KR920001352B1 - Process for polymerizing olefin - Google Patents

Abstract

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Description

[Name of invention]

Polymerization Method of Olefin

Detailed description of the invention

[Technical Field]

The present invention relates to a polymerization method of olefins, and more particularly, when the olefins are polymerized by a catalyst exhibiting excellent polymerization activity in the use of less alinooxane, the molecular weight distribution is narrow and the molecular weight is applied to the copolymerization of two or more olefins. The present invention relates to a polymerization method capable of producing an olefin copolymer having a narrow distribution and composition distribution.

[Background]

[Prior art]

Conventionally, a method for producing an α-olefin polymer, in particular an ethylene copolymer or an ethylene-α-olefin copolymer, is ethylene or ethylene in the presence of a titanium catalyst made of a titanium compound and an organoaluminum compound or a vanadium catalyst made of a vanadium compound and an organic aluminum compound. And methods for copolymerizing α-olefins are known. In general, the ethylene-α-olefin copolymer obtained from a titanium catalyst has a wide molecular weight distribution and a composition distribution, and is not excellent in transparency, surface non-tackiness, and mechanical properties. In addition, the ethylene-α-olefin copolymer obtained by the vanadium catalyst has a narrower molecular weight distribution and composition distribution than the titanium catalyst, and the transparency, surface non-tackiness, and mechanical properties are significantly improved, but they are insufficient for applications requiring their performance. It was. Therefore, there is a need for α-olefin polymers, in particular ethylene-α-olefin copolymers, in which their performance is further improved. On the other hand, a catalyst of a zirconium compound and an aminooxane has recently been proposed as a new Ziegler type olefin polymerization catalyst.

Japanese Patent Laid-Open No. 58-19309 discloses the following formula,

Wherein R ¹ is cyclopentadienyl, C ₁ -C ₈ -alkyl, halogen, Me is a transition metal, and Hal is halogen.

The transition metal-containing compound and the following formula,

Wherein R ² is methyl or ethyl and n is a number from 4-20.

Linear alinoxane or the following formula represented by

Here, the definitions of R ² and n are as above.

A method of polymerizing one or two or more of ethylene and an α-olefin of C ₃ -C ₁₂ at a temperature of -50 ° C -200 ° C in the presence of a catalyst of cyclic aminooxane represented by is described. The publication states that in order to control the density of the resulting polyethylene, polymerization of ethylene must be carried out in the presence of small amounts of long chain α-olefins or mixtures of up to 10% by weight.

Japanese Patent Laid-Open No. 59-92292 discloses the following formula,

Wherein n is 2-40 and R ³ is C ₁ -C ₈ alkyl.

Linear aminooxanes represented by

Here, the definitions of n and R ³ are as above.

The invention regarding the manufacturing method of cyclic aminooxane represented by is described. The publication contains a mixture of, for example, methylaminooxane and bis (cyclopentadienyl) compounds of titanium or zirconium, prepared by the same method, for the polymerization of olefins. It is described that polyethylene can be obtained.

Japanese Patent Application Laid-Open No. 60-35005 discloses the following formula,

Here, R ⁴ is C ₁ -C ₁₀ alkyl, and R ⁰ is bonded to R ⁴ to represent —O—.

A method for producing an olefin polymerization catalyst is disclosed by first reacting an aminooxane compound represented by a magnesium compound, followed by chlorination of the reaction product, and further treatment with a compound of Ti, V, Zr or Cr. The publication describes that the catalysts are particularly suitable for the copolymerization of mixtures of ethylene and C ₃ -C ₁₂ α-olefins.

4.56 및 프로필렌성분 20.6몰%의 가용성 부분과 분자량 분포 3.04 및 프로필렌 성분 2.9몰%의 불용성 부분으로 된 LL DPE와 에틸렌 프로필렌 공중합체의 브랜드물이 기재되어 있다.Japanese Patent Application Laid-Open No. 60-35006 discloses mono, di or tri-cyclopentadienyl or derivatives thereof of two or more different transition metals as catalyst systems for the production of reactor brand polymers (a) and aminooxanes (alminooxanes) (b). The combination of is disclosed. Example 1 of this publication contains bis (pentamethylcyclopentadienyl) zirconium dimethyl and aminooxane as catalysts to polymerize ethylene and propylene 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 to be obtained is obtained. In Example 2, ethylene and propylene were polymerized using bis (pentamethylcyclopentadienyl) zirconium dichromide, bis (methylcyclopentadienyl) zirconium dichromide and aminooxane as catalysts. A number average consisting of a toluene soluble portion containing a number average molecular weight of 2,200, a weight average molecular weight of 11,900 and a 30 mol% propylene component, and a toluene insoluble portion containing a number average molecular weight of 3,000, a weight average molecular weight of 7,400 and a 4.8 mole percent propylene component. Brand products of ethylene and an ethylene-propylene copolymer containing a propylene component having a molecular weight of 2,000, a weight average molecular weight of 8,300, and 7.1 mol% are obtained. Thus in Example 3, the molecular weight distribution

A brand of LL DPE and an ethylene propylene copolymer with 4.56 and a soluble portion of 20.6 mol% of propylene component and a molecular weight distribution 3.04 and an insoluble portion of 2.9 mol% of propylene component is described.

Japanese Patent Application Laid-Open No. 60-35007 discloses ethylene alone or in combination with an α-olefin having 3 or more carbon atoms.

R ⁵ is a C 1-5 alkyl group and n is an integer of 1 to about 20.

Cyclic aminooxanes represented by

Here, the definitions of R ⁵ and n are as above.

A method of polymerization in the presence of a catalyst system containing linear aminooxanes represented by is described. The polymer obtained by this method has a weight average molecular weight of about 500 to about 1.4 million according to the description of the publication and also has a molecular weight distribution of 15 to 4.0.

2-50을 갖는 것이 기재되어 있다.Also, Japanese Patent Application Laid-Open No. 60-35008 discloses the production of polyethylene or ethylene and C ₃ -C ₁₀ α-olefin copolymers having a broad molecular weight distribution by using a catalyst system containing at least two metallocenes and almooxanes. It is described. The publication discloses that the copolymer has a molecular weight distribution.

It is described to have 2-50.

Catalysts formed of these transition metal compounds and aminooxanes are remarkably superior in polymerization activity compared to conventionally known catalyst systems.

On the other hand, a method of using a catalyst formed of a solid catalyst component and an aminooxane supported by the transition metal compound on a porous inorganic oxide carrier such as silica, silica, alumina or alumina is disclosed in Japanese Patent Application Laid-Open No. 60-35006, It is proposed in Japanese Patent Laid-Open No. 60-35007 and Japanese Patent Laid-Open No. 60-35008. Further, Japanese Patent Application Laid-Open Nos. 61-31404, 61-108610, and 60-106808 disclose a method of using a solid catalyst component supported on a similar porous inorganic oxide carrier.

In addition, Japanese Patent Application Laid-Open No. 60-260602 and Japanese Patent Application Laid-Open No. 60-130604 propose a method of polymerizing an olefin using a transition metal compound and a catalyst formed of a mixed organic aluminum compound composed of an aluminoxane and an organoaluminum compound.

That is to Japanese Patent Application Laid-Open No. 60-260602

(1) As a transition metal compound,

Wherein C _p is cyclopentadienyl, M is Ti, V, Zr or Hf, and R ⁶ , R ⁷ and R ⁸ are each C ₁ -C ₆ alkyl, cyclopentadienyl, halogen or Represents hydrogen.

Using the compound represented by (2) as the organic aluminum compound, (2) -1. Alminooxane synthesized from trialkylammonium and water and (2) -2. Formula

Wherein R ⁹ is C ₁ -C ₁₀ , alkyl, cycloalkyl or allyl, X is halogen and n is a number from 1-3.

