JPH0780931B2 - Olefin Polymerization Method - Google Patents

Description

The present invention relates to a method for polymerizing olefins. More particularly, it relates to a method capable of polymerizing olefin with excellent polymerization activity even when the amount of aluminoxane used is reduced, and capable of producing an olefin polymer having a large molecular weight. More specifically, it relates to a method for polymerizing an olefin copolymer having a narrow molecular weight distribution and a narrow molecular weight distribution and composition distribution when it is applied to copolymerization of two or more kinds of olefins with excellent polymerization activity.

[Conventional technology]

Conventionally, as a method for producing an α-olefin polymer, particularly an ethylene polymer or an ethylene / α-olefin copolymer, a titanium catalyst composed of a titanium compound and an organoaluminum compound or a vanadium catalyst composed of a vanadium compound and an organoaluminum compound has been used. It is known to copolymerize ethylene or ethylene and α-olefin in the presence of Generally, an ethylene / α-olefin copolymer obtained by a titanium-based catalyst has a wide molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. Further, the ethylene / α-olefin copolymer obtained with the vanadium catalyst has a narrower molecular weight distribution and composition distribution than those obtained with the titanium catalyst, and the transparency, surface non-adhesiveness and mechanical properties are considerably improved. However, they are still insufficient for applications requiring these performances, and further, α-olefin polymers having improved performance, particularly ethylene / α-olefin copolymers are required.

On the other hand, a catalyst comprising a zirconium compound and aluminoxane has recently been proposed as a new Ziegler type olefin polymerization catalyst.

JP-A-58-19309 discloses that the following formula (cyclopentadienyl) ₂ Me RHal [wherein R is cyclopentadienyl, C ₁ -C ₆ alkyl, halogen, and Me is a transition metal. And Hal is halogen], and a transition metal-containing compound represented by the following formula Al ₂ OR ₄ (Al (R) -O) _n [wherein R is methyl or ethyl, and _n is 4 to 20]. A linear aluminoxane represented by the following formula or the following formula [Wherein R and _n are the same as defined above] in the presence of a catalyst consisting of a cyclic aluminoxane represented by the following formula: ethylene and one or more of C _{3 to} C ₁₂ α-olefins. A method of polymerizing at a temperature of -50 ° C to 200 ° C is described. The same publication describes that in order to control the density of the resulting polyethylene, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of somewhat longer-chain α-olefins or mixtures. .

JP-A-59-95292 discloses the following formula: [Wherein _n is 2 to 40, R is a linear aluminoxane represented by C _{1 to} C ₆ and the following formula: An invention relating to a method for producing a cyclic aluminoxane represented by [wherein _n and R are the same as defined above] is described. In the publication, for example, a mixture of methylaminooxane and a bis (cyclopentadienyl) compound of titanium or zirconium produced by the same production method is used to polymerize olefin, and 1 g of transition metal and It is stated that more than 25 million g of polyethylene can be obtained per hour.

JP-A-60-35005 discloses the following formula [Wherein R ¹ is C ₁ -C ₁₀ alkyl, R ⁰ is R ¹ or is bonded to represent -0-], and the aluminoxane compound is first reacted with a magnesium compound,
The reaction product is then chlorinated and further Ti, V, Zr or Cr is added.
A method for producing a polymerization catalyst for olefin by treating the compound with the above compound is disclosed. The publication describes that the catalyst is particularly suitable for the copolymerization of a mixture of ethylene and C ₃ -C ₁₂ α-olefin.

