Process for the preparation of an ethylene copolymer and an olefin polymer, and catalysts for olefin polymerization

Catalyst for olefin polymerization

The present invention relates to a solid catalyst for olefin polymerization and a method of using the catalyst for olefin polymerization, and particularly relates to a solid catalyst for olefin polymerization that can be applied to suspension polymerization and gas phase polymerization. When a small amount of organoaluminum oxy compound is applied to these polymerization methods, it can produce spherical olefin polymer with excellent particle properties and excellent melt tension with high polymerization activity, and use the catalyst to carry out olefin polymerization reaction.

So far, ethylene copolymers have been molded using a variety of molding methods and used in many fields. The requirements for the characteristics of the ethylene copolymer vary depending on the molding method and usage. For example, when molding an inflatable film at high speed, it is necessary to select an ethylene copolymer with a higher melt tension than its molecular weight in order to perform high-speed molding stably without fluctuations or bubble tearing. Ethylene copolymers are required to have similar characteristics to avoid sagging or tearing during the blowing process, or to minimize the width reduction during T-mold molding.

High-pressure low-density polyethylene has higher melt tension than ethylene copolymers made with Ziegler-type catalysts, and can be used as a material for films and hollow containers. The aforementioned high-pressure low-density polyethylene has lower mechanical strength such as tensile strength , Tear strength and face impact strength, in addition, it also has low heat resistance, low stress crack resistance and so on.

On the other hand, Japanese Patent LOP No. 90810/1981 and 106806/1985 proposes a melt tension and inflation ratio (mold/expansion ratio) of ethylene polymers obtained by using Ziegler type catalysts, especially titanium type catalysts. The improved method.

However, ethylene polymers obtained by using titanium catalysts, especially low-density ethylene polymers, usually have problems such as wide composition distribution and stickiness of molded parts such as films.

Therefore, the development of ethylene polymers with excellent melt tension and narrow composition density has considerable industrial value.

Recently, a new type of Ziegler-type olefin polymerization catalyst including a zirconium compound and aluminoxane has been developed, and the catalyst can produce ethylene/α-olefin copolymer with high polymerization activity. A method for preparing ethylene/α-olefin copolymers using this new catalyst has also been proposed.

For example, Japanese Patent LOP No. 19309/1983 discloses a method of polymerizing ethylene and one or at least two C₃-C₁₂ In the method of α-olefin, the catalyst is composed of a transition metal compound represented by the following formula

(Cyclopentadienyl)₂Me R Hal, where R is cyclopentadienyl, C₁-C₆Alkyl or halo, Me is transition metal and Hal is halo; and linear aluminoxane Al represented by the following formula₂OR₄[Al(R)-O] n where R is methyl or ethyl, and the value of n is 4 to 20; or a cyclic aluminoxane represented by the following formula<chemistry general="n"><img file="TW237461B_D0001.tif" /></chemistry>In the formula, R and n are as defined above.

Japanese Patent LOP No. 19309/1983 discloses an invention related to the production method of linear aluminoxane represented by the following formula<chemistry general="n"><img file="TW237461B_D0002.tif" /></chemistry>In the formula, the value of n is 2 to 40 and R is C₁-C₈Alkyl; and cyclic aluminoxane represented by the following formula<chemistry general="n"><img file="TW237461B_D0003.tif" /></chemistry>In the formula, n and R are as defined above. The patent publication also discloses a method for polymerizing olefins using a catalyst. The catalyst is prepared, for example, by mixing the methylaluminoxane produced by the aforementioned method with a bis(cyclopentadienyl) compound of titanium or zirconium. .

Japanese Patent LOP No. 35005/1985 discloses a method for preparing an olefin polymerization catalyst, wherein the method includes making an aluminoxane represented by the following formula<chemistry general="n"><img file="TW237461B_D0004.tif" /></chemistry>(Where R is C₁-C₁₀Alkyl, and R⁰For R¹Or R⁰It stands for -O-linkage) firstly react with magnesium compound, then chlorinate the reaction product, and treat with Ti, V, Zr or Cr compound.

Japanese Patent LOP No. 35006/1985 discloses a combination of mono-, di- or tricyclopentadienyl-transition metal (a) (transition metal is at least two different metals) or its derivatives and aluminoxane The composition of the catalyst. The examples of the disclosure reveal that ethylene and propylene are polymerized to produce polyethylene under the coexistence of a catalyst composed of bis(pentamethylcyclopentadienyl) zirconium dimethyl and aluminoxane. In Example 2 of this patent publication, ethylene and propylene are polymerized to form a polymer blend of polyethylene and ethylene/propylene copolymer. The reaction is based on bis(pentamethylcyclopentadienyl) zirconium two It is carried out under the coexistence of a catalyst composed of chloride, bis(methylcyclopentadienyl) zirconium dichloride and aluminoxane.

Japanese Patent LOP No. 35007/1985 discloses a method for the polymerization of ethylene alone, or the copolymerization of ethylene and α-olefins with no less than 3 carbon atoms in the presence of metal octane and a cyclic aluminoxane represented by the following formula method<chemistry general="n"><img file="TW237461B_D0005.tif" /></chemistry>In the formula, R is an alkyl group with 1 to 5 carbon atoms, and n is an integer from 1 to about 20; or a linear aluminoxane represented by the following formula<chemistry general="n"><img file="TW237461B_D0006.tif" /></chemistry>In the formula, R and n are as defined above.

Japanese Patent LOP No. 35008/1985 discloses a method for preparing polyethylene or ethylene and C₃-C₁₀ The method of copolymer of α-olefin uses a catalyst system including no less than two types of metal octane and aluminoxane.

Although the catalysts produced from transition metal compounds and aluminoxanes proposed in the prior art have excellent polymerization activity, especially the polymerization activity of ethylene is compared with the emergence of these catalysts. These catalysts are known to be active. The catalyst system described later It is produced from transition metal compounds and organoaluminum compounds, but most of the aforementioned catalysts are soluble in the reaction system, and in most cases, the preparation method is limited to the solution polymerization system. In addition, the catalyst has the following problem: when trying to produce a polymer with a high molecular weight, the viscosity of the polymer-containing reaction solution increases significantly, resulting in a decrease in the productivity of the polymer, and the polymer obtained by post-polymerization treatment has a low volume specific gravity. , And the preparation of spherical polymers with excellent particle properties is difficult.

On the other hand, an attempt has been made to use a catalyst to polymerize olefins in a suspension polymerization system or a gas phase polymerization system. In the catalyst, at least one of the transition metal compound component and the aluminoxane component is supported by Porous inorganic oxide carriers such as silica, alumina and silica-alumina.

For example, the aforementioned Japanese Patent LOP Nos. 35006/1985, 35007/1985 and 35008/1985 disclose that transition metal compounds and aluminoxanes can be used to support silica, alumina, silica-alumina, etc. The catalyst.

In addition, Japanese Patent LOP Nos. 106808/1985 and 106809/1985 disclose a method for preparing a composition composed of an ethylene polymer and a filler. The method includes polymerizing ethylene or copolymerizing ethylene with α- Olefins, which are prepared by contacting highly activated catalyst components including hydrocarbon-soluble titanium compounds and/or zirconium compounds with fillers, organoaluminum compounds, and fillers that have affinity for polyolefins.

Japanese Patent LOP No. 31404/1986 discloses a method for polymerizing ethylene or copolymerizing ethylene and α-olefins under the coexistence of a catalyst mixture. The catalyst mixture is composed of a transition metal compound and a product. It is obtained by reacting trialkyl aluminum and water in the coexistence of silica or alumina.

In addition, Japanese Patent LOP No. 276805/1986 discloses polymerizing olefins under the coexistence of a catalyst. The catalyst is composed of a zirconium compound and a reaction mixture. The reaction product is obtained by reacting the resulting reaction product with such an inorganic oxide having a hydroxyl group on the surface, such as silicon oxide.

In addition, Japanese Patent LOP Nos. 108610/1986 and 296008/1986 disclose a method of polymerizing olefins under the coexistence of a catalyst. In the catalyst, transition metal compounds such as metal octane and aluminoxane are supported on a carrier such as an inorganic oxide. superior.

However, during the polymerization or copolymerization of olefins in suspension or gas phase using these solid catalyst components supported on the carrier described in the aforementioned patent publications, the catalyst components are compared with the aforementioned solution polymerization reactions. Significantly reduce the polymerization activity, and the bulk density of the obtained polymer is not satisfactory.

The purpose of the invention

The present invention intends to solve the aforementioned problems related to the prior art.

The purpose of the present invention is to provide a solid catalyst for olefin polymerization, even if the catalyst is used in suspension polymerization and gas phase polymerization and does not use a large amount of organoaluminum oxy compounds, it can still produce particles with high activity and melting properties. Spherical olefin polymer with excellent bulk tension, and the use of this catalyst with good properties for olefin polymerization.

According to the solid catalyst for polymerizing ethylene copolymers of the present invention, the ethylene copolymer includes a constituent unit (a) derived from ethylene and a constituent unit (b) derived from an α-olefin having 3 to 20 carbon atoms, so The characteristic of the ethylene copolymer is (A) the density (d) of the ethylene copolymer is 0.86 to 0.95g/cm³(B) The MFR of the ethylene copolymer measured at a temperature of 190°C and a load of 2.16kg is 0.001 to 50g/10min; (C) The melt tension (MT) and MFR of the ethylene copolymer satisfy the following relationship logMT&gt;- 0.66 logMFR+0.6; and (D) The temperature (T) and density (d) of the highest peak of the exothermic curve of the ethylene copolymer measured by the differential scanning card meter (DSC) shows the following relationship T&lt;400d-250

In addition, the first method for preparing an olefin polymer includes polymerizing an olefin under the coexistence of the following solid catalyst of the present invention, which is produced from the following components: (A) A transition metal compound of Group IVB of the Periodic Table , Which has at least two bases each having a cyclopentadienyl backbone, the at least two bases are crosslinked via carbon and/or silicon-containing groups, and (B) organoaluminum oxy compounds, and the reaction conditions are determined The resultant polymer exists in the polymerization system as a solid phase, thus producing an olefin polymer meeting the following conditions: a) The MFR of the olefin polymer measured at a temperature of 190°C and a load of 2.16kg is 0.001 to 100g/ 10min; and b) The melt tension (MT) and MFR of the olefin polymer can satisfy the following relationship log MT&gt;-0.66 log MFR+0.6

According to the olefin polymerization reaction of the present invention, the first solid catalyst containing prepolymerized polyolefin (hereinafter referred to as prepolymerized solid catalyst) is characterized in that the solid catalyst passes through the following catalyst It is produced by pre-polymerizing olefin in suspension or gas phase under coexistence. The catalyst includes [A] fine particle carrier, [B] transition metal compound (hereinafter referred to as non-bridging transition metal compound) ) Includes ligands with cyclopentadienyl backbones, and the cyclopentadienyl backbones are not bonded to each other. [C] Transition metal compounds (hereinafter referred to as bridge metal compounds) include at least two ligands individually Having a cyclopentadienyl backbone, the at least two ligands are bonded to each other via alkylene, substituted subalkyl, subsilyl or substituted subsilyl, and [D] organoaluminum oxy compound .

