CN1057657A - The method of polymerization of olefines - Google Patents

Abstract

The invention provides the method for polymerization of olefines, it be included in contain a kind of have less than 10% (representing) with the Al atom in keeping 60 ℃ benzene the organoaluminum oxy-compound of dissolved Al component olefin polymerization catalysis in the presence of, make polymerization of olefines or copolymerization.Olefin polymerization catalysis has fabulous polymerization activity and can make alkene (being total to) polymkeric substance have narrow molecular weight distribution and narrow composition distribution.

Description

The method of polymerization of olefines

The present invention relates to the method for olefinic polymerization, more particularly, relate to have fabulous polymerization activity and can make alkene (being total to) polymkeric substance have olefin polymerization catalysis that narrow molecular weight distribution and narrow composition distribute in the presence of, make the method for polymerization of olefines or copolymerization.

As everyone knows, so far as the preparation alpha-olefinic polymer for example the catalyzer of ethene polymers or ethylene/alpha-olefin copolymer be Ti-base catalyst of forming by titanium compound and organo-aluminium compound or the catalytic component based on vanadium of forming by vanadium compound and organo-aluminium compound.

In general, the ethylene/alpha-olefin copolymer that obtains with Ti-base catalyst has wide molecular weight distribution and wide composition distribution and transparency, surface not viscosity and dynamic property inequality.The ethylene/alpha-olefin copolymer that obtains with catalytic component based on vanadium has narrow molecular weight distribution and narrow composition distribution, compare with the ethylene/alpha-olefin copolymer that obtains with aluminium-based catalyst, all there is sizable improvement on transparency, surface not viscosity and dynamic property, but the polymerization activity of said catalyzer is low and the ethylene/alpha-olefin copolymer of gained requires to remove ash manipulation.So, require catalyst system further to improve its performance and succeed in developing.

In this case, proposed already recently to use by the zirconium thing with the catalyzer that Lv oxane class is formed prepares the certain methods of ethylene/alpha-olefin copolymer as novel Ziegler (Ziegler) catalyzer of olefinic polymerization.

For example, Japanese kokai publication sho has disclosed the method for preparing ethylene/alpha-olefin copolymer No. 19309/1983, and it comprises makes ethene and one or at least two C ₃-C ₁₂Alpha-olefines polymerization, polymerization temperature are 50 °-200 °, adopt catalyzer composed of the following components, promptly a kind of transition metal that contains the compound of representing by following general expression,

（Cycopentadienyl） ₂MeRHal

In the formula: R is cyclopentadienyl, C ₁-C ₆Alkyl or halogen, Me are transition metal, and Hal is halogen and the linear Lv oxane represented by following general expression

Al ₂OR ₄（Al（R）-O） _n

In the formula: R is methyl or ethyl, and n is the number of 4-20 or the Huan Lv oxane of being represented by following general expression

In the formula: R and n are as defined above.

This patent points out that in order to regulate the poly density of gained, the polymerization of ethene should have on a small quantity up to 10%(weight) carry out under the situation that quite long-chain alpha-olefin class or its mixture are participated in.

Japanese kokai publication sho has disclosed a kind of invention about linear Lv oxane and Huan Lv oxane preparation method for No. 95292/1984.Linear Lv oxane is represented by following general expression:

In the formula: n is the numeral of 2-40, and R is C ₁-C ₆Alkyl.Huan Lv oxane is represented by following general expression:

In the formula: n and R are as defined above.

The disclosure patents state prepare De Lv oxane when a kind of comprising that be aggregated in of ethene by said patented method, as methyl Lv oxane, and under the situation of the mixture participation of a kind of two (cyclopentadienyl) zirconium compounds or a kind of two (cyclopentadienyl) titanium compounds, then every gram transition metal per hour can obtain polyethylene at least two 1,500 myriagrams.

TOHKEMY shines the preparation method who has disclosed a kind of olefin polymerization catalysis for No. 35005/1985, and it comprises at first makes a kind of Lv oxane compound and magnesium compound reaction, and this Lv oxane compound is represented by following general expression:

In the formula: R is C ₁-C ₁₀Alkyl, R ⁰Be R ¹Or R ⁰Expression-O-key then, makes the reaction product chlorination, then uses the compound treatment of Ti, V, Zr or Cr.This patents state be specially adapted to ethene and C by the catalyzer of this method preparation ₃-C ₁₂The copolymerization of alpha-olefines.

TOHKEMY according to disclosed for No. 35006/1985 (a) two kinds or more different single, two-or the derivative of three-cyclopentadienyl or its transition metal with (b) Lv oxane combines as a kind of catalyzer, is used for preparation feedback device blended polymkeric substance.The embodiment 1 of this part patent has disclosed ethene and propylene polymerization under the situation that the catalyzer participation of being made up of two (pentamethyl-cyclopentadienyl) zirconium dimethyls and a kind of Lv oxane is arranged, obtaining having number average molecular weight is 15,300, weight average molecular weight is 36,400 and contains the polyethylene of 3.4% propylene component.In the embodiment 2 of this part patent, ethene and propylene are having by two (pentamethyl-cyclopentadienyl) zirconium dichloride, polymerization under the situation that the catalyzer that two (methyl cyclopentadienyl) zirconium dichlorides and a kind of Lv oxane are formed is participated in, obtain the mixture of a kind of polyethylene and ethylene/propene copolymer, multipolymer has and has number average molecular weight is 2,200 and weight average molecular weight be 11,900 and contain the 30%(mole) part that is dissolved in toluene of propylene component and to have number average molecular weight be 3,000 and weight average molecular weight be 7,400 and contain the 4.8%(mole) part that is insoluble to toluene of propylene component forms, it is 2 that said mixture has number average molecular weight, 000 and weight average molecular weight be 8,300 and contain the 7.1%(mole) propylene component.Equally, embodiment 3 has disclosed the mixture of a kind of LLDPE and ethylene/propene copolymer, and it is by to have molecular weight distribution (Mw/ Mn) be 4.57 and contain the 20.6%(mole) soluble part of propylene component and to have molecular weight distribution be 3.04 and contain the 2.9%(mole) insoluble part of propylene component forms.

Japanese kokai publication sho has disclosed a kind of method No. 35007/1985, wherein only ethene is aggregated, or the alpha-olefin of ethene and 3 or 3 above carbon atoms is having in the presence of the catalyst system that contains metallocene and Huan Lv oxane of being represented by following general expression or linear Lv oxane by copolymerization Huan Lv oxane general expression:

In the formula: R is the 1-5 carbon atom alkyl, and n is 1 to about 20 integer, linear Lv oxane general expression:

In the formula: R and n are as defined above.

According to this part patent, the weight average molecular weight of the polymkeric substance that in this way obtains is about 500-1, and 400,000, molecular weight distribution is 1.5-4.0.

Japanese kokai publication sho has disclosed for No. 35008/1985 with comprising two kinds of metallocenes with polyethylene or ethene/C that the preparation of the catalyst system of Lv oxane has wide molecular weight distribution at least ₃-C ₁₀Alpha-olefin copolymer.This part patent points out that the molecular weight distribution of the multipolymer that in this way obtains (Mw/ Mn) is 2.50.

Japanese kokai publication sho has proposed for No. 260602/1985 and No. 130604/1985 to use by transistion metal compound and has comprised the method that is mixed with the polymerizing olefins with catalyst that machine aluminium compound forms of transistion metal compound, Lv oxane and organo-aluminium compound and disclosed by being added with machine aluminium compound and improved the polymerization activity of unit transition metal.

Japanese kokai publication sho thinks that the Lv oxane is to obtain by organo-aluminium compound and the iron cpd reaction that contains crystal water for No. 36390/1987, Japanese kokai publication sho points out that Lv oxane can be selected from by magnesium compound with containing by organo-aluminium compound for No. 148491/1987, the compound reaction of the crystal water of the group that nickel compound and lanthanum compound are formed obtains, No. the 56507/1988th, Japanese kokai publication sho and the 56508/1988th points out that ， Lv oxane can be with at a high speed, high-shear induction type stirrer or ultrasonic wave are directly reacted at unreactive hydrocarbons solvent with organo-aluminium compound by water and are obtained.

Is Dang Lv oxane compound during as a component of this catalyzer in prepare alpha-olefin (being total to) polymkeric substance with described method, can obtain having alpha-olefin (being total to) polymkeric substance that narrow molecular weight distribution and narrow composition distribute with fabulous polymerization activity.

Yet extremely urgent requirement is that alpha-olefin is had good polymerization activity and can make alkene (being total to) polymkeric substance have the appearance of narrow molecular weight distribution and narrow composition distribution De Lv oxane type organo-aluminium compound concerning industrial.

In this connection, so far the known Lv oxane compound of in olefinic polymerization, using, even when they during with liquid or solid-state use, all to be produced and be recycled into and dissolve in varsol such as benzene or toluene, and after it dissolves in benzene, measure its molecular weight with cryoscopy again, and, be by in benzene, measuring the structure that its zero pour decides said Lv oxane.

From the point of view, the inventor has carried out deep research, has finished the present invention understanding fully on the basis that olefinic polymerization is had good catalytic activity by the not known as yet and insoluble at present of known Lv oxane or organo-aluminium compound preparation or the novel organoaluminum oxy-compound that is slightly soluble in benzene and toluene finally.

Consider aforesaid prior art, and finished the present invention, and the object of the present invention is to provide new olefin polymerization catalyst components and containing can make alkene (be total to) polymkeric substance have narrow molecular weight distribution and narrow composition distribution said catalyst component olefin polymerization catalysis and with the method for said olefin polymerization catalysis olefin polymerization.

Olefin polymerization catalyst components of the present invention be characterised in that it comprise a kind of in 60 ℃ of following benzene the Al atom of dissolved Al component less than 10% organoaluminum oxy-compound (A).

First kind of olefin polymerization catalysis of the present invention be characterised in that it comprise a kind of in 60 ℃ of following benzene the Al atom of dissolved Al component less than 10% organoaluminum oxy-compound (A), and a kind of transistion metal compound (B) that contains ligand with loop chain dialkylene skeleton.

Second kind of olefin polymerization catalysis of the present invention be characterised in that it comprise a kind of in 60 ℃ of following benzene the Al atom of dissolved Al component less than 10% organoaluminum oxy-compound (A), a kind of transistion metal compound (B) and a kind of organo-aluminium compound (C) that contains ligand with loop chain dialkylene skeleton.

The third olefin polymerization catalysis of the present invention be characterised in that it comprise a kind of in 60 ℃ of following benzene the Al atom of dissolved Al component be combined in aluminium oxane (D) on the aluminium atom less than 10% organoaluminum oxy-compound (A), a kind of transistion metal compound (B) that contains ligand and a kind of alkyl with at least one non-positive alkyl with loop chain dialkylene skeleton.

The 4th kind of olefin polymerization catalysis of the present invention be characterised in that it comprise a kind of in 60 ℃ of following benzene the Al atom of dissolved Al component be combined in aluminium oxane (D) on the aluminium atom less than 10% organoaluminum oxy-compound (A), a kind of transistion metal compound (B) of ligand, a kind of organo-aluminium compound (C) and a kind of alkyl of containing with at least one non-positive alkyl with loop chain dialkylene skeleton.

Polymerization of olefines method of the present invention is characterised in that with aforesaid olefin polymerization catalysis and makes alpha-olefines aggregate into copolymerization.

Figure 1 shows that the infrared spectrogram of benzene-insoluble organoaluminum oxy-compound used among the present invention;

Figure 2 shows that a kind of known infrared spectrogram that is dissolved in the organo-aluminium compound of benzene.

Below, will describe catalyst component for olefin polymerization, olefin polymerization catalysis in detail and with the method for said olefin polymerization catalysis polymerizable alkenyl hydro carbons.

In the present invention, frequently use " polymerization " term, its implication not only comprises homogeneous polymerization, and comprises copolymerization, in addition, sometimes uses " polymer " term, and its implication not only comprises homopolymers, and comprises copolymer.