JP-A-60-35006 discloses a catalyst system for producing a reactor blend polymer, which comprises mono-, di- or tri-cyclopentadienyl of two or more different transition metals or its derivative (a) and alumoxane ( Aluminoxane)
The combination of (b) is disclosed. In Example 1 of the publication, ethylene and propylene are polymerized using bis (pentamethylcyclopentadienyl) zirconium dimethyl and alumoxane as catalysts to contain a number average molecular weight of 15,300, a weight average molecular weight of 36,400 and a propylene component of 3.4%. It is disclosed that polyethylene was obtained. Also,
In Example 2, ethylene and propylene were polymerized using bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and alumoxane as catalysts,
A number-average molecular weight of 2,000 consisting of a number-average molecular weight of 2,200, a weight-average molecular weight of 11,900 and a toluene-soluble portion containing 30 mol% of a propylene component and a number-average molecular weight of 3,000, a weight-average molecular weight of 7,400 and a toluene-insoluble portion containing a propylene component of 4.8 mol%. A blend of polyethylene and an ethylene / propylene copolymer having a weight average molecular weight of 8,300 and a propylene component of 7.1 mol% is obtained. Similarly, in Example 3, the molecular weight distribution (w / n) is 4.57 and the propylene component is
Blends of LLDPE and ethylene-propylene copolymers are described which consist of 20.6 mol% soluble part and molecular weight distribution 3.04 and 2.9 mol% insoluble part of propylene component.

JP-A-60-35007 discloses ethylene alone or together with α-olefin having 3 or more carbon atoms and metallocene and the following formula. [Wherein R is an alkyl group having 1 to 5 carbon atoms, and _n is an integer of 1 to about 20] or a cyclic alumoxane represented by the following formula: A method of polymerizing in the presence of a catalyst system comprising a linear alumoxane represented by [wherein R and _n are the same as defined above] is described. According to the description of the publication, the polymer obtained by the same method has a weight average molecular weight of about 500 to about 1.4 million and a molecular weight distribution of 1.5 to 4.0.

Further, in JP-A-60-35008, by using a catalyst system containing at least two kinds of metallocene and alumoxane, polyethylene having a broad molecular weight distribution or a mixture of ethylene and α-olefin of C ₃ -C ₁₀ is used. It is described that a polymer is produced. The publication describes that the above copolymer has a molecular weight distribution (w / n) of 2 to 50.

Further, a method for polymerizing olefin using a catalyst formed from a transition metal compound and a mixed organoaluminum compound composed of an aluminoxane and an organoaluminum compound is disclosed in JP-A-60-260602 and JP-A-60-130604. It has been proposed in the publication that the addition of an organoaluminum compound improves the polymerization activity per unit transition metal. However, all of these methods have a problem that the amount of aluminoxane used is large and the activity per aluminoxane is still low.

Furthermore, using a catalyst formed from these conventionally known transition metal compounds and aluminoxane,
When α-olefin, for example, ethylene and propylene are copolymerized, there is a drawback that it is difficult to obtain a polymer having a sufficiently large molecular weight.

[Problems to be solved by the invention]

The present inventors have found that an olefin copolymer having a narrow molecular weight distribution and a narrow molecular weight distribution and composition distribution when applied to the copolymerization of two or more kinds of olefins, particularly ethylene / α- with a narrow molecular weight distribution and composition distribution. As a result of studying a method capable of producing an olefin copolymer with excellent polymerization activity in the use of a small amount of aluminoxane and easily producing an α-olefin polymer having a large molecular weight, [A] periodic Table IVB group transition metal catalyst components,
The inventors have found that the above object can be achieved by using a catalyst formed from [B] aluminoxane and [C] a specific organoaluminum compound, and have reached the present invention.

[Means and Actions for Solving Problems]

According to the present invention, [A] a hetero atom-containing ligand capable of forming a bond between a transition metal atom and a hetero atom composed of oxygen, sulfur, nitrogen or phosphorus, and a ligand having a conjugated π electron, respectively. An olefin in the presence of a catalyst formed from a transition metal compound of Group IVB of the periodic table having: [B] aluminoxane, and [C] an organoaluminum compound having a hydrocarbon group other than an n-alkyl group. A method for polymerizing olefins, which comprises polymerizing or copolymerizing, is provided as the first invention, and further, [A] forming a bond between a transition metal atom and a heteroatom composed of oxygen, sulfur, nitrogen or phosphorus. A transition metal compound (a) of Group IVB of the Periodic Table having a heteroatom-containing ligand and a ligand having a conjugated π electron, respectively, is treated with an organometallic compound (b). Polymerizing or copolymerizing olefin in the presence of a catalyst formed from the resulting transition metal compound, [B] aluminoxane, and [C] an organoaluminum compound having a hydrocarbon group other than an n-alkyl group. A method for polymerizing olefin, which is characterized by the above, is provided as a second invention.