The second olefin polymerization catalyst according to the present invention is characterized in that the olefin polymerization catalyst is produced from the aforementioned components [A], [B], [C] and [D], and [E] an organoaluminum compound.

In addition, the second method for preparing an olefin polymer prepared using the solid catalyst of the present invention includes polymerizing or copolymerizing an olefin under the coexistence of the solid catalyst of the present invention.

Figure 1 shows the endothermic curve obtained by measuring the heat absorption of the ethylene copolymer of the present invention (prepared in Example 2) using DSC (Differential Scanning Card Meter).

Figure 2 is an example of the IR spectrum of the organoaluminumoxy compound of the present invention.

Figure 3 is an example of the IR spectrum of a known benzene-soluble organoaluminum oxy compound.

Detailed description of the invention

Specific examples of ethylene copolymers polymerized using the solid catalyst of the present invention are as follows.

First, the ethylene copolymer prepared by the solid catalyst of the present invention is an organic copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. The density (d) of the ethylene copolymer is 0.86 to 0.95g/cm³, Preferably 0.87 to 0.94g/cm³, Better 0.88 to 0.93g/cm³。

The density is measured by using a density gradient tube using a cable. The cable is obtained during MFR measurement at 190°C under a load of 2.16kg, and the cable is heated at 120°C for 1 hour for heat treatment and slowly cooled to the room for 1 hour. Gentle handlers.

The aforementioned ethylene copolymer desirably includes the constituent unit (a) derived from ethylene in an amount of 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 70 to 96% by weight, and derived from 3 to 20% by weight. The amount of the constituent unit (b) of the α-olefin of carbon atoms is 1 to 45% by weight, preferably 2 to 35% by weight, more preferably 4 to 30% by weight.

The composition of the copolymer is usually based on¹³C-NMR spectrum analysis of the sample is determined by dissolving 200 mg of the copolymer uniformly in 1 ml of hexachlorobutadiene in a sample tube with a diameter of 10 nm. The measurement conditions are as follows: measuring temperature 120°C, measuring frequency 25.05 MHz, and spectrum The width is 1500Hz, the pulse repetition time is 4.2sec and the pulse width is 6μsec.

Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

The ethylene copolymer prepared by using the solid catalyst of the present invention desirably has an MFR of 0.001 to 50 g/10 min, preferably 0.01 to 20 g/10 min.

The measurement of MFR is carried out in accordance with ASTM D1238-65T at a temperature of 190°C and a load of 2.16 kg.

In addition, the melt tension (MT) and MFR of the ethylene copolymer prepared by the solid catalyst of the present invention can satisfy the following relationship: log MT&gt;-0.66 log MFR+0.6, which is better

log MT&gt;-0.66 log MFR+0.7, better

log MT&gt;-0.66 log MFR+0.8

As mentioned above, the ethylene copolymer prepared with the solid catalyst of the present invention has excellent melt tension (MT) and good moldability.

In addition, the melt tension (MT) is determined by measuring the stress of the molten copolymer. At this time, the molten copolymer is stretched at a constant rate. In other words, the copolymer powder or polymer obtained by precipitating the copolymer powder or polymer is used as Sample for measurement. The measurement method is to use an MT measuring device (manufactured by Toyo Seiki Seisakusho, Ltd.) with a nozzle diameter of 2.09 mm and a nozzle length of 8 mm using the sample at a resin temperature of 190°C, an extrusion rate of 10 mm/min and a coiling rate of 10 to 20 m/min. Squeeze and measure. During the measurement of melt tension, the ethylene copolymer is pre-mixed with 0.1% by weight of 2.6-di-tertiary butyl-p-cresol as a cross-linking stabilizer.

In addition, in the ethylene copolymer of the present invention, the temperature (T) and its density (d) of the highest peak in the endothermic curve measured by a differential scanning card meter (DSC) can satisfy the following relationship: T&lt;400d-250, better

T&lt;450d-297, better

T&lt;500d-344, very good

T&lt;550d-391

In addition, a DSC-7 type device manufactured by Perkin Elmer was used for measurement using DSC. The temperature (T) of the highest peak indicated by the endothermic curve is obtained from the following endothermic curve: by filling about 5 mg of sample in an aluminum pan, heating to 200°C at a rate of 10°C/min, and maintaining the sample at 200°C for 5 In minutes, the temperature is lowered back to room temperature at a rate of 20°C/min, and then heated at a rate of 10°C/min to obtain an endothermic curve.

In the ethylene copolymer prepared by the solid catalyst of the present invention, it is expected that the weight (W) of the n-decane soluble component and the density of the copolymer at 23°C can satisfy the following relationship: log W&lt;-50d+46.5, which is more it is good

log W&lt;-50d+46.4, better

log W&lt;-50d+46.3

From the relationship between temperature (T) and density (d), and the relationship between n-decane soluble components (W) and density (d), the following conclusions can be drawn: Ethylene prepared by the solid catalyst of the present invention The copolymer has a narrow composition distribution.

In addition, the quantity of n-decane soluble components can be obtained by the aforementioned procedure.

The quantity of n-decane soluble components (the polymer with a smaller quantity of soluble components has a narrower composition distribution) is measured by adding 3 g of copolymer to 450 ml of n-decane and dissolving the copolymer at 145°C. The solution was cooled to 23°C, filtered to remove the n-decane insoluble components, and the n-decane soluble components were recovered from the filtrate.

The ethylene copolymer prepared with the solid catalyst of the present invention having the aforementioned characteristics can be prepared, for example, by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the following catalyst of the present invention. , The catalyst is produced by the following components

(i) By making a diligand compound (wherein the two bases selected from the anionized indenyl group or its substituents are bonded via a carbon and/or silicon-containing group such as a lower alkyl group) and the IVB group of the periodic table The catalyst component obtained by the reaction of the transition metal halide (the catalyst component is generally the same as the transition metal compound, and the transition metal compound includes at least two ligands each having a -cyclopentadienyl backbone, and at least two ligands The position group is bonded via a carbon and/or silicon-containing group such as a lower alkyl group).

(ii) Organoaluminum oxy compound, (iii) Organoaluminum compound, and (iV) carrier. Therefore, the resulting copolymer has a density of 0.86 to 0.95 g/cm³。

In the catalyst component (i) of the present invention, the diligand compound (i-1) has a dibasic group selected from the anionized indenyl group or its substituents (the dibasic group is formed by carbon and/or silicon Groups such as those bonded by lower alkyl groups), the didentate compound (i-1) can be represented by the following formula MR¹-R²-R³M in R¹And R³Each is indenyl anion, substituted indenyl anion or partial hydrogenation anion of these anions, R¹With R³Can be the same or different, R²Is a lower alkyl group, and M is an alkali metal cation. Specific examples of the diligand compound (i-1) include ethylene bis indenyl dilithium, ethylene bis indenyl disodium, and ethylene bis (4,5,6,7-tetrahydro-1- Indenyl) dilithium, ethylene bis(4-methyl-1-indenyl) dilithium, ethylene bis(5-methyl-1-indenyl) dilithium, ethylene bis(6-methyl 1-indenyl) dilithium and ethylene bis(7-methyl-1-indenyl) dilithium.

Specific examples of transition metal halides (i-2) of group IVB of the periodic table include zirconium tetrachloride, hafnium tetrachloride, titanium tetrachloride and titanium tetrabromide.

The catalyst component (i) of the present invention is prepared by mixing the aforementioned diligand compound and the aforementioned transition metal compound and halide in an organic solvent such as ether, tetrahydrofuran, benzene, toluene, and dichloromethane and making Its contact. During preparation, the mixed molecular ratio (MR) of the two ligand compound (i-1) to the transition metal halide (i-2)¹-R²-R³M/transition metal) is 0.5 to 2, preferably 0.75 to 1.25, and the concentration of the transition metal is usually 0.03 to 0.5 mol/l, preferably 0.05 to 0.3 mol/l.

Next, the organoaluminum oxy compound (ii) will be explained as follows.

The organoaluminum oxy compound (ii) may be a known aluminoxane or the benzene-insoluble organoaluminum oxy compound that the present inventors have discovered.

The aforementioned aluminoxane can be prepared, for example, by the following procedure: (1) The procedure for recovering the aluminoxane in its hydrocarbon solution includes adding organoaluminum compounds such as trialkylaluminum to a suspension of the following compounds in a hydrocarbon medium: containing adsorbed water Compounds, or salts containing crystal water such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate; and react with organoaluminum compounds; and (2) aluminoxanes as such The procedure of hydrocarbon solution recovery includes direct reaction of water, ice or water vapor with organoaluminum compounds such as trialkylaluminum in solvents such as benzene, toluene, ether and tetrahydrofuran.

In addition, the aluminoxane may contain a small amount of organometallic components. In addition, the solvent or unreacted organoaluminum compound can be removed from the recovered aluminoxane-containing solution by distillation, and the aluminoxane can be dissolved in the solvent again.

Specific examples of the organoaluminum compound used in the preparation of aluminoxane include trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl Aluminum, tertiary butyl aluminum, tertiary butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricyclohexyl aluminum and tricyclooctyl aluminum; dialkyl aluminum Halides such as dimethyl aluminum chloride, diethyl aluminum chloride, monoethyl aluminum bromide and diisobutyl aluminum chloride; dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum Hydrides; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; and dialkyl aluminum aryl oxides such as diethyl aluminum phenoxide.

Among these compounds, trialkylaluminum is particularly preferred.

In addition, isoprenyl aluminum represented by the following general formula can also be used as an organoaluminum compound (iC₄H₉)_xAl_y(C₅H₁₀)_zWhere x, y, and z are positive numbers, and z<img file="TW237461B_D0007.tif" />2x.

The aforementioned organoaluminum compounds can be used alone or in combination.

Solvents used for aluminoxane solutions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, twelve Alkanes, hexadecane and octadecane; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, methane and gas oil; and derived from the aforementioned aromatic hydrocarbons , Halogenated compounds of aliphatic hydrocarbons and cycloaliphatic hydrocarbons, especially chlorinated and brominated hydrocarbons.