Catalyst component for olefin polymerization of the present invention comprises a kind of benzene-insoluble organo-aluminium hydroxy compounds (A).

Benzene-insoluble organo-aluminium hydroxy compounds (A)

The Al atom of used its Al component of dissolving in 60 ℃ of lower benzene of benzene-insoluble organo-aluminium hydroxy compounds (A) preferentially is adopted as less than 5% less than 10% among the present invention, particularly less than 2% and in benzene insoluble or slightly soluble. That is, the Al atom of the Al component of the organo-aluminium hydroxy compounds that dissolves in 60 ℃ of lower benzene preferentially is adopted as less than 5% less than 10%, particularly less than 2%.

The solubility of aforesaid this organo-aluminium hydroxy compounds in benzene is to obtain like this: the said organo-aluminium hydroxy compounds that will be equivalent to the quantity of 100mg atom (Al atom) is suspended in the 100ml benzene, gained suspension is 60 ℃ of lower stirrings 6 hours, filter the mixture of gained with the G-5 glass filter that the chuck that remains on 60 ℃ is housed, wash solid portion separated on filter with 60 ℃ of benzene of 50ml again, totally 4 times, measure existing Al atomic quantity in whole filtrates (* mmol).

When analyzing benzene-insoluble organo-aluminium hydroxy compounds of the present invention with infrared spectrophotometry, at about 1260cm^-1The place absorbance (D1260) with at about 1220cm^-1The ratio (D1260/D1220) of the absorbance at place is preferably less than 0.08, particularly in the 0.04-0.07 scope less than 0.09.

The ir spectrophotometry analysis of the organo-aluminium hydroxy compounds of indication is carried out in the following manner in this specification:

At first, the agate mortar with placing nitrogen box grinds to form paste to the organoaluminum oxy-compound with whiteruss.

Then, the pasty state sample that obtains is thus placed between two KBr, in nitrogen atmosphere, use IR-810 to measure infrared spectra by Nippon Bunko Co., Ltd. produce and market.

The infrared spectra of organoaluminum oxy-compound gained of the present invention is shown in Fig. 1.

By the infrared spectra of such gained, obtain the ratio of D1260/D1220 and obtain said ratio in the following manner:

(a) with at about 1280cm ^-1The place maximum point and at about 1240cm ^-1The line of the maximum point at place is as baseline L ₁

(b) read out in about 1260cm ^-1The transmittance (T%) of the absorption smallest point at place and the transmittance (To%) of intersection point, said intersection point makes said vertical line and said baseline L again by draw a vertical line from said absorption smallest point to the wave number X-coordinate ₁Crossing obtaining, thus absorbancy (D1260=log To/T) calculated.

(c) same, with at about 1280cm ^-1The place and at about 1180cm ^-1The line of two maximum points at place is as baseline L ₂

(d) read out in about 1220cm ^-1((T ' o%), said intersection point makes said vertical line and said baseline L by draw a vertical line from said absorption smallest point to the wave number X-coordinate to the transmittance of T ' %) and intersection point to the transmittance of the absorption smallest point at place again ₂Crossing obtaining, thus absorbancy (D1220=log T ' o/T ') calculated.

(e) by the value of gained, calculate D1260/D1220.

The known infrared spectra that is dissolved in the organoaluminum oxy-compound of benzene is shown in Fig. 2.As seen from Figure 2, the value of D1260/D1220 that is dissolved in the organoaluminum oxy-compound of benzene is actually 0.10-0.13, therefore, benzene-insoluble organoaluminum oxy-compound of the present invention is obviously different with the known organoaluminum oxy-compound that is dissolved in benzene on the numerical value of D1260/D1220.

Tentatively think that benzene-insoluble organoaluminum oxy-compound of the present invention has the alkyl hydroxyl aluminium unit that a following general expression is represented:

In the formula: R ¹Alkyl family for 1-12 carbon atom.

In above-mentioned alkyl hydroxyl aluminium unit, R ₁Comprise such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl, octyl group, decyl, cyclohexyl and ring octyl group.In the above alkyl of enumerating, preferentially be adopted as methyl and ethyl, especially preferentially be adopted as methyl.

Except general expression is

Alkyl hydroxyl aluminium unit outside, benzene-insoluble organoaluminum oxy-compound of the present invention can also contain one by general expression

The hydroxyl aluminium unit of expression is in the formula: R ¹Be as above defined, R ²For the alkyl of 1-12 carbon atom, the alkoxyl group of 1-12 carbon atom, aryloxy, hydroxyl, halogen or the hydrogen of 6-20 carbon atom, suppose R ¹And R ²Differ from one another.Under the sort of situation, the organoaluminum oxy-compound then wishes to contain alkyl hydroxyl aluminium unit , its ratio is at least the 30%(mole), preferentially be adopted as 50%(mole at least), particularly be at least the 70%(mole).

Below, will describe the preparation method of aforesaid benzene-insoluble organoaluminum oxy-compound in detail.

Above-mentioned benzene-insoluble organoaluminum oxy-compound (A) is by Shi Lv oxane solution and water or comprise compound bearing active hydrogen and contact and obtain.

Used De Lv oxane solution can be by such as the preparation of following method among the present invention:

(1) reclaim the method for Lv oxane class with the hydrocarbon solution form, it comprise make organo-aluminium compound such as trialkylaluminium with have the water of absorption or contain the salt of crystal water such as the compound hydrocarbon solvent of the hydrate of magnesium chloride, copper sulfate, Tai-Ace S 150, single nickel salt or cerous compounds in suspension react.

(2) with the method for hydrocarbon solution form recovery Lv oxane class, it comprises makes organo-aluminium compound such as trialkylaluminium direct and water, ice or water vapour interaction in solvent such as benzene, toluene, ether and tetrahydrofuran (THF).

In this respect, De Lv oxane can contain a small amount of organo-metallic component in the above-mentioned Lv oxane solution.And, reclaim De Lv oxane solution by aforesaid method and can distill and remove wherein solvent or unreacted organo-aluminium compound, then be dissolved in the solvent again.

The organo-aluminium compound that is used to prepare aforesaid this Lv oxane solution for example comprises trialkylaluminium such as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three sec-butyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, three decyl aluminium, thricyclohexyl aluminium, three ring octyl group aluminium; Dialkylaluminum halides such as dimethylaluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride; Dialkyl group aluminum hydride such as ADEH and diisobutyl aluminium hydride; Aluminum dialkyl alkoxide such as dimethyl aluminium methylate and diethyl aluminum ethylate; And aluminum dialkyl aryl oxide such as diethyl aluminum phenates.

In the above organo-aluminium compound of enumerating, what especially preferentially adopt is trialkylaluminium.

In addition, can also be used as organo-aluminium compound to the isopentene group aluminium of representing by following general expression:

（i-C ₄H ₉） _xAl _y（C ₅H ₁₀） _z

In the formula: X, Y and Z are respectively positive number, Z 〉=2X.

Above-mentioned organo-aluminium compound can use separately or be used in combination.

Used solvent comprises aromatic hydrocarbons such as benzene,toluene,xylene, cumene, Cymene in the solution of Lv oxane; Aliphatic hydrocarbon such as pentane, hexane, heptane, octane, decane, dodecane, n-Hexadecane and octadecane; Alicyclic hydro carbons such as pentamethylene, hexanaphthene, cyclooctane and methylcyclopentane; Petroleum fractions such as gasoline, kerosene and gas oil; The perhaps halogenide of halogenated hydrocarbons such as above-mentioned aromatics, aliphatic series and alicyclic hydro carbons, particularly their muriate and bromide.In addition, can also use ethers such as ether and tetrahydrofuran (THF).In above-named these solvents, what especially preferentially adopt is aromatic hydrocarbons.

As mentioned above, in the present invention, benzene-insoluble organoaluminum oxy-compound (A) contacts and obtains by making above-mentioned Lv oxane solution and water or containing compound bearing active hydrogen.

The compound bearing active hydrogen that contains used among the present invention comprises alcohols such as methyl alcohol, ethanol, n-propyl alcohol and Virahol; Glycols such as second (support) two pure and mild quinhydrones; And organic acid such as acetate and propionic acid.In above-mentioned these compounds, what preferentially adopt is alcohols and glycols, and what especially preferentially adopt is alcohols.

Yu the contacted water of Lv oxane solution or contain compound bearing active hydrogen can be at hydrocarbon solvent such as benzene, toluene and hexane, ether solvents such as tetrahydrofuran (THF) or amine solvent such as triethylamine, as solution or dispersion, perhaps can steam or solid state use.Yu the contacted water of Lv oxane solution can be crystal water such as magnesium chloride, sal epsom, Tai-Ace S 150, copper sulfate, single nickel salt, ferric sulfate and the cerous compounds of salt, the perhaps absorption water such as silicon oxide, aluminum oxide and aluminium hydroxide or the polymkeric substance that absorb of mineral compound.

The reaction of Lv oxane solution and water or active hydrogen-contg compound is carried out in such as the solvent of varsol usually.Used in this case solvent is aromatic hydrocarbons such as benzene,toluene,xylene, cumene and Cymene; Aliphatic hydrocarbon such as pentane, hexane, heptane, octane, decane, dodecane, n-Hexadecane and octadecane; Alicyclic hydro carbons such as pentamethylene, hexanaphthene, cyclooctane and methylcyclohexane; Petroleum fractions such as gasoline, kerosene and gas oil; The halogenide of halogenated hydrocarbons such as above-mentioned aromatic hydrocarbons, aliphatic hydrocarbon and alicyclic hydro carbons, particularly their muriate and bromide; And ethers such as ether and tetrahydrofuran (THF).In these solvents of enumerating in the above, what especially preferentially adopt is aromatic hydrocarbons.

In above-mentioned reaction, for there being 1 mole of Al atom in the Lv oxane solution, water or the amount that contains compound bearing active hydrogen are the 0.1-5 mole, preferentially are adopted as the 0.2-3 mole.The concentration requirement of representing with aluminium atom in the reactive system is 1 * 10 ^-3-5 grammeatom/liter, what preferentially adopt is 1 * 10 ^-2-3 grammeatom/liter, the concentration requirement of water is 2 * 10 in the reactive system ^-4-5 mol, what preferentially adopt is 2 * 10 ^-3-3 mol.

By following method, aluminium Costumes alkane solution is contacted with water or active hydrogen-contg compound:

(1) comprises that Shi Lv oxane solution is with moisture or contain the method that the hydrocarbon solvent of compound bearing active hydrogen contacts.

(2) comprise water or the steam that contains compound bearing active hydrogen are blown in the Lv oxane solution, thus the method that Shi Lv oxane contacts with steam.

(3) comprise Shi Lv oxane solution directly with water, ice or contain the method that compound bearing active hydrogen contacts.

(4) being included in Shi Lv oxane solution in the hydrocarbon mixes with the suspension that contains the compound that absorbs water or contain the compound of crystal water, perhaps in hydrocarbon, mix with a kind of suspension of compound, reach and contain compound bearing active hydrogen and be absorbed already, thus Shi Lv oxane with absorb water or crystal water or contain the method that compound bearing active hydrogen contacts.

Lv oxane solution can contain other components, as long as their Dui Lv oxanes and water or the reaction that contains compound bearing active hydrogen do not produce adverse influence.

Above-mentioned De Lv oxane solution and water or the reaction that contains compound bearing active hydrogen are carried out under-50-150 ℃ usually, preferentially carry out under 0-120 ℃, are preferably under 20-100 ℃ and carry out.The used reaction times is generally 0.5-300 hour, and what preferentially adopt is 1-150 hour, though the said reaction times is depended on used temperature of reaction to a large extent.

Benzene-insoluble organoaluminum oxy-compound (A) used among the present invention can also directly obtain by above-mentioned organoaluminum is contacted with water.In this case, the used water yield to make in reactive system dissolved organoaluminum atom less than 20%(by total organoaluminum atom).