Hereinafter, the present invention will be described in detail.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may be used to mean not only homopolymer but also copolymer. .

The catalyst used in the process of the present invention is formed from three catalyst components [A], [B] and [C].

The transition metal catalyst component [A] used in the method of the present invention is a transition metal compound of Group IVB of the periodic table represented by the following formula (I).

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 and R ² is O
R ^a , SR ^b , NR ^c ₂ or PR ^d ₂ , R ³ and R ⁴ are cycloalkadienyl group, aryl group, aralkyl group, alkyl group, halogen atom or hydrogen atom, and R ^a , R ^b , R ^c
And R ^d is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or a silyl group, and R ^c and R ^d can also form a ring with an adjacent group. However, the cycloalkadienyl group includes an indenyl group and a tetrahydroindenyl group, and the cycloalkadienyl group may have a substituent,
Furthermore, a cycloalkadienyl group such as an indenyl group of R ³ or R ⁴ , a substituted indenyl group or a partial hydrogen compound thereof and a cycloalkadienyl group of R ¹ are bonded to each other through a divalent group such as a lower alkylene group. May be. k ≧ 1, k
+ L + m + n = 4. Examples of the cycloalkadienyl group include, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group,
Examples thereof include a dimethylcyclopentadienyl group, an indenyl group, and a tetrahydroindenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and an oleyl group. For example,
Examples thereof include a phenyl group and a tolyl group, examples of the aralkyl group include a benzyl group and a neophyl group, and examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, and a triphenyl group. Examples thereof include an enylmethylsilyl group and a triphenylsilyl group, and examples of the halogen atom include fluorine, chlorine, bromine and the like.

The following compounds can be illustrated as this zirconium compound.

Bis (cyclopentadienyl) methoxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium chloride, bis (cyclopentadienyl) butoxyzirconium chloride, bis (cyclopentadienyl) 2-ethylhexoxyzirconium chloride, bis ( Cyclopentadienyl) methyl zirconium ethoxide bis (cyclopentadienyl) methyl zirconium butoxide, bis (cyclopentadienyl) ethyl zirconium ethoxide, bis (cyclopentadienyl) phenyl zirconium ethoxide, bis (cyclopentadienyl) (Enyl) benzyl zirconium ethoxide, bis (methylcyclopentadienyl) ethoxy zirconium chloride, bis (indenyl) ethoxy zirconium chloride, bis (cycl Pentadienyl) ethoxyzirconium, bis (cyclopentadienyl) butoxyzirconium, bis (cyclopentadienyl) 2-ethylhexoxyzirconium, bis (cyclopentadienyl) phenoxyzirconium chloride, bis (cyclopentadienyl) cyclohexyl Soxyzirconium chloride, bis (cyclopentadienyl) phenylmethoxyzirconium chloride, bis (cyclopentadienyl) methylzirconium phenylmethoxide, bis (cyclopentadienyl) trimethylsiloxyzirconium chloride, bis (cyclopentadienyl) Triphenylsiloxyzirconium chloride, bis (cyclopentadienyl) thiophenezirconium chloride, bis (cyclopentadienyl) bis (dimethylamide)
Zirconium, bis (cyclopentadienyl) diethylamide zirconium chloride, ethylenebis (indenyl) ethoxyzirconium chloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ethoxyzirconium chloride, Compounds of

Bis (cyclopentadienyl) ethoxy titanium chloride, Bis (cyclopentadienyl) butoxy titanium chloride, Bis (cyclopentadienyl) methyl titanium ethoxide, Bis (cyclopentadienyl) phenoxy titanium chloride, Bis (cyclo Pentadienyl) trimethylsiloxy titanium chloride, bis (cyclopentadienyl) thiophene titanium chloride, bis (cyclopentadienyl) bis (dimethylamide)
Titanium, bis (cyclopentadienyl) ethoxytitanium, and as the hafnium compound, the following compounds can be exemplified.