In addition, ethers such as diethyl ether and tetrahydrofuran can also be used. Among the solvents exemplified above, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxygen compound used in the present invention contains Al component that can be dissolved in benzene at 60°C and its amount is not more than 10%, preferably not more than 5%, particularly preferably not more than 2% (expressed by Al atoms), and is insoluble In or very slightly soluble in benzene.

The solubility of the aforementioned organoaluminum oxy compound in benzene can be determined by suspending the organoaluminum oxy compound in an amount equivalent to 100 mg atoms (expressed as Al) in 100 ml of benzene, and mixing the resulting suspension at 60°C for 6 hours by stirring. The resulting mixture was filtered with a G-5 glass filter with a jacket and maintained at 60°C, the solid part separated on the filter was washed 4 times with 50ml of benzene at 60°C, and the amount of Al atoms in the whole filtrate was measured (x Millimoles).

When the aforementioned benzene-insoluble organoaluminum oxy compound of the present invention is analyzed by infrared spectroscopy (IR), it is about 1260 cm^-1The absorbance (D₁₂₆₀) For about 1220cm^-1The absorbance (D₁₂₂₀) Ratio (D₁₂₆₀/D₁₂₂₀) Is preferably not more than 0.09, more preferably not more than 0.08, particularly better than the range of 0.04 to 0.07.

The infrared spectrum analysis of the organoaluminum oxy compound is performed in the following manner.

First, the organoaluminum oxy compound and nujol are ground in an agate mortar in a nitrogen box to form a paste.

Secondly, the obtained paste-like sample was fixed between KBr plates, and the IR spectrum was measured by IR-810 manufactured by Bunko Corporation, Japan under a nitrogen atmosphere.

The IR spectrum of the organoaluminum oxy compound used in the present invention is shown in Figure 2.

From the obtained IR spectrum, obtain D₁₂₆₀/D₁₂₂₀Ratio, and the value of the ratio is obtained in the following manner.

(a) Connect to about 1280cm^-1The highest point is about 1240cm^-1The line of the highest point is taken as the baseline L₁。

(b) Read at about 1260cm^-1The light transmittance (T%) of the lowest absorption point and the vertical line from the lowest absorption point to the wave number axis (horizontal axis) and the baseline L₁Transmittance of the generated intersection point (T₀%), calculate the absorbance (D₁₂₆₀=log T₀/T).

(c) In a similar way, connect to about 1280cm^-1The highest point and about 1180cm^-1The line of the highest point is taken as the baseline L₂。

(d) Read at about 1220cm^-1The light transmittance of the lowest absorption point (T<i>'</i>%) and the vertical line from the lowest absorption point to the wave number axis (horizontal axis) and the baseline L₂Transmittance of the generated intersection point (T₀<i>'</i>%), calculate the absorbance (D₁₂₂₀=log T<i>'</i>₀/T<i>'</i>)。

(e) Calculate D from the aforementioned value₁₂₆₀/D₁₂₂₀Compare.

The IR spectrum of the known benzene-soluble organoaluminum oxy compound is shown in Figure 3. It can be seen from Figure 3 that the benzene-soluble organoaluminum oxy compound has D₁₂₆₀/D₁₂₂₀Value is about 0.10 to 0.13, so the benzene-insoluble organoaluminum oxy compound of the present invention is D₁₂₆₀/D₁₂₂₀In terms of value, it is obviously different from the known benzene-soluble organoaluminum oxy compounds.

The aforementioned benzene-insoluble organoaluminum oxygen compound is estimated to have the aluminum alkoxide unit represented by the following formula<chemistry general="n"><img file="TW237461B_D0008.tif" /></chemistry>Where R¹It is a hydrocarbon group of 1 to 12 carbon atoms.

In the aforementioned aluminum alkoxide unit, R¹Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl and cyclooctyl. Among the hydrocarbon groups exemplified above, methyl and ethyl are preferred, and methyl is particularly preferred.

Except for the aluminum alkoxide unit of the following formula [I]<chemistry general="n"><img file="TW237461B_D0009.tif" /></chemistry>(Where R¹Is a hydrocarbon group with 1 to 12 carbon atoms), the benzene-insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula [II]<chemistry general="n"><img file="TW237461B_D0010.tif" /></chemistry>(Where R²It is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an aryloxy group of 6 to 20 carbon atoms, a hydroxyl group, a halogen group or hydrogen, and R in the aluminum alkoxide unit [I] is specified¹With R²Different from each other). In this case, it is desirable for the organoaluminum oxy compound that the content ratio of the aluminum alkoxide unit [I] is not less than 30 mol%, preferably not less than 50 mol%, and particularly preferably not less than 70 mol%.

The aforementioned method for preparing the benzene-insoluble organoaluminum oxy compound will be specifically illustrated as follows.

The benzene-insoluble organoaluminum oxy compound is obtained by contacting the aluminoxane solution with water or an active hydrogen-containing compound.

Examples of active hydrogen-containing compounds include alcohols such as methanol, ethanol, n-propanol, and isopropanol; glycols such as ethylene glycol and hydroquinone; and organic acids such as acetic acid and propionic acid.

Among these compounds, preferred are alcohols and diols, and particularly preferred are alcohols.

The water or active hydrogen-containing compound with which the aluminoxane solution is in contact can be used in hydrocarbon solvents such as benzene, toluene and hexane, in ether solvents such as tetrahydrofuran, or in amine solvents such as triethylamine in the form of solutions or dispersions, or It can be used in gas or solid form. The water that the aluminoxane solution will contact with can be crystalline water, such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerium chloride; or it can be adsorbed on inorganic compounds such as silicon oxide, Absorb water on alumina and aluminum hydroxide or polymers.

The reaction of aluminoxane with water or active hydrogen-containing compounds in solution is usually carried out in a solvent such as a hydrocarbon solvent. Examples of solvents used in this case include

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane ; Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclohexane; petroleum fractions such as gasoline, methane and gas oil; or halogenation of the aforementioned aromatic hydrocarbons, aliphatic hydrocarbons and cycloaliphatic hydrocarbons Compounds, especially chlorides and bromides; and ethers such as diethyl ether and tetrahydrofuran.

Among the solvents exemplified above, aromatic hydrocarbons are particularly preferred.

In the foregoing reaction, the amount of water or active hydrogen-containing compound is 0.1-5 mol, preferably 0.2-3 mol based on 1 g of Al atoms present in the aluminoxane solution. The concentration expressed by aluminum atoms in the reaction system is expected to be 1×10^-3-5 g atoms/liter, preferably 1×10^-2-3 g atoms/liter, and the water concentration in the reaction system is hoped to be 2×10^-4-5mol/l, preferably 2×10^-3-3mol/l.

The aluminoxane solution can be mixed in water or active hydrogen-containing compounds, for example, by the following procedure.

(1) A procedure involves contacting the aluminoxane solution with a hydrocarbon solvent containing water or an active hydrocarbon compound.

(2) A procedure includes blowing water vapor or vapor with active hydrogen compound into the aluminoxane solution, thereby bringing the aluminoxane into contact with the water vapor or vapor.

(3) A procedure involves direct contact of the aluminoxane solution with water, ice, or an active hydrogen-containing compound.

(4) A procedure involves mixing the aluminoxane solution with a suspension containing adsorbed water compounds or crystalline water containing compounds in hydrocarbons, or with a suspension of compounds that have adsorbed active hydrogen compounds and hydrocarbons, thereby making the aluminoxane Contact with adsorbed water or crystal water.

The aluminoxane solution may contain other components as long as it does not adversely affect the reaction of the aluminoxane with water or active hydrogen-containing compounds.

The reaction of the aforementioned aluminoxane with water or an active hydrogen-containing compound in a solution is usually carried out at a temperature of -50 to 150°C, preferably 0 to 120°C, more preferably 20 to 100°C. The reaction time used is usually 0.5 to 300 hours, preferably about 1 to 150 hours, but the reaction time varies greatly depending on the reaction temperature used.

The benzene-insoluble organoaluminum oxy compound can also be prepared by directly contacting the aforementioned organoaluminum with water. In this case, the amount of water used is such that the amount of organic aluminum atoms dissolved in the reaction system is not more than 20% based on the total organic aluminum atoms.

The water in contact with the organoaluminum compound can be used in the form of a solution or dispersion in hydrocarbon solvents such as benzene, toluene and hexane, in ether solvents such as tetrahydrofuran or amine solvents such as triethylamine, or in the form of water vapor or ice use. The water in contact with the organoaluminum compound can be crystalline water, such as magnesium chloride, magnesium sulfate, aluminum sulfate, ketone sulfate, nickel sulfate, iron sulfate and cerium chloride; or adsorbed water on inorganic compounds, inorganic compounds For example, silicon oxide, aluminum oxide and aluminum hydroxide or polymers.

The reaction of the organoaluminum compound with water is usually carried out in a solvent such as a hydrocarbon solvent. Examples of solvents used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, twelve Alkanes, hexadecane and octadecane; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclohexane; petroleum fractions such as gasoline, methane and gas oil; or the aforementioned aromatic hydrocarbons and fats Halogenated compounds of group hydrocarbons and cycloaliphatic hydrocarbons, especially chlorides and bromides; and ethers such as diethyl ether and tetrahydrofuran. Among the solvents exemplified above, aromatic hydrocarbons are particularly preferred.

In the reaction, the concentration of the organoaluminum compound expressed in terms of aluminum atom is expected to be 1×10^-3-5 g atoms/liter, preferably 1×10^-2-3 grams atoms/liter, and the water concentration in the reaction system is hoped to be 1×10^-3-5mol/l, preferably 1×10^-2-3mol/l. In the foregoing reaction, based on the total organoaluminum atoms, the amount of organoaluminum atoms dissolved in the reaction system is not more than 20%, preferably not more than 10%, and more preferably 0 to 5%.

The organoaluminum compound can be contacted with water, for example, by the following procedure.

(1) A procedure involves contacting a hydrocarbon solution of an organoaluminum compound with an aqueous hydrocarbon solvent.

(2) A procedure involves blowing water vapor into a hydrocarbon solution such as organoaluminum, thereby bringing the organoaluminum into contact with the water vapor.

(3) A procedure involves mixing the organoaluminum hydrocarbon solution with the compound containing adsorbed water or the compound containing crystal water in a suspension of the hydrocarbon, thereby bringing the organoaluminum into contact with the adsorbed water or crystal water.

(4) A procedure involves direct contact of the organoaluminum hydrocarbon solution with ice.

The aforementioned hydrocarbon solution of organoaluminum may contain other components as long as it does not adversely affect the reaction of organoaluminum with water.