A method for producing a polyolefin by polymerizing an olefin using a compound represented by is disclosed. Examples of this publication describe an example of polymerizing ethylene in a system containing 3 mmol of aminooxane, 3 mmol of triethylaluminum and 0.003 mmol of bis (cyclopentadienyl) zirconium chromide in 400 ml of toluene as a polymerization medium. It is.

In Japanese Patent Application Laid-Open No. 60-130604,

(1) the following formula

Wherein Cp is cyclopentadienyl, M is T, Zr or Hf and R ¹⁰ and R ¹¹ are H, halogen C ₁ -C ₆ alkyl or cyclopentadienyl, respectively.

Transition metal compound represented by.

(2) the following formula

Wherein R ¹² is methyl or ethyl and X ¹ is halogen.

Alminooxane obtained by reaction of dialkyl monohydride represented by water, and

(3) the following formula

Wherein R ¹³ is C ₁ -C ₁₀ alkyl or cycloalkyl, X ² is halogen and m is a number from 1-3.

A method for producing polyolefins by polymerizing olefins using a catalyst composed mainly of an organic aluminum compound represented by In the examples of the publication, the amount of aminooxane used is 4.5 mmol (Examples 1-4 and 8), 3.6 mmol (Example 5), 3.25 mmol (Example 6), 10.0 mmol (per 400 ml of toluene as a polymerization medium). Example 7) and 9.0 mmol (Example 9) are described.

An object of the present invention is to provide an olefin copolymer having a narrow molecular weight distribution and a composition distribution, particularly a high molecular weight ethylene-α-olefin copolymer having a narrow molecular weight distribution and a composition distribution, when the molecular weight distribution is narrow and the copolymerization of two or more kinds of olefins is carried out. It is to provide a method for producing a good polymerization activity in the use of less aminooxane.

Another object of the present invention is an olefin copolymer having an excellent powder phase, a narrow molecular weight distribution, and furthermore, a copolymer of two or more kinds of olefins, in particular an olefin copolymer having a narrow molecular weight distribution and a composition distribution, in particular, having an excellent powder phase and a molecular weight distribution and / or composition distribution. A method for producing a narrow ethylene polymer or ethylene-α-olefin copolymer.

[Initiation of invention]

According to the present invention, these objects and advantages of the present invention are firstly,

(A) Solid catalyst component in which an inorganic carrier carries a compound of transition metal of group IVB of the periodic table

(B) aminooxanes and

(C) A polymerization of olefins is achieved by polymerizing or copolymerizing olefins in the presence of a catalyst made of an organoaluminum compound having a hydrocarbon group other than an n-alkyl group.

The catalyst of the present invention is formed of an organoaluminum compound (C) having a hydrocarbon group other than the solid catalyst component (A), the alminooxanes (B) and the n-alkyl group. The catalyst component (A) is a solid catalyst component in which a transition metal compound of group IVB of the periodic table is supported on a carrier.

In the catalyst component (A), the transition metal of Group IVB of the periodic table is preferably selected from the group consisting of titanium, zirconium and hafnium, for example. Among these, titanium and zirconium are more preferable, and among them, zirconium is particularly preferable.

As the transition metal compound of Group IVB of the periodic table in the catalyst component (A), for example, a transition metal compound having a ligand having a group having conjugated? Electrons can be mentioned.

Examples of transition metal compounds having a group having a conjugated? Electron as a ligand include the following formula (I),

Here, R ¹ represents a cycloalkadienyl group, R ² , R ³ and R ⁴ are the same or different cycloalkadienyl group, aryl group, alkyl group, cycloalkyl group, aralkyl group, halogen atom, hydrogen atom, Group-OR ^a , -SR ^b or -NR ₂ ^c , and R ^a , R ^b and R ^c are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organylsilyl group.

Me is zirconium, titanium or hafnium and K is 1, 2, 3 or 4. l, m, n are each 0, 1, 2 or 3 and k + l + m + n = 4.

The compound represented by these is mentioned.

As a cycloalkadienyl group which R <^1> represents, a cyclopentadienyl group, a methyl cyclopentadienyl group, an ethyl cyclopentadienyl group, a dimethyl cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group etc. are illustrated, for example. can do. As an aryl group which R <^2> , R <^3> and R <^4> represent, a phenyl group, a toryl group, etc. can be illustrated as a preferable thing, for example.

As an aralkyl group, a benzyl group, a neofill group, etc. can be illustrated as a preferable thing, for example.

Moreover, as an alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, a hexyl group, an octyl group, 2-ethylhexyl group, a decyl group, an oleyl group etc. are mentioned, for example.

As a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a nobornyl group etc. are mentioned as a preferable thing, for example. In addition, examples of the halogen atom include fluorine, chlorine, and cancellation.

And embodiments of the groups -OR ^a , -SR ^b and NR ₂ ^c are evident in the above embodiments of their groups when -R ^a , -R ^b and R ^c are alkyl, cycloalkyl, aryl and aralkyl something to do.

The organic silyl group of R ^a, R ^b and R ^c may be for example, trimethyl silyl group, triethyl silyl group, a phenyl dimethyl silyl group, diphenylmethyl silyl group, and a triphenyl silyl group.

In said Formula (1), the following compound can be illustrated as a zirconium compound whose Me is zirconium.

In addition, in said Formula (1), the following compound can be illustrated as a titanium compound whose Me is titanium.

In the formula (1), the following compounds can be exemplified as a hafnium compound in which Me is hafnium.

In the catalyst component (A), the transition metal compound of Group IVB of the periodic table may be previously treated with an organometallic compound or a halogen-containing silicon compound before supporting. Examples of the organometallic compound include organic aluminum, organic boron, organic magnesium, organic zinc, organic titanium, and the like. Of these, organic aluminum compounds are preferred.

(여기에서, R¹및 R²는 알킬기이다)로 표시되는 평균조성을 갖는 부분적으로 알콕시화된 알킬알미늄, 디메틸알미늄크로라이드, 디에틸알미늄크로라이드, 디메틸알미늄브로마이드와 같은 디알킬알미늄할라이드, 메틸알미늄 세스키크로라이드, 에틸알미늄세스키크로라이드와 같은 알킬알미늄 할라이드, 메틸알미늄디크로라이드, 에틸알미늄 디크로라이드와 같은 알킬알미늄디할라이드등의 부분적으로 할로겐화된 알킬알미늄 등을 예시할 수 있다.As an organic aluminum compound, For example, trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, and tributyl aluminum, alkenyl aluminum, such as isoprenyl aluminum, dimethyl aluminum methoxide, diethyl aluminum ethoxide, and dibutyl aluminum butoxide Alkyl aluminum sesky alkoxides, such as dialkyl aluminum alkoxide, methyl aluminum sesquimethoxide, and ethyl aluminum sesquiethoxy, etc.

Partially alkoxylated alkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dialkylaluminum halides such as dimethylaluminum bromide, methylaluminum having an average composition represented by (wherein R ¹ and R ² are alkyl groups) Partially halogenated alkyl aluminum, such as an alkyl aluminum halide such as cesky chromide and an ethyl aluminum seski chromide, an alkyl aluminum di halide such as methyl aluminum dichromide, and an ethyl aluminum dichromide, may be exemplified.

Trialkylaluminum dialkylaluminum chromides are preferred, and trimethylaluminum triethylaluminum and dimethylaluminum fluoride are particularly preferred.

As an organoboron compound, triethyl boron can be illustrated as a preferable thing, for example.

Examples of the organomagnesium compound include ethylbutyl methyl, di-n-hexane magnesium, ethyl magnesium bromide, phenylmagnesium bromide, benzyl magnesium chloride and the like.

As an organic zinc compound, diethyl zinc can be illustrated as a preferable thing, for example.

Examples of the organolithium compound include methyllithium, butylithium, phenyllithium and the like. As the organometallic compound (c), organoaluminum is preferable. Moreover, as a halogen-containing silicon compound as a processing agent, it is following formula (IV),

Here, Y is a chlorine atom or a cancel atom, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group or a cycloalkyl group having 3 to 12 carbon atoms.

d is a number from 1-4 and e is a number from 0-4. However, the sum of d and e is a number of 1-4.