Bis (cyclopentadienyl) ethoxy hafnium chloride, bis (cyclopentadienyl) butoxy hafnium chloride, bis (cyclopentadienyl) methyl hafnium ethoxide, bis (cyclopentadienyl) phenoxy hafnium chloride, bis (cyclo) Pentadienyl) thiofenyl hafnium chloride, bis (cyclopentadienyl) bis (diethylamide)
Hafnium, and in the method of the present invention, as the transition metal compound catalyst component [A], a hetero atom-containing coordination capable of forming a bond between a transition metal atom and a hetero atom composed of oxygen, sulfur, nitrogen or phosphorus. The transition metal compound catalyst component obtained by treating a transition metal compound (a) of Group IVB of the periodic table with an organometallic compound (b) having a child and a ligand having a conjugated π electron It is preferable because a catalyst having excellent activity is formed.

Examples of the organometallic compound (b) include organoaluminum compounds, organoboron compounds, organomagnesium compounds, organozinc compounds, organolithium compounds, etc.
~ Group III organometallic compounds can be mentioned.

The organoaluminum compound used for treating the transition metal compound of Group IVB of the periodic table is specifically trimethylaluminum, triethylaluminum, trialkylaluminum such as tributylaluminum, dimethylaluminum methoxide, diethylaluminum ethoxide, dibutyl. In addition to dialkylaluminum alkoxides such as aluminum butoxide, alkylaluminum sesquimethoxides such as methylaluminum sesquimethoxide and ethylaluminum sesquiethoxide, partially alkoxy having an average composition represented by R ¹ _1.5 Al (OR ² ) _0.5, etc. Alkyl aluminum,
Dialkyl aluminum chlorides such as dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride Examples thereof include partially halogenated alkyl aluminum and the like.

Examples of the organoboron compound include triethylboron, and examples of the organomagnesium compound include ethylbutylmagnesium, di-n-hexylmagnesium, ethylmagnesium bromide, phenylmagnesium bromide, and benzylmagnesium chloride.
Examples of the organic zinc compound include diethyl zinc,
Examples of the organic lithium compound include methyllithium, butyllithium, phenyllithium and the like.

The organometallic compound is preferably organoaluminum.

In the method of the present invention, the amount of the organometallic compound (b) used is usually 0.1 to 20 mol, preferably 0.3 to 15 mol, based on 1 mol of the transition metal compound (a). The amount is more preferably 0.5 to 10 mol.

In the method of the present invention, the reaction of the transition metal compound (a) and the organometallic compound (b) is generally carried out in an organic solvent. Further, it can be carried out in an α-olefin atmosphere, which will be described later, if necessary. Examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbons such as methylcyclopentane, cyclopentane, cyclooctane, cyclodecane and cyclododecane, benzene, toluene and xylene. And aromatic hydrocarbons such as cumene and cymene.

Of the organic solvents, aromatic hydrocarbons are preferred.

In the method of the present invention. The concentration of the organometallic compound (b) in the reaction system is usually in the range of 1 × 10 ^-8 to 1 gram atom / l, preferably 1 × 10 ^-7 to 0.1 gram atom / l in terms of metal atom. The concentration of the transition metal compound maintained in the reaction system is usually in the range of 1 × 10 ^-8 to 1 gram atom / l, preferably 1 × 10 ^-7 to 0.1 gram atom / l in terms of the transition metal atom. Maintained.

The temperature during the reaction is usually 0 to 100 ° C., preferably 10
The reaction time is usually 0.1 minutes or longer, preferably 1 minute to 200 minutes.

The catalyst component [B] used in the method of the present invention is aluminoxane. As the aluminoxane used as the catalyst component [B], the general formula (II) and the general formula (II
I) The organoaluminum compound represented by can be exemplified. In the aminooxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and _m is 2 or more, preferably 5 or more. Is an integer. The following method can be exemplified as a method for producing the aluminoxane.

(1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, chloride first
A method in which a trialkylaluminum is added to a hydrocarbon medium suspension such as cerium hydrate and reacted.

(2) A method in which water is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of organic metal component.