The aforementioned reaction of organoaluminum with water is usually carried out at a temperature of -100 to 150°C, preferably -70 to 100°C, more preferably -50 to 80°C. The reaction time used is usually 1 to 200 hours, preferably 2 to 100 hours, but the reaction time varies greatly depending on the reaction temperature used.

Next, the organoaluminum compound (iii) of the present invention will be illustrated as follows.

The organoaluminum compound (iii) used here includes the organoaluminum compound R represented by the following formula⁶_nAlX_3-nWhere R⁶Is a hydrocarbon group of 1 to 12 carbon atoms, x is a halogen group or hydrogen, and n is 1 to 3.

In the above formula, R⁶It is a hydrocarbon group of 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group. R⁶Specific examples include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.

Specific examples of these organoaluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum; Alkenyl aluminum such as isoprenyl aluminum; dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride and two Methyl aluminum bromide; alkyl aluminum sesquichloride such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum Sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; and alkyl aluminum hydrides such as diethyl Base aluminum hydride and dibutyl aluminum hydride.

In addition, other organoaluminum compounds represented by the following formula R can also be used⁶_nAlY_3-nWhere R⁶The definition is as before, Y is -OR⁷, -OSiR⁸₃, -OAlR⁹₂, -NR¹⁰₂, -SiR¹¹₃Or -N(R¹²)AlR¹³₂, N is 1 to 2, R⁷, R⁸, R⁹And R¹³Each is methyl, ethyl, isopropyl, isobutyl, cyclohexyl or phenyl, R¹⁰Is hydrogen, methyl, ethyl, isopropyl, phenyl or trimethylsilyl, R¹¹And R¹²Each is methyl or ethyl.

The aforementioned organoaluminum compound specifically includes the following compounds.

(1) Formula R⁶_nAl(OR⁷)_3-nCompounds such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and diisobutyl aluminum methoxide.

(2) Formula R⁶_nAl(OSiR⁸₃)_3-nThe compound such as Et₂Al(OSiMe₃)'(iso-Bu)₂Al(OSiMe₃) And (iso-Bu)₂Al(OSiEt₃)。

(3) Formula R⁶_nAl(OAlR⁹₂)_3-nThe compound such as Et₂AlOAlEt₂And (iso-Bu)₂AlOAl(iso-Bu)₂。

(4) Formula R⁶_nAl(NR¹⁰₂)_3-nThe compound such as Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt, Et₂AlN(SiMe₃)₂, (Iso-Bu)₂AlN(SiMe₃)₂。

(5) Formula R⁶_nAl(SiR¹¹₃)_3-nThe compound such as (iso-Bu)₂AlSiMe₃。

(6) formula<img file="TW237461B_D0011.tif" />The compound such as<img file="TW237461B_D0012.tif" />and<chemistry general="n"><img file="TW237461B_D0013.tif" /></chemistry>

Among the organoaluminum compounds exemplified above, the preferred one has the following general formula R⁶₃Al, R⁶_nAl(OR⁷)_3-nAnd R⁶_nAl(OAlR⁹₂)_3-n, And particularly preferred ones have the aforementioned general formula where R⁶Is an isoalkyl group and n is 2. Two or more of these organoaluminum compounds may be used in combination.

The carrier used as the catalyst component (iv) of the present invention is a solid inorganic or organic compound in the form of particles or fine particles having a particle size of 10 to 300 μm, preferably 20 to 200 μm. Among these carriers, porous oxides are preferably used as inorganic carriers. Specific examples of oxide carriers include SiO₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, Or a mixture of these compounds such as SiO₂-MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂-Cr₂O₃And SiO₂-TiO₂-MgO. Among these carriers, the preferred ones include those selected from SiO₂And Al₂O₃As at least one compound in the main component.

In addition, the aforementioned inorganic oxides may also contain a small amount of carbonate, sulfuric acid, nitric acid and oxides such as Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃ Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₃, Na₂O, K₂O and LiO₂。

Although the porous inorganic carrier has different properties depending on the type and preparation method, the preferred carrier used in the present invention has a specific surface area of 50 to 1000 m²/g, preferably 100 to 700m²/g, the pore volume is expected to be 0.3 to 2.5cm²/g. If necessary, the carrier is prepared by firing at a temperature of 150 to 1000°C, preferably 200 to 800°C.

In addition, it is worth mentioning that organic compounds each having a particle size of 10 to 300 μm in the form of solid particles or solid fine particles can be used as carriers in the present invention. Examples of these organic compounds include (co)polymers containing as main components the constituent units of alpha olefins derived from 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene ; Or a polymer or copolymer containing constituent units derived from vinyl cyclohexane or styrene as the main component.

In the present invention, it is expected that the catalyst produced by the olefin prepolymerization reaction on the aforementioned catalyst components (i), (ii), (iii) and (iv) can be used for the preparation of ethylene copolymers.

Before the pre-polymerization reaction, the catalyst component (i), the catalyst component (i) and (ii), or the catalyst component (i), (ii) and (iii) can be supported on the catalyst component ( iv) on the carrier; or each catalyst component can be freely contacted and mixed with each other for pre-polymerization.

Spherical olefin copolymers with excellent particle shapes can be prepared under the following conditions: the catalyst component (i) and the transition metal compound (vi) are used in the prepolymerization reaction, including each having a cyclopentadienyl backbone and unbonded The coordinator together.

Specific examples including transition metal compounds (vi) having a cyclopentadienyl backbone and unbonded ligands include bis(cyclopentadienyl) zirconium dichloride, bis(methylcyclopentadiene) Alkenyl) zirconium dichloride, bis(dimethylcyclopentadienyl) zirconium dichloride, bis(ethylcyclopentadienyl) zirconium dichloride, bis(n-butylcyclopentadienyl) Zirconium dichloride, and bis(indenyl) zirconium dichloride.

The amount ratio of the transition metal compound (vi) to the catalyst component (i) is 0 to 50 mol%, preferably 5 to 40 mol%, more preferably 10 to 30 mol%, based on the total of components (i) and (vi) The amount is defined as 100 mol% as the basis.

In the prepolymerization reaction, the production amount of the olefin polymer (v) is 0.05 to 100 g based on 1 g of the carrier, preferably 0.1 to 50 g, more preferably 0.2 to 30 g.

Examples of olefins include ethylene and α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1 -Decene, 1-dodecene and 1-tetradecene. Among them, ethylene is preferred.

The prepolymerization reaction can be carried out without solvent coexistence or in an inert hydrocarbon solvent. In the prepolymerization method, the amount of the organoaluminum compound is 0.2 to 20 millimoles, preferably 0.5 to 10 millimoles, and the amount of the organoaluminum oxy compound is 1 to 50 mg atoms, preferably 2 to 20 mg atoms (expressed as Al) The amount of the catalyst component (i) is 0.02 to 2 mg atoms, preferably 0.05 to 1 mg atoms (expressed in transition metals), and all amounts are based on 1 g carrier.

In addition, the desired molecular ratio [Al(iii)/Al(ii)] of the organoaluminum compound (iii) (expressed by Al atoms) to the organoaluminum oxy compound (ii) (expressed by Al atoms) is usually 0.02 to 3, which is more Good 0.05 to 1.5. The molecular ratio [Al(ii)/M] of organoaluminum oxygen compound (ii) (expressed by Al atom) to catalyst component (i) (expressed by transition metal atom (M)) is usually 5 to 250, preferably For 10 to 150. When the prepolymerization reaction is carried out in an inert hydrocarbon solvent, the concentration of the catalyst component (i) in terms of transition metal is usually 0.1 to 10 mg atoms/liter, preferably 0.5 to 5 mg atoms/liter.

The prepolymerization reaction is carried out at a temperature of -20 to 70°C, preferably -10 to 60°C, more preferably 0 to 50°C.

The prepolymerization reaction can be carried out batchwise or continuously, and under reduced pressure, normal pressure or under pressure. Although the molecular weight modifier such as hydrogen may be present in the prepolymerization reaction process, its quantity is better limited, so that the intrinsic viscosity [η] measured in decalin at 135°C is not less than 0.2dl/g, which is more A prepolymer of 0.5 to 10 dl/g is good.

In the prepolymerized reaction catalyst thus obtained, the supported amount of catalyst component (i) (expressed as transition metal atoms, based on 1 g of the carrier) is 0.1 to 50 mg, preferably 0.3 to 30 mg, more preferably 0.5 to 20 mg . The molecular ratio (Al/M) of catalyst component (ii) and (iii) (expressed by Al atoms) to catalyst component (i) (expressed by transition metal (M)) is 5 to 200, preferably 10 To 150, better 15 to 100.

In the present invention, the ethylene copolymer is obtained by copolymerizing ethylene with the following alpha olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In the present invention, the olefin is usually polymerized in the gas or liquid phase, for example, in a slurry. In the slurry polymerization reaction, inert hydrocarbons or olefins themselves can be used as solvents.

Specific examples of hydrocarbon solvents include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cycloaliphatic hydrocarbons such as cyclopentane, Methyl cyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and petroleum fractions such as gasoline, methane and gas oil. Among these hydrocarbons, preferred are aliphatic hydrocarbons, cycloaliphatic hydrocarbons and petroleum fractions.

In the present invention, the slurry polymerization reaction is carried out at a temperature of usually -50 to 100°C, preferably 0 to 90°C.

In the present invention, the gas phase polymerization reaction is carried out at a temperature of usually 0 to 120°C, preferably 20 to 100°C.

In the slurry polymerization reaction or gas phase polymerization reaction of the present invention, the transition metal is expressed, and the concentration of the transition metal compound is usually 10^-8To 10^-2Gram atom/liter, preferably 10^-7To 10^-3Gram atom/liter.

In addition, in the polymerization reaction of the present invention, aluminum oxide compounds or aluminum compounds similar to those used in the catalyst components (ii) and (iii) can be added. During the polymerization reaction, the ratio (Al/M) of the aluminum compound (expressed as Al atom) to the transition metal atom (M) is 5 to 300, preferably 10 to 200, more preferably 15 to 150.

The polymerization reaction is usually at atmospheric pressure to 100kg/cm², Preferably 2 to 50kg/cm²Under the pressurized conditions. The polymerization reaction can be carried out batchwise, semi-continuously or continuously.

In addition, the polymerization reaction can also be carried out in not less than 2 steps, and the reaction conditions of the 2 steps are different from each other.

The second method for preparing an olefin polymer according to the present invention will be specifically illustrated as follows.

The olefin polymer prepared by the second method of preparing the olefin polymer of the present invention, especially the ethylene polymer is an ethylene homopolymer or an opportunistic copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

The opportunistic copolymer of ethylene produced by the second production method of the olefin polymer according to the present invention and α-olefin having 3 to 20 carbon atoms has the above-mentioned characteristics.