Can make its dissolving or be dispersed in hydrocarbon solvent such as benzene, toluene and hexane with the contacted water of organo-aluminium compound, just use afterwards in ether solvents such as tetrahydrofuran (THF) or amine solvent such as the triethylamine, perhaps can use with the state of water vapour or ice.In addition, can also be the crystal water of salt such as magnesium chloride, sal epsom, Tai-Ace S 150, copper sulfate, single nickel salt, ferric sulfate and cerous compounds, perhaps the absorption water that absorbs on mineral compound such as silicon oxide, aluminum oxide and aluminium hydroxide or polymkeric substance is used as water.

The reaction of organo-aluminium compound and water is carried out in hydrocarbon solvent usually.In this case, used hydrocarbon solvent comprises aromatic hydrocarbons such as benzene,toluene,xylene, cumene and Cymene, aliphatic hydrocarbon such as butane, Trimethylmethane, pentane, hexane, heptane, octane, decane, dodecane, n-Hexadecane and octadecane, alicyclic hydro carbons such as pentamethylene, hexanaphthene, cyclooctane, cyclodecane, cyclododecane and methylcyclohexane, petroleum fractions such as gasoline, kerosene or gas oil, the halogenide of perhaps above-mentioned aromatics, aliphatic series and alicyclic hydro carbons, particularly their muriate and bromide.In addition, can also use ethers such as ether and tetrahydrofuran (THF).In these solvents of enumerating in the above, what especially preferentially adopt is aromatic hydrocarbons.

It would be desirable that the concentration of representing with the aluminium atom of organo-aluminium compound in the reactive system is generally 1 * 10 ^-3-20 mol, what preferentially adopt is 1 * 10 ^-3-10 mol, what more preferably adopt is 1 * 10 ^-35 grammeatom/liter, particularly 1 * 10 ^-2-3 grammeatom/liter.The concentration of water is generally 1 * 10 in the reactive system ^-3-5 mol, what preferentially adopt is 1 * 10 ^-2-3 mol.In this case, institute's dissolved aluminium atom it would be desirable less than 20% in the reactive system, and what preferentially adopt is less than 10%, and what more preferably adopt is that 0-5%(is by total organoaluminum atom).

Organo-aluminium compound can pass through to contact with water such as following method:

(1) comprises the method that the hydrocarbon solution that makes organoaluminum contacts with the water of hydrocarbonaceous solution.

(2) comprise in the hydrocarbon solution that makes water vapour be blown into organoaluminum, thus the method that organoaluminum is contacted with water.

(3) comprise that the hydrocarbon solution that makes organoaluminum mixes with the hydrocarbon suspension that contains the compound that absorbs water or contain the compound of crystal water, thereby make organoaluminum and absorb water or method that crystal water contacts.

(4) comprise the method that organoaluminum hydrocarbon solution is contacted with ice.

Above-mentioned organoaluminum hydrocarbon solution can contain other components, as long as they do not produce adverse influence to the reaction of organoaluminum and water.

The reaction of organo-aluminium compound and water is carried out under-100-150 ℃ usually, and preferential what adopt is to carry out under-70-100 ℃, and what more preferably adopt is to carry out under-50-80 ℃.Though the reaction times is depended on used temperature of reaction to a great extent, the reaction times is generally 1-200 hour, and what preferentially adopt is 2-100 hour.

Below, olefin polymerization catalysis of the present invention will be described.

First kind of olefin polymerization catalysis of the present invention comprise above-mentioned in 60 ℃ of following benzene the Al atom of dissolved Al component less than 10% organoaluminum oxy-compound (A) and a kind of transistion metal compound (B) that contains ligand with loop chain dialkylene skeleton.Below, will describe aforesaid transistion metal compound (B) in detail.

Transistion metal compound (B)

Transistion metal compound used among the present invention is represented with general expression MLX, in the formula: M is a transition metal, L is the ligand with transition-metal coordination, L's is at least a for having the ligand of loop chain dialkylene skeleton, non-L with ligand of loop chain dialkylene skeleton is alkyl, alkoxyl group, aryloxy, halogen or the hydrogen of 1-12 carbon atom, and X is the valency of transition metal.

In above-mentioned general expression, for the M of transition metal preferentially comprises zirconium, titanium, hafnium, chromium or vanadium, preferential especially what adopt is zirconium and hafnium.

Ligand with loop chain dialkylene skeleton for example comprises, cyclopentadienyl such as methyl cyclopentadienyl, ethyl cyclopentadienyl, n-butyl cyclopentadienyl, dimethyl cyclopentadienyl and pentamethyl-cyclopentadienyl that cyclopentadienyl, alkyl replace, indenyl, 4,5,6,7-tetrahydroindenyl and fluorenyl.

Above-mentioned have loop chain dialkylene skeleton two or more ligand can with transition-metal coordination, in this case, at least two kinds of ligands with loop chain dialkylene skeleton can combine through rudimentary alkylene.

The non-L that those have the ligand of loop chain dialkylene skeleton is alkyl, alkoxyl group, aryloxy, halogen or the hydrogen of 1-12 carbon atom.

The alkyl of the above-mentioned 1-12 of having carbon atom for example comprises that alkyl, cycloalkyl, aryl and aralkyl, alkyl comprise methyl, ethyl, propyl group, sec.-propyl and butyl.

Above-mentioned cycloalkyl for example comprises that cyclopentyl and cyclohexyl, aryl for example comprise that phenyl and tolyl, aralkyl for example comprise, benzyl and neophyl(2-methyl-2-hydrocinnamyl).

Above-mentioned alkoxyl group for example comprises that methoxyl group, oxyethyl group and butoxy, aryloxy for example comprise, phenoxy group.

Above-mentioned halogen for example comprises, fluorine, chlorine, bromine and iodine.

This transistion metal compound (B) that contains ligand with loop chain dialkylene skeleton, its transition metal is 4 valencys when for example using in the present invention, can be represented by following general expression more particularly:

R ²kR ³lR ⁴mR ⁵nM

In the formula: M is zirconium, titanium, hafnium or vanadium, R ²For having the group of loop chain dialkylene skeleton, R ³, R ⁴And R ⁵Be respectively group, alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group or aryloxy, halogen or hydrogen with loop chain dialkylene skeleton, K is at least 1 integer, and K+1+m+n=4.

Transistion metal compound is above-mentioned general expression R ²KR ³LR ⁴MR ⁵The compound of nM, R in the formula ², R ³, R ⁴And R ⁵In at least two, promptly ²R and R ³Be respectively the group with loop chain dialkylene skeleton, said two groups with loop chain dialkylene skeleton can mutually combine R through rudimentary alkylene such as methylene, ethylene, third (neighbour) support or the like ⁴And R ⁵Can be respectively a group, alkyl, cycloalkyl, aryl, aralkyl alkoxyl group or aryloxy, halogen or hydrogen with loop chain dialkylene skeleton.

Below listed be by above-mentioned general expression MLX, M is the typical typical example of the transistion metal compound with loop chain dialkylene skeleton (B) represented of zirconium in the formula:

Two (cyclopentadienyl) hydrogen monochlor(in)ate zirconium,

Two (cyclopentadienyl) hydrogen monobromination zirconium,

Two (cyclopentadienyl) hydrogenated methyl zirconium,

Two (cyclopentadienyl) ethyl zircoium hydride,

Two (cyclopentadienyl) phenyl zircoium hydride,

Two (cyclopentadienyl) benzyl zircoium hydride,

Two (cyclopentadienyl) neo-pentyl zircoium hydride,

Two (methyl cyclopentadienyl) hydrogen monochlor(in)ate zirconium,

Two (indenyl) hydrogen monochlor(in)ate zirconium,

Two (cyclopentadienyl) zirconium dichloride,

Two (cyclopentadienyl) dibrominated zirconium,

Two (cyclopentadienyl) methyl monochlor(in)ate zirconium,

Two (cyclopentadienyl) ethyl monochlor(in)ate zirconium,

Two (cyclopentadienyl) cyclohexyl monochlor(in)ate zirconium,

Two (cyclopentadienyl) phenyl monochlor(in)ate zirconium,

Two (cyclopentadienyl) benzyl monochlor(in)ate zirconium,

Two (methyl cyclopentadienyl) zirconium dichloride,

Two (n-butyl cyclopentadienyl) zirconium dichloride,

Two (indenyl) zirconium dichloride,

Two (indenyl) dibrominated zirconium,

Two (cyclopentadienyl) zirconium dimethyl,

Two (cyclopentadienyl) phenylbenzene zirconium,

Two (cyclopentadienyl) dibenzyl zirconium,

Two (cyclopentadienyl) methoxyl group chlorination zirconium,

Two (cyclopentadienyl) oxyethyl group zirconium chloride,

Two (methyl cyclopentadienyl) oxyethyl group zirconium chloride,

Two (cyclopentadienyl) phenoxy group zirconium chloride,

Two (fluorenyl) zirconium dichloride.

Below listed be by above-mentioned general expression, M is zirconium and contains two kinds of ligands with loop chain dialkylene skeleton at least, the typical typical example of the transistion metal compound that said ligand combines through rudimentary alkylene (B) in the formula:

Two (indenyl) zirconium dimethyls of ethylene,

Two (indenyl) diethyl zirconiums of ethylene,

Two (indenyl) phenylbenzene zirconiums of ethylene,

Two (indenyl) methyl monochlor(in)ate zirconiums of ethylene,

Two (indenyl) ethyl monochlor(in)ate zirconiums of ethylene,

Two (indenyl) methyl monobromination zirconiums of ethylene,

Two (indenyl) zirconium dichlorides of ethylene,

Two (indenyl) dibrominated zirconiums of ethylene,

Two (indenyl) methoxyl group monochlor(in)ate zirconiums of ethylene,

Two (indenyl) oxyethyl group monochlor(in)ate zirconiums of ethylene,

Two (indenyl) phenoxy group monochlor(in)ate zirconiums of ethylene,

Two (cyclopentadienyl) zirconium dichlorides of ethylene,

Two (cyclopentadienyl) zirconium dichlorides of Propylene,

Two (tertiary butyl cyclopentadienyl) zirconium dichlorides of ethylene,

Two (4,5,6, the 7-tetrahydrochysene generation-1-indenyl) zirconium dimethyls of ethylene,

Two (4,5,6,7-tetrahydrochysene generation-1-indenyl) the methyl monochlor(in)ate zirconiums of ethylene,

Two (4,5,6, the 7-tetrahydrochysene generation-1-indenyl) zirconium dichlorides of ethylene,

Two (4,5,6,7-tetrahydrochysene generation-1-indenyl) the dibrominated zirconiums of ethylene,

Two (4-methyl isophthalic acid-indenyl) zirconium dichlorides of ethylene,

Two (5-methyl isophthalic acid-indenyl) zirconium dichlorides of ethylene,

Two (6-methyl isophthalic acid-indenyl) zirconium dichlorides of ethylene,

Two (7-methyl isophthalic acid-indenyl) zirconium dichlorides of ethylene,

Two (5-methoxyl group-1-indenyl) zirconium dichlorides of ethylene,

Two (2, the 3-dimethyl-1-indenyl) zirconium dichlorides of ethylene,

Two (4, the 7-dimethyl-1-indenyl) zirconium dichlorides of ethylene,

Two (4, the 7-dimethoxy-1-indenyl) zirconium dichlorides of ethylene.

Can also use by replacing the transistion metal compound that the zirconium metal in the above listed zirconium compounds obtains with titanium metal, hafnium metal or vanadium metal.

Can also use these transistion metal compounds with two or more form of mixtures.

In the present invention, when being used as, the compound of two indenyl type zirconiums of this ethylene or hafnium contains at least two kinds of ligands with loop chain dialkylene skeleton, during the transistion metal compound that said ligand combines through rudimentary alkylene (B), then obtain the extra high polymkeric substance of stereospecific.

Below, second kind of olefin polymerization catalysis of the present invention will be described.

This olefin polymerization catalysis comprises that the Al atom with dissolved Al component in 60 ℃ of following benzene is less than 10% above-mentioned organoaluminum oxy-compound (A), the above-mentioned transistion metal compound (B) that contains the ligand with loop chain dialkylene skeleton and organo-aluminium compound (C).Below, will describe organo-aluminium compound (C) in detail.