The organoaluminum compound [C] used as a catalyst constituent in the method of the present invention is an organoaluminum compound having a hydrocarbon group other than the n-alkyl group. n
-As the hydrocarbon group other than the alkyl group, an alkyl group having a branched chain such as isoalkyl, a cycloalkyl group,
An aryl group etc. can be illustrated. Specific examples of the organoaluminum compound include triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri2-methylpentylaluminum and tri-3-methylaluminum.
Methylpentylaluminum, tri-4-methylpentylaluminum, tri2-methylhexylaluminum,
Trialkylaluminums such as tri-3-methylhexylaluminum and tri2-ethylhexylaluminum, tricycloalkylaluminums such as tricyclohexylaluminum, triarylaluminums such as triphenylaluminum and tritolylaluminum, and dialkylaluminums such as diisobutylaluminum hydride. Examples thereof include hydrides, alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide. Among these organoaluminum compounds, an aluminum compound having a branched alkyl group is preferable, and a trialkylaluminum compound is particularly preferable. In general formula _{(iC 4 H 9) x Al} y (C 5 H 10) z (x, y, z are each a positive number, and _z ≧ 2 _x) isoprenylaluminum represented by is preferable. It should be noted that a compound capable of forming the organoaluminum compound in the polymerization system, for example, aluminum halide and alkyllithium or aluminum halide and alkylmagnesium may be added.

In the method of the present invention, the olefin polymerization reaction can be carried out by either a liquid phase polymerization method such as a thriller polymerization method or a solution polymerization method, or a gas phase polymerization method.

The proportion of the transition metal atom compound used in carrying out the method of the present invention is usually 10 ^-8 to 10 ^-2 gram atom / l, preferably 10 ^-7 to 10 as the concentration of the transition metal atom in the polymerization reaction system. It is in the range of 10 ^-3 gram atom / l.

In the method of the present invention, the amount of aluminoxane used is 3 mg / l or less, preferably 0.1 to 2 mg / l, in terms of aluminum atoms in the reaction system.
l, particularly preferably in the range of 0.2 to 1 milligram atom / l. Further, the ratio of the aluminum atoms of the aluminoxane component [B] to the total amount of the total aluminum atoms of the aluminoxane component [B] and the organoaluminum compound component [C] in the reaction system is usually 20 to 80%, Preferably 25 to 75%, particularly preferably 30
The proportion of aluminum atoms in the organoaluminum compound component [C] is usually 20 to 80%, preferably 25 to 75%, and particularly preferably 30.
Or in the range of 70%. In the method of the present invention, the ratio of the total amount of aluminum atoms of the aluminoxane component [B] and the organoaluminum compound component [C] to the transition metal atom in the reaction system is usually 20 to 10000, preferably 50 to 5000. , Particularly preferably 100 to 2000
Is the range.

The method of the present invention is effective for producing olefin polymers, particularly ethylene polymers and ethylene-α-olefin copolymers. Examples of olefins that can be used in the present invention include ethylene and α-C3-20.
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 and the like can be mentioned. If necessary, a polyene such as a diene can be copolymerized.

In the process of the present invention, the polymerization of olefins is usually carried out in the gas phase or in the liquid phase, for example in solution. In the liquid phase polymerization, an inert hydrocarbon may be used as a solvent,
Olefin itself can also be used as the solvent.

Specific examples of the hydrocarbon medium include butane, isobutane,
Aliphatic hydrocarbons such as pentane, hexane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane, aromatics such as benzene, toluene and xylene Examples include petroleum fractions such as system hydrocarbons, gasoline, kerosene, and light oil.

In the method of the present invention, the polymerization temperature is usually -50 to 200.
C., preferably 0 to 120.degree. Polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to 50 k
It is under the condition of g / cm ² , and the polymerization can be carried out by any of batch, semi-continuous and continuous methods. It is also possible to carry out the polymerization in two or more stages under different reaction conditions. The molecular weight of the polymer can be adjusted by hydrogen and / or the polymerization temperature.

〔The invention's effect〕

When applied to olefin polymerization in the present invention, particularly ethylene polymerization or copolymerization of ethylene and α-olefin, it is significantly more active and has a large molecular weight than conventional methods even when less aluminoxane is used. When applied to the copolymerization of two or more kinds of olefins, it is possible to obtain an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution.

