JPS6389506A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To polymerize an olefin in a high polymerization activity even in a decreased amount of an aluminoxane used, by using a catalyst comprising a Group IV B transition metal catalyst component, an aluminoxane and a specified organoaluminum compound. CONSTITUTION:An olefin is (co)polymerized in the presence of a catalyst comprising a Group IV B transition metal compound (A) having both of a hetero atom-containing ligand which can form a bond between a transition metal atom and a hetero atom comprising O, S, N or P and a ligand having conjugated pi electrons [e.g., bis(cyclopentadienyl)phenoxyzirconium monochloride], an aluminoxane (B) [e.g., a compound of formula I or II (wherein R is methyl or the like and m>=2)] and an organoaluminum compound (C) containing a hydrocarbon group other than an n-alkyl (e.g., triisopropylaluminum). When this process is applied to, especially, ethylene polymerization or copolymerization of ethylene with an alpha-olefin, the catalytic activity is high even in a decreased amount of the aluminoxane used, and when at least two olefins are copolymerized, a copolymer of a narrow MW distribution and a narrow composition distribution can be obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for polymerizing olefins.

In particular, the present invention relates to a method for polymerizing olefins with excellent polymerization activity even when the amount of aluminoxane used is reduced. More specifically, the present invention relates to a method for polymerizing an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution with excellent polymerization activity when applied to the copolymerization of two or more types of olefins.

[Conventional technology]

Conventionally, methods for producing α-olefin polymers, particularly ethylene polymers or ethylene/α-olefin copolymers, have been carried out using titanium-based catalysts consisting of a titanium compound and an organic anoleminium compound, or vanadium catalysts consisting of a vanadium compound and an organic aluminum compound. A method of copolymerizing ethylene or ethylene and an α-olefin in the presence of a catalyst is known. In general, ethylene/α-olefin copolymers obtained using titanium-based catalysts have a wide molecular weight distribution and composition distribution, and are poor in transparency, surface non-adhesion, and mechanical properties. In addition, the ethylene/α-olefin copolymer obtained using a vanadium-based catalyst has a narrower molecular weight distribution and composition distribution than that obtained using a titanium-based catalyst, and its transparency, surface non-adhesiveness, and mechanical properties are significantly improved. However, these properties are still insufficient for applications requiring these properties, and there is a demand for α-olefin polymers, especially ethylene/α-olefin copolymers, with improved performance.

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

JP-A No. 58-19309 describes the following formula:
is a halogen] and a transition metal-containing compound represented by the following formula %)) [where R is methyl or ethyl and 7 is 4-20
] or the following formula [where R and ]. The definition is the same as above. A method for polymerization is described. The publication states that in order to adjust the density of the polyethylene obtained, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of somewhat long-chain α-olefins or mixtures. .

JP-A No. 59-95292 describes the following formula, [where, is 2 to 40, and R is a linear aluminoxane represented by 01 to C1 and the following formula [where 7 and R
The definitions are the same as above] is described. The publication states that when olefin polymerization is carried out by mixing, for example, methylaminooxane and a titanium or zirconium bis(cyclopentagenyl) compound produced by the same production method, the It is stated that more than 25 million g of polyethylene can be obtained per hour.

JP-A No. 60-35005 describes the following formula [where,
RI is C1-Cl11 alkyl, Ro is R1 or combined to represent 10-] is first reacted with a magnesium compound, then the reaction product is chlorinated, and then Ti , V, Z
A method for producing an olefin polymerization catalyst by treatment with an r or Cr compound is disclosed. The publication states that the above catalyst contains ethylene and Cl-Cl! It is described as being particularly suitable for the copolymerization of mixtures of α-olefins.

JP-A No. 60-35006 discloses that mono-, di- or tri-cyclopentadienyl or its HA Nl' form (a) of two or more different transition metals and an alumoxane are used as a catalyst system for producing a reactor-blended polymer. (aluminoxane) (b) combinations are disclosed.