The compound represented by is used preferably.

As such a compound, for example, silicon tetrachloride, silicon tetrachloride, silicon trichloride, methyl trichloride, ethyl trichloride, propyl silicon trichloride, silicon trichloride, tricyclohexyl silicon, trifluorosilicon, Triethylethyl trichloride, dimethylsilicon dichloride, methyldichlorochloride, phenylsilicon dichloride, methoxysilicon trichloride, ethoxysilicon trichloride, propoxysilicon trichloride, phenoxychloride, triethoxyethoxysilicone, 2 Methoxy silicon chloride, dimethoxysilicon dichloride, trichlorosilane, and the like can be exemplified. This can be used 1 type or in combination or 2 or more types. Among these, silicon tetrachloride, silicon trichloride, and methyl trichloride are preferable.

The mixing ratio of the organometallic compound and the inorganic carrier in the treatment is in the range of 0.5 to 50, preferably 1 to 30, and more preferably 1.5 to 20 as the gram ratio of millimoles / carriers of the organometallic compound.

In the catalyst component (A), treatment of the inorganic carrier with the organometallic compound is carried out by dispersing the carrier in an inert solvent and then adding one or two or more of the organometallic compounds to 0 to 120 ° C, preferably 10 to The treatment may be carried out at a temperature of 100 ° C., more preferably at 20 ° C. to 90 ° C., for 10 minutes to 10 hours, preferably 20 minutes to 5 hours, more preferably 30 minutes to 3 hours at atmospheric pressure, under reduced pressure or under pressure.

Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane and isooctane, and alicyclic hydrocarbons such as cyclohexane.

The mixing ratio of the halogen-containing silicon compound and the inorganic carrier in the treatment is in the range of 0.001 to 10 mol, preferably 0.01 to 50 mol, more preferably 0.05 to 1 mol of the halogen-containing silicon compound per 1 g of the carrier compound. In addition, it is preferable to remove the liquid phase containing the surplus halogen compound and the like from the reaction mixture after the treatment by filtration or gradient.

The treatment of the inorganic carrier with the halogen-containing silicon compound in the catalyst (A) is from 10 to 10 hours, preferably from 0 to 100 ° C, more preferably from 20 to 70 ° C, preferably Can be performed for 20 minutes to 5 hours at atmospheric pressure, reduced pressure or under pressure.

An inert solvent may be used during the treatment. Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, isooctane, and decane, chlorobenzene, and ethylene dichloride. And halogenated hydrocarbons.

In the catalyst component (A), when the transition metal compound of the periodic table Group IVB is supported on the inorganic carrier, it is not necessary to use an inert solvent when the transition metal compound is a liquid substance, but when the transition metal compound is a solid substance at room temperature It is generally preferable to use an inert solvent capable of dissolving this transition metal compound.

As an inert solvent which can be used at this time, the inert solvent which may be used when processing an inorganic support with a halogen containing silicon compound can be illustrated. In particular, aromatic hydrocarbons such as benzene and toluene or halogenated hydrocarbons such as chlorobenzene are preferable.

The amount of the transition metal compound used in the supporting reaction is in the range of 0.001 to 500 mmol, more preferably 0.01 to 100 mmol, particularly 0.1 to 50 mmol, per 1 g of the inorganic carrier.

The amount of the inert solvent used in the supporting reaction is in the range of 0.5 to 1000 ml, preferably 1 to 100 ml, especially 2 to 50 ml, per 1 g of the inorganic carrier treated with the halogen-containing silane compound.

In addition, the supporting reaction is carried out at 1 to 10 hours, 5 to 5 hours, 10 minutes to the inorganic carrier and the transition metal compound at a temperature in the range of 0 to 200 ℃, preferably 0 to 100 ℃, especially 20 to 80 ℃ It can carry out by carrying out contact mixing for 3 hours.

After carrying out the supporting reaction by the above method, it is preferable to remove the liquid phase in the reaction mixture by a method such as filtration or decantation and to wash several times with an inert solvent.

In the catalyst of the present invention, the solid catalyst component (A) is a carrier of a compound of the transition metal of Group IVB of the periodic table as described above.

As the inorganic carrier, for example, a granular or fine particulate solid having a particle diameter of 10 to 300 m, more preferably 20 to 200 m is advantageously used. As the inorganic carrier, a porous oxide is preferable, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a mixture thereof, for example, SiO ₂ -MgO, SiO-Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO and the like can be exemplified. Among these, a carrier containing as a main component at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ is preferred.

In addition, the inorganic oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Al (NO ₃₎ ) _3, Na ₂ O, may contain the carbonate, sulfate, nitrate, oxide component, such as K ₂ O, Li ₂ O is no hindrance.

Porous inorganic carriers differ in their properties by their type and preparation method, but carriers preferably used in the present invention have a specific surface area of 50 to 1000 m ² / g, more preferably 100 to 700 m ² / g, and pore volume of 0.3 to 2.5. cm ² / g. This carrier is usually used by firing at 150 to 1000 캜, preferably at 200 to 800 캜.

In the catalyst component (A) according to the present invention, the transition metal compound of Group IVB of the Periodic Table of the inorganic carrier treated with the organometallic compound is converted into a transition metal atom in the range of 3 x 10 ^-3 to 3 milligram atoms, preferably 5 x 10- ^{. 3} to 2 milligram atoms, more preferably 1 x 10 ^-2 to 1 milligram atoms.

In addition, for 1 g of the inorganic carrier treated with the halogen-containing silicon compound, the transition metal compound is usually contained in 0.005 mmol to 5 mmol, preferably 0.01 mmol to 1 mmol, particularly preferably 0.03 mmol to 0.3 mmol.

Catalyst component (B) is an aminooxane. As the aminooxanes used as the catalyst component (B), for example, the following formula (II)

Here, R is a hydrocarbon group, X is a halogen atom, and a and b are the numbers of 0-80 independently of each other. Provided that a and b are not zero at the same time (the degree of polymerization in this transplant is a + b + 2)

Or lower formula (III)

Here, the definition of R, X, a, and b can be the same as that of Formula (II) (the polymerization degree is a + b in transplantation), and the organic aluminum compound can be illustrated.

In the formulas (II) and (III), R is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an arylalkyl group. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, are preferable, for example. As a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are preferable, for example. As an aryl group, a phenyl group and a toryl group are preferable, for example. As the aralkyl group, for example, a pen group and a neofill group are preferable. Of these, alkyl groups are particularly preferred.

X is a halogen atom, for example, fluorine, chlorine, cancellation, oxo, and especially chlorine is preferable.

a and b are independently of each other a number from 0-80. However, a and b are not zero at the same time.

When b is 0, Formula (II) is represented by Formula (II) -1

Here, the definitions of R and a are as above.

In addition, the formula (III) is represented by the following formula (III) -1

Here, the definitions of R and A are as above.

Is displayed.

In Formula (II) -1, a is preferably 2-50, More preferably, it is 4-30. In formula (III) -1, a is preferably 4-52, and more preferably 6-32.

a is preferably 0-40, more preferably 3-30. And b is preferably 1-40, more preferably 3-30. The value of a + b is preferably 4-50, more preferably 8-30.

는 블록적으로 결합되어 있거나 랜덤결합되어 있어도 좋다.In the formulas (II) and (III), two units

May be combined blockwise or randomly coupled.

In formulas (II) and (III), when a is 0, the following formula (V) together with the halogenated aminooxane

R ⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, Z is a halogen atom, and f is a number of 1-3.

It is preferable to use together the organoaluminum compound represented by. Thus, as an organoaluminum compound, a trimethyl aluminum, a triethyl aluminum, a tributyl aluminum, a trihexyl aluminum, diethyl aluminum, a chromide, an ethyl aluminum ses cellulose, etc. can be illustrated, for example.

