to 70 ° C, preferably
-10 ° C to 60 ° C, more preferably 0 ° C to 50 ° C
It is in the range of ° C. The treatment is either batch type or continuous type.
Can also be used, or under reduced pressure, normal pressure or
Can be performed. In prepolymerization
Although a molecular weight regulator such as hydrogen may be present,
Intrinsic viscosity [η] measured in at least 135 ° C decalin
Is at least 0.2 dl / g, preferably 0.5 to 20 dl / g
The amount of prepolymer that can be produced
No. The method of the present invention may be carried out by a slurry polymerization method or a gas phase method.
The ratio of the transition metal compound used in the polymerization method is as follows:
The concentration of the transition metal atom in the polymerization reaction system is usually 10
^-8Or 10^-2Gram atoms / liter, preferably 10
^-7Or 10^-3It is in the range of gram atoms / liter. In the method of the present invention, alumino
The amount of xan used is converted to aluminum atoms in the reaction system.
Not more than 3 milligram atoms / liter, preferably 0.1
Or 2.5 mg atom / liter, especially preferred
In the range of 0.2 to 2 milligram atoms / liter
is there. The aluminoxane component in the reaction system
Total of [B] and organoaluminum compound component [C]
Of aluminoxane with respect to the total amount of aluminum atoms in water
The proportion of aluminum atoms in the fraction [B] is usually not 20
80%, preferably 25-75%, especially preferred
In the range of 30 to 70%.
The proportion of aluminum atoms in the compound [C] is as follows:
Usually 20-80%, preferably 25-75%
%, Particularly preferably in the range from 30 to 70%.
In the method of the present invention, the transition metal atom in the reaction system
Aluminoxane component [B] and organic aluminum
Ratio of the total amount of aluminum atoms of the aluminum compound component [C]
Is usually 20 to 10000, preferably 50
5000, particularly preferably 100 to 2000
Range. The process of the present invention relates to olefin polymers, especially
Ethylene polymer and copolymer of ethylene and α-olefin
It is effective for the manufacture of coalescence. Use in the present invention
Examples of olefins that can be produced are ethylene and carbon number
Having 3 to 20 α-olefins such as propylene
1-butene, 1-hexene, 4-methyl-1-pentene, 1-
Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-
Hexadecene, 1-octadecene, 1-eicosene, etc.
I can do it. Polyene such as diene as required
Can also be copolymerized. In the method of the present invention, the polymerization of olefin
Is usually carried out in the gas phase or in the liquid phase, for example in the form of a slurry.
It is. In slurry polymerization, inert hydrocarbons are
Or using olefin itself as the solvent.
Wear. Specific examples of the hydrocarbon medium include butane,
Isobutane, pentane, hexane, octane, decane,
Aliphatic such as dodecane, hexadecane, octadecane
Hydrocarbon, cyclopentane, methylcyclopentane,
Alicyclic hydrocarbons such as cyclohexane and cyclooctane
Aromatic carbonization such as nitrogen, benzene, toluene and xylene
Hydrogen, gasoline, kerosene, petroleum fractions such as diesel, etc.
Can be In the method of the present invention, the slurry polymerization method
When carried out, usually the polymerization temperature is -50 to 120 ° C,
Preferably it is in the range of 0 to 100 ° C. The present invention
When performing the gas phase polymerization method in the method, usually the polymerization temperature
Is -50 to 120 ° C, preferably 20 to 100
It is in the range of ° C. The polymerization pressure is usually from normal pressure to 100 kg /
cm^Two, Preferably 2 to 50 kg / cm^TwoUnder pressurized conditions
The polymerization can be batch, semi-continuous, or continuous.
Can also be performed. In addition, polymerization was performed under different reaction conditions.
It is also possible to perform the processing in two or more stages. Also, heavy
The molecular weight of the coalesced depends on the hydrogen and / or polymerization temperature.
Can be knotted. [0049] EFFECT OF THE INVENTION Olefin polymerization in the present invention, especially
Ethylene polymerization or slurry of ethylene and α-olefin
If the Lie polymerization method or gas phase polymerization method is used,
Higher in the use of aluminoxane than in the law
It has the characteristic of being active, and the polymer
No adhesion and suitable for copolymerization of two or more olefins
When used, the narrow molecular weight distribution and composition distribution
A fin copolymer can be obtained. [0050] EXAMPLES Next, the method of the present invention will be specifically described by way of examples.
Will be described. In addition, the MFR in Examples and Comparative Examples
Is measured at a temperature of 190 ° C. under a load of 2.16 kg.
The w / Mn value is measured by Takeuchi, “Gel Permie” published by Maruzen.
As described below.
U. (1) Standard polystyrene of known molecular weight (Toyo Soda
Using a monodisperse polystyrene (manufactured by K.K.)
And its GPC (Gel Permeation Chromatograph) counter
And the correlation between molecular weight M and EV (Elution Volume)
Create a diagram calibration curve. The concentration at this time was 0.02 wt%.