Organo-aluminium compound (C)

Organo-aluminium compound (C) used among the present invention is by general expression R ⁶MAlX _3-mExpression is in the formula: R ⁶Be 1-12 carbon atom hydrocarbon, X is a halogen, and m is 1-3, perhaps by general expression R ⁶NAlY _3-nExpression is in the formula: R ⁶As above decide, Y be hydrogen ,-OR ⁷,-OSiR ⁸3 ,-OAlR ⁹2,

,-NR ¹²2 or SiR ¹³3, n is 1-2, R ⁷-R ¹³Be respectively hydrogen, halogen or hydrocarbon.

In above-mentioned general expression, R ⁶For 1-12 carbon atom hydrocarbon such as alkyl, cycloalkyl or aryl, specifically comprise methyl, ethyl, n-propyl, sec.-propyl, isobutyl-, amyl group, hexyl, octyl group, decyl, cyclopentyl, cyclohexyl, phenyl, tolyl or the like.

General expression R ⁶MAlX _3-mOrgano-aluminium compound specifically comprise compound as described below:

Trialkylaluminium such as trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three hexyl aluminium, trioctylaluminum, three-2-ethylhexyl aluminium etc.,

Alkenyl aluminium such as isopentene group aluminium etc.,

Dialkyl aluminum halide class such as dimethylaluminum chloride, diethyl aluminum chloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, diisobutyl aluminum bromide etc.,

Aluminum alkyls sesquihalide class such as tri-chlorination dimethyl aluminium, tri-chlorination diethyl aluminum, tri-chlorination di-isopropyl aluminium, tri-chlorination diisobutyl aluminum, tribromide diethyl aluminum etc.,

Alkyllithium dihalide class such as methylaluminium dichloride, ethylaluminium dichloride, dichloride sec.-propyl aluminium, aluminium isobutyl dichloride, dibrominated aluminium triethyl etc.,

General expression R ⁶NAlY _3-nOrgano-aluminium compound specifically comprise the following compound of enumerating:

(ⅰ) general expression R ⁶NAl(OR ⁷) _3-nCompound such as dimethyl aluminium methylate, diethyl aluminum ethylate, diisobutyl aluminum butanolate, diisobutyl aluminum methylate etc.

(ⅱ) general expression R ⁶NAl(OSiR ⁸3) _3-nCompound as (C ₂H ₅) ₂AlOSi(CH ₃) ₃, (iso-C ₄H ₉) ₂AlOSi(CH ₃) ₃, (iso-C ₄H ₉) ₂AlOSi(C ₂H ₅) ₂Deng.

(ⅲ) general expression R ⁶NAl(OAlR ⁹2) _3-nCompound as

(C ₂H ₅) ₂AlOAl(C ₂H ₅) ₂, (iso-C ₄H ₉) ₂AlOAl(iso-C ₄H ₉) ₂Deng

(ⅳ) general expression

Compound as ,

Deng

(ⅴ) general expression R ⁶NAl(NR ¹²3) _3-nCompound as

(CH ₃) ₂AlN(C ₂H ₅) ₂, (C ₂H ₅) ₂AlNHCH ₃, (CH ₃) ₂AlNH(C ₂H ₅), (C ₂H ₅) ₂AlN (Si(CH ₃) ₃) ₂, (iso-C ₄H ₉) ₂AlN (Si(CH ₃) ₃) ₂Deng

(ⅵ) general expression R ⁶NAl(SiR ¹³3) _3-nAs (iso-C ₄H ₉) ₂AlSl(CH ₃) ₃Deng

In the above organo-aluminium compound of enumerating, that preferentially adopt is general expression R ⁶3Al, R ⁶2Al(OR ⁷) or R ⁶2Al(OAlR ⁹2) compound, that especially preferentially adopt is general expression R ⁶3Al, R ⁶2Al(OR ⁷) or R ⁶2Al(OAlR ⁹2), R in the formula ⁶Compound for branched-chain alkyl.It is specifically, preferential especially that what adopt is three iso-alkyl aluminum compounds such as triisobutyl aluminium, three-2-ethylhexyl aluminium or the like.

These organo-aluminium compounds can separately or be used in combination.

Below, the third olefin polymerization catalysis of the present invention will be described.

This olefin polymerization catalysis comprises that Al atom with dissolved Al component in 60 ℃ of following benzene is combined in aluminium oxane (D) on the aluminium atom less than 10% above-mentioned organoaluminum oxy-compound (A), the alkyl that contains the above-mentioned transistion metal compound (B) of the ligand with loop chain dialkylene skeleton and have at least one non-positive alkyl.

Below, will describe this Lv oxane (D) in detail.

Alkyl with at least one non-positive alkyl is combined in the aluminium oxane on the aluminium atom

The alkyl that used aluminium oxane has at least one non-positive alkyl among the present invention is combined on the aluminium atom.

Above-mentioned such De Lv oxane can be prepared by following method:

(1) comprises that the suspension that makes a kind of salt of containing a kind of compound that absorbs water or containing crystal water such as hydrated magnesium chloride, hydrated copper sulfate, hydrazine aluminum sulfate, hydration nickel sulfate or hydration cerous compounds is combined in the organo-aluminium compound on the aluminium atom such as the method for trialkylaluminium reaction with the alkyl with at least one non-positive alkyl in the hydrocarbon medium.

(2) be included in the alkyl that has at least one non-positive alkyl in the medium such as benzene, toluene, ether or tetrahydrofuran (THF) and be combined in the method that organo-aluminium compound on the aluminium atom such as trialkylaluminium directly react with water, ice or water vapour.

Prepare De Lv oxane by these methods and can contain a small amount of organometallic compound.The above-mentioned Lv oxane solution that reclaims can distill removes wherein flux or unreacted organo-aluminium compound, then is dissolved in the solvent again.

Be combined in the alkyl that used organo-aluminium compound in the aluminium oxane on the aluminium atom contains at least one non-positive alkyl at the alkyl that preparation has at least one non-positive alkyl.This alkyl of non-positive alkyl comprises for example branched-chain alkyl, as iso-alkyl, cycloalkyl and aryl.

Typical case's representative of aforesaid organo-aluminium compound specifically comprises trialkylaluminium such as triisopropylaluminiuand, triisobutyl aluminium, three-2-methyl butyl aluminium, three-3-methyl butyl aluminium, three-2-methyl amyl aluminium, three-3-methyl amyl aluminium, three-4-methyl amyl aluminium, three-2-methyl hexyl aluminium, three-3-methyl hexyl aluminium and three-2-ethylhexyl aluminium; Tricyclic alkyl aluminium such as thricyclohexyl aluminium; And triaryl aluminum such as triphenyl aluminum, trimethylphenyl aluminium; Dialkyl group aluminum hydride such as diisobutyl aluminium hydride; Aluminum alkyls alkoxide such as aluminium isobutyl methylate, aluminium isobutyl ethylate, aluminium isobutyl isopropoxide.In the above organo-aluminium compound of enumerating, what preferentially adopt is the trialkyl aluminium compound with branched-chain alkyl, and what especially preferentially adopt is the triisobutyl aluminum compound.

Alkyl with at least one non-positive alkyl is combined in the solubleness of above-mentioned aluminium oxane in keeping 23 ℃ benzene on the aluminium atom and is at least 1 grammeatom Al/ and rises and dissolve in benzene.

Below, the 4th kind of olefin polymerization catalysis of the present invention will be described.

This olefin polymerization catalysis comprises that Al atom with dissolved Al component in 60 ℃ of following benzene is combined in the aluminium oxane (D) of hydrocarbon on the aluminium atom less than 10% above-mentioned organoaluminum oxy-compound (A), the alkyl that contains the above-mentioned transistion metal compound (B) of the ligand with loop chain dialkylene skeleton, above-mentioned organo-aluminium compound (C) and have at least one non-positive alkyl.

The polymerization of olefines

In the present invention, prepare polymkeric substance with aforesaid olefin polymerization catalysis by making alpha-olefines polymerization or copolymerization.

Can comprise ethene and 3-20 carbonatom class such as propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-laurylene, 1-amylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene, 1-icosa alkene, cyclopentenes, suberene, norbornylene, 5-methyl-2-norbornylene, tetracyclododecen and 2-methyl isophthalic acid with olefin polymerization catalysis polymeric olefines of the present invention, 4,5,8-two methylenes-1,2,3,4,4a, 5,8, the 8a-octalin.

In addition, can also use vinylbenzene, vinyl cyclohexane and diene.

In the present invention, polymerization can perhaps be reached by vapour phase polymerization by liquid polymerization such as solution polymerization and suspension polymerization.

Temperature with aforesaid olefin polymerization catalysis olefin polymerization is generally-50-200 ℃, and it is preferential that what adopt is 0-150 ℃.Polymerization is arrived 100kg/cm at normal pressure usually ²Pressure under carry out, it is preferential that what adopt is that normal pressure is to 50kg/cm ², polyreaction can be carried out with batch process, semi continuous method or continous way method.Polymerization can also be under different reaction conditionss, in two steps or above step of two steps carry out.The molecular weight of gained olefin polymer can be regulated by the hydrogen that exists in the paradigmatic system or by changing polymerization temperature.

In practice with above-mentioned first kind of polymerizing catalyst olefin polymerization of the present invention, preferably use benzene-insoluble organoaluminum oxy-compound (A), its consumption is generally 10 ^-6-0.1 grammeatom Al/ liter, what preferentially adopt is 10 ^-5-10 ^-2Grammeatom Al/ liter, and the transistion metal compound (B) that contains the ligand with loop chain dialkylene skeleton, its consumption is generally 10 ^-8-10 ^-3Mol, what preferentially adopt is 10 ^-7-10 ^-4Mol.

Equally, under the situation of second kind of olefin polymerization catalysis of the present invention, the consumption of benzene-insoluble organoaluminum oxy-compound (A) is generally 10 ^-6-0.1 grammeatom-Al/ liter, what preferentially adopt is 10 ^-5-10 ^-2Grammeatom-Al/ liter, the consumption that contains the transistion metal compound (B) of the ligand with loop chain dialkylene skeleton is generally 10 ^-8-10 ^-3Mol, what preferentially adopt is 10 ^-7-10 ^-4Mol, the consumption of organic aluminide (C) is generally 10 ^-5-0.1 mol, what preferentially adopt is 10 ^-4-10 ^-2Mol.In addition, the ratio (representing with the Al atom) of benzene-insoluble organoaluminum oxy-compound (A) and organo-aluminium compound (C) is preferably 0.01-5, and that preferentially adopt is 0.02-2.

Under the situation of the third olefin polymerization catalysis of the present invention, the consumption of benzene-insoluble organoaluminum oxy-compound (A) is generally 10 ^-6-0.1 grammeatom-Al/ liter, what preferentially adopt is 10 ^-5-10 ^-2Grammeatom-Al/ liter, the consumption that contains the transistion metal compound (B) of the ligand with loop chain dialkylene skeleton is generally 10 ^-8-10 ^-3Mol, what preferentially adopt is 10 ^-7-10 ^-4Mol, and the consumption of above-mentioned Lv oxane (D) is generally 10 ^-5-0.1 grammeatom-Al/ liter, what preferentially adopt is 10 ^-4-10 ^-2Grammeatom-Al/ liter.In addition, benzene-insoluble organoaluminum oxy-compound (A) is preferably 0.01-5 with the ratio (representing with the Al atom) of aluminium oxane (D), and that preferentially adopt is 0.02-2.