In Example 1 of the same publication, ethylene and propylene components were combined using bis(pentamethylcyclopentagenyl)zirconium dimethyl and alumoxane as catalysts to obtain a number average molecular weight of 15,300, a weight average molecular weight of 36.400, and a propylene component. It is disclosed that polyethylene containing a target of 4% was obtained. In addition, in Example 2, ethylene and propylene were polymerized using bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentagenyl)zirconium dichloride, and alumoxane as catalysts, and the number average molecular weight was 2.20.
0, weight average molecular weight 11, 900 and 30 mol%
A toluene soluble portion containing a propylene component with a number average molecular weight of 3,000, a weight average molecular weight of 7,400 and 4.8.
A number-average molecule consisting of a toluene-insoluble portion with mole % propylene content! 2,000, weight average molecule ff18,3
A blend of polyethylene and ethylene-propylene copolymer containing 0.00 and 7.1 mol% of propylene components was obtained. Similarly, in Example 3, molecular weight distribution (L/M
n) soluble portion of 4.57 and propylene component 20.6 mol% and molecular weight distribution 3.04 and propylene component 2.
LLDPE consisting of 9 mol% insoluble portion and ethylene-
Blends of propylene copolymers are described.

JP-A No. 60-35007 discloses that ethylene alone or together with an α-olefin having 3 or more carbon atoms is used with metallocene and the following formula [where R is an alkyl group having 1 to 5 carbon atoms, and 7 is 1 to ca. is an integer of 20] or a linear alumoxane represented by the following formula % [wherein the definitions of R and are the same as above]. The method is described. According to the description in the same publication, the polymer obtained by this method has a molecular weight of about 500 to about 14
It has a weight average molecular weight of 0,000 and a molecular weight distribution of 1.5 to 4.0.

In addition, JP-A-60-35008 discloses a copolymer of polyethylene or ethylene and α-olefins of 03 to CIG having a wide molecular weight distribution by using a catalyst system containing at least two types of metallocene and alumoxane. It is stated that it is manufactured. The publication describes that the above copolymer has a molecular weight distribution (&/detent) of 2 to 50.

Furthermore, a method for polymerizing olefins using a catalyst formed from a transition metal compound and a mixed organoaluminum compound consisting of an aluminoxane and an organoaluminum compound is disclosed in JP-A-60-260602 and JP-A-60.
It is proposed in Japanese Patent No. 130604, and it is stated that the polymerization activity per unit transition metal is improved by adding an organoaluminum compound. However, all of these methods have the problem that the amount of aluminoxane used is large and the activity per aluminoxane is still low.

[Problem that the invention seeks to solve]

The present inventors have developed an olefin copolymer with a narrow molecular weight distribution and a narrow molecular weight distribution and a narrow composition distribution when applied to the copolymerization of two or more types of olefins. As a result of studying a method for producing an α-olefin copolymer with excellent polymerization activity while using a small amount of aluminoxane, we found that (2) [A] a catalyst component of a group rVB transition metal in the periodic table; (B) an aluminoxane; and (C) It has been found that the above object can be achieved by using a catalyst formed from a specific organoaluminum compound, and the present invention has been achieved.

[Means and effects for solving the problems] According to the present invention, (2) [A] a heteroatom capable of forming a bond between a transition metal atom and a heteroatom consisting of oxygen, sulfur, nitrogen, or phosphorus; A transition metal compound of Group IVB of the periodic table each having a containing ligand and a ligand having conjugated π electrons, (B) an aluminoxane, and [C] having a hydrocarbon group other than an n-alkyl group An olefin polymerization method is provided as a first invention, which is characterized in that an olefin is polymerized or copolymerized in the presence of a catalyst formed from an organoaluminum compound, and further includes (2) [A] a transition metal atom and Transition metal compounds of group IVB of the periodic table each having a heteroatom-containing ligand capable of forming a bond with a heteroatom consisting of oxygen, sulfur, nitrogen or phosphorus and a ligand having conjugated π electrons ( A transition metal compound obtained by treating a) with an organometallic compound (b); and (B) an aluminoxane and an organoaluminum compound having a hydrocarbon group other than the [C] n-alkyl group. A second invention provides a method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst.