In this case, the halogenated aminooxane and the organometallic compound are preferably used in an amount of 0.1 to 10 moles, preferably 0.3 to 3.0 moles, particularly 0.5 to 2.0 moles, with respect to 1 mole of Al atoms in the halogenated aminooxane.

The manufacturing method of this aminooxane or halogenated aminooxane can illustrate the following method, for example.

(1) Compounds containing adsorbed water and salts containing crystallized water, such as magnesium chloride hydrate, nickel sulfate hydrate, and first cerium chloride hydrate, for example, benzene, toluene, ethyl ether, tetrahydrofuran, etc. A trialkyl aluminum or dialkyl aluminum monohalide is reacted while suspended in a medium of.

(2) A method in which water is directly applied to trialkylaluminum and / or dialkylaluminum monohalide in a medium such as benzene, toluene, ethyl ether, tetrahydrofuran or the like.

It is preferable to employ | adopt the method of (1) among these methods. In addition, this aminooxane may contain a small amount of organometallic components.

The catalyst component (C) is an organic aluminum compound having a hydrocarbon group other than the n-alkyl group. As a hydrocarbon group other than n-alkyl group, the alkyl group which has a branched chain, such as isoalkyl, a cycloalkyl group, an aryl group, etc. can be illustrated, for example. As this organoaluminum compound, for example, triisopropyl aluminum, triisobutyl aluminum, tri 2-methyl butyl aluminum, tri 3-methyl butyl aluminum, tri 2-methyl pentyl aluminum, tri 3-methyl pentyl aluminum, tri 4-methyl Trialkyl aluminum, such as pentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methylhexyl aluminum, and tri 2-ethylhexyl aluminum, tricyclo, such as tricyclo hexyl aluminum, alkyl aluminum, triphenyl aluminum, tritoryl aluminum, etc. And alkyl aluminum alkoxy such as dialkyl aluminum hydride such as triallyl aluminum and diisobutyl aluminum hydride, isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide. Among these organic aluminum compounds, organic aluminum compounds having a branched alkyl group are preferred, and trialkyl aluminum compounds are particularly preferred. Another general formula

Isoprenyl aluminum represented by (x, y, z is a positive number and Z ≧ 2x) is also preferably used. In addition, a compound in which the organoaluminum compound is formed in the polymerization system, for example, a combination of aluminum halide and alkyllithium or a combination of aluminum halide and alkyl magnesium may be used.

In the method of the present invention, the polymerization of the olefin is carried out by any of liquid phase polymerization methods such as slurry polymerization method and solution polymerization method or gas phase polymerization method. Alternatively, the prepolymerization may be performed using a small amount of olefin prior to the polymerization of the olefin.

Prepolymerization is carried out in (1) solvent-free or (2) inert hydrocarbon media. Among these methods, the method of (1) is preferable. At this time, it is preferable to first mix the catalyst components (A) and (B) in an inert hydrocarbon medium, and then increase the room temperature or temperature, and remove the solvent using, for example, Evapore under normal pressure or reduced pressure. The molar ratio (Al / transition metal atom) of the aluminum atom of the catalyst component (B) to the transition metal atom of the catalyst component (A) in the prepolymerization treatment is 20 to 5,000, preferably 25 to 2000, more preferably It is in the range of 1000.

The prepolymerization temperature is in the range of -20 ° C to 70 ° C, preferably -10 ° C to 60 ° C, more preferably 0 ° C to 50 ° C.

This treatment can be either batch or continuous, and can be carried out either under reduced pressure, atmospheric pressure or under pressure. In prepolymerization, a molecular weight modifier such as hydrogen may coexist, but a prepolymer having an intrinsic viscosity [η] of at least 135 ° C. in decarin of at least 0.2 dl / g, preferably 0.5 to 20 dl / g can be prepared. It is good to suppress the amount.

The use ratio of this transition metal compound (A) when the method of the present invention is carried out by slurry polymerization method or gas phase polymerization method is usually 10 ^-8 to 10 ^-2 gram atoms / L as the concentration of the transition metal atom in the polymerization reaction system. The following ranges from 10 ⁻⁷ to 10 ⁻³ gram atoms / L.

In the method of the present invention, the amount of the aminooxane (B) used is 3 mg / l or less, preferably 0.1 to 2.5 mg / l, and preferably 0.2 to 2 mg / ml, in terms of aluminum atoms in the reaction system. is in the range of l. Moreover, the ratio of the aluminum atom of the aminooxane component (B) to the total amount of the aluminum of the sum of the aminooxane component (B) and the organic aluminum compound component (C) in the reaction system is usually 20 to 80%, preferably 25. To 75%, particularly preferably 30 to 70%, and the proportion of the aluminum atoms of the organoaluminum compound component (C) corresponding to this amount is usually 20 to 80%, preferably 25 to 75%, in particular Preferably it is 30 to 70% of range. In the method of the present invention, the ratio of the aluminum atoms in the total amount of the aminooxane component (B) and the 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. Below is the range of 100-2000.

According to the catalyst of the present invention, polymerization or copolymerization of olefins can be advantageously performed.

According to the research of the present inventors, a ligand containing a hetero atom selected from the group consisting of transition metals, oxygen, sulfur, nitrogen, or phosphorus in the Group IVB of the periodic table as the transition metal compound of the catalyst system and which can be bonded to the transition metal And a transition metal compound composed of a ligand having conjugated π electrons, it is not necessary to carry the transition metal compound on an inorganic carrier, and thus has excellent activity as in the catalyst system composed of the components (A), (B) and (C). It was obvious.

Therefore, according to the present invention, there is provided a ligand comprising a heteroatom selected from the group consisting of transition metals, oxygen, sulfur, nitrogen or phosphorus of Group IVB of the Periodic Table (A ') and bondable to the transition metal and Characterized in that the olefin is polymerized or copolymerized in the presence of a catalyst made of a transition metal compound having a ligand having a conjugated π electron, (B) an alminooxane and (C) an organoaluminum compound having a hydrocarbon group other than the n-alkali group. There is provided a polymerization method of an olefin. As said transition metal compound (A '), for example, following formula (I)'

Wherein R ¹¹ is cycloalkadienyl, R ¹² is ^a group selected from the group consisting of -OR ^a , -SR ^b , NR ₂ ^c and -PR ₂ ^d , and R ¹³ and R ¹⁴ independently seek each other Ralkadienyl, aryl, aralkyl, halogen or hydrogen atom, R ^a , R ^b and R ^c are alkyl, cycloalkyl aryl, aralkyl or organosyl, Me is zirconium, titanium or hafnium, k And l is 1.2 or 3, m and n are 0.1 or 2, and k + l + m + n = 4.

The compound represented by is used suitably.

In the method of the present invention using the catalyst system of the catalyst components (A) (B) and (C), the preferred concentrations of use and the mutually preferred ratios of the respective catalyst components (A '), (B) and (C) It should be understood that it is the same as the catalyst system.

Further, according to the research of the present inventors, the aluminoxane was prepared as described above by the catalyst system composed of the components (A), (B) and (C) and the catalyst system composed of the components (A '), (B) and (C). It was evident that the amount of used was 3 mg / l or less in terms of aluminum atom in the reaction system, so that excellent catalytic activity could be exhibited.

When the amount of the aminooxane is limited to 3 mg / l or less in terms of aluminum atoms in the reaction system, any of the compounds represented by the above formula (I) as a transition metal compound of group IVB of the periodic table is inorganic. It was also clear that the same excellent catalytic activity could be exhibited by using it without being supported on a carrier.

Therefore, according to the present invention, the third concentration (A ″) of the transition metal compound of group IVB of the periodic table, (B) aminooxane, and the concentration in the reaction system is 3 mg / l or less in terms of aluminum atom. And (C) polymerizing or copolymerizing the olefin in the presence of a catalyst made of an organoaluminum compound having a hydrocarbon group other than the n-alkyl group.

As the transition metal compound (A ″), the same compound as the compound represented by formula (I) can be used.