In the second production method of the olefin polymer of the present invention, the solid catalyst of the present invention produced from the following components (A) a transition metal compound of group IVB of the periodic table, at least two bases with a cyclopentadienyl backbone As the ligand, the at least two groups are cross-linked via carbon and/or silicon-containing groups, and (B) organoaluminum oxy compound, olefin polymerization reaction is when the resulting polymer exists in the polymerization system in a solid state Under the conditions.

The transition metal compound (A) used in the second preparation method of the olefin polymer according to the present invention can be represented by the following formula: M¹L¹x in the formula M¹For transition metal, L¹Is the ligand corresponding to the transition metal, L¹At least two of them are ligands that have a cyclopentadienyl backbone and are bonded via a carbon and/or silicon-containing group, and L other than the ligand that has a cyclopentadienyl backbone¹Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen group or hydrogen; and x is the valence of the transition metal.

In the above formula, M¹Is a transition metal, and M¹Preferred specific examples include zirconium, titanium, hafnium, chromium and vanadium. Among them, zirconium and hafnium are particularly preferred.

The ligand having a cyclopentadienyl backbone includes, for example, cyclopentadienyl, alkyl-substituted cyclopentadienyl such as methylcyclopentadienyl, ethylcyclopentadienyl, and n-butylcyclopenta. Dienyl, dimethylcyclopentadienyl and pentamethylcyclopentadienyl, indenyl, 4,5,6,7-tetrahydroindenyl and fluorenyl.

Ligand groups other than those having a cyclopentadienyl backbone are hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, halogen groups or hydrogen.

Hydrocarbon groups having 1 to 12 carbon atoms include, for example, alkyl, cycloalkyl, aryl, aralkyl, and specific examples of these groups are as follows: alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl Cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and neophenyl; alkoxy groups such as methoxy, ethoxy and butoxy; aryl Oxy groups such as phenoxy; and halo groups such as fluorine, chlorine, bromine and iodine.

The transition metal compound (A) that includes a ligand having a cyclopentadienyl backbone and a transition metal having a valence of 4 used in the present invention can be represented by the following formula: R²R³R⁴R⁵M¹Where M¹Zirconium, titanium, hafnium or vanadium, R², R³, R⁴And R⁵At least two of them, in other words, R²And R³Each is a group with a cyclopentadienyl backbone, and the two groups with a cyclopentadienyl backbone are through carbon and/or silicon-containing groups such as alkylene (such as ethylene and propylene), Substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene group, and substituted silylene groups such as dimethylsilylene group are bonded together; R⁴And R⁵Each is a group having a cyclopentadienyl backbone, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen group or a hydrogen group.

Listed below are ligands having at least two cyclopentadienyl backbones, the two ligands having a cyclopentadienyl backbone are through alkylene, substituted alkylene, silyloxy or substituted silylane A specific example of a transition metal compound (A) bonded together.

Ethylene bis(indenyl) dimethyl zirconium, ethylene bis(indenyl) diethyl zirconium, ethylene bis(indenyl) diphenyl zirconium monochloride, ethylene bis(indenyl) Methyl zirconium monochloride, ethylene bis(indenyl) ethyl zirconium monochloride, ethylene bis(indenyl) methyl zirconium monobromide, ethylene bis(indenyl) zirconium dichloride, Ethylene bis(indenyl) zirconium dibromide, ethylene bis(4,5,6,7-tetrahydro-1-indenyl) dimethyl zirconium' ethylene bis(4,5,6, 7-tetrahydro-1-indenyl) methyl zirconium monochloride, ethylene bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene bis(4, 5,6,7-Tetrahydro-1-indenyl) zirconium dibromide, ethylene bis(4-methyl-1-indenyl) zirconium dichloride, ethylene bis(5-methyl-1) -Indenyl) zirconium dichloride, ethylene bis(6-methyl-1-indenyl) zirconium dichloride, ethylene bis(7-methyl-1-indenyl) zirconium dichloride, times Ethyl bis(5-methoxy-1-indenyl) zirconium dichloride, ethylene bis(2,3-dimethyl-1-indenyl) zirconium dichloride, ethylene bis(4, 7-dimethyl-1-indenyl) zirconium dichloride, ethylene bis(4,7-dimethoxy-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-tertiary butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl methyl ring Pentadienyl) zirconium dichloride, dimethylsilyl bis(cyclopentadienyl) zirconium dichloride, dimethylsilyl bis(methylcyclopentadienyl) zirconium dichloride, Dimethylsilyl bis(dimethylcyclopentadienyl) zirconium dichloride, dimethylsilyl bis(trimethylcyclopentadienyl) zirconium dichloride, and dimethyl silylene Base bis(indenyl) zirconium dichloride.

A transition metal compound obtained by substituting titanium, hafnium, or vanadium for the zirconium in each example of the aforementioned zirconium compound can also be used.

In the second production method of the olefin polymer according to the present invention, a compound similar to the organoaluminum oxy compound (ii) can be used as the organoaluminum oxy compound (B).

In addition, in the second production method of the olefin polymer according to the present invention, if necessary, in addition to the aforementioned transition metal compound (A) and organoaluminum oxy compound (B) in the production process of the olefin polymer, The organoaluminum compound (C) is used.

A compound similar to the organoaluminum compound (iii) can be used as such an organoaluminum compound (C).

The catalyst component used in the second production method of the olefin polymer according to the present invention is in a solid phase. Such a solid catalyst component can be supported by, for example, the catalyst component (A) on the carrier (D) or Prepared on solid organoaluminum oxy compounds.

A carrier similar to the aforementioned carrier can be used as the carrier (D).

In the process of preparing an ethylene polymer by the second method of preparing an olefin polymer according to the present invention, it is preferable to use the catalyst produced as follows. The olefin includes the catalyst components (A) and (B), and if any Pre-polymerization is required on the catalyst components of the catalyst component (C) and/or the catalyst component (D), and all these catalyst components are the aforementioned ones.

Before the pre-polymerization reaction, the catalyst component (A), the catalyst component (A) and (B) or the catalyst component (A), (B) and (C) can be pre-supported on the carrier, or These catalyst components can be simply freely contacted and mixed.

When the transition metal compound (E) and the catalyst component (A) that contain ligands each having a cyclopentadienyl backbone and these ligands are not bonded together are used for contact and mixing, A spherical olefin copolymer with excellent particle properties can be obtained.

If necessary, the transition metal compound (E) used in the present invention is similar to the aforementioned transition metal compound (vi ), this transition metal compound (E) will be exemplified in more detail as follows. The transition metal compound (E) can be represented by the following formula: M²L²x in the formula M²For transition metal, L²Is the ligand corresponding to the transition metal, in which at least one L²It is a ligand with a cyclopentadienyl backbone, and L other than a ligand with a cyclopentadienyl backbone²Is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a halogen group or hydrogen, and x is the valence of the transition metal.

In the foregoing formula, M²Is a transition metal, and M²Preferred specific examples include zirconium, titanium, hafnium, chromium and vanadium. Among them, zirconium and hafnium are particularly preferred.

Examples of ligands having a cyclopentadienyl backbone include cyclopentadienyl, alkyl-substituted cyclopentadienyl such as methylcyclopentadienyl, ethylcyclopentadienyl, and n-butyl ring Pentadienyl, dimethylcyclopentadienyl and pentamethylcyclopentadienyl, indenyl and fluorenyl.

As mentioned above, at least one preferred two ligands each having a cyclopentadienyl backbone is equivalent to the transition metal M²。

The ligand other than the ligand having a cyclopentadienyl backbone is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen group or a hydrogen group.

The hydrocarbon group having 1 to 12 carbon atoms includes, for example, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and specific examples thereof are listed below.

The alkyl group includes methyl, ethyl, propyl, isopropyl and butyl.

Cycloalkyl groups include cyclopentyl and cyclohexyl.

The aryl group includes a phenyl group and a tolyl group.

Aralkyl groups include benzyl and neophenyl.

Alkoxy includes methoxy, ethoxy and butoxy.

The aryloxy group includes a phenoxy group.

The halogen group includes fluorine, chlorine, bromine and iodine.

The transition metal compound (E) containing a ligand having a cyclopentadienyl backbone and not bonded to other cyclopentadienyl backbones and a transition metal having a tetravalent transition metal as used in the present invention can be specifically represented by the following formula R^2<i>'</i>kR^3<i>'</i>lR^4<i>'</i>mR^5<i>'</i>nM²Where M²Zirconium, titanium, hafnium or vanadium, R^2<i>'</i>Is a base with a cyclopentadienyl backbone, R^3<i>'</i>, R^4<i>'</i>And R^5<i>'</i>Each is a group having a cyclopentadienyl backbone, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen group or a hydrogen group, k is an integer not less than 1, and k +l+m+n=4.

Listed below are specific examples of transition metal compounds (E), which have zirconium as M²And each contains a cyclopentadienyl backbone and is not bonded to the ligands of other cyclopentadienyl backbones.

Bis(cyclopentadienyl)zirconium-chloride-hydride, bis(cyclopentadienyl)zirconium-bromide-hydride, bis(cyclopentadienyl)methyl zirconium hydride, bis(cyclopentadienyl)zirconium-bromide-hydride Dienyl) ethyl zirconium hydride, bis(cyclopentadienyl) phenyl zirconium hydride, bis(cyclopentadienyl) benzyl zirconium hydride, bis(cyclopentadienyl) neopentyl zirconium Hydride, bis(methylcyclopentadienyl)zirconium-chloride hydride, bis(indenyl)zirconium-chloride-hydride, bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dichloride Dienyl) zirconium dibromide, bis(cyclopentadienyl) methyl zirconium monochloride, bis(cyclopentadienyl) ethyl zirconium monochloride, bis(cyclopentadienyl) cyclohexyl zirconium Monochloride, bis(cyclopentadienyl)phenyl zirconium monochloride, bis(cyclopentadienyl)benzyl zirconium monochloride, bis(methylcyclopentadienyl)zirconium dichloride, double (Dimethylcyclopentadienyl) zirconium dichloride, bis(n-butylcyclopentadienyl) zirconium dichloride, bis(indenyl) zirconium dichloride, bis(indenyl) zirconium dibromide , Bis(cyclopentadienyl) zirconium dimethyl, bis(cyclopentadienyl) zirconium diphenyl, bis(cyclopentadienyl) zirconium dibenzyl, bis(cyclopentadienyl) zirconium methyl Oxychloride, bis(cyclopentadienyl) zirconium ethoxy chloride, bis(methylcyclopentadienyl) zirconium ethoxy chloride, bis(cyclopentadienyl) zirconium phenoxy chloride Compounds, and bis (fluorenyl) zirconium dichloride.