The present invention will be explained in detail below.

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymers but also copolymers. .

The catalyst used in the method of the invention is formed from three catalyst components (2) [A], [B] and [C].

Transition metal catalyst component (2) used in the present invention [A
] is the number rVB of the periodic table having a heteroatom-containing ligand capable of forming a bond between a transition metal atom and a heteroatom consisting of oxygen, sulfur, nitrogen or phosphorus, and a ligand having a conjugated π electron, respectively. It is a transition metal compound of the group
The transition metal of group rVB of the periodic table in the catalyst (2) [A] is selected from the group consisting of titanium, zirconium and hafnium. Titanium and zirconium are preferred as the transition metal in catalyst component (2) [A],
Zirconium is particularly preferred.

As the transition metal compound catalyst component (2) [A], for example, the following formula (I) R'J2iR'aR'J (1) [where M
indicates a titanium, zirconium or hafnium atom,
RI represents a cycloalkagenyl group, R: is OR''
, SR'5NRC, or PR', R3 and R4 are a cycloalkagenyl group, an aralkyl group, an aralkyl group, an alkyl group, a halogen atom or hydrogen, and R''SRb, Re and R′I is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a silyl group, and two Rc and R′ can also be linked to form a ring. ll ≧
1, L≠01. +l+, +7=4]. Examples of the cycloalkagenyl group include a cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, a dimethylcyclopentagenyl group, an indenyl group, and a tetrahydroindenyl group. can. Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, and oleyl group, and examples of the aryl group include: For example, phenyl group, tolyl group, etc. can be exemplified, aralkyl group can be exemplified benzyl group, neophyl group, etc., and silyl group is trimethylsilyl group, triethylsilyl group, diphenylmethylsilyl group,
Examples include a triphenylmethylsilyl group and a triphenylsilyl group, and examples of the halogen atom include fluorine, chlorine, and bromine.

Examples of the zirconium compound include the following compounds.

Bis(cyclopentagenyl)methoxyzirconium chloride, Bis(cyclopentagenyl)ethoxyzirconium chloride, Bis(cyclopentagenyl)butoxyzirconium chloride, Bis(cyclopentagenyl)2-ethylpequinoxyzirconium chloride, Bis( cyclopentagenyl)methylzirconium ethoxide, bis(cyclopentagenyl)methylzirconium butoxide, bis(cyclopentagenyl)ethylzirconium ethoxide, bis(cyclopentagenyl)phenylzirconium ethoxide, bis(cyclopentagenyl)methylzirconium ethoxide, bis(cyclopentagenyl)methylzirconium ethoxide, ) benzylzirconium ethoxide, bis(methylcyclopentagenyl)ethoxyzirconium chloride, bis(indenyl)ethoxyzirconium chloride, bis(cyclopentagenyl)ethoxyzirconium, bis(cyclopentagenyl)butoxyzirconium, bis(cyclopentadienyl)butoxyzirconium pentagenyl)2-ethylhexoxyzirconium, bis(cyclopentagenyl)phenoxyzirconium chloride, bis(cyclopentagenyl)cyclohexoxyzirconium chloride, bis(cyclopentagenyl)phenylmethoxyzirconium chloride, bis(cyclopentajenyl)phenoxyzirconium chloride bis(cyclopentadienyl)trimethylsiloxyzirconium chloride, bis(cyclopentajenyl)triphenylsiloxyzirconium chloride, bis(cyclopentajenyl)thiophenylzirconium chloride, bis(cyclopentajenyl)thiophenylzirconium chloride, genyl)bis(dimethylamide)
Zirconium, bis(cyclopentagenyl)diethylamide zirconium chloride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, and the titanium compound: The following compounds can be exemplified.

Bis(cyclopentagenyl)ethoxytitanium chloride, Bis(cyclopentagenyl)butoxytitanium chloride, Bis(cyclopentagenyl)methyltitanium ethoxide, Bis(cyclopentagenyl)phenoxytitanium chloride, Bis(cyclopentagenyl)butoxytitanium chloride trimethylsiloxytitanium chloride, bis(cyclopentagenyl)thiophenyltitanium chloride, bis(cyclopentagenyl)bis(dimethylamide)
Examples of titanium, bis(cyclopentagenyl)ethoxytitanium, and the hafnium compound include the following compounds.