Under the situation of the 4th kind of olefin polymerization catalysis of the present invention, the consumption of benzene-insoluble organoaluminum oxy-compound (A) is generally 10 ^-6-0.1 grammeatom Al/ liter, what preferentially adopt is 10 ^-5-10 ^-2Grammeatom Al/ liter, the consumption that contains the transistion metal compound (B) of the ligand with loop chain dialkylene skeleton is generally 10 ^-8-10 ^-3Mol, what preferentially adopt is 10 ^-7-10 ^-4Mol, the consumption of organo-aluminium compound (C) is generally 10 ^-5-0.1 mol, what preferentially adopt is 10 ^-4-10 ^-2The consumption of mol ， Lv oxane (D) is preferably 10 ^-5-0.1 grammeatom Al/ liter, what preferentially adopt is 10 ^-4-10 ^-2Grammeatom Al/ liter.In addition, benzene-insoluble organoaluminum oxy-compound (A) is preferably in 0.01-5 with the ratio (representing with the Al atom) of organo-aluminium compound (C), that preferentially adopt is 0.02-2, benzene-insoluble organoaluminum oxy-compound (A) is 0.01-5 with the ratio (representing with the Al atom) of aluminium oxane (D), and that preferentially adopt is 0.02-2.

Olefin polymerization catalysis of the present invention has good polymerization activity.That is to say that it is to use by the about 1.2-20 that is dissolved in the quantity that known olefin polymerization catalysis that benzene De Lv oxane and metallocene compound form obtains doubly that olefin polymerization catalysis of the present invention can make the olefin polymer of the organoaluminum oxy-compound of per unit weight.Also have, olefin polymerization catalysis of the present invention and is used by being dissolved in benzene De Lv oxane and comparing that known olefin polymerization catalysis that metallocene compound is formed obtains, and can make polymkeric substance have high molecular weight.

In addition, can obtain having alkene (being total to) polymkeric substance that narrow molecular weight distribution and narrow composition distribute with olefin polymerization catalysis copolyolefine class of the present invention.

And olefin polymerization catalysis of the present invention also can contain the olefinic polymerization useful components except the aforesaid component of this paper.

Below, with the present invention will be described in conjunction with the embodiments, still will be understood that the present invention never only limits to these embodiment.

Embodiment 1

The preparation of 〔 Lv oxane)

With 37g Al ₂(SO ₄) ₃14H ₂O and 125ml toluene join in the 400ml retort bottle of crossing with the thorough purge of nitrogen and are chilled to 0 ℃, add the trimethyl aluminium of 500 mmoles with the 125ml dilution with toluene then dropwise.The temperature of retort bottle is risen to 40 ℃ and carry out reaction in 10 hours under this temperature.After reaction finishes, the reaction mixture solid-liquid is separated, from filtrate, remove toluene again, thereby obtain 12g white solid Lv oxane by filtration.

(preparation of benzene-insoluble organoaluminum oxy-compound)

With the solution of 59.7ml toluene, 40.3ml Lv oxane and toluene (2.48 moles-Al/ of Al liter) and 25g as teflon (Teflon) post of dispersion agent (

2mm * 1.2mm) joins in the 400ml retort bottle that thorough purge crosses.Then, make retort bottle be chilled to-5 ℃, little by little add 0.72ml water with whole pipet.Reaction was carried out 40 minutes, in 1 hour, temperature risen to 80 ℃ and carry out reaction in 3 hours thereafter in this temperature.After reaction in these 3 hours, by screening out the Teflon post in the reaction mixture, by filtration said reaction mixture solid-liquid is separated again, obtain benzene-insoluble organoaluminum oxy-compound.Mensuration is dissolved in the concentration of the aluminium in the filtrate, and the concentration of mensuration is less than the limit of detection of 5mg-Al/1.

100mg(is represented with the Al atom) by on the benzene-insoluble organoaluminum oxy-compound that obtains and 100ml benzene join 200ml and be equipped with in the reactor of agitator, under 60 ℃, make mixture stir prepare suspension 6 hours.This suspension filters with the G5 glass filter that chuck is housed, and is marked with 60 ℃ insulation silicone oil in the chuck, and the compound on the glass filter keeps 60 ℃ benzene to wash 4 times with 50ml.Reclaim filtrate and measure Al amount in the filtrate, the Al of detection is equivalent to 0.7 mmole.That is to say, can think that the above-mentioned Al group component that is dissolved in 60 ℃ of organoaluminum oxy-compound in the following benzene is that 0.7%(represents with the Al atom).And then, to by on the SOLID ORGANIC aluminium oxy-compound that obtains carry out infrared analysis, at 600-800cm ^-1Infrared spectra on observe the absorption and the 1260cm of Al-O-Al atomic group ^-1Under absorbancy (D1260) and 1220cm ^-1Under the ratio (D1260/D1220) of absorbancy (D1220) be 0.053.When with water decomposition SOLID ORGANIC aluminium oxy-compound, finding has methane to emit.

(polymerization)

The 900ml 4-methyl-1-pentene is joined in 2 liters of stainless steel autoclaves crossing with the thorough purge of nitrogen, then be warming up to 130 ℃.1.14ml by the benzene-insoluble organoaluminum oxy-compound of last preparation and toluene (0.44 mole-Al/1) suspension and two (methyl cyclopentadienyl) zirconium dichlorides of 1ml and toluene (0.001 mole-Zr/1) solution and ethene injection autoclave begin polymerization.Being aggregated in total pressure is 20kg/cm ²Carry out 30 minutes under-G and 140 ℃, and ethene is supplied with paradigmatic system continuously, thereby obtain 12.0g ethene/4 methyl 1 pentene copolymer, its limiting viscosity (η) of measuring in 135 ℃ of following naphthalanes is 0.47dl/g, and density is 0.908g/cm ³, Mw/ Mn is 2.4.

Comparative examples 1

Except the aluminium oxane of embodiment 1 preparation of using 0.5mg atom (representing) and the alternative benzene-insoluble organoaluminum oxy-compound of the solution of toluene with the Al atom, carry out the polymerization of embodiment 1 by the method identical with embodiment 1, thereby obtain 8.4g ethene/4 methyl 1 pentene copolymer, its limiting viscosity (η) is 0.41dl/g, and density is 0.910g/cm ³, Mw/ Mn is 2.5.

Embodiment 2

(preparing benzene-insoluble organo-aluminium compound)

With 134ml toluene and 10.9g by 32 mesh sieve classifications and the Al that on sieve, stays ₂(SO ₄) ₃14H ₂O joins in the 400ml glass retort with the thorough purge of nitrogen, makes the content in the retort bottle be suspension.At room temperature, (2.34 moles-Al/l) solution adds 100ml to be prepared De Lv oxane and toluene by the method identical with embodiment 1.Little by little the temperature of retort bottle is risen to 80 ℃ and stirred 7 hours under this temperature.Thereafter, in nitrogen atmosphere, remove the Tai-Ace S 150 compound that generates with 80 mesh sieves in reaction mixture, residual reaction mixture makes solid-liquid separate after filtration, obtains benzene-insoluble organoaluminum oxy-compound.Mensuration is dissolved in the aluminum concentration in the filtrate, and aluminum concentration is less than the limit of detection of 5mg-Al/1.

With the method identical with embodiment 1 measure by on the organoaluminum oxy-compound that the obtains solubleness in keeping 60 ℃ benzene be 0.3%.

In addition, at 1260cm ^-1The absorbancy (D1260) and the 1220cm at place ^-1The ratio (D1260/D1220) of the absorbancy (D1220) at place is 0.067.

(polymerization)

Except benzene-insoluble organoaluminum oxy-compound with as above preparation, repeat the polymerization of embodiment 1, thereby obtain 10.8g ethene/4 methyl 1 pentene copolymer, its limiting viscosity (η) is 0.49dl/g, density is 0.907g/cm ³, Mw/ Mn is 2.6.

Embodiment 3

(preparation of benzene-insoluble organoaluminum oxy-compound)

32.8ml toluene and the 0.78g Magnesium dichloride hexahydrate through grinding is joined in the 400ml glass retort with the thorough purge of nitrogen, stir the content in the retort bottle then.At room temperature add 25ml again and in embodiment 1, prepare (2.31 moles-Al/l) solution of De Lv oxane and toluene.Thereafter, the temperature of retort bottle is raised to 80 ℃ and stirred 7 hours under this temperature, after stirring 7 hours, makes the separation of reaction mixture solid-liquid, obtain benzene-insoluble organoaluminum oxy-compound by filtration.Mensuration is dissolved in the concentration of the aluminium in the filtrate, and the aluminum concentration of mensuration is less than limit of detection (5mg-Al/l).

With the method identical with embodiment 1 measure by on the organoaluminum oxy-compound that the obtains solubleness in keeping 60 ℃ benzene be 0.3%.

(polymerization)

Except using as above prepared benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 1, thereby obtain 11.3g ethene/4 methyl 1 pentene copolymer, its limiting viscosity (η) is 0.46dl/g, density is 0.907g/cm ³, Mw/ Mn is 2.5.

Embodiment 4-6

Except using every kind of transistion metal compound as shown in table 1, repeat the polymerization of embodiment 1.

Gained the results are shown in table 1.

Table 1

Embodiment transistion metal compound polymer yield (η) density Mw/ Mn

Sequence number kind mmole (g) is (g/cm (dl/g) ³)

3 （MeCp） ₂ZrCl ₂0.001 11.3 0.46 0.907 2.5

4 CpZrCl ₂0.001 6.5 0.40 0.912 2.6

5 CpZrMe ₂0.001 4.8 0.41 0.913 2.5

6 （Ind） ₂ZrCl ₂0.001 12.8 0.52 0.906 2.4

Cp; Cyclopentadiene (Cyclopentadienyl group)

MeCP; Methyl cyclopentadienyl (Methyiclopentadienyl group)

Ind: indenyl (Indenyl group)

Me; Methyl (Methyl group)

Embodiment 7

The 900ml 4-methyl-1-pentene is joined in 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 130 ℃.((0.0005 mole-Zr/l) solution injection autoclave begins polymerization for 0.44 mole-Al/l) suspension and two (indenyl) zirconium dichlorides of 2ml ethene and toluene at the benzene-insoluble organoaluminum oxy-compound of embodiment 1 preparation and toluene 1.14ml.Being aggregated in total pressure is 20kg/cm ²Carry out 30 minutes under-G and 130 ℃, and ethene is supplied with continuously, thereby obtained 26.1g ethene/4 methyl 1 pentene copolymer, its limiting viscosity (η) of measuring in 135 ℃ of following naphthalanes is 0.48dl/g, and density is 0.895g/cm ³, Mw/ Mn is 2.4.

Comparative examples 2

Except the alternative benzene-insoluble organoaluminum oxy-compound of solution that uses aluminium oxane that 0.5mg atom (representing with the Al atom) prepare and toluene in embodiment 1, repeat the polymerization of embodiment 7, thereby obtain 20.8g ethene/4 methyl 1 pentene copolymer, its intrinsic viscosity (η) is 0.37dl/g, and density is 2.4 for Mw/ M.

Embodiment 8

Except using the benzene-insoluble organoaluminum oxy-compound of embodiment 2 preparations, repeat the polymerization of embodiment 7, thereby obtain 24.8g ethene/4 methyl 1 pentene copolymer, its intrinsic viscosity (η) is 0.45dl/g, density is 0.893g/cm ³, Mw/ Mn is 2.5.

Embodiment 9

(polymerization)

Except using the benzene-insoluble organoaluminum oxy-compound of embodiment 3 preparations, repeat the polymerization of embodiment 7, thereby obtain 25.6g ethene/4 methyl 1 pentene copolymer, its limiting viscosity (η) is 0.46dl/g, density is 0.894g/cm ³, Mw/ Mn is 2.3.

Embodiment 10

(polymerization)

The 900ml4-Methyl-1-pentene is joined in 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 50 ℃.((0.44 mole-Al/l) suspension joins in the autoclave at the benzene-insoluble organoaluminum oxy-compound of embodiment 1 preparation and toluene for 1 mole-Al/l) solution and 0.22ml 1ml triisobutyl aluminium and toluene.Be warming up to 75 ℃ again, (0.001 mole-Zr/l) solution and ethene inject autoclave and begin polymerization with toluene two (methyl cyclopentadienyl) zirconium dichlorides of 1ml.Being aggregated in total pressure is 8kg/cm ²Carry out 40 minutes under-G and 80 ℃, thereby obtain 85.8g ethene/4 methyl 1 pentene copolymer, its MFR is 1.03g/10 minute, and density is 0.884g/cm ³, Mw/ Mn is 2.1.