I do. (2) GPC chromatography of the sample by GPC measurement
According to the above (1), the number average molecule in terms of polystyrene is
The amount Mn and the weight average molecular weight Mw are calculated, and the Mw / Mn value is calculated as
Ask. Sample preparation conditions and GPC measurement conditions
The matter is as follows. [Sample preparation] (A) O-dichlorobenze so that the sample is 0.1 wt%
Dispense into an Erlenmeyer flask together with the solvent. (B) Heat the Erlenmeyer flask to 140 ° C,
The filtrate is subjected to GPC. [GPC Measurement Conditions] The measurement was performed under the following conditions. (B) Equipment Waters (150C-ALC / G
PC) (B) Column made by Toyo Soda (GMH type) (C) Sample amount 400μl (D) Temperature 140 ° C (E) Flow rate 1ml / min Amount of n-decane soluble part (less soluble part) in copolymer
The composition distribution is narrower), about 3 g of the copolymer was n-deca
Melt at 145 ° C and cool to 23 ° C
Then, the n-decane insoluble portion was removed by filtration, and n-decane was removed from the filtrate.
This was performed by recovering the soluble portion. [0051] Embodiment 1Preparation of aluminoxane Al is placed in a 400 ml flask which is sufficiently purged with nitrogen._Two(S
O_Four)_Three・ 14H_TwoCharge 37g of O and 125ml of toluene
After cooling to 0 ° C, the
500 mmol of chilled aluminum was added dropwise. Next, at 40 ° C
The reaction was continued at that temperature for 10 hours. reaction
After that, solid-liquid separation is performed by filtration,
Aluminoxane as a white solid
13 g were obtained. Determined by freezing point depression in benzene
Its molecular weight was 930, and was shown in the catalyst component [B].
The m value was 14.Preparation of zirconium catalyst Silica (average) in a 200 ml flask
Particle size 70μ, specific surface area 260m^Two/ G, pore volume 1.65
cm^Three/ G) was calcined at 300 ° C for 4 hours.
Solution of aluminoxane and aluminoxane (0.49 mol of Al)
/ L) and stirred at room temperature for 10 minutes. So
After that, remove toluene by evaporator at room temperature
To give a solid product. Bis (cyclo)
Pentadienyl) zirconium dichloride in toluene
7.9 ml of the liquid (Zr 0.04 mol / l) was added,
By removing the toluene with an evaporator below.
A catalyst component having a Zr content of 0.54% by weight was obtained. In addition,
A mixture of ethylene and nitrogen is added to the catalyst component obtained in
Combined gas (30 l / hr, 45 l / h respectively)
r) at room temperature for 30 minutes to give 1 g of catalyst.
0.86 g of ethylene is polymerized per solid catalyst component
Obtained.Compound 2 liter stainless steel autoclave fully purged with nitrogen
900ml of hexane and 100ml of 1-hexane are charged
Then, the temperature was raised to 45 ° C. Then, triisobutyl alcohol
Jil pre-polymerized with ethylene, 1 mmol of minium
0.015 mm in terms of zirconium atom
Gram atom charged. In addition, heat up to 60 ° C and continue
Then, ethylene was introduced to initiate polymerization. 7kg / cm total pressure
^Two・ Continuously supply ethylene to maintain gauge
Polymerization was performed at 0 ° C. for 2 hours. After polymerization is complete,
To a large excess of methanol and filtered off.
Dry under reduced pressure for 12 hours. As a result, MFR 0.1
6g / 10min, density 0.916g / cm^Three, MW / Mn 2.
98, bulk density 0.33 g / cm^ThreeN-decane soluble part at room temperature
101.2 g of 0.31% by weight of polymer were obtained. [0052] Example 2 In Example 1, the prepolymerization amount of ethylene
Was the same as Example 1 except that
I went.Compound In Example 1, 1-hexene was not used, and hexane was used as a solvent.
Using 1000ml, total pressure 6kg / cm^Two・ Echile with gauge
In the same manner as in Example 1 except that the homopolymerization of
Was. Table 2 shows the results. [0053] [Comparative Example 1]Compound In Example 2, no triisobutylaluminum was used.
Except for this, the procedure was the same as in Example 2. The results are shown in Table 2.
You. [0054] Embodiment 3Compound 2 liter stainless steel autoclave sufficiently purged with nitrogen
250 g of sodium chloride (Wako Pure Chemicals special grade)
Then, it was dried under reduced pressure at 90 ° C. for 1 hour. Then to 65 ° C
After cooling, the inside of the system was replaced with ethylene. Continue Triisobu
1 mmol of chilled aluminum,
The ruconium catalyst is 0.015 mi in terms of zirconium atoms.
Insert 10 ml of regram atoms and 1-hexene, and
Into the reactor, and a total pressure of 8 kg / cm^Two・ As a gauge
The polymerization was started. After that, replenish only ethylene, total pressure 8
kg / cm^TwoPolymerization was performed at 70 ° C. for 2 hours while maintaining the gauge.
After completion of the polymerization, sodium chloride was removed by washing with water and remained.
After washing the polymer with methanol, the pressure was reduced at 80 ° C overnight.