Bis(cyclopentagenyl)ethoxyhafnium chloride, bis(cyclopentagenyl)butoxyhafnium chloride, bis(cyclopentagenyl)methylhafnium ethoxide, bis(cyclopentagenyl)phenoxyhafnium chloride, bis(cyclopentagenyl)butoxyhafnium chloride )thiophenylhafnium chloride, bis(cyclopentagenyl)bis(diethylamide)
Hafnium; In addition, in the method of the present invention, the transition metal compound catalyst component (2) [A] is a heteroatom capable of forming a bond between a transition metal atom and a heteroatom consisting of oxygen, sulfur, nitrogen, or phosphorus. A transition metal compound catalyst component obtained by treating a transition metal compound (a) of group rVB of the periodic table having each of a containing ligand and a ligand having conjugated π electrons with a metal compound (b). When used, a catalyst with excellent polymerization activity is formed, which is preferable.

Examples of the organometallic compound (b) include organoaluminum compounds, organoboron compounds, organomagnesium compounds, organozinc compounds, and organolithium compounds.

Specifically, the organic aluminum compounds used in the treatment of the transition metal compounds of group rVB of the periodic table include trialkylaluminum such as trimethylaluminum, triethylaluminum, and tributylaluminum, dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum. In addition to dialkylaluminum alkoxides such as aluminum butoxide, alkylaluminum sesquialkoxides such as methylaluminum sesquimethoxide, ethylaluminum sesquiethoxide, R'1. s A l (OR”) o, sf,
K Table t) Partially alkoxylated alkylaluminums, dialkylaluminum halides, methylaluminum sesquichloride, such as dimethylaluminum chloride, diethylaluminium chloride, dimethylaluminum bromide, with an average composition of
Examples include partially halogenated alkyl aluminum such as alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, methyl aluminum dichloride, and alkyl aluminum cybarides such as ethyl aluminum dichloride.

Examples of the organic boron compound include triethylboron, and examples of the organic magnesium compound include ethylbutylmagnesium, moro-hexylmagnesium, ethylmagnesium bromide, phenylmagnesium bromide, benzylmagnesium chloride, etc.
As the organic zinc compound, diethylzinc can be exemplified,
Examples of the organic lithium compound include methyllithium, butyllithium, phenyllithium, and the like.

As the organometallic compound, organoaluminium is preferable.

In the method of the present invention, the proportion of the organometallic compound (b) to be used is usually 0.1 to 20 moles relative to 1 mole of the transition metal compound (a).
mol, preferably in the range of 0.3 to 15 mol, more preferably 0.5 to 10 mol.

In the method of the present invention, the reaction of the transition metal compound (al) and the organometallic compound (b) is generally carried out in an organic solvent. If necessary, it is also carried out in an α-olefin atmosphere as described below. Examples of organic solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, and decane; aliphatic N group R hydrogen atoms such as methylcyclopentane, cyclopentane, cyclooctane, cyclodecane, and cyclododecane; benzene; Examples include aromatic hydrocarbons such as toluene, xylene, cumene, and cymene.

Among the organic solvents, aromatic hydrocarbons are preferred.

In the method of the invention. The organometallic compound in the reaction system (
The degree of flaw in b) is usually 1 x 10- in terms of metal atoms.
' to 1 gram atom/J, preferably lXl0-'
and 0.1 gram atom/l, and the concentration of the transition metal compound in the reaction system is usually lXl0"" to 1 g atom/l, preferably lXl0-' to 0, in terms of transition metal atoms. .1 gram atom/1.

The temperature during the reaction is usually 0 to 100°C, preferably 10 to 80°C, and the time required for the reaction is usually 0 to 100°C.
．． The duration is 1 minute or more, preferably in the range of 1 minute to 200 minutes.