Alminooxane (B) and an organoaluminum compound (C) can use the same thing as mentioned above.

In the above method of the present invention, the catalyst components (A ″), (B) and (C) may be respectively supplied to the reaction system, a mixture of the two catalyst components in advance, and the other one of the catalyst components may be supplied to the reaction system, respectively. After mixing all components previously, you may supply to a reaction system. In mixing the two catalyst components in advance, it is preferable to mix the catalyst components (A) and (B) in advance.

The premixing of the catalyst components (A) and (B) is a concentration of transition metal atoms, usually 2.5 × 10 −4 to 1.5 × 10 −1 gram atoms / L, preferably 5.0 × 10 −4 to 1.0 × 10 − It is in the range of 1 gram atom / l, and the concentration of the alminooxane is usually in the range of 0.05 to 5 gram atoms / l, preferably 0.1 to 3 gram atoms / l in terms of aluminum atoms. The concentration in the premix is usually -50 to 100 ° C, and the mixing time is usually 0.1 minutes to 50 hours.

It is to be understood that the preferred use concentrations and the preferred use ratios in the polymerization reactions of the respective catalyst components (A ″), (B) and (C) are the same as those of the catalyst system.

Any catalyst of the present invention described above can be advantageously used for homopolymerization or copolymerization of olefins. It is especially effective for the production of ethylene polymers and copolymers of ethylene and α-olefins.

Examples of olefins that can be used in the present invention are ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1- Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.

In the method of the present invention, polymerization of olefins is usually carried out in a gaseous phase or a liquid phase, for example, in the form of a slurry. In slurry polymerization, an inert hydrocarbon may be used as a solvent and olefin itself may be used as a solvent.

Specific examples of the hydrocarbon solvent include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane, cyclopentane, methylcyclopentane, cyclohexane and cyclooctane. And alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, petroleum such as volatiles, kerosene and diesel. Among these hydrocarbon media, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, petroleum fractions and the like are preferable.

In performing the slurry polymerization method in the method of the present invention, the polymerization temperature is usually in the range of -50 to 120 ° C, preferably 0 to 100 ° C.

In the method of the present invention, the use ratio of the transition metal compound in the slurry polymerization method or the gas phase polymerization method is usually 10 ^-8 to 10 ^-2 gram atoms / L as the concentration of the transition metal atom in the polymerization reaction system. ^-7 to 10 ^-3 gram atoms / l.

In addition, in the present polymerization reaction, the aminooxane may or may not be additionally used, but in order to obtain a polymer having excellent powder property, it is preferable that no aminooxane is used.

The polymerization pressure is usually under a pressurized condition of from 100 to 100 kg / cm ² , preferably from 2 to 50 kg / cm ² , and the polymerization may be carried out by any of batch, semi-continuous and continuous methods.

Moreover, superposition | polymerization can also be performed in 2 or more steps from which reaction conditions differ.

When the slurry polymerization method or the gas phase polymerization method is employed for the olefin polymers, especially ethylene polymerization or ethylene and α-olefin polymerization, in the present invention, there is no adhesion to the polymer in the reactor, the powdery phase is excellent, and the molecular weight distribution is narrow. When applied to the copolymerization of olefins of species or more, an olefin copolymer having a narrow molecular weight distribution and a composition distribution can be obtained.

EXAMPLE

값의 측정은 다께우찌저마루젠 발생의“겔퍼미에이숀·크로마토그래피”에 준하여 다음과 같이 행한다.Next, the method of this invention is demonstrated concretely by an Example. Also

The measurement of the value is carried out as follows in accordance with "gel permeation chromatography" of Tochigi Maruzen generation.

(1) Molecular weight M and its GPC (Gel Permeation Chromatograph) count were measured using a standard molecular weight known polystyrene (manufactured by Toyo Soda Co., Ltd.), and the correlation between molecular weight M and EV (Elutoon Volume) was corrected. Make a curve. The concentration at this time is 0.02 ml.

중량평균분자량

를 산출하고

를 구한다. 그때의 샘플 조제조건 및 GPC의 측정조건은 아래와 같다.(2) GPC chromatograph of sample was taken by GPC measurement, and the number average molecular weight of polyethylene conversion according to (1).

Weight average molecular weight

Yields

Obtain Sample preparation conditions and GPC measurement conditions at that time are as follows.

Sample preparation:

(A) Samples are divided into three flasks with a 0-dichlorobenzene solvent to make 0.1wt%.

(B) The triangular flask is heated to 140 ° C and stirred for about 30 minutes to dissolve.

(C) The filtrate is measured by GPC.

GPC measurement condition:

It carried out on the following conditions.

(A) Device undus company (150C-ALC / GPC)

(B) Column Toyo Soda Co., Ltd. product (GMH type)

(C) Sample volume 400μl

(D) Temperature 140 ℃

(E) Flow rate 1ml / min

The measurement of n-decane soluble amount in the copolymer (the smaller the soluble amount is, the narrower the compositional distribution) is that about 3 g of the copolymer is added to 450 ml of n-decane, dissolved at 145 ° C, cooled to 23 ° C, and filtered by n-. This was done by removing the decane insolubles and recovering the n-decane solubles in the filtrate.

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

(Wherein P _E represents the mole fraction of the ethylene component in the copolymer, P _O represents the mole fraction of the α-olefin component, and P _OE represents the mole fraction of the α-olefin and ethylene chains of all the dyad chains) B Values are indicative of the distribution state of each monomer component in the copolymer chain, GJ Ray (Macromolecules, 10.773 (1977), JC Randall (Macromolecules, 15, 353 (1982)), J Polymer Science, Polymer Physics Calculated by obtaining P _E , P _O and P _EO of the above definition in accordance with the reports of Ed., 11, 275 (1973), K. Kimura (Polymer, 25, 441 (1984)).

The larger the value of B, the smaller the block chains, the more uniform the ethylene and α-olefin buoys and the narrower the composition distribution. In addition, the composition distribution B value is ¹³ C-NMR specter of a sample obtained by uniformly dissolving a copolymer of about 200 mg in 10 ml of sample tube in 10 ml of hexachlorobrodiene, at a measurement temperature of 120 DEG C, a measurement frequency of 25.05 MHz, and a specter. It is calculated by measuring under the measurement conditions of 1500 Hz in width, 1500 Hz in filter-width, 4.2 sec in pulse repetition time, 7 sec in pulse width, and 2000-5000 computation counts, and calculating P _E , P _O and P _EO from this specter.

Example 1

37 g of Al ₂ (SO ₄ ) ₂ .14H ₂ O and 125 ml of toluene were charged into a fully nitrogen-substituted 400 ml flask, and 500 mmol of trimethyl aluminum diluted with 125 ml of toluene was added dropwise after cooling to 0 ° C. Then, it heated up to 40 degreeC and continued reaction at that temperature for 10 hours. After the reaction, solid-liquid separation was carried out by filtration and toluene was removed from the region, thereby obtaining 13 g of white solid aminooxane. The molecular weight determined by the freezing point drop in benzene was 930, and the m value indicated in the catalyst component (B) was 14.

[polymerization]

500 ml of toluene was charged into a 1-liter glass autoclave, which was sufficiently nitrogen-substituted, and a mixed gas of ethylene and propylene (120 L / hr and 80 L / hr, respectively) was passed through and left at 20 ° C. for 10 minutes. Thereafter, 0.5 mmol of triisobutyl aluminum was added, and 5 minutes later, 0.25 mg of the aminooxane in terms of aluminum atoms was added, followed by 2.5 × 10 ⁻³ mmol of bis (cyclopentadienyl) zirconium dichromide. The polymerization was initiated.

2.39, B값 1.13의 폴리머 19.1g을 얻었다.The mixed gas of ethylene and propylene was continuously supplied, and it polymerized at 20 degreeC under atmospheric pressure for 1 hour. After the completion of the polymerization, a small amount of methanol was added to terminate the polymerization. The polymer solution was added to excess methanol and the polymer was precipitated and dried at 130 ° C. under reduced pressure for 12 hours. As a result, 0.3 g / min of MFRO, 84.1 mol% of ethylene content determined by ¹³ C-NMR,

2.39 and 19.1 g of polymers having a B value of 1.13 were obtained.