Dried. MFR 1.45g / 10min, density 0.92
5g / cm^Three, Mw / Mn 3.03, bulk density 0.31 g / c
m^ThreePolymer having a n-decane soluble part content of 0.10 wt% at room temperature
8 g were obtained. [0055] Example 4 In the polymerization of Example 3, 1-hexene was used.
Without triisobutylaluminum and zirconium
A medium was added at 75 ° C and polymerization was performed at 80 ° C for 1 hour.
Was performed in the same manner as in Example 3. Table 2 shows the results. [0056] Examples 5-8 Same as Example 1 under the conditions described in Table 1.
Polymerization was carried out in the same manner. Table 2 shows the results. [0057] Embodiment 9Preparation of zirconium catalyst Alumina (flat) was placed in a 200 ml flask which was sufficiently purged with nitrogen.
Uniform particle size 60μ, specific surface area 290m^Two/ G, pore volume 1.0
5.8 g obtained by calcining 5 ml / g) at 500 ° C. for 5 hours,
Dimethyl aluminum monochloride in toluene solution (A
(1 mol / l) 17 ml and toluene 50 ml
Heated at 80 ° C. for 2 hours. After that, solid-liquid separation by filtration
And transfer the solid part to 50 ml of toluene.
And bis (cyclopentadienyl) zirconium dik
32 ml of toluene solution of chloride (Zr 0.04 mol / l)
In addition, it was heated at 80 ° C. for 1 hour. Solid-liquid separation by filtration again
Was carried out to obtain a solid catalyst. Jill in solid catalyst
The conium content was 0.27 wt%. This solid catalyst
0.1 mg atom in terms of zirconium atom, Example
Aluminoxane in toluene solution (Al
(0.49 mol / l) and 20 ml of toluene,
The mixture was stirred at room temperature for 30 minutes. Then, evaporate at room temperature
The toluene was removed with a filter. In this way
A mixed gas of ethylene and nitrogen (such as
30 liters / hr and 45 liters / hr) at room temperature
By flowing for 30 minutes, the
A solid catalyst component obtained by polymerizing 0.30 g of styrene was obtained.Compound Polymerization was carried out in the same manner as in Example 4. Table 2 shows the results. [0058] Comparative Example 2 Triisobutylaluminum was used in Example 9.
Example 9 was carried out in the same manner as in Example 9 except that no aluminum was used. result
Are shown in Table 2. [0059] [Table 1] [0060] [Table 2] [0061] Example 10 In Example 1, bis (cyclopentane
Instead of dienyl) zirconium dichloride,
Clopentadienyl) hafnium dichloride
Except for the above, a catalyst was prepared in the same manner as in Example 1, and the Hf content was adjusted.
1.06% by weight of the catalyst component was obtained. Using this catalyst component, in the same manner as in Example 1,
To conduct pre-polymerization of ethylene.
A solid polymerization catalyst obtained by polymerization of 0.20 g was obtained. Example 1
Polymerization was carried out in the same manner as described above. Table 1 (continued) and Table
2 (continued). [0063] Example 11 In Example 1, bis (cyclopentane
Instead of dienyl) zirconium dichloride,
Clopentadienyl) phenoxyzirconium monochrome
A catalyst was prepared in the same manner as in Example 1 except that the lid was used.
Thus, a catalyst component having a Zr content of 0.55% by weight was obtained. Using this catalyst component, in the same manner as in Example 1,
To conduct pre-polymerization of ethylene.
A solid polymerization catalyst obtained by polymerization of 0.80 g was obtained. Example 1
Polymerization was carried out in the same manner as described above. Table 1 (continued) and Table
2 (continued). [0065] [Table 3] [0066] [Table 4]

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

Continuation of the front page (56) References JP-A-63-89505 (JP, A) JP-A-4-11604 (JP, A) JP-A-7-53625 (JP, A) JP-A-4-8704 (JP) JP-A-60-260602 (JP, A) JP-A-61-108610 (JP, A) JP-A-60-35006 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C08F 4/655 C08F 10/00

Claims (1)

(57) [Claims] [A] R ¹ _k R ² _l R ³ _m R ⁴ _n M (I) [where M is titanium, zirconium or hafnium, R ¹ is a cycloalkadienyl group, R ² , R
³ and R ⁴ are a cycloalkadienyl group, an aryl group, an alkyl group, an aralkyl group, an alkoxy group, a halogen atom or a hydrogen atom. However, the cycloalkadienyl group includes an indenyl group and a tetrahydroindenyl group, and the cycloalkadienyl group, aryl group and aralkyl group may have a substituent, and further have an indenyl group, a substituted indenyl group and At least two groups selected from the group consisting of the partial hydrides may be bonded via a lower alkylene group. k ≧ 1, l ≠
0, k + 1 + m + n = 4. A transition metal compound of Group IVB of the Periodic Table represented by the following formula: [B] an aluminoxane, a solid catalyst component supported on an inorganic carrier, and [C] an organic compound having a hydrocarbon group other than an n-alkyl group. An olefin polymerization method, comprising polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an aluminum compound.