Comparative examples 3

Except using 0.1mg atom (representing) to substitute the benzene-insoluble organoaluminum oxy-compound at the aluminium oxane of embodiment 1 preparation with the Al atom, repeat the polymerization of embodiment 10, thereby obtain 40.9g ethene/4 methyl 1 pentene copolymer, its MFR is 0.82g/10 minute, and density is 0.887g/cm ³, Mw/ Mn is 2.2.

Comparative examples 4

Except using 0.5mg atom (representing) to substitute the benzene-insoluble organoaluminum oxy-compound at the aluminium oxane of embodiment 1 preparation and without triisobutyl aluminium with the Al atom, repeat the polymerization of embodiment 10, thereby obtain 50.1g ethene/4 methyl 1 pentene copolymer, its MFR is 9.55g/10 minute, and density is 0.890g/cm ³, Mw/ Mn is 2.2.

Embodiment 11

(polymerization)

350ml toluene and 25ml1-octene are joined in the 500ml glass autoclave with the thorough purge of nitrogen, then be warming up to 65 ℃, thereafter, speed with 120 liters/hour, make ethylene gas pass through autoclave, and 0.5 mmole triisobutyl aluminium, 0.2mg(represented with the Al atom) add the beginning polymerization at benzene-insoluble organoaluminum oxy-compound and two (cyclopentadienyl) zirconium dichlorides of 0.002 mmole of the preparation of embodiment.Be aggregated under normal pressure and 70 ℃ and carry out 30 minutes, and ethylene gas is supplied with continuously, thereby obtain 14.9g ethene/1-octene copolymer, its MFR is 3.90g/10 minute, and density is 0.902g/cm ³, Mw/ Mn is 2.4.

Embodiment 12

(polymerization)

Except using the benzene-insoluble organoaluminum oxy-compound of embodiment 3 preparations, repeat the polymerization of embodiment 7, thereby obtain 90.4g ethene/4 methyl 1 pentene copolymer, its MFR is 1.68g/10 minute, density is 0.887g/cm ³, Mw/ Mn is 2.1.

Embodiment 13-17

Except using every kind of transistion metal compound and organo-aluminium compound that is shown in table 2 respectively, repeat the polymerization of embodiment 12.

Gained the results are shown in table 2.

Table 2

Embodiment transistion metal compound organo-aluminium compound

Sequence number kind mmole kind mmole

12 (MeCp) ₂ZrCl ₂0.001 triisobutyl aluminium 1

13 Cp ₂ZrCl ₂0.001 triisobutyl aluminium 1

14 Cp ₂ZrMe ₂0.001 triisobutyl aluminium 1

15 (Ind) ₂ZrCl ₂0.001 triisobutyl aluminium 1

16 (MeCp) ₂ZrCl ₂0.001 triisobutyl aluminium 0.25

17 (MeCp) ₂ZrCl ₂0.001 three-2-ethylhexyl aluminium 1

Table 2(is continuous)

Embodiment sequence number polymer yield MFR density Mw/ Mn

（g/10min） （g/cm ³）

12??90.4??1.68??0.887??2.1

13??60.3??4.95??0.895??2.2

14??57.3??5.11??0.894??2.3

15??83.1??1.05??0.888??2.2

16??88.5??2.02??0.888??2.1

17??85.7??1.50??0.889??2.3

Cp; Cyclopentadiene (Cyclopentadienyl group)

MeCP; Methyl cyclopentadienyl (Methyiclopentadienyl group)

Ind: indenyl (Indenyl group)

Me; Methyl (Methyl group)

Embodiment 18

(polymerization)

The 900ml 4-methyl-1-pentene is joined in 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 50 ℃.0.22ml at the benzene-insoluble organoaluminum oxy-compound of embodiment 1 preparation and toluene (0.44 mole-Al/l) suspension and 1ml(i-Bu) Al-O-Al(i-Bu) (1 mole-Al/l) solution joins in the autoclave.Be warming up to after 75 ℃, (0.001 mole-Zr/l) solution and ethene inject autoclave and begin polymerization, and being aggregated in total pressure is 8kg/cm with toluene two (methyl cyclopentadienyl) zirconium dichlorides of 1ml again ²Carry out 40 minutes under-G and 80 ℃, and ethene is supplied with continuously, thereby obtained 83.9g ethene/4 methyl 1 pentene copolymer, its MFR is 0.93g/10 minute, and density is 0.883g/cm ³, Mw/ Mn is 2.2.

Comparative examples 5

Except using 0.1mg atom (representing) to substitute the benzene-insoluble organoaluminum oxy-compound at the aluminium oxane of embodiment 1 preparation with the Al atom, repeat the polymerization of embodiment 18, thereby obtain 43.2g ethene/4 methyl 1 pentene copolymer, its MFR is 0.78g/10 minute, and density is 0.888g/cm ³, Mw/ Mn is 2.2.

Comparative examples 6

Except using 0.5mg atom (representing) at the aluminium oxane of embodiment 1 preparation and need not (i-Bu) with the Al atom ₂Al-O-Al(i-Bu) ₂Substitute outside the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 18, thereby obtain 50.1g ethene/4 methyl 1 pentene copolymer, its MFR is 9.55g/10 minute, and density is 0.890g/cm ³, Mw/ Mn is 2.2.

Embodiment 19

(polymerization)

350ml toluene and 25ml1-octene are joined in the 500ml glass autoclave with the thorough purge of nitrogen, then be warming up to 65 ℃.Thereafter,, make ethylene gas pass through autoclave, again 0.5 mmole (i-Bu) with 120 liters/hour speed ₂Al OMe, 0.2mg(represent with the Al atom) add the beginning polymerization at benzene-insoluble organoaluminum oxy-compound and two (cyclopentadienyl) zirconium dichlorides of 0.002 mmole of embodiment 2 preparation.Be aggregated under normal pressure and 70 ℃ and carry out 30 minutes, and ethylene gas is supplied with continuously, thereby obtain 11.5g ethene/1-octene copolymer, its MFR is 5.12g/10 minute, and density is 0.906g/cm ³, Mw/ Mn is 2.3.

Embodiment 20

(polymerization)

Except the benzene-insoluble organoaluminum oxy-compound that uses embodiment 3 preparations, repeat the polymerization of embodiment 18, thereby obtain 95.4g ethene/4 methyl 1 pentene copolymer, its MFR is 1.51g/10 minute, density is 0.885g/cm ³, Mw/ Mn is 2.1.

Embodiment 21-24

Except using every kind of filtering metal thing and organo-aluminium compound that is shown in Table 3 respectively, repeat the polymerization of embodiment 20.

Gained the results are shown in table 3.

Table 3

Embodiment transistion metal compound polymer yield MFR density Mw/ Mn

Sequence number kind milli despatch that (g/10min) (g/cm ³)

20 （MeCp） ₂ZrCl ₂0.001 95.4 1.51 0.885 2.1

21 CP ₂ZrCl ₂0.001 62.5 5.55 0.893 2.1

22 CpZrMe ₂0.001 54.9 6.02 0.895 2.3

23 （Ind） ₂ZrCl ₂0.001 85.2 0.96 0.887 2.2

24＊ （MeCp） ₂ZrCl ₂0.001 97.5 2.66 0.882 2.3

* (i-Bu) ₂Al-O-Al(i-Bn) ₂Consumption be 0.25mg(with Al former with expression)

Cp; Cyclopentadiene (Cyclopentadienyl group)

MeCP; Methyl cyclopentadienyl (Methyiclopentadienyl group)

Ind: indenyl (Indenyl group)

Me; Methyl (Methyl group)

Embodiment 25

(polymerization)

600ml toluene and 300ml4-Methyl-1-pentene are joined in 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 50 ℃.Again the benzene-insoluble organoaluminum oxy-compound of 0.11ml embodiment 1 preparation and toluene (0.44 mole-Al/l) suspension and not 1ml triisobutyl aluminium and toluene (1 mole-Al/l) solution joins in the autoclave.Be warming up to after 75 ℃, (0.0005 mole-Zr/l) solution and ethene inject autoclave and begin polymerization with toluene two (indenyl) zirconium dichlorides of 0.3ml ethylene again.Being aggregated in total pressure is 8kg/cm ²Carry out 40 minutes under-G and 80 ℃, and ethene is supplied with continuously, thereby obtained 98.9g ethene/4 methyl 1 pentene copolymer, its MFR is 14.0g/10 minute, and density is 0.898g/cm ³, Mw/ Mn is 2.3.

Comparative examples 7

Except using 0.05mg atom (representing) to substitute the benzene-insoluble organoaluminum oxy-compound at the aluminium oxane of embodiment 1 preparation with the Al atom, repeat the polymerization of embodiment 25, thereby obtain 55.1g ethene/4 methyl 1 pentene copolymer, its MFR is 9.73g/10 minute, and density is 0.905g/cm ³, Mw/ Mn is 2.3.

Comparative examples 8

Except using 0.5mg atom (representing) to substitute the benzene-insoluble organoaluminum oxy-compound at the aluminium oxane of embodiment 1 preparation and without triisobutyl aluminium with the Al atom, repeat the polymerization of embodiment 25, thereby obtain 62.8g ethene/4 methyl 1 pentene copolymer, its MFR is 35.6g/10 minute, and density is 0.897g/cm ³, Mw/ Mn is 2.2.

Embodiment 26

(polymerization)

280ml toluene is joined with being warming up to 65 ℃ in the 500ml glass autoclave of the thorough purge of nitrogen and when leading to propylene gas.Thereafter, 0.5 mmole triisobutyl aluminium, 0.5mg atom (the Al atom is represented) are joined at the benzene-insoluble organoaluminum oxy-compound of embodiment 2 preparations and two (indenyl) zirconium dichloride succeedinglys of 0.005 mmole ethylene begin polymerization in the autoclave.Be aggregated under normal pressure and 70 ℃ and carry out 1 hour, and propylene gas is supplied with continuously, thereby obtain the 16.9g isotatic polypropylene, its limiting viscosity (η) of measuring in 135 ℃ of naphthalanes is 0.28dl/g, and Mw/ Mn is 1.9.

Comparative examples 9

Except using solution at embodiment 1 preparation De Lv oxane and toluene, wherein the amount of representing with the aluminium atom is 2.5mg and substitutes outside the benzene-insoluble organoaluminum oxy-compound without triisobutyl aluminium, repeat the polymerization of embodiment 26, thereby obtain the 12.0g isotatic polypropylene, its limiting viscosity (η) is 0.14dl/g, and Mw/ Mn is 1.9.

Embodiment 27

(polymerization)

Except the amount of the triisobutyl aluminium that uses changes 0.25 mmole into and uses 0.05mg atom (representing with the Al atom) the benzene-insoluble organoaluminum oxy-compound of embodiment 3 preparations, repeat the polymerization of embodiment 25, thereby obtain 93.3g ethene/4 methyl 1 pentene copolymer, its MFR is 11.5g/10 minute, and density is 0.900g/cm ³, Mw/ Mn is 2.3.

Embodiment 28

Make 7 * 10 respectively into except using the 1-octene to substitute 4-methyl-1-pentene and used two (indenyl) zirconium dichlorides of ethylene and the consumption of triisobutyl aluminium ^-8Outside mole and 1 mmole, repeat the polymerization of embodiment 27, thereby obtain 70.8g ethene/1-octene copolymer, its MFR is 8.94g/10 minute, and density is 0.896g/cm ³, Mw/ Mn is 2.2.

Embodiment 29

Except using 0.5 mmole, three-2-ethylhexyl aluminium to substitute the triisobutyl aluminium, repeat the polymerization of embodiment 27, thereby obtain 90.5g ethene/4 methyl 1 pentene copolymer, its MFR is 12.1g/10 minute, density is 0.900g/cm ³, Mw/ Mn is 2.4.