Comparative Example 1

The polymerization was carried out in the same manner as in Example 1, except that triisobutyl aluminum was not used in the polymerization of Example 1. However, almost no polymer was obtained.

[Example 2-9, Comparative Example 2-6]

The polymerization was carried out in the same manner as in Example 1 under the conditions described in Table 1. The results are shown in Table 2.

Example 10

[polymerization]

2.92, 실온데칸 가용부 중량분을 1.8wt%의 폴리머 33.1g을 얻었다.250 ml of hexane and 750 ml of 4-methyl- 1-pentene were charged to the 2 L stainless autoclave fully nitrogen-substituted, and it heated up to 35 degreeC. Thereafter, 0.25 mmol of triisobutyl aluminum and the aminooxane synthesized in Example 1 were charged with 0.5 milligram atoms and bis (cyclopentadienyl) zirconium dichromide in terms of aluminum atoms to 1 × 10 ⁻¹ mmol. Subsequently, ethylene was introduced to initiate polymerization. Ethylene was continuously fed to maintain a high pressure of 8 kg / cm ² G and polymerization was performed at 45 ° C. for 1 hour. Subsequent operations were performed in the same manner as in Example 1, with an MFR of 0.5 g / 10 min and a density of 0.901 g / cm ² ,

33.1 g of polymers of 1.8 wt% were obtained as a 2.92 and room temperature decane soluble part weight.

[Examples 11-13 and Comparative Example 7]

The same operation as in Example 10 was carried out by polymerization under the conditions described in Table 3. The results are shown in Table 4.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

Example 14

2.45, 옥소값 11의 에틸렌·프로필렌·ENB 코폴리머를 얻었다.Alminooxane synthesized as in Example 1 using 500 L / hr of toluene using 1 L of continuous polymerization reactor, 0.5 mg atom / hr and bis (cyclopentadienyl) zirconium dichromide in terms of aluminum atom Was continuously fed at a rate of 5 × 10 ⁻³ mmol / hr and simultaneously in a polymerization reactor at a rate of 1.2 g / hr of ethylene 150 L / hr, propylene 100 / hr and 5-ethylidene-2-olbolene (ENB) at the same time. The polymerization was carried out under the conditions of a polymerization temperature of 20 deg. C, atmospheric pressure, residence time for 1 hour, and polymolecular concentration of 15 g / l. The resulting polymer was treated in the same manner as in Example 1. Thus, MFR 2.25g / 10min, ethylene content 86.9 mol% determined by ¹³ C-NMR,

2.45 and the ethylene propylene ENB copolymer of oxo value 11 were obtained.

Comparative Example 8

1.92, B값 1.14의 폴리머 22.8g을 얻었다.Example 1 The polymerization was carried out in the same manner as in Example 1, except that 2.5 mg of the aminooxane was converted to aluminum atoms without polymerization of triisobutyl aluminum, and then polymerized for 30 minutes. MFR 1.63 g / 10 min ethylene Content 82.8 mol%,

2.92g of polymers of 1.92 and a B value of 1.14 were obtained.

[Prepolymerization of Catalyst Components (A) and (B)]

Toluene of bis (cyclopentadienyl) zirconium dichromide was added to 4.7 ml of toluene solution (al 0.85 mol / l) of the aminooxane synthesized in Example 1 in a 100 ml glass-plaque flask sufficiently nitrogen-substituted. 2.4 ml of a solution (Zr 0.01 mol / l) and 12.9 ml of toluene were added, followed by stirring at 22 ° C. for 1 hour to obtain a yellow transparent solution.

[polymerization]

2.90, 실온데칸가용부 중량분을 1.5wt%의 폴리머 71.4g을 얻었다.500 ml of hexane, 500 ml of 4-methyl-1- petene, and 0.5 mmol of triisobutyl aluminum were charged into a 2 L stainless steel autoclave sufficiently nitrogen-substituted, and the temperature was raised to 47 ° C. Thereafter, 2.5 ml of the prepared solution was pressed into ethylene to initiate polymerization. Ethylene was continuously fed to maintain the voltage at 7 kg / cm ² G, and polymerization was carried out at 50 ° C. for 1 hour. Subsequent operations were performed in the same manner as in Example 1, with an MFR of 1.08 g / 10 minutes and a density of 0.902 g / cm ³ ,

2.90 and room temperature decane soluble part weight fraction obtained 71.4 g of polymer of 1.5 wt%.

Example 16

[Premixing Catalyst Components (A) and (B)]

In Example 15, it carried out similarly to Example 15 except having used 4.8 ml of toluene solutions (Zr 0.01 mol / L) and 10.5 ml of toluene of (cyclopentadienyl) zirconium dichromide.

[polymerization]

2.86, 실온데칸가용부 중량분을 1.3wt%의 폴리머 46.1g을 얻었다.Polymerization was carried out in the same manner as in Example 15, except that 1.25 ml of the solution prepared above was used, and MFR 0.82 g / min, density 0.904 g / cm ³ ,

2.86 and room temperature decane soluble part by weight of 46.1 g of 1.3 wt% of a polymer were obtained.

Example 17

[Premixing Catalyst Components (A) and (B)]

Toluene solution of aluminum oxane synthesized in Example 1 (12.0 ml) of toluene solution (Zr 0.04 mol / L) of bis (cyclopentadienyl) zirconium dichromide in Example 15 (Al 2.55 mol / L) 6.3 ml of L) and 1.7 ml of toluene were added, followed by stirring at 22 ° C. for 30 minutes to give a dark yellow transparent solution.

[polymerization]

2.82, 실온데칸가용부 중량분을 1.3wt%의 폴리머 38.5g을 얻었다.0.125 ml of the solution prepared above and 1.0 mmol of triisobutyl aluminum were polymerized at 60 ° C. for 1 hour, except that the polymerization was carried out in the same manner as in Example 15, followed by MFR 1.09 g / 10 min, density 0.902 g / cm ³ ,

2.82 and room temperature decane soluble part weight fraction 38.5g of 1.3 wt% of polymer were obtained.

Example 18

[polymerization]

A sufficiently nitrogen-substituted 2 liter stainless steel autoclave was charged with 1 milligram atom and 2 millimoles of triisobutyl aluminum in terms of aluminum atoms of 500 ml of toluene and the alminooxane synthesized in Example 1. Further, propylene was introduced to obtain 5 kg / cm ² G pressure at 30 ° C. After the introduction of propylene, the mixture was cooled to −10 ° C. to charge 1 × 10 ⁻³ mmol of ethylene bis (indenyl) zirconium dichromide to initiate polymerization. 44.2 g of a polymer was obtained by superposing | polymerizing at -10 degreeC for 6 hours.

Comparative Example 9

[polymerization]

In the polymerization of Example 18, polymerization was carried out in the same manner as in Example 18 except that triisobutyl aluminum was not used to obtain 2.4 g of a polymer.

Example 19

[Preparation of Alminooxane]

37 g of Al ₂ (SO ₄ ) ₂ .14H ₂ O and 125 ml of toluene were charged into a fully nitrogen-substituted 400 ml flask, and 500 mmol of trimethyl aluminum diluted with 125 ml of toluene was added dropwise after cooling to 0 ° C. Then, it heated up to 40 degreeC and continued reaction for 10 hours at that temperature. After the reaction, solid-liquid separation was carried out by filtration, and the filtrate was removed from toluene, thereby obtaining 13 g of white solid aminooxane. The molecular weight determined by the freezing point drop in benzene was 930, and the m value shown in the catalyst component (B) was 14.