〔Example〕

Next, the method of the present invention will be specifically described with reference to examples. In the examples and comparative examples, the MFR has a temperature of 190
Measurement is carried out under conditions of ℃ and load of 2.16 kg, and the w / n value is measured according to "Gel Permeation Chromatography" published by Maruzen by Takeuchi.

(1) A standard polystyrene having a known molecular weight (manufactured by Toyo Soda Co., Ltd., monodisperse polystyrene) is used to obtain a molecular weight M.
And its GPC (Gel Permeation Chromato-graph) count are measured, and a correlation diagram calibration curve of molecular weight M and EV (Elution Volume) is prepared. The concentration at this time is 0.02 wt%.

(2) Take a GPC chromatograph of the sample by GPC measurement,
The number average molecular weight n and the weight average molecular weight w in terms of polystyrene are calculated by the above (1), and the w / n value is obtained. The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample preparation]

(A) The sample is dispensed into an Erlenmeyer flask together with an o-dichlorobenzene solvent so as to have a concentration of 0.1 wt%.

(B) The Erlenmeyer flask is heated to 140 ° C, and the filtrate is applied to GPC for about 30 minutes.

[GPC measurement conditions]

 It carried out on the following conditions.

(A) Equipment Waters (150C-ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample volume 400 μl (d) Temperature 140 ° C (e) Flow rate 1 ml / min Copolymer The amount of n-decane soluble portion in the solution (the smaller the soluble portion, the narrower the composition distribution) was measured by adding about 3 g of the copolymer to 450 ml of n-decane, dissolving at 145 ° C, and cooling to 23 ° C. Then, the n-decane-insoluble portion was removed by filtration, and the n-decane-soluble portion was recovered from the filtrate.

Further, the B value of the ethylene copolymer of the present invention is defined as follows.

[In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α-olefin component, and P _OE is the α-olefin / ethylene chain of the entire dyad chain. The above B value is an index showing the distribution state of each monomer component in the copolymer chain, and GJRay (Macro-molecules, 10 ,
773 (1977), JCRandall (Macro-molecules, 15 , 353
(1982), J. Polymer Science, Polymer Physics Ed., 1
1 , 275 (1973)), K. Kimura (Polymer, 25 , 441 (1984))
It is calculated by obtaining P _E , P _O and P _OE as defined above based on these reports. The larger the B value, the smaller the number of blocky chains, the more uniform the distribution of ethylene and α-olefin, which indicates that the copolymer has a narrow composition distribution.

The composition distribution B value is the ¹³ C-NMR spectrum of a sample prepared by uniformly dissolving about 200 mg of a copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.
Measured under the conditions of 120 ℃, measurement frequency 25.05MHz, spectrum width 1500Hz, filter width 1500Hz, pulse repetition time 4.2sec, pulse width 7μsec, integration number 2000 ~ 5000 times, and from this spectrum, P _E , P _O , P It is calculated by calculating _OE .

Example 1 Preparation of aluminoxane Al ₂ (SO ₄ ) ₃ · 14H _{2 was} placed in a 400 ml flask which had been thoroughly purged with nitrogen.
After charging 37 g of O and 125 ml of toluene and cooling to 0 ° C., 500 mmol of trimethylaluminum diluted with 125 ml of toluene was added dropwise. Next, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was further removed from the filtrate to obtain 13 g of a white solid aluminoxane. The molecular weight determined by freezing point depression in benzene was 930, and the m value shown in the catalyst component [B] was 14.

Polymerization 500 ml of toluene was charged into a glass autoclave with an internal volume of 1 that had been sufficiently replaced with nitrogen, and a mixed gas of ethylene and propylene (120 l / hr and 80 l / hr, respectively) was circulated, and 20
It was left at ℃ for 10 minutes. Then, 0.5 mmol of triisobutylaluminum was added, and 5 minutes later, aluminoxane was added in an amount of 0.25 mg atom in terms of aluminum atom, and then bis (cyclopentadienyl) phenoxyzirconium monochloride was added in an amount of 2.5 × 10 ⁻³ mmol to perform polymerization. Started. A mixed gas of ethylene and propylene was continuously supplied, and polymerization was carried out at 20 ° C. for 1 hour under normal pressure. After completion of polymerization
Polymerization was stopped by adding a small amount of methanol. The polymer solution was added to a large excess of methanol to cause the polymer to break out,
It was dried under reduced pressure at 130 ° C. for 12 hours. As a result, MFR 0.2
1g / 10min, ethylene content 85.5mol% determined by ¹³ C-NMR,
10.9 g of a polymer having a w / n of 2.35 and a B value of 1.11 was obtained.