It is also possible to use a transition metal compound obtained by replacing zirconium with titanium, hafnium or vanadium in the zirconium compound exemplified above.

During the pre-polymerization reaction, based on 1 g of the carrier, the amount of olefin polymer produced is 0.05 to 100 g, preferably 0.1 to 50 g, more preferably 0.2 to 30 g.

Examples of olefins include ethylene and α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1 -Decene, 1-dodecene and 1-tetradecene. Among them, ethylene is preferred.

The pre-polymerization reaction is carried out in the absence of solvent coexistence or in an inert hydrocarbon solvent. During the prepolymerization reaction, the amount of the organoaluminum compound is 0.2 to 20 millimoles, preferably 0.5 to 10 millimoles, and the amount of the organoaluminum oxy compound is 1 to 50 milligram atoms, preferably 2 to 20 millimoles (in Al is represented), and the amount of catalyst component (A) is 0.02 to 2 milligram atoms, preferably 0.05 to 1 milligram atoms (expressed as transition metals), and all amounts are based on 1 g of the carrier.

In addition, the desired molecular ratio of organoaluminum compound (represented by Al atom) [Al(C)] to organoaluminum oxy compound (represented by Al atom) [Al(B)] [Al(C)/Al(B) ] It is usually 0.02 to 3, preferably 0.05 to 1.5. The expected molecular ratio of the organoaluminum oxy compound (expressed by Al atom) [Al(B)] to the catalyst component (A) (expressed by transition metal (M)) [Al(B)/M] is usually 5 to 250 , Preferably 10 to 150. When the prepolymerization reaction is carried out in an inert hydrocarbon solvent, the concentration of the catalyst component (A) in terms of transition metal atoms is usually 0.1 to 10 mg atoms/liter, preferably 0.5 to 5 mg atoms/liter.

The prepolymerization reaction is carried out at a temperature of -20 to 70°C, preferably -10 to 60°C, more preferably 0 to 50°C.

The prepolymerization reaction can be carried out batchwise or continuously, and under reduced pressure, normal pressure or under pressure. Although the molecular weight modifier such as hydrogen may be present in the prepolymerization reaction process, its quantity is better limited, so that the intrinsic viscosity [η] measured in decalin at 135°C is not less than 0.2dl/g, which is more A prepolymer of 0.5 to 10 dl/g is good.

In the prepolymerization catalyst thus obtained, the supported amount of the catalyst component (A) (expressed by transition metal atoms, based on 1 g of the carrier) is 0.1 to 50 mg, preferably 0.3 to 30 mg, more preferably 0.5 to 20 mg . The molecular ratio (Al/M) of catalyst component (B) and (C) (expressed by Al atom) to catalyst component (A) (expressed by transition metal (M)) is 5 to 200, preferably 10 To 150, better 15 to 100.

In the present invention, the ethylene copolymer is obtained by copolymerizing ethylene with the following alpha olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In the second method of olefin polymerization according to the present invention, the olefin is usually polymerized under the condition that the produced polymer exists in a solid state, such as a gas phase or a slurry. In the slurry polymerization reaction, inert hydrocarbons or olefins themselves can be used as solvents.

Specific examples of hydrocarbon solvents include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cycloaliphatic hydrocarbons such as cyclopentane, Methylcyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and petroleum fractions such as gasoline, methane and gas oil. Among these hydrocarbons, preferred are aliphatic hydrocarbons, cycloaliphatic hydrocarbons and petroleum fractions.

In the present invention, the slurry polymerization reaction is usually carried out at a temperature of -50 to 100°C, preferably 0 to 90°C.

In the present invention, the gas phase polymerization reaction is usually carried out at a temperature of 0 to 120°C, preferably 20 to 100°C.

In the slurry polymerization reaction or gas phase polymerization reaction of the present invention, the transition metal concentration in the polymerization reaction system is usually 10^-8To 10^-2Gram atom/liter, preferably 10^-7To 10^-3Gram atom/liter.

In addition, in the polymerization reaction of the present invention, the aluminum oxy compound or aluminum compound used in the preparation of the catalyst components (B) and (C) can be added to the reaction system. During the polymerization reaction, the ratio (Al/M) of the aluminum compound (expressed as Al atom) to the transition metal atom (M) is 5 to 300, preferably 10 to 200, more preferably 15 to 150.

The polymerization reaction is usually at atmospheric pressure to 100kg/cm², Better than 2 to 50kg/cm²Under pressure. The polymerization reaction can be carried out batchwise, semi-continuously or in a continuous manner.

In addition, the polymerization reaction can also be carried out in not less than 2 steps, and each step has different reaction conditions.

The solid catalyst used in the olefin polymerization reaction of the present invention will be illustrated as follows.

The first pre-polymerized solid catalyst for olefin polymerization according to the present invention is produced by pre-polymerizing olefin in a suspension or gas phase under the coexistence of a solid catalyst including the following components [A] Fine particle carrier, [B] transition metal compound (hereinafter referred to as non-bridged transition metal compound) includes ligands with cyclopentadienyl backbones, and the cyclopentadienyl backbones are not bonded to each other, [C ] Transition metal compounds (hereinafter referred to as bridge-type metal compounds) include at least two ligands each having a cyclopentadienyl backbone, and the at least two ligands are substituted by an alkylene group and a secondary alkyl group, Those that are bonded to each other by silyl or substituted silyl groups, and [D] organoaluminum oxy compounds.

The second prepolymerized solid catalyst for olefin polymerization according to the present invention is produced from the aforementioned components [A], [B], [C], [D], and [E] organoaluminum compounds.

The aforementioned carrier (iv) can be used as the fine particle carrier [A].

It is also possible to use the same compound as the aforementioned transition metal compound (E), which includes a ligand having a cyclopentadienyl backbone, and the cyclopentadienyl backbone is not bonded to each other as the non-bridged transition metal compound [B ].

The same compound as described above can also be used as the bridge-type transition metal compound [C].

In addition, the same compound as described above can also be used as the organoaluminum oxy compound [D].

In addition, the same compound as described above can be used as the organoaluminum compound [E].

The prepolymerized solid catalyst for the olefin polymerization reaction of the present invention is obtained by mixing the fine particle carrier [A], the non-bridged transition metal compound [B], the bridged transition metal compound [C], and the organoaluminum oxy compound [D] And if the desired organoaluminum compound [E] is mixed in an inert hydrocarbon solvent, and prepared by introducing olefins for prepolymerization.

Although the mixing can be carried out in any order selected, the mixing and contacting are preferably carried out in the order of [A](E])DB]olefinColefin, orA(E ])D{B+C}alkenes in the order.

The prepolymerized solid catalyst for olefin polymerization reaction of the present invention can also be obtained by combining non-bridged transition metal compound [B], bridged transition metal compound [C], organoaluminum compound [D] and if necessary organoaluminum compound [E] It is prepared by supporting on a fine particle carrier [A], introducing olefin, and conducting prepolymerization in the absence of solvent.

When components [A] to [D], and if required component [E] are mixed, the total amount of component [B] and component [C] is usually 10^-5To 5×10^-3mol, preferably 5×10^-5To 10^-3mol (based on 1g component [A]), and the total concentration is about 10^-4To 2×10^-2mol/l, preferably 2×10^-4To 10^-2mol/l. The amount of component [B] is 5 to 80 mol%, preferably 7 to 70 mol%, more preferably 10 to 60 mol%, based on the total amount of component [B] and component [C] being 100 mol%.

The atomic ratio of aluminum in component [D] to transition metal in components [B] and [C] [Al/(transition metal)] is usually 10 to 500, preferably 20 to 200. If necessary, use the aluminum atom (Al_E) For the aluminum atom (Al_D) Atomic ratio (Al_E/Al_D) Is usually 0.02 to 3, preferably 0.05 to 1.5. Components [A] to [D], and if necessary, [E] are usually mixed at a temperature of -20 to 80°C, preferably 0 to 60°C, and the contact time is 1 to 200 minutes, which is more Good for 5 to 120 minutes.

The alkene is pre-polymerized under the coexistence of components [A] to [D] and, if necessary, the aforementioned component [E]. During the pre-polymerization reaction, the amount of transition metal compound is usually 10^-4To 2×10^-2mol/l, preferably 5×10^-4To 10^-2mol/l, the reaction temperature is -20 to 80°C, preferably 0 to 50°C, and the reaction time is 0.5 to 100 hours, preferably 1 to 50 hours.

Although the olefin used in the prepolymerization reaction is selected from the olefins used in the polymerization reaction, ethylene is preferred.

In the prepolymerized solid catalyst used in the olefin polymerization reaction of the present invention as obtained above, the supporting amount of transition metal is 5×10^-6To 5×10^-4Gram atom, preferably 10^-5To 3×10^-4Gram atom, and the supporting capacity of aluminum is 10^-3To 10^-1Gram atom, preferably 2×10^-3To 5×10^-2Gram atom, all quantities are based on 1g component [A].

In addition, the amount of polymer produced during the pre-polymerization reaction is about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g based on 1 g of the fine particle carrier.

Specific examples of inert hydrocarbons used as a solvent for preparing the solid catalyst for olefin polymerization of the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and Carrier oil; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and methylene chloride; and this A mixture of other hydrocarbons.

When using the pre-polymerized solid catalyst for olefin polymerization with the aforementioned pre-polymerized olefin to perform the olefin reaction, the desired amount of transition metal compound [B] and [C] (relative to per liter Polymerization volume) is usually 10^-8To 10^-3Gram atom, preferably 10^-7To 10^-4Gram atom (expressed as transition metal). In the polymerization reaction, organoaluminum compounds and aluminoxanes can be used if necessary. Examples of the organoaluminum compound used in the polymerization reaction include compounds similar to the aforementioned organoaluminum compound [E]. The amount of the organoaluminum compound used is 0 to 500 mol, preferably 5 to 200 mol, based on 1 gram atom of the transition metal.

The olefins that can be polymerized using this prepolymerization catalyst for olefin polymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, ring Pentene, cycloheptene, orthobornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethylene-1,2,3 ,4,4a,5,8,8a-octahydronaphthalene. In addition, styrene, vinyl cyclohexane and dienes can also be used.

In the present invention, the polymerization reaction can be carried out by liquid-phase polymerization reactions such as solution polymerization and suspension polymerization methods, or by gas-phase polymerization methods.

In the liquid phase polymerization method, the same inert hydrocarbon solvent as used in the preparation of the catalyst can be used, and the olefin itself can also be used as the solvent.