Embodiment 30

(polymerization)

600ml toluene and 300ml 4-methyl-1-pentene are joined 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 50 ℃.The benzene-insoluble organoaluminum oxy-compound of 0.11ml embodiment 1 preparation and toluene (0.44 mole-Al/l) suspension and 1ml(i-Bu) ₂Al-O-Al(i-Bu) ₂(1 mole-Al/l) solution joins in the autoclave with toluene.Be warming up to after 75 ℃, (0.0005 mole-Zr/l) solution and ethene inject autoclave and begin polymerization with toluene with two (indenyl) zirconium dichlorides of 0.3ml ethylene.Being aggregated in total pressure is 8kg/cm ²Carry out 40 minutes under-G and 80 ℃, and ethene is supplied with continuously, thereby obtained 101.2g ethene/4 methyl 1 pentene copolymer, its MFR is 14.6g/10 minute, and density is 0.899g/cm ³, Mw/ Mn is 2.2.

Comparative examples 10

Except using 0.05mg atom (representing) to substitute the benzene-insoluble organoaluminum oxy-compound at the aluminium oxane of embodiment 1 preparation with the Al atom, repeat the polymerization of embodiment 30, thereby obtain 53.9g ethene/4 methyl 1 pentene copolymer, its MFR is 10.6g/10 minute, and density is 0.904g/cm ³, Mw/ Mn is 2.3.

Comparative examples 11

Except using 0.5mg atom (representing) at the solution of the aluminium oxane of embodiment 1 preparation and toluene and need not (i-Bu) with the Al atom ₂Al-O-Al(i-Bu) ₂Substitute outside the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 30, thereby obtain 62.8g ethene/4 methyl 1 pentene copolymer, its MFR is 35.6g/10 minute, and density is 0.897g/cm ³, Mw/ Mn is 2.2.

Embodiment 31

(polymerization)

250ml toluene is joined in the 500ml glass autoclave with the thorough purge of nitrogen, then be warming up to 65 ℃, and propylene gas is by wherein.Thereafter, little by little (i-Bu) 0.5mg atom (representing) with the aluminium atom ₂Al-O-Al(i-Bu) ₂, 0.5mg atom (representing with the aluminium atom) joins at the benzene-insoluble organoaluminum oxy-compound of embodiment 2 preparation and two (indenyl) zirconium dichlorides of 0.005 mmole ethylene and begins polymerization in the autoclave.Be aggregated under normal pressure and 70 ℃ and carry out 1 hour, and propylene gas is supplied with continuously, thereby obtain the 17.5g isotatic polypropylene, its limiting viscosity (η) of measuring in 135 ℃ of naphthalanes is 0.30dl/g, and Mw/ Mn is 2.0.

Comparative examples 12

Except using 2.5mg(to represent with the Al atom) at the aluminium oxane (i-Bu) of embodiment 1 preparation ₂Al-O-Al(i-Bu) ₂Substitute outside the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 31, thereby obtain the 12.0g isotatic polypropylene, its limiting viscosity (η) is 0.14dl/g, and Mw/ Mn is 1.9.

Embodiment 32

Except with (i-Bu) ₂Al-O-Al(i-Bu) ₂Consumption make 2.5mg atom (representing) into and the consumption of the benzene-insoluble organoaluminum oxy-compound of embodiment 3 preparation made into outside the 0.05mg atom (representing with the aluminium atom) with the Al atom, repeat the polymerization of embodiment 30, thereby obtain 95.6g ethene/4 methyl 1 pentene copolymer, its MFR is 10.0g/10 minute, and density is 0.899g/cm ³, Mw/ Mn is 2.2.

Embodiment 33

Except using the 1-octene to substitute 4-methyl-1-pentene and two (indenyl) zirconium dichlorides of ethylene and (i-Bu) ₂Al-O-Al(i-Bu) ₂Consumption be respectively 7 * 10 ^-8Outside mole and 1mg atom and the 1mg atom (representing with the aluminium atom), repeat the polymerization of embodiment 32, thereby obtain 78.1g ethene/1-octene copolymer, its MFR is 9.22g/10 minute, and density is 0.894g/cm ³, Mw/ Mn is 2.2.

Embodiment 34

Except using 2.0 mmoles (i-Bu) ₂Al OMe substitutes (i-Bu) ₂Al-O-Al(i-Bu) ₂Outside, repeating the polymerization of embodiment 32, thereby obtain 71.6g ethene/4 methyl 1 pentene copolymer, its MFR is 18.0g/10 minute, density is 0.902g/cm ³, Mw/ Mn is 2.3.

Embodiment 35

(polymerization)

The 900ml 4-methyl-1-pentene is joined in 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 50 ℃.Benzene-insoluble organoaluminum oxy-compound and the suspension of toluene (0.44 mole of Al/l) and the aluminium oxane that 1ml has at least one alkyl that is combined in the non-positive alkyl on the aluminium atom of 0.22ml embodiment 1 preparation, promptly

(1 mole-Al/l) suspension joins in the autoclave with toluene.Be warming up to after 75 ℃, (0.001 mole-Zr/l) solution and ethene are injected into and begin polymerization in the autoclave with toluene two (methyl cyclopentadienyl) zirconium dichlorides of 1ml.Being aggregated in total pressure is 8kg/cm ²Carry out 40 minutes under-G and 80 ℃, and ethene is supplied with continuously, thereby obtained 82.6g ethene/4 methyl 1 pentene copolymer, its MFR is 1.10g/10 minute, and density is 0.887g/cm ³, Mw/ Mn is 2.3.

Comparative examples 13

Except using 0.1mg atom (representing) to substitute the benzene-insoluble organoaluminum oxy-compound at the aluminium oxane of embodiment 1 preparation with the Al atom, repeat the polymerization of embodiment 35, thereby obtain 41.0g ethene/4 methyl 1 pentene copolymer, its MFR is 0.85g/10 minute, and density is 0.891g/cm ³, Mw/ Mn is 2.2.

Comparative examples 14

Except using 0.5mg atom (representing) at the aluminium oxane of embodiment 1 preparation and need not with the Al atom

Substitute outside the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 35, thereby obtain 50.1g ethene/4 methyl 1 pentene copolymer, its MFR is 9.55g/10 minute, and density is 0.890g/cm ³, Mw/ Mn is 2.2.

Embodiment 36

(polymerization)

350ml toluene and 25ml1-octene are added in the 500ml glass autoclave with the thorough purge of nitrogen, then are warming up to 65 ℃.With 120 liters/hour speed ethylene gas is passed through then.Again with 0.5mg atom-Al's

0.2mg atom-Al at the benzene-insoluble organoaluminum oxy-compound of embodiment 2 preparation and the 22(cyclopentadienyl of 0.002 mmole) the zirconium dichloride succeedingly is added to and begins polymerization in the autoclave.Be aggregated in and carried out under 70 ℃ 30 minutes, at this moment add ethylene gas continuously.Thereby obtain 13.5g ethene/1-octene copolymer, its MFR is 4.20g/10 minute, and density is 0.904g/cm ³, Mw/ Mn is 2.3.

Embodiment 37

(polymerization)

Except the benzene-insoluble organoaluminum oxy-compound that uses embodiment 3 preparations, repeat the polymerization of embodiment 35, thereby obtain 82.3g ethene/4 methyl 1 pentene copolymer, its MFR is 1.05g/10 minute, density is 0.888g/cm ³, Mw/ Mn is 2.3.

Embodiment 38-42

Except using every kind of transistion metal compound and organo-aluminium compound that is shown in table 4 respectively, repeat the polymerization of embodiment 35.It the results are shown in table 4.

Table 4

Embodiment transistion metal compound polymer yield MFR density Mw/ Mn

Sequence number kind milli despatch that (g/10min) (g/cm ³)

37 （MeCp） ₂ZrCl ₂0.001 82.3 1.05 0.888 2.3

38 CP ₂ZrCl ₂0.001 60.1 4.78 0.895 2.2

39 CpZrMe ₂0.001 49.5 6.20 0.897 2.4

30 （Ind） ₂ZrCl ₂0.001 79.1 1.87 0.888 2.3

41＊ （MeCp） ₂ZrCl ₂0.001 80.6 1.50 0.887 2.2

42＊＊ （MeCp） ₂ZrCl ₂0.001 76.4 2.10 0.887 2.4

＊

* isobutyl-Lv oxane (is 1090 with cryoscopy mensuration and molecular weight), consumption 1.0mg atom A l

Embodiment 43

(polymerization)

600ml toluene and 300ml 4-methyl-1-pentene are joined in 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 50 ℃.(0.44 mole-Al/l) suspension and 1ml has the alkyl that at least one is combined in the non-positive alkyl on the aluminium atom, promptly the benzene-insoluble organoaluminum oxy-compound of 0.11ml embodiment 1 preparation and toluene

Join in the autoclave with the solution of toluene (1ml-Al/l).Be warming up to after 75 ℃, (0.0005 mole-Zr/l) solution and ethene inject autoclave and begin polymerization with toluene two (indenyl) zirconium dichlorides of 0.3ml ethylene.Being aggregated in total pressure is 8kg/cm ²Carry out 40 minutes under-G and 80 ℃, and ethene is supplied with continuously, thereby obtained 89.5g ethene/4 methyl 1 pentene copolymer, its MFR is 9.08g/10 minute, and density is 0.900g/cm ³, Mw/ Mn is 2.4.

Comparative examples 15

Except using 0.05mg atom (representing) to substitute the benzene-insoluble organoaluminum oxy-compound at the aluminium oxane of embodiment 1 preparation with the Al atom, repeat the polymerization of embodiment 43, thereby obtain 50.2g ethene/4 methyl 1 pentene copolymer, its MFR is 7.55g/10 minute, and density is 0.905g/cm ³, Mw/ Mn is 2.3.

Comparative examples 16

Except using 0.05mg atom (representing) at the aluminium oxane of embodiment 1 preparation and need not with the Al atom

Substitute outside the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 43, thereby obtain 62.8g ethene/4 methyl 1 pentene copolymer, its MFR is 35.6g/10 minute, and density is 0.897g/cm ³, Mw/ Mn is 2.2.

Embodiment 44

(polymerization)

250ml toluene is joined with in the 500ml glass autoclave of the thorough purge of nitrogen and be warming up to 65 ℃, and propylene gas is by wherein.Thereafter, little by little 0.5mg atom (representing) with the aluminium atom

0.5mg the benzene-insoluble organoaluminum oxy-compound of embodiment 2 preparations of atom (representing with the aluminium atom) and two (indenyl) zirconium dichlorides of 0.005 mmole ethylene join and begin polymerization in the autoclave.Be aggregated in and carried out under 70 ℃ 1 hour, and propylene gas is supplied with continuously, thereby obtain the 15.7g isotatic polypropylene, its limiting viscosity (η) of measuring in 135 ℃ of naphthalanes is 0.27dl/g, and Mw/ Mn is 1.9.

Comparative examples 17

Except using 2.5mg atom (representing) at the aluminium oxane of embodiment 1 preparation and need not with the Al atom

Substitute outside the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 44, thereby obtain the 12.0g isotatic polypropylene, its limiting viscosity (η) is 0.14dl/g, and Mw/ Mn is 1.9.

Embodiment 45

(polymerization)

Except

Consumption makes 0.5mg atom-Al into and uses outside the benzene-insoluble organoaluminum oxy-compound of embodiment 3 preparations of 0.05mg atom-Al, repeat the polymerization of embodiment 43, thereby obtain 88.2g ethene 4 methyl 1 pentene copolymer, its MFR is 12.2g/10 minute, and density is 0.901g/cm ³, Mw/ Mn is 2.3.

Embodiment 46

Except using the 1-octene to substitute 4-methyl-1-pentene and using 7 * 10 ^-8Two (indenyl) zirconium dihydrides of mole ethylene and 1ml atom

Outside, repeating the polymerization of embodiment 45, thereby obtain 74.4g ethene/1-octene copolymer, its MFR is 10.3g/10 minute, density is 0.895g/cm ³, Mw/ Mn is 2.3.