Comparative Example 1 The procedure of Example 1 was repeated, except that triisobutylaluminum was not used in the polymerization of Example 1, but no polymer was obtained.

Examples 2 to 5 Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1. The results are shown in Table 1.

Example 6 Preparation of catalyst component (A) 50 ml of a solution (Zr 1.35 mmol / l) of bis (cyclopentadienyl) ethoxyzirconium monochloride dissolved in toluene in a 200 ml glass flask sufficiently replaced with nitrogen.
Charged with dimethyl aluminum chloride (Al 4mm
34 ml of ol / l) was added and reacted at 25 ° C. for 30 minutes to obtain a catalyst component (A).

Polymerization Example 1 was repeated except that the catalyst component (A) prepared above was used instead of bis (cyclopentadienyl) phenoxyzirconium monochloride.

Comparative Example 2 The procedure of Example 6 was repeated except that triisobutylaluminum was not used in the polymerization of Example 6, but almost no polymer was obtained.

Examples 7 to 13 Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1. The results are shown in Table 1.

Example 14 Polymerization 250 ml of hexane and 750 ml of 4-methyl-1-pentene were placed in a stainless steel autoclave having an internal volume of 2 l which had been sufficiently replaced with nitrogen.
Was charged and the temperature was raised to 35 ° C. Thereafter, 0.25 mmol triisobutylaluminum, 0.5 mg atom of aluminoxane synthesized in Example 1 in terms of aluminum atom, and 1 x 10 ^-3 mg atom of catalyst component (A) synthesized in Example 6 in terms of zirconium atom. I entered. Subsequently, ethylene was introduced to initiate polymerization. Continuously feed ethylene to keep the total pressure at 8 kg / cm ² -gauge,
Time polymerization was performed. Subsequent operations were performed in the same manner as in Example 1, with MFR 0.62 g / 10 min, density 0.902 g / cm ³ , w / n 2.9.
8. Room temperature decane soluble part weight fraction 1.9wt% polymer 30.5g
Got

Example 15 In the same manner as in Example 14, except that 750 ml of 1-hexene was used instead of 4-methyl-1-pentene in the polymerization of Example 14, MFR was 1.01 g / 10 min, and density was 0.891 g / cm ^3. , W /
28.5 g of polymer with n = 2.79 was obtained.

Comparative Example 3 The procedure of Example 14 was repeated except that triisobutylaluminum was not used in the polymerization of Example 14, and MFR 1.94 g /
2.5 g of a polymer having a density of 0.908 g / cm ³ , w / n 2.95, and a room temperature decane-soluble part weight fraction of 1.1 wt% was obtained for 10 minutes.

Example 16 Using the continuous polymerization reactor of 1, 500 ml / hr of toluene,
Triisobutylaluminum was 0.5 mmol / hr, aluminoxane synthesized in the same manner as in Example 1 was 0.5 mg atom / hr in terms of aluminum atom, and the catalyst component (A) synthesized in the same manner as in Example 13 was in terms of zirconium atom. In 5
× 10 ^-3 mg atom / hr was continuously supplied at a rate of 150 l / hr ethylene and 100 propylene simultaneously in the polymerization vessel.
l / hr and 5-ethylidene-2-norbornene (ENB) 1.2
It was continuously fed at a rate of g / hr, and the polymerization was carried out under the conditions of a polymerization temperature of 20 ° C., an atmospheric pressure, a residence time of 1 hour and a polymer concentration of 14 g / l. The polymer thus produced was treated in the same manner as in Example 1. Thus, MFR 2.04g / 10min, ethylene content 85.8mol% determined by ¹³ C-NMR, w / n 2.49, iodine value 10
Of ethylene propylene-EMB copolymer was obtained.