The olefin polymerization reaction usually uses the aforementioned catalyst for the olefin polymerization reaction, at a temperature of usually -50 to 150°C, preferably 0 to 100°C, and usually at a normal pressure to 100 kg/cm², Preferably normal pressure to 50kg/cm²Under pressure. The polymerization reaction can be carried out batchwise, semi-continuously or in a continuous manner. In addition, the polymerization reaction can also be carried out in two or more steps. The reaction conditions of each step are different from each other. The molecular weight of the obtained olefin polymer can be adjusted by putting hydrogen in the polymerization system or by changing the polymerization temperature.

In addition, in the present invention, the olefin polymerization catalyst may also contain components different from the aforementioned components, and these components can be used in olefin polymerization reactors.

Hereinafter, the present invention will be illustrated with reference to embodiments, but the present invention is by no means limited to these embodiments.

In addition, the melt tension (occasionally abbreviated as MT hereinafter) in this specification is measured by the following procedure.

Melt tension (MT) is determined by measuring the stress of the molten polymer when the polymer is stretched at a steady rate. In other words, use the fine particles of the resulting polymer, or use by dissolving the fine particles in decane at one time, and using a methanol/acetone (volume ratio 1/1) solution to precipitate a volume not less than 5 times the volume of decane. The polymer obtained from the dissolved powder was used as a measurement sample; and an MT measuring device (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a nozzle diameter of 2.09 mm and a nozzle length of 8 mm was used at a resin temperature of 190°C, an extrusion rate of 10 mm/min and a coiling rate Measure under the condition of 10 to 20m/min.

During the measurement of melt tension, the ethylene copolymer sample was mixed with 0.1% by weight of 2,6-di-tertiary butyl-p-cresol, which is a cross-linking stabilizer.

<u style="single">Example 1</u>

Preparation of catalyst component (A)

A 400ml glass bottle washed with nitrogen was charged with 20g of bis(indenyl)ethane and 200ml of THF. The content was cooled to -50°C with stirring, and 100 ml of n-BuLi solution (1.6M solution) was added over 50 minutes. Subsequently, the resulting mixture was stirred at -50°C for 1 hour and allowed to warm to room temperature, thereby making bis(indenyl)ethane anionic. 100ml of THF was added to the contents to generate a homogeneous solution.

Another 1 liter glass bottle using nitrogen washing was charged with 250ml THF, cooled to -50°C and 16.54g zirconium tetrachloride was slowly added. The contents were warmed to 60°C and stirred for 1 hour. The anionic ligand prepared as above is added dropwise. The resulting mixture was stirred at 60°C for 3 hours, and filtered using a glass filter. The filtrate was concentrated to 1/5 of the original volume at room temperature to precipitate a solid. The solid was separated by filtration with a glass filter. The solid residue was washed with a solvent mixture of hexane/ether (volume ratio 1/1) and dried under reduced pressure. Get the catalyst component (A).

[Preparation of catalyst component (B)]

Fill a 400ml bottle with 37g of Al thoroughly washed with nitrogen₂(SO₄)₃．₁₄H₂O and 125ml toluene. The contents were cooled to 0°C, and 500 millimoles of trimethylaluminum diluted with 125 ml of toluene was added dropwise. The resulting mixture was warmed to 40°C, and the reaction was continued at this temperature for 48 hours. After the reaction was completed, the reaction mixture was subjected to solid-liquid separation by filtration, and toluene was removed from the filtrate, thereby obtaining 9.1 g of a white solid catalyst component (B).

Preparation of prepolymerized catalyst

A 400ml bottle thoroughly washed with nitrogen was charged with 1.29g of silica (F-948 obtained from Fuji Davison, fired at 700°C for 6 hours before feeding into the bottle) and 20ml of toluene to form a suspension. To the suspension was added 4.51 ml of a triisobutylaluminum solution in decane (Al: 1 mol/L), and the mixture was stirred at room temperature for 30 minutes. Subsequently, 7.91 ml of the toluene solution (Al: 0.95 mol/liter) of the catalyst component (B) prepared as above was added, and the mixture was stirred at room temperature for 30 minutes. Then, 72 ml of the toluene solution (Zr: 0.00298 mol/liter) of the catalyst component (A) prepared as above was added, and the resulting mixture was stirred for 10 minutes. Then, 52 ml of decane was added, and prepolymerization was carried out at 30° C. for 4 hours through continuous introduction of ethylene under normal pressure.

After the pre-polymerization was completed, the solvent was removed by decantation. The residue was washed 3 times with 200ml hexane at 60°C, and then washed 3 times with 200ml hexane at room temperature, thus obtaining a pre-polymerized catalyst, which contained 1g silica as the standard. 8.5mg Zr, 160mg Al and 15g polyethylene.

Polymerization

An autoclave with an inner volume of 2 liters was thoroughly washed with nitrogen, 150 g of sodium chloride (special grade, available from Wako Junyaku KK) was fed into it, and the contents were dried under reduced pressure at 90°C for 1 hour. Subsequently, by introducing a gas mixture of ethylene and 1-butene (1-butene content: 6.3 mol%), the system pressure was returned to normal pressure, and the system temperature was reduced to 70°C.

The pre-polymerized catalyst prepared as above is added to the autoclave, the amount of which is 0.0075 milligram atoms (calculated as zirconium atoms) and 1.13 millimoles of triisobutyl aluminum.

Subsequently, 50Nml hydrogen and the above-mentioned gas mixture of ethylene and 1-butene were introduced into it in sequence, at 4kg/cm²The polymerization reaction started under the total pressure of -G, whereby the temperature of the reaction system was immediately raised to 80°C. Subsequently, the polymerization reaction was carried out at 80°C for 1 hour while maintaining the total pressure at 4 kg/cm by simply feeding the gas mixture.²-G.

After the polymerization reaction was completed, sodium chloride was removed from the reaction mixture by washing with water, and the remaining polymer was washed with methanol and dried under reduced pressure at 80°C overnight, thereby obtaining 116 g of ethylene/1-butene copolymer, which contained 8.1% by weight Compared with the 1-butene composition unit and 2.8% by weight of the decane soluble component, the temperature is 23°C, the MFR measured at 190°C and the load of 2.16kg is 2.30g/10min, and the density is 0.915g/cm³And melt tension (MT) 5.3g and volume specific gravity 0.31g/cm³, When measured by a differential scanning card meter (DSC), the endothermic curve is displayed, with the highest peak at 94°C.

<u style="single">Example 2</u>

Preparation of prepolymerized catalyst

20ml of decane was added to 1.30g of the same silica used in Example 1 to form a suspension. 3.24ml of triisobutylaluminum in decane solution (Al:1 mol/L) was added to the suspension, and the mixture was stirred at room temperature for 30 minutes.

Then, 17.1 ml of a toluene solution (Al: 0.95 mol/L) of an organoaluminum oxy compound synthesized by the same procedure as in Example 1 was added to the suspension, and the resulting mixture was stirred at room temperature for 30 minutes.

Subsequently, 1.03 ml of a toluene solution of bis(cyclopentadienyl) zirconium dichloride (Zr: 0.0417 mol/liter) was added to the suspension, and the resulting mixture was stirred for 15 minutes. 50ml of decane was added to the mixture, and prepolymerization was carried out at 30°C for 2 hours while continuously introducing ethylene under normal pressure. Subsequently, 100.5 ml of a toluene solution containing 0.00172 mol/L of the catalyst component (A) of Zr was introduced, and the pre-polymerization reaction was continued at 30° C. for 4 hours. Subsequent operations similar to Example 1 were performed to obtain a prepolymerized catalyst containing 9.3 mg of zirconium, 190 mg of aluminum, and 20 g of polyethylene.

Polymerization

Repeat the polymerization procedure similar to Example 1, but use a gas mixture containing 3.6 mol% 1-butene, 10 Nml hydrogen and the aforementioned pre-polymerization catalyst. The amount is 0.005 milligram atoms (calculated as zirconium atoms) and 0.75 millimoles ( Calculated as triisobutyl aluminum) and polymerized at 70°C for 2 hours to obtain 88g of ethylene/1-butene copolymer, which contains 6.7% by weight of 1-butene unit and 0.25% by weight of decene Alkane soluble component, with MFR 0.48g/10min, density 0.922g/cm³, Melt tension 11g and volume specific gravity 0.35g/cm³, And show that the highest peak of the endothermic curve is at 103°C (determined by DSC).

<u style="single">Example 3</u>

Preparation of prepolymerized catalyst

30 ml of decane was added to 3.0 g of the same silica used in Example 1 to form a suspension. 7.45ml of triisobutylaluminum in decane solution (Al:1 mol/L) was added to the suspension, and the mixture was stirred at room temperature for 25 minutes.

Then, 39.4 ml of a toluene solution (Al: 0.95 mol/L) of an organoaluminum oxy compound synthesized by the same procedure as in Example 1 was added to the suspension, and the resulting mixture was stirred at room temperature for 25 minutes.

Subsequently, 2.14 ml of a toluene solution of bis(methylcyclopentadienyl)zirconium dichloride (Zr: 0.0465 mol/L) was added to the suspension, and the resulting mixture was stirred for 10 minutes. 100ml of decane was added to the mixture, and prepolymerization was carried out at 25°C for 2.5 hours while continuously introducing ethylene under normal pressure.

Subsequently, 166.4 ml of a toluene solution containing 0.00240 mol/L of the catalyst component (A) of Zr was introduced, and the pre-polymerization reaction was continued at 30° C. for 5 hours. Subsequent operations similar to Example 1 were performed to obtain a prepolymerized catalyst containing 8.2 mg of zirconium, 150 mg of aluminum and 20 g of polyethylene.

Polymerization

Repeat the polymerization procedure similar to Example 1, but add 30Nml hydrogen and use the aforementioned prepolymerization catalyst, thus obtaining 149g of ethylene/1-butene copolymer which contains 10.1% by weight of 1-butene unit and 3.1% The weight ratio of decane soluble component, with MFR 1.78g/10min, density 0.912g/cm³, Melt tension 5.3g and volume specific gravity 0.36g/cm³, And show that the highest peak of the endothermic curve is at 94°C (determined by DSC).

<u style="single">Example 4</u>

Preparation of prepolymerized catalyst

25ml of decane was added to 1.49g of the same silica used in Example 1 to form a suspension. 3.72ml of triisobutylaluminum in decane solution (Al:1 mol/L) was added to the suspension, and the mixture was stirred at room temperature for 45 minutes.

Then, 19.6 ml of a toluene solution (Al: 0.95 mol/L) of the organoaluminum oxy compound synthesized by the same procedure as in Example 1 was added to the suspension, and the resulting mixture was stirred at room temperature for 45 minutes.