Embodiment 47

Except the isobutyl-Lv oxane (molecular weight of measuring with cryoscopy is 1090) that uses 1.0ml atom-Al substitutes

Outside, repeating the polymerization of embodiment 45, thereby obtain 84.2g ethene/4 methyl 1 pentene copolymer, its MFR is 12.5g/10 minute, density is 0.899g/cm ³, Mw/ Mn is 2.4.

Embodiment 48

(polymerization)

The 900ml 4-methyl-1-pentene is joined in 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 50 ℃.(0.44 mole-suspension Al/l), 0.5ml have the aluminium oxane of at least one alkyl that is combined in the non-positive alkyl on the aluminium atom, promptly the benzene-insoluble organoaluminum oxy-compound of 0.22ml embodiment 1 preparation and toluene

((1 mole-Al/l) solution joins in the autoclave for 1 mole-Al/l) solution and 0.5ml triisobutyl aluminium and toluene with toluene.Be warming up to after 75 ℃, (0.001 mole-Zr/l) solution and ethene inject autoclave and begin polymerization with toluene two (methyl cyclopentadienyl) zirconium dichlorides of 1ml.Being aggregated in total pressure is 8kg/cm ²Carry out 40 minutes under-G and 80 ℃, and ethene is supplied with continuously, thereby obtained 84.0g ethene/4 methyl 1 pentene copolymer, its MFR is 0.95g/10 minute, and density is 0.886g/cm ³, Mw/ Mn is 2.3.

Comparative examples 18

The aluminium oxane for preparing except the embodiment 1 that uses 0.1mg atom (representing with the Al atom) substitutes the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 48, thereby obtain 42.1g ethene/4 methyl 1 pentene copolymer, its MFR is 0.88g/10 minute, and density is 0.890g/cm ³, Mw/ Mn is 2.3.

Comparative examples 19

Except the aluminium oxane of embodiment 1 preparation of using 0.5mg atom (representing) and need not with the Al atom

Substitute outside the benzene-insoluble organoaluminum oxy-compound with triisobutyl aluminium, repeat the polymerization of embodiment 48, thereby obtain 50.1g ethene/4 methyl 1 pentene copolymer, its MFR is 9.55g/10 minute, and density is 0.890gcm ³, Mw/ Mn is 2.2.

Embodiment 49

(polymerization)

Join 350ml toluene and 25ml 1-octene with the 500ml glass autoclave of the thorough purge of nitrogen and be warming up to 65 ℃.Thereafter, in the time of therein by ethylene gas, little by little 0.4mg atom-Al(is represented with the Al atom)

The benzene-insoluble organoaluminum oxy-compound of embodiment 2 preparations of (i-Bu) A10Me of atom (representing with the Al atom), 0.2mg atom (representing with the Al atom) and two (cyclopentadienyl) zirconium dichlorides of 0.002 mmole join and begin polymerization in the autoclave.Be aggregated in and carried out under 70 ℃ 30 minutes, and ethylene gas is supplied with continuously, thereby obtaining 11.6g ethene/1-octene copolymer closes, its MFR is 4.56g/10 minute, and density is 0.904g/cm ³, Mw/ Mn is 2.3.

Embodiment 50

(polymerization)

The benzene-insoluble organoaluminum oxy-compound that the benzene-insoluble organoaluminum oxy-compound alternate embodiment 1 for preparing except the embodiment 3 that uses 0.05mg atom-Al prepares, repeat the polymerization of embodiment 48, thereby obtain 80.8g/ ethene/4 methyl 1 pentene copolymer, its MFR is 1.13g/10 minute, and density is 0.887g/cm ³, Mw/ Mn is 2.2.

Embodiment 51

(polymerization)

600ml toluene and 300ml 4-methyl-1-pentene are joined in 2 liters of stainless steel autoclaves with the thorough purge of nitrogen, then be warming up to 50 ℃.The benzene-insoluble organoaluminum oxy-compound of 0.11ml embodiment 1 preparation and toluene (0.44 mole-(1 mole-Al/l) solution and 0.5ml has the alkyl that at least one is combined in the non-positive alkyl on the aluminium atom, promptly for Al/l) suspension, 0.5ml triisobutyl aluminium and toluene

(1 mole-Al/l) solution joins in the autoclave with toluene.Be warming up to after 75 ℃, (0.0005 mole-Zr/l) solution and ethene are injected into and begin polymerization in the autoclave with toluene two (indenyl) zirconium dichlorides of 0.3ml ethylene.Being aggregated in total pressure is 8kg/cm ²Carry out 40 minutes under-G and 80 ℃, and ethene is supplied with continuously, thereby obtained 95.5g ethene/4 methyl 1 pentene copolymer, its MFR is 15.2g/10 minute, and density is 0.899g/cm ³, Mw/ Mn is 2.3.

Comparative examples 20

The aluminium oxane for preparing except the embodiment 1 that uses 0.05mg atom (representing with the Al atom) substitutes the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 51, thereby obtain 53.9g ethene/4-methyl-1-pentene and join thing altogether, its MFR is 10.2g/10 minute, and density is 0.906g/cm ³, Mw/ Mn is 2.4.

Comparative examples 21

Except the aluminium oxane of embodiment 1 preparation of using 0.5mg atom (representing) with the Al atom and without triisobutyl aluminium and

Substitute outside the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 51, thereby obtain 62.8g ethene/4 methyl 1 pentene copolymer, its MFR is 35.6g/10 minute, and density is 0.897g/cm ³, Mw/ Mn is 2.2.

Embodiment 52

(polymerization)

250ml toluene is joined with in the 500ml glass autoclave of the thorough purge of nitrogen and be warming up to 65 ℃, and propylene gas passes through therein.Thereafter, little by little 0.2mg atom-Al(is represented with the Al atom)

0.3mg atom-Al(represents with the Al atom) (i-Bu) ₂Al-O-Al(i-Bu) ₂, the benzene-insoluble organoaluminum oxy-compound of embodiment 2 preparation of 0.5mg atom (representing with the Al atom) and two (indenyl) zirconium dichlorides of 0.005 mmole ethylene join and begin polymerization in the autoclave.Be aggregated in and carried out under 70 ℃ 1 hour, and propylene gas is supplied with continuously, thereby obtain the 16.2g isotatic polypropylene, its limiting viscosity (η) of measuring under 135 ℃ of naphthalanes is 0.29dl/g, and Mw/ Mn is 2.1.

Comparative examples 22

Except the aluminium oxane of embodiment 1 preparation of using 2.5mg atom (representing) and need not with the Al atom

(i-Bu) ₂Al-O-Al(i-Bu) ₂Substitute outside the benzene-insoluble organoaluminum oxy-compound, repeat the polymerization of embodiment 52, thereby obtain the 12.0g isotatic polypropylene, its limiting viscosity is 0.14dl/g, and Mw/ Mn is 1.9.

Claims (12)

1, a kind of olefine polymerizing process, it is characterized in that said method is included in to contain and a kind ofly has less than in the presence of the olefin polymerization catalysis of the organoaluminum oxy-compound [A] of dissolved A1 component in keeping 60 ℃ benzene of 10% (representing with the A1 atom) and a kind of transistion metal compound [B] that contains the ligand with loop chain dialkylene skeleton, makes polymerization of olefines or copolymerization.

2, a kind of olefine polymerizing process, it is characterized in that said method is included under the existence of the olefin polymerization catalysis described in claim 1, wherein transistion metal compound (B) is a kind of at least 2 transistion metal compounds with ligand of loop chain dialkylene skeleton that contain, said ligand combines by rudimentary alkylene, makes polymerization of olefines or copolymerization.

3, a kind of olefine polymerizing process, it is characterized in that said method be included in contain a kind of have less than 10%(represent with the Al atom) in keeping 60 ℃ benzene organoaluminum oxy-compound (A), a kind of transistion metal compound (B) that contains ligand and a kind of organo-aluminium compound (C) of dissolved Al component with loop chain dialkylene skeleton olefin polymerization catalysis in the presence of, make polymerization of olefines or copolymerization.

4, a kind of olefine polymerizing process, it is characterized in that said method is included under the existence of the olefin polymerization catalysis described in claim 3, wherein transistion metal compound (B) is a kind of at least 2 transistion metal compounds with ligand of loop chain dialkylene skeleton that contain, said ligand combines by rudimentary alkylene, makes polymerization of olefines or copolymerization.

5, a kind of olefine polymerizing process is characterized in that said method is included under the existence of the olefin polymerization catalysis described in claim 3, and wherein organo-aluminium compound (C) is a kind of by general expression R ⁶MAlX _3-mThe organo-aluminium compound of expression is in the formula: R ⁶Be the hydrocarbon of 1-12 carbon atom, X is a halogen, and m is 1-3, or a kind of by general expression R ⁶NAlY _3-nThe compound of expression is in the formula: R ⁶As defined above, Y be hydrogen ,-OR ⁷,-OSiR ⁸3 ,-OAlR ⁹2,

,-NR ¹²2 or-SlR ¹³3, n is 1-2, R ⁷-R ¹³Be respectively hydrogen, halogen or hydrocarbon, make polymerization of olefines or copolymerization.

6, a kind of olefine polymerizing process, it is characterized in that said method be included in contain a kind of have less than 10%(represent with the Al atom) in keeping 60 ℃ benzene dissolved Al component organoaluminum oxy-compound (A), a kind of transistion metal compound (B) that contains ligand with loop chain dialkylene skeleton and a kind ofly have at least one in the presence of the olefin polymerization catalysis of the aluminium oxane (D) of the alkyl of the non-positive alkyl of bonded on the aluminium atom, make polymerization of olefines or copolymerization.

7, a kind of olefine polymerizing process, it is characterized in that said method is included under the existence of the olefin polymerization catalysis described in claim 6, wherein transistion metal compound (B) is a kind of at least 2 transistion metal compounds with ligand of loop chain dialkylene skeleton that contain, said ligand combines by rudimentary alkylene, makes polymerization of olefines or copolymerization.

8, a kind of olefine polymerizing process is characterized in that said method is included under the existence of the olefin polymerization catalysis described in claim 6, and wherein the alkyl of non-positive alkyl is branched-chain alkyl, cycloalkyl or aryl, makes polymerization of olefines or copolymerization.

9, a kind of olefine polymerizing process, it is characterized in that said method be included in contain a kind of have less than 10%(represent with the Al atom) in keeping 60 ℃ benzene dissolved Al component organoaluminum oxy-compound (A), a kind ofly contain the transistion metal compound (B) of ligand, a kind of organo-aluminium compound (C) and a kind ofly have at least one in the presence of the olefin polymerization catalysis of the aluminium oxane (D) of the alkyl of the non-positive alkyl of bonded on the aluminium atom with loop chain dialkylene skeleton, make polymerization of olefines or copolymerization.

10, a kind of olefine polymerizing process, it is characterized in that said method is included under the existence of the olefin polymerization catalysis described in claim 9, wherein transistion metal compound (B) is a kind of at least 2 transistion metal compounds with ligand of loop chain dialkylene skeleton that contain, said ligand combines by rudimentary alkylene, makes polymerization of olefines or copolymerization.

11, a kind of olefine polymerizing process is characterized in that said method is included under the existence of the olefin polymerization catalysis described in claim 9, and wherein organo-aluminium compound (C) is a kind of by general expression R ⁶MAlX _3-mThe organo-aluminium compound of expression is in the formula: R ⁶Be the hydrocarbon of 1-12 carbon atom, X is a halogen, and m is 1-3, or a kind of by general expression R ⁶NAlY _3-nThe compound of expression is in the formula: R ⁶As defined above, Y be hydrogen ,-OR ⁷,-OSiR ⁸3 ,-OAlR ⁹2,

,-NR ¹²2 or-SlR ¹³3, n is 1-2, R ⁷-R ¹³Be respectively hydrogen, halogen or hydrocarbon, make polymerization of olefines or copolymerization.

12, a kind of olefine polymerizing process is characterized in that said method is included under the existence of the olefin polymerization catalysis described in claim 9, and wherein the alkyl of non-positive alkyl is branched-chain alkyl, cycloalkyl or aryl, makes polymerization of olefines or copolymerization.

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