Comparative Example 4 Polymerization of Example 6 was repeated except that triisobutylaluminum was not used and 2.5 mg of aluminoxane in terms of aluminum atom was used to polymerize for 30 minutes. Polymer 22.0 with 10min, ethylene content 82.5mol%, w / n 2.11, B value 1.14
g was obtained.

Example 17 In Example 1, instead of bis (cyclopentadienyl) phenoxyzirconium monochloride, bis (cyclopentadienyl) phenoxyhafnium monochloride was 5 × 10 ⁻³ mmol, and aluminoxane was converted to aluminum atoms. Polymerization was conducted in the same manner as in Example 1 except that 0.5 milligram atom and 1 mmol of triisobutylaluminum were used.

As a result, 3.4 g of a polymer having an MFR of 0.18 g / 10 min, an ethylene content of 87 mol%, ▲ ▼ / ▲ ▼ 2.29, and a B value of 1.10 was obtained.

Example 18 Example 17 was repeated except that bis (cyclopentadienyl) titanium monochloride diethylamide was used in place of bis (cyclopentadienyl) phenoxyhafnium monochloride in 5 × 10 ⁻³ mmol. Polymerization was performed in the same manner as in.

As a result, 4.6 g of a polymer having MFR of 0.12 g / 10 min, ethylene content of 85 mol%, ▲ ▼ / ▲ ▼ 2.41 and B value of 1.12 was obtained.

[Brief description of drawings]

1 and 2 are flow chart drawings showing an example of preparation of a catalyst in the polymerization of olefin of the present invention.

Claims (2)

[Claims] 1. [A] The following formula (I) R ¹ _k R ² _l R ³ _m R ⁴ _n M (I) [wherein M is titanium, zirconium or hafnium, and R ¹ is cycloalkadienyl. And R ² is O
R ^a , SR ^b , NR ^c ₂ or PR ^d ₂ , R ³ and R ⁴ are cycloalkadienyl group, aryl group, aralkyl group, alkyl group, halogen atom or hydrogen atom, and R ^a , R ^b , R ^c
And R ^d is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or a silyl group, and R ^c and R ^d can also form a ring with an adjacent group. However, the cycloalkadienyl group includes an indenyl group and a tetrahydroindenyl group, and the cycloalkadienyl group may have a substituent,
Further, a cycloalkadienyl group such as an indenyl group of R ³ or R ⁴ , a substituted indenyl group and a partial hydride thereof and a cycloalkadienyl group of R ¹ are bonded via a divalent group such as a lower alkylene group. You may have. k ≧ 1,
k + l + m + n = 4. ] In the presence of a catalyst formed from a transition metal compound of Group IVB of the periodic table, [B] aluminoxane, and [C] an organoaluminum compound having a hydrocarbon group other than an n-alkyl group, A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin. 2. [A] R ¹ _k R ² _l R ³ _m R ⁴ _n M (I) [wherein M is titanium, zirconium or hafnium and R ¹ is cycloalkadienyl] And R ² is O
R ^a , SR ^b , NR ^c ₂ or PR ^d ₂ , R ³ and R ⁴ are cycloalkadienyl group, aryl group, aralkyl group, alkyl group, halogen atom or hydrogen atom, and R ^a , R ^b , R ^c
And R ^d is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or a silyl group, and R ^c and R ^d can also form a ring with an adjacent group. However, the cycloalkadienyl group includes an indenyl group and a tetrahydroindenyl group, and the cycloalkadienyl group may have a substituent,
Further, a cycloalkadienyl group such as an indenyl group of R ³ or R ⁴ , a substituted indenyl group and a partial hydride thereof and a cycloalkadienyl group of R ¹ are bonded via a divalent group such as a lower alkylene group. You may have. k ≧ 1,
k + l + m + n = 4. ] A transition metal compound (a) of Group IVB of the periodic table shown by
Are treated with an organometallic compound (b) of Group I to III of the periodic table, [B] aluminoxane, and [C] organoaluminum having a hydrocarbon group other than an n-alkyl group. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst formed from the compound.