The catalyst component [B] used in the method of the present invention is aluminoxane. General formula (n) and general formula (I
[I) R1Ai→O-A l )-0-A ff R2(II
) can be exemplified by organoaluminum compounds represented by: In the 8-aminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, preferably a methyl group or an ethyl group, and particularly preferably a methyl group.1. is an integer of 2 or more, preferably 5 or more. The following method can be exemplified as a method for producing the aluminoxane.

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

(2) A method in which water is directly applied to trialkylaluminium in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, method (1) is preferably employed. Note that the aluminoxane may contain a small amount of organometallic component.

The organoaluminum compound (C) used as a catalyst component in the method of the present invention is an organoaluminum compound having a hydrocarbon group other than an n-alkyl group. n
- Hydrocarbon groups other than alkyl groups include alkyl groups having a branched chain such as isoalkyl, cycloalkyl groups,
Examples include aryl groups. Specifically, the organoaluminum compounds include triisopropylaluminium, triisobutylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-
Methylpentylaluminium, tri-4-methylpentylaluminium, tri-2-methylhexylaluminum,
trialkyl aluminum such as tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum, tricycloalkylaluminum such as tricyclohexylaluminum, triarylaluminum such as triphenylaluminum, tritolylaluminum,
Examples include dialkyl aluminum hydride such as diisobutyl aluminum hydride, alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide. Among these organoaluminum compounds, aluminum compounds having a branched alkyl group are preferred, and trialkylaluminum compounds are particularly preferred. Also preferred is isoprenylaluminum represented by the general formula %.

Note that there is no problem in adding a compound that forms the above-mentioned organoaluminum compound in the polymerization system, such as aluminum halide and alkyllithium or aluminum halide and alkylmagnesium.

In the method of the present invention, the olefin polymerization reaction can be carried out in 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 to be used when carrying out the method of the present invention is usually 101 to 10-2 gram atoms/l, preferably 10-7 to 10" as the concentration of the transition metal atom in the polymerization reaction system. 'The range is gram atom/1.

Further, in the method of the present invention, the amount of aluminoxane used is 3 milligram atoms/l or less, preferably 0.1 to 2 milligram atoms/l, particularly preferably 0.2 milligram atoms/l, in terms of aluminum atoms in the reaction system. and 1 milligram atom/l.

In addition, the aluminoxane component [B] in the reaction system
and the aluminoxane component [B
The proportion of aluminum atoms in ] is usually 20 to 80%
, preferably 25 to 75%, particularly preferably 30%
Similarly, the proportion of aluminum atoms in the organoaluminum compound component (C) is usually 20% to 70%.
It ranges from 80% to 80%, preferably from 25 to 75%, particularly preferably from 30 to 70%. In the method of the present invention, the ratio of aluminum atoms in the total amount of the aluminoxane component (B) and organoaluminum compound component (C) to the transition metal atoms in the reaction system is usually 20 to 10,000, preferably 50 to 5,000. ,
Particularly preferred is a range of 100 to 2000.

The method of the present invention is effective for producing olefin polymers, particularly ethylene polymers and ethylene and α-olefin coelectrics. Examples of olefins that can be used in the present invention include ethylene and α having 3 to 20 carbon atoms.
-Olefins, such as propylene, 1-butene, 1-
hexene, 4-methyl-1-pentene, 1-octene,
Examples include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

Polyenes such as dienes can also be copolymerized if necessary.

In the method of the invention, the olefin polymerization is usually carried out in the gas phase or in the liquid phase, for example in the form of a solution. In liquid phase polymerization, an inert hydrocarbon may be used as a solvent,
The olefin itself can also be used as a solvent.

Specifically, the hydrocarbon medium includes butane, isobutane,
Aliphatic hydrocarbons such as pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, alicyclic hydrocarbons such as cyclopentane, methylcyclobencune, cyclohexane, cyclooctane, benzene,
Examples include aromatic hydrocarbons such as toluene and xylene, petroleum fractions such as gasoline, kerosene, and light oil.