[Preparation of Zirconium Catalyst]

A fully nitrogen-substituted 200 ml flask was calcined at 300 ° C. for 4 hours with silica (average particle size: 70 μ, specific surface area of 260 m ² / g, pore volume of 1.65 cm ³ g) of 3.8 g of toluene solution of aminooxane ( 52.5 ml of Al 0.49 mol / l) was added and 7.9 ml of toluene solution of bis (cyclopentadienyl) zirconium dichromide (Zr 0.04 mmol / l) was added to this solid product at room temperature, and the evaporator was again at room temperature. By removing toluene, the catalyst component having a Zr content of 0.54 wt% was obtained. In addition, a solid catalyst component obtained by polymerizing 0.86 g of ethylene per 1 g of catalyst was obtained by passing a mixed gas of ethylene and nitrogen (30 L / hr, 45 L / hr, respectively) for 30 minutes at room temperature in the catalyst component thus obtained.

[polymerization]

2.98, 숭밀도 0.33g/cm³, 실온 n-데칸가용부량 0.31wt%의 폴리머 101.2g이 얻어졌다. 표 5에 중합조건등을 나타냈다.900 ml of hexane and 100 ml of 1-hexane were charged to the 2 L stainless autoclave fully nitrogen-substituted, and it heated up to 45 degreeC. Subsequently, 0.15 milligrams of atoms of the zirconium catalyst prepolymerized with 1 millimolar of triisobutyl aluminum and ethylene were charged in terms of the zirconium atom. Moreover, it heated up to 60 degreeC and then introduce | transduced ethylene and started superposition | polymerization. Ethylene was continuously fed to maintain the voltage at 70 kg / cm ² G and polymerization was carried out at 70 ° C. for 2 hours. After the end of the polymerization, the polymer slurry was added to excess methanol and filtered off and dried at 80 ° C. under reduced pressure for 12 hours. As a result, MFR 0.16 g / 10 min, density 0.916 g / cm ³ ,

Is 2.98, bulk density 0.33g / cm ^3, a room temperature n- decane-soluble fraction of the polymer 101.2g 0.31wt% was obtained. Table 5 shows polymerization conditions and the like.

Example 20

In Example 19, it carried out similarly to Example 19 except having made the prepolymerization amount of ethylene 0.66g per 1g of catalysts.

[polymerization]

In Example 19, it carried out similarly to Example 19 except not having carried out homopolymerization of ethylene at the voltage of 6t kg / cm <^2> G using 1000 ml of hexane as a solvent without using 1-hexane.

Comparative Example 10

[polymerization]

The same procedure as in Example 20 was carried out except that isobutyl aluminum was not used in Example 20.

Example 21

[polymerization]

3.03, 숭밀도 0.31g/cm³, 실온 n-데칸가용부량 0.10wt%의 폴리머 46.8g을 얻었다.250 g of sodium chloride (Ogwa Jun Baseball Express) was charged into an autoclave in 2 L of stainless steel sufficiently nitrogen-substituted, and dried under reduced pressure at 90 ° C for 1 hour. Then, it cooled to 65 degreeC, and replaced the system with ethylene. Subsequently, 0.01 mmol of the zirconium catalyst prepared in Example 19 and 1 ml of 1-hexene were added to the zirconium catalyst prepared in Example 19, and triethylene butyl aluminum was introduced. The polymerization was initiated by introducing ethylene to a voltage of 8 kg / cm ² G. did. Thereafter, only ethylene was replenished, maintained at a voltage of 8 kg / cm ² G, and polymerization was performed at 70 ° C for 2 hours. After the synthesis, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol and dried overnight at 80 ° C. MFR 1.45 g / 10 min, density 0.925 g / cm ³ ,

46.8 g of polymers having a density of 3.03, 0.31 g / cm ^{3 of} soot and 0.10 wt% of soluble n-decane at room temperature were obtained.

Example 22

In the polymerization of Example 21, triisobutyl aluminum and zirconium catalysts were added at 75 ° C without using 1-hexane, and polymerization was carried out in the same manner as in Example 21 except that polymerization was performed at 80 ° C for 1 hour. The results are shown in Table 6.

Example 23-26

The polymerization was carried out in the same manner as in Example 19 under the conditions described in Table 5. The results are shown in Table 6.

Example 27

[Preparation of Zirconium Catalyst]

200 ml of nitrogen-substituted flasks were calcined at 500 ° C. for 5 hours with alumina (average particle diameter: 60 μm, specific surface area of 290 m / g pore volume, 5.8 g, toluene solution of dimethyl aluminum monochloride) 1 mol / L of Al) and 50 ml of toluene were added and heated at 80 ° C. for 2 hours. Subsequently, solid-liquid separation was carried out by filtration, and the solid part was transferred to 50 ml of toluene, and 32 ml of toluene solution of bis (cyclopentadienyl) zirconium dichromide (Zr 0.04 mol / l) was added thereto, and the mixture was dried at 80 캜. Heated for hours. A solid catalyst was obtained by performing solid-liquid separation again by filtration. The zirconium content in the solid catalyst was 0.27 wt%. This solid catalyst was added to 20 ml of toluene solution (al 0.49 mol / l) of alminooxane synthesized in Example 19 in terms of zirconium atom and 20 ml of toluene, followed by stirring at room temperature for 30 minutes. Thereafter, toluene was removed by evaporator at room temperature. The mixed catalyst of ethylene and nitrogen (30 L / hr, 45 L / hr, respectively) was passed through the catalyst component thus obtained at room temperature for 30 minutes to obtain a solid catalyst component in which 0.30 g of ethylene was polymerized per 1 g of catalyst.

[polymerization]

The polymerization was carried out as in Example 22. The results are shown in Table 6.

Comparative Example 11

The same procedure as in Example 27 was carried out except that triisobutyl aluminum was not used in Example 27. The results are shown in Table 6.

TABLE 5

TABLE 6

Example 28

[Preparation of Alminooxane]

37 g of Al ₂ (SO ₄ ) ₃ .14H ₂ O and 125 ml of toluene were charged into a fully nitrogen-substituted 400 ml flask, and 500 mmol of trimethyl aluminum diluted with 125 ml of toluene was added dropwise after cooling to 0 ° C. Next, it heated up to 40 degreeC, and reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation was carried out by filtration and toluene was removed from the filtrate to obtain 13 g of aluminoxane as a white solid. The molecular weight determined by the freezing point drop in benzene was 930, and the m value shown in the catalyst component (B) was 14.

[polymerization]

2.35, B값 1.11의 폴리머 10.9g을 얻었다. 표 7에 중합조건등을 나타내었다.500 ml of toluene was charged into a 1 L glass autoclave sufficiently nitrogen-substituted, and a mixed gas of ethylene and propylene (120 L / hr and 80 L / hr, respectively) was passed through and allowed to stand at 20 ° C. for 10 minutes. Thereafter, 0.5 mmol of triisobutyl aluminum was added, and after 5 minutes, aminooxane was 0.25 mg in terms of aluminum atoms, and 2.5 × 10 ⁻³ mmol of bis (cyclopentadienyl) phenoxy lipidconium monochloride was added. Started. The mixed gas of ethylene and propylene was continuously supplied, and superposition | polymerization was performed at 20 degreeC under atmospheric pressure for 1 hour. After the end of the polymerization, a small amount of methanol was added to terminate the polymerization. The polymer solution was added to excess methanol to precipitate the polymer, and dried at 130 ° C. under reduced pressure for 12 hours. As a result, MFR 0.21 g / 10 min, ethylene content 85.5 mol%, determined by ¹³ C-NMR,

2.35 and 10.9 g of polymers having a B value of 1.11 were obtained. Table 7 shows the polymerization conditions and the like.

Comparative Example 12

The polymerization was carried out in the same manner as in Example 28 except that trivyl aluminum was not used in the polymerization of Example 28, but a polymer was not obtained.

Example 29-32

The polymerization was carried out in the same manner as in Example 28 under the conditions described in Table 7. The results are shown in Table 7.