In the method of the present invention, the polymerization temperature is usually -50 to 2
00°C, preferably in the range of 0 to 120°C. The polymerization pressure is usually normal pressure to 100 kg/a (preferably normal pressure to 50 kg/cnf), and the polymerization can be carried out in any of the batch, semi-continuous, and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.The molecular weight of the polymer can be controlled by hydrogen and/or polymerization temperature.

〔Effect of the invention〕

When applied to olefin polymerization in the present invention, especially ethylene polymerization or copolymerization of ethylene and α-olefin, the present invention has the characteristic that it is extremely highly active even when using less aluminoxane than conventional methods (compared to conventional methods). can be,
Moreover, when it is used for copolymerization of two or more types of olefins, it is possible to obtain an olefin copolymer with a narrow molecular weight distribution and a narrow composition distribution.

[Example] Next, the method of the present invention will be specifically explained using Examples. In addition, in the examples and comparative examples, the MFR is at a temperature of 1
Measured at 90℃ and a load of 2.16kg, &/t
The inn value is measured as follows according to "Gel Permeation Chromatography" written by Takeuchi and published by Maruzen.

(1) Using standard polystyrene with a known molecular weight (manufactured by Toyo Soda ■, monodisperse polystyrene), calculate the molecular weight M and its G P C (Get Permeation Chr
omato-graph) counts and molecule i
A correlation diagram calibration curve between M and EV (Elution Volume) is created. The concentration at this time is 0.02 wt%.

(2) Obtain a GPC chromatograph of the sample by GPC measurement, calculate the number average molecular weight Inn and weight average molecular weight L in terms of polystyrene according to the above (1), and obtain the L/- value. The sample preparation conditions and GPC measurement conditions at that time are as follows.

[Sample preparation]

(b) Make the sample 0.1 company%. - Transfer into an Erlenmeyer flask together with dichlorobenzene solvent.

(b) Heat the Erlenmeyer flask to 140°C and apply the filtrate to GPC for about 30 minutes.

CG　PC　C measurement conditions〕 It was conducted under the following conditions.

(a) Mounting 'gl Made by Waters (150C
-ALC/GPC) (b) Column manufactured by Toyo Soda (
GMH type) (c) Sample amount 400μ! (d) Temperature: 140°C (e) Flow rate: n in 1+++f/ff1in copolymer
-Measurement of the amount of decane soluble portion (the smaller the amount of soluble portion, the narrower the composition distribution), approximately 3 g of the copolymer was mixed with 450 y of n-decane.
ml, dissolved at 145°C, cooled to 23°C, removed n-decane insoluble portion by filtration, and collected n-decane soluble portion from the filtrate.

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

B = "kL--2Po' PI [In the formula, PE represents the molar fraction of the ethylene component in the copolymer, Po represents the molar fraction of the α-olefin component, and poz represents the molar fraction of the entire dyad chain. [Indicates the mole fraction of α-olefin/ethylene chain] The above B value is an index representing the distribution state of each monomer component in the copolymer chain;
, J. Ray (Macro-molecules
, 10.773 (1977)), J. C. Randa.
ll(Macro-molecules, 15,35
3 (1982), J. Polymer 5science
.

Polymer Physics Ed, 11, 27
5 (1973)), K. Kimura (Polyme
PE, P, and P as defined above based on the report of J.R., 25, 441 (1984) et al. It is calculated by finding E. The larger the B value, the fewer block-like chains, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution of the copolymer.

The composition distribution B value is approximately 20% in a 10mmφ sample tube.
The C-NMR spectrum of a sample in which 0 mg of copolymer was uniformly dissolved in 1-hexachlorobutadiene was
Normally, measurement temperature is 120℃, measurement frequency is 25.05MHz
, spectrum width 1500Hz, filter width 15001
(z, pulse repetition time 4.2 sec, pulse width 7μ
It is calculated by measuring under the measurement conditions of 2000 to 5000 5eC1 integrations and determining Pt, Po, and POE from this spectrum.

Example 1 Aluminoxane! , ' A 7! in a 40011d flask that was sufficiently purged with nitrogen.
z(SO2)s ・14L037 g and toluene 125
After cooling to 0° C., 500 mmol of trimethylaluminum diluted with 125 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 white solid aluminoxane. The molecular weight determined by freezing point depression in benzene was 930, and the m value shown in catalyst component (B) was 14.

1-Toluene (500 g) was charged into a glass autoclave with an internal volume of 11 which had been sufficiently purged with nitrogen, and a mixed gas of ethylene and propylene (1201 g/hr each) was charged.

801/hr) and left at 20°C for 10 minutes.

Then, 0.5 mmol of triisobutylaluminum was added, and after 5 minutes, 0.25 mg atom of aluminoxane was added in terms of aluminum atom, followed by the addition of 2.5 x 10-3 mmol of bis(cyclopentadienyl) phenoxyzirconium monochloride. 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 the polymerization was completed, a small amount of methanol was added to stop the polymerization. Add the polymer solution to a large excess of methanol to precipitate the polymer, and heat at 130°C.
The mixture was dried under reduced pressure for 12 hours. As a result, MFR0,
21g/10m1n% "Ethylene content determined by C-NMR 185.5 mol%, &/Pn 2.35,
10.9 g of polymer with a B value of 1611 was obtained.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that triisobutylaluminum was not used in the polymerization, but no polymer was obtained.

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

Example 6 2) [A] - Bis(cyclobentadienyl)ethoxyzirconium monochloride dissolved in toluene in a 200-mm glass flask that was sufficiently purged with nitrogen. Liquid (Zr 1.35m
mof/l) 50- and further dimethylaluminum chloride (Al4mmol/j2)34
- was added and reacted at 25°C for 30 minutes to obtain catalyst component (2) [A].

Example 1 was carried out in the same manner as in Example 1, except that the catalyst component (2) [A] prepared above was used in place of bis(cyclopentadienyl)phenoxyzirconium monochloride.

Comparative Example 2 The polymerization of Example 6 was carried out in the same manner as in Example 6 except that triisobutylaluminum was not used, 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 listed in Table 1. The results are shown in Table 1.

Example 14 Into a stainless steel autoclave having an inner volume of 21 and which had been fully purged with nitrogen to 1 unit, 250 ml of hexane and 750 ml of 4-methyl-1-pentene were charged, and the temperature was raised to 35°C. Thereafter, 0.25 mmol of triisobutylaluminum and 0.25 mmol of the aluminoxane synthesized in Example 1 were added in terms of aluminum atoms.
．． 5 milligram atoms, the catalyst component synthesized in Example 6 (2
) [A] was charged in an amount of 1X10-' milligram atoms in terms of zirconium atoms. Subsequently, ethylene was introduced to start polymerization. Ethylene was continuously supplied so as to maintain the total pressure at 8 kg/ad-gauge, and polymerization was carried out at 45° C. for 1 hour.

The subsequent operations were performed in the same manner as in Example 1, and MFR0,62
g/10m1n, density 0.902 g/crA, l/mo 2.98, room temperature decane soluble weight fraction 1.9wt
% polymer was obtained.

Example 15 The polymerization of Example 14 was carried out in the same manner as in Example 14, except that 1-hexene was used in place of 4-methyl-1-pentene, and the MFR was 1.01 g/10n.
+in s density 0.891 g/cl, ~/&-
28.5 g of polymer of 2.79 was obtained.

Comparative Example 3 The same procedure as Example 14 was carried out except that triisobutylaluminum was not used in the polymerization of Example 14, and the MFR
1,94g/10m1n, density 0.908g/c
d, ~/lHn 2.95, and 2.5 g of a polymer having a room temperature decane soluble weight fraction of 1.1 wt% was obtained.