Example 33

[Preparation of Catalyst Component (A)]

Charge a 50 ml solution of bis (cyclopentadienyl) ethoxy zirconium monochromide (Zr 1.35 mmol) dissolved in toluene in a 200 ml glass-plaque flask fully nitrogen-substituted, and dimethyl aluminum chromide (Al 4 mmol / L). ), 34 ml was added, and the catalyst component (A) was obtained by reacting at 25 ° C for 30 minutes.

[polymerization]

In Example 23, it carried out similarly to Example 23 except having used the catalyst component (A) prepared above instead of the bis (cyclopentadienyl) phenoxy zirconium monochromide.

Comparative Example 13

In the polymerization of Example 33, the same procedure as in Example 33 was carried out except that triisobutyl aluminum was not used, but almost no polymer was obtained.

Example 34-40

The polymerization was carried out in the same manner as in Example 28 under the conditions described in Table 7. The results are shown in Table 7.

Example 41

[polymerization]

2.98, 실온데칸 가용부 중량분율 1.9wt%의 폴리머 30.5g을 얻었다.250 ml of hexane and 750 ml of 4-methyl-1-pentene were charged to a sufficiently nitrogenated internal volume autoclave of 2 L, and the temperature was raised to 35 ° C. Subsequently, 0.25 millimoles of triisobutyl aluminum, 0.5 milligram atoms in terms of aluminum atoms of the alminooxane synthesized in Example 1, and 1 × 10 ^-3 milligrams of the catalyst component (A) synthesized in Example 6 in terms of zirconium atoms Charged. Ethylene was then introduced to initiate polymerization. Ethylene was continuously supplied to maintain the voltage at 8 gk / cm ² G, and polymerization was carried out at 45 ° C. for 1 hour. Subsequent operations were performed in the same manner as in Example 1, with an MFR of 0.62 g / 10 minutes and a density of 0.902 g / cm ² ,

3.98 and 30.5 g of polymers of 1.9 wt% of the room temperature decane soluble part weight fraction were obtained.

Example 42

=2.79의 폴리머 28.5g을 얻었다.The polymerization of Example 41 was carried out in the same manner as in Example 41, except that 750 ml of 1-hexene was used instead of 4-methyl-1-pentene, and the MFR was 1.01 g / 10 min, the density 0.891 g / cm ³ ,

28.5 g of a polymer of = 2.79 was obtained.

Comparative Example 14

2.95, 실온데칸 가용부 중량분율 1.1wt%의 폴리머 2.5ng을 얻었다.The polymerization of Example 41 was carried out in the same manner as in Example 41, except that triisobutyl aluminum was not used. The MFR was 1.94 g / 10 minutes and the density was 0.908 g / cm ³ ,

2.95 and 2.5ng of polymers with 1.1 wt% of a room temperature decane soluble part weight fraction were obtained.

Example 43

2.49, 옥소가 10의 에틸렌·프로필렌-ENB 코폴리머가 얻어졌다.Alminooxane synthesized in the same manner as in Example 28 using 500 ml / hr of toluene, 0.5 mmol./hr of trivyl aluminum, and 0.5 milligram atoms / hr of aluminum atom diffusion using a 1 L continuous polymerization reactor, and Example 40 The catalyst component (A) synthesized as described above was continuously supplied at the rate of 5 × 10 ^-3 milligram atoms / hr in terms of zirconium atoms, and simultaneously 150 l / hr ethylene, 100 l / hr propylene and 5-ethylene- in the polymerization reactor. 2-Nolbornene (ENB) was continuously fed at a rate of 1.2 g / hr, and the polymerization was carried out under conditions of a polymerization temperature of 20 deg. C, atmospheric pressure, residence for 1 hour, and a polymer concentration of 14 g / l. The resulting polymer was treated in the same manner as in Example 28. 85.5 mol% of ethylene content determined in this way by MFR 2.04 g / 10 min ¹³ C-NMR,

Ethylene propylene-ENB copolymer of 2.49 and oxo 10 was obtained.

TABLE 7

Claims (7)

(A) Solid catalyst component carrying a transition metal compound represented by the following formula (I) on the inorganic carrier (B) Alminooxane and (C) n-alkyl group represented by the following formula (II) or (III) A polymerization method of olefins, characterized in that the olefins are polymerized or copolymerized in the presence of a catalyst made of an organoaluminum compound having a hydrocarbon group.

Wherein R ¹ represents a cycloalkadienyl group, R ² , R ³ and R ⁴ represent the same or different cycloalkadienyl groups, aryl groups, alkyl groups, aralkyl groups, cycloalkyl groups, halogen atoms, hydrogen atoms, -OR ^a , -SR ^b or -NR ₂ ^c group, R ^a , R ^b and R ^c are alkyl, cycloalkyl, aryl, aralkyl or organosylyl group, Me is zirconium, titanium or hafnium, k Is 1, 2, 3 or 4, l, m and n are each 0, 1, 2 or 3 and k + l + m + n = 4.

Wherein R is a hydrocarbon group, X is a halogen atom, a and b are independently of each other a number from 0 to 80, provided that a and b are not zero at the same time.

Wherein the definitions of R, X, a and b are as in formula (II) above. The method for polymerizing olefins according to claim 1, wherein the inorganic carrier is previously treated with an organometallic compound or a halogen-containing silicon compound before supporting the transition metal compound. The polymerization method of olefin according to claim 2, wherein the halogen-containing silicon compound is represented by the following formula (IV).

Wherein Y is a chlorine atom or a cancel atom, R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group or a cycloalkyl group having 3 to 12 carbon atoms, and d is a number of 1-4 And e is a number of 0-4, provided that the sum of d and e is a number of 1-4. (A ') A transition metal compound represented by the following formula (I'). (B) A polymerization method of olefins, characterized in that the olefin is polymerized or copolymerized in the presence of a catalyst comprising an aluminoxane represented by the following formula (II) and (C) an organoaluminum compound having a hydrocarbon group other than an n-alkaline group.

Wherein R ¹¹ is cycloalkadienyl, R ¹² is a group selected from the group consisting of the groups -OR ^a , -SR ^b , NR ₂ ^c and -PR ₂ ^d , and R ¹³ and R ¹⁴ independently seek each other Ralkadienyl, aryl, aralkyl, halogen or hydrogen atom, R ^a , R ^b and R ^c are alkyl, cycloalkyl aryl, aralkyl or organosyl, Me is zirconium, titanium or hafnium, k And l is 1.2 or 3, m and n are 0.1 or 2 and k + l + m + n = 4.

Wherein R, X, a and b are as defined in claim 1 above. The polymerization method of olefin according to claim 4, wherein the transition metal compound is treated with an organometallic compound. 6. The method for polymerizing olefins according to claim 5, wherein the organometallic compound is organoaluminum, organoboron, organomagnesium, organozinc or organolithium. (A ″) Transition metal compound represented by the following formula (I) (B) Alminooxane represented by the following formula (II) or the following formula (III), except that the concentration in the reaction system is 3 milligram atoms in terms of aluminum atoms / less than or equal to And (C) polymerizing or copolymerizing the olefin in the presence of a catalyst made of an organoaluminum compound having a hydrocarbon group other than the n-alkaline group.

Wherein R ¹ represents a cycloalkadienyl group, R ² , R ³ and R ⁴ represent the same or different cycloalkadienyl groups, aryl groups, alkyl groups, aralkyl groups, cycloalkyl groups, halogen atoms, hydrogen atoms,- OR ^a , -SR ^b or -NR ₂ ^c group, R ^a , R ^b and R ^c are alkyl group, cycloalkyl group, aryl group, aralkyl group or organosyl group, Me is zirconium, titanium or hafnium, k is 1, 2, 3 or 4, l, m and n are respectively 0, 1, 2 or 3 and k + l + m + n = 4.

Wherein R is a hydrocarbon group, X is a halogen atom, a and b are independently of each other a number from 0 to 80, provided that a and b are not zero at the same time.

Wherein the definitions of R, X, a and b are as in formula (II) above.