Example 16 Toluene was converted to 5001R using 11 continuous polymerization reactors.
1/hr, triisobutylaluminum 0.511R
IIIOl/hr, 0.5 milligram atom/hr in terms of aluminum atom of aluminoxane synthesized in the same manner as in Example 1, and catalyst component (2) [A] synthesized in the same manner as in Example 13 in terms of zirconium atom. So 5x
Continuously supplied at a rate of 10 milligram atoms/hr,
150j of ethylene at the same time in the polymerization vessel! /hr,
Propylene 1001/hr and 5-ethylidene-2-
Norbornene (ENB) was continuously supplied at a rate of 1.2 g/hr, polymerization temperature was 20°C, normal pressure, residence time was 1 hour,
Polymerization was carried out under conditions such that the polymer concentration was 14 g/It. The produced polymer was treated in the same manner as in Example 1.

In this way, M F R2,04g/10m1n,
Ethylene content ffl determined by I3C-NMR 85.8
Mol%, &/Mn2.49, ethylene value of iodine value 10.
Propylene-ENB copolymer

[Brief explanation of the drawing]

FIGS. 1 and 2 are flowchart drawings showing one example of the preparation of a catalyst for olefin polymerization according to the present invention. Applicant Mitsui Petrochemical Industries Co., Ltd. agent Yamaguchi Writ of procedural amendment (spontaneous) July 2, 1932 Commissioner of the Patent Office Kuro 1) Akio Tono1, Indication of case Patent Application No. 231242 of 19852, Title of the invention: Olefin polymerization method 3, relationship with the amended case Patent applicant (588) Mitsui Petrochemical Industries Co., Ltd. Representative: Shogo Takebayashi 4, Ryojin 3-chome Kasumigaseki, Chiyoda-ku, Tokyo 100 No. 2 No. 5, Part 5 of Mitsui Petrochemical Industries, Ltd., Detailed explanation of the invention in the specification on the date of the amendment order, 7, Contents of the amendment (1) On page 2 of the specification tube, line 4, it says “ ``Related to a method capable of producing an olefin polymer with a large molecular weight.'' should be corrected to ``Related to a method capable of producing an olefin polymer with a large molecular weight.'' (2) On page 10, line 1, add the following sentence after "There was." without a line break. [Furthermore, when α-olefins such as ethylene and propylene are copolymerized using catalysts formed from these conventionally known transition metal compounds and aluminoxane, polymers with sufficiently large molecular weights can be obtained. The disadvantage was that it was difficult to obtain. (3) Same No. 1
On page 0, lines 8-9, the statement ``As a result of studying methods for producing by polymerization activity,'' was changed to ``It was found that it is possible to easily produce α-olefin polymers that can be produced by polymerization activity and have a large molecular weight. As a result of considering possible methods, the following has been revised. (4) “It is said to be highly active” on page 29, lines 5-6.
The statement has been corrected to ``It is said that it is possible to obtain polymers with high activity and large molecular weight.'' (5) On page 38 of the same page, add the following sentence on a new line after the unlined "obtained." Comparative Example 4 The polymerization was carried out in the same manner as in Example 6, except that triisobutylaluminum was not used, aluminoxane was used at 2.5 milligrams in terms of aluminum atoms, and polymerization was carried out for 30 minutes. F R2,02g /
10mln, ethylene content 82.5mol%, parrot/¥
4n 2.11, 22.0 g of polymer with B value 1.14
was gotten. "that's all

Claims (2)

[Claims] (1) [A] A period containing a heteroatom-containing ligand capable of forming a bond between a transition metal atom and a heteroatom consisting of oxygen, sulfur, nitrogen, or phosphorus, and a ligand having conjugated π electrons, respectively. Polymerizing or polymerizing an olefin in the presence of a catalyst formed from a transition metal compound of Group IVB of the Table of Contents, [B] an aluminoxane, and [C] an organoaluminum compound having a hydrocarbon group other than an n-alkyl group. A method for polymerizing olefins, characterized by copolymerization. (2) [A] A period containing a heteroatom-containing ligand capable of forming a bond between a transition metal atom and a heteroatom consisting of oxygen, sulfur, nitrogen, or phosphorus, and a ligand having conjugated π electrons, respectively. A transition metal compound obtained by treating a transition metal compound (a) of Group IVB of the Table of Contents with an organometallic compound (b), and [B] an aluminoxane, and [C] a hydrocarbon 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 an organoaluminum compound having a group.