Subsequently, 2.13 ml of a toluene solution of bis(methylcyclopentadienyl)zirconium dichloride (Zr: 0.0465 mol/L) was added to the suspension, and the resulting mixture was stirred for 10 minutes. 75ml of decane was added to the mixture, and prepolymerization was carried out at 30°C for 1.5 hours while continuously introducing ethylene under normal pressure.

Subsequently, 51.9 ml of a toluene solution containing 0.00287 mol/L of Zr and the catalyst component (A) prepared as in Example 1 was added to the reaction mixture, and the pre-polymerization reaction was continued at 30° C. for 4 hours. Subsequent operations similar to Example 1 were performed to obtain a prepolymerized catalyst containing 10.5 mg of zirconium, 190 mg of aluminum, and 17 g of polyethylene, based on 1 g of silica.

Polymerization

Repeat the polymerization procedure similar to Example 1, but use a gas mixture containing 4.4 mol% 1-butene, 30 Nml hydrogen and the aforementioned pre-polymerization catalyst. The amount is 0.005 milligram atoms (calculated as zirconium atoms) and 0.5 millimoles ( In terms of triisobutyl aluminum), 48g of ethylene/1-butene copolymer was obtained, which contained 6.5% by weight of 1-butene unit and 0.32% by weight of decane soluble components, with MFR 3.1g/ 10min, density 0.922g/cm³, Melt tension 4.9g and volume specific gravity 0.36g/cm³, And show that the highest peak of the endothermic curve is at 115°C (determined by DSC).

<u style="single">Example 5</u>

Polymerization

Repeat the polymerization procedure similar to Example 1, but use a gas mixture containing 3.6 mol% 1-butene, 10 Nml hydrogen and the aforementioned pre-polymerization catalyst. The amount is 0.005 milligram atoms (calculated as zirconium atoms) and 0.75 millimoles ( Calculated as triisobutyl aluminum) and polymerized at 70°C for 1 hour to obtain 95g of ethylene/1-butene copolymer which contains 7.4% by weight of 1-butene unit and 0.18% by weight of decene Alkane soluble component, with MFR 0.075g/10min, density 0.920g/cm³, Melt tension 42g and volume specific gravity 0.24g/cm³, And show that the highest peak of the endothermic curve is at 103°C (determined by DSC).

<u style="single">Comparative example 1</u>

Preparation of prepolymerized catalyst

25ml of decane was added to 3.14g of the same silica used in Example 1 to form a suspension. 13.1 ml of triisobutylaluminum in decane solution (Al: 1 mol/liter) was added to the suspension, and the mixture was stirred at room temperature for 45 minutes.

Then, 36.5 ml of a toluene solution (Al: 1.79 mol/L) of an organoaluminum oxy compound synthesized by the same procedure as in Example 1 was added to the suspension, and the resulting mixture was stirred at room temperature for 20 minutes.

Subsequently, 10.9 ml of a toluene solution of bis(methylcyclopentadienyl)zirconium dichloride (Zr: 0.0480 mol/L) was added to the suspension, and the resulting mixture was stirred for 30 minutes. Add 100ml of decane to the mixture, and conduct prepolymerization at 30°C for 4.5 hours while continuously introducing ethylene under normal pressure. Subsequently, a washing operation similar to that of Example 1 was performed to obtain a pre-polymerized catalyst, which contained 7.6 mg of zirconium, 190 mg of aluminum and 9.7 g of polyethylene based on 1 g of silica.

Polymerization

Repeat the polymerization procedure similar to Example 1, but use the pre-polymerized catalyst containing 6.1 mol% 1-butene and the aforementioned pre-polymerization catalyst, the amount of which is 0.015 milligram atoms (calculated as zirconium atoms) and 0.75 millimoles (triisobutyl aluminum) Meter), and at 85°C and 8kg/cm²The polymerization reaction was carried out under the total pressure of -G for 1 hour, thus 137g of ethylene/1-butene copolymer was obtained, which contained 7.2% by weight of 1-butene unit and 1.1% by weight of decane soluble components, with MFR 1.29g/10min, density 0.920g/cm³, Melt tension 1.9g and volume specific gravity 0.37g/cm³, And show that the highest peak of the endothermic curve is at 114°C (determined by DSC).

<u style="single">Example 6</u>

Polymerization

Repeat the polymerization procedure similar to Example 1, but the amount of polymerization catalyst used is 0.003 milligram atoms in terms of zirconium atoms, and 0.54 millimoles in terms of triisobutyl aluminum at 85°C and 8 kg/cm²Under the total pressure of -G, the polymerization reaction of ethylene alone was carried out for 1 hour, thus obtaining 121g of ethylene polymer with MFR 0.29g/10min, melt tension 17.5g and volumetric specific gravity 0.32g/cm³。

<u style="single">Example 7</u>

Polymerization

Repeat the polymerization procedure similar to Example 3, but use a gas mixture containing 3.9 mol% 1-butene, 50 Nml hydrogen and the aforementioned pre-polymerization catalyst. The amount is 0.005 mg atoms (calculated as zirconium atoms) and 0.5 millimoles ( Calculated as triisobutyl aluminum), and the polymerization reaction is 2.5kg/cm²Under the total pressure of -G, 119g of ethylene/1-butene copolymer is obtained, which contains 7.0% by weight of 1-butene unit and 0.35% by weight of decane soluble components, with MFR 1.97g/10min , Density 0.920g/cm³, Melt tension 4.6g and volume specific gravity 0.36g/cm³, And show that the highest peak of the endothermic curve is at 103°C (determined by DSC).

<u style="single">Example 8</u>

Polymerization

Repeat the polymerization procedure similar to Example 4, but use 50Nml hydrogen and the amount of pre-polymerization catalyst to be 0.75 millimoles in terms of triisobutyl aluminum, and at 85°C and 7kg/cm²The pre-combination reaction is carried out under the total pressure of -G, thus 141g of ethylene/1-butene copolymer is obtained, which contains 6.8% by weight of 1-butene unit and 0.67% by weight of decane soluble components, with MFR 1.99 g/10min, density 0.920g/cm³, Melt tension 6.0g and volume specific gravity 0.37g/cm³。

<u style="single">Example 9</u>

Preparation of prepolymerized catalyst

15ml of toluene was added to 1.11g of the same silica used in Example 1 to form a suspension. 7.76 ml of a toluene solution of triisobutylaluminum (Al: 1 mol/liter) was added to the suspension, and the mixture was stirred at room temperature for 30 minutes. Then, 13.6 ml of a toluene solution (Al: 0.95 mol/L) of an organoaluminum oxy compound synthesized by a similar procedure in Example 1 was added to the suspension, and the resulting mixture was stirred at room temperature for 35 minutes. Subsequently, 162.0 ml of a toluene solution of ethylene bis(indenyl) zirconium dichloride (Zr: 0.00228 mol/L) was added to the suspension, and the resulting mixture was stirred for another 30 minutes. 100ml of decane was added to the mixture, and prepolymerization was carried out at 30°C for 5 hours through continuous introduction of ethylene under normal pressure. Subsequent operations similar to Example 1 were performed to obtain a pre-polymerized catalyst containing 20.6 mg of zirconium, 310 mg of aluminum and 27 g of polyethylene, based on 1 g of silica.

Polymerization

A glass autoclave with an internal volume of 1.5 liters and thoroughly washed with nitrogen, 1 liter of decane is fed into it, and a gas mixture of ethylene and hydrogen is introduced into it at a flow rate of 250 liters/hour and 1 liter/hour, respectively. The temperature of the system was increased to 75°C, and 0.5 millimoles of triisobutylaluminum and a mixture of the aforementioned prepolymerized catalyst were added to the autoclave. The amount of the catalyst was 0.005 mg atoms (calculated as zirconium atoms). Subsequently, the polymerization reaction was carried out at 75° C. and normal pressure for 3 hours while continuously feeding the aforementioned gas mixture, so that the polymerization reaction was carried out in a slurry state.

After the polymerization reaction was completed, the obtained polymer was recovered by filtration, and dried at 80° C. under reduced pressure overnight to obtain 16.9 g of ethylene polymer with MFR 1.18 g/10 min and melt tension 6.5 g.

<u style="single">Example 10</u>

Preparation of catalyst

A 100ml eggplant-shaped flask and thoroughly cleaned with nitrogen is fed with 20ml decane, 27.9ml organoaluminum oxy compound toluene solution (Al: 0.716 mol/l) and 37.3ml ethylene bis(indenyl) zirconium dichloride Toluene solution (Zr: 0.00268 mol/liter) of the compound, and the content was stirred for 5 minutes. Toluene was distilled off from the mixture at room temperature under reduced pressure over a period of 2 hours. The resulting precipitated solid product was recovered by filtration, washed with hexane, and dried under reduced pressure at room temperature to obtain a solid catalyst having an Al/Zr atomic ratio of 112.

Polymerization

Repeat the polymerization procedure similar to Example 1, but only use the solid catalyst component prepared as above as the catalyst component. The amount is 0.005 milligram atoms in terms of zirconium atom. The homopolymerization of ethylene is conducted at 85°C and 8kg. /cm²-G total pressure for 1 hour, thus obtaining 26.4g of ethylene homopolymer with MFR 0.42g/10min and melt tension 12.0g.

<u style="single">Example 11</u>

Polymerization

Repeat the polymerization procedure similar to Example 10, but add 100 Nml of hydrogen, thus obtaining 34.0 g of ethylene homopolymer with MFR 3.10 g/10 min and melt tension 5.0 g.

<u style="single">Comparative example 2</u>

Polymerization

Repeat the polymerization procedure similar to Example 9, but use toluene as the solvent, and the flow rates of ethylene, 1-butene (both are polymerization monomers), and hydrogen gas mixture are 285 liters/hour, 15 liters/hour and At 2 liters/hour, the copolymerization reaction was carried out for 20 minutes, so the polymerization reaction was carried out in a solution state. After the polymerization reaction was completed, the polymer was recovered by precipitation in a large amount of methanol, and dried under reduced pressure at 130°C overnight to obtain 33.1 g of ethylene/1-butene copolymer containing 6.5% by weight of 1-butene constituent units , With MFR 1.44g/10min, density 0.922g/cm³And melt tension.

<u style="single">Comparative example 3</u>

Polymerization

Repeat the polymerization procedure similar to Example 9, but change the flow rates of ethylene and hydrogen in the gas mixture to 100 liters/hour and 5 liters/hour, respectively, and use 3.42ml of toluene solution of organoaluminum oxy compound (Al: 1.46 Mo Ears/liter) and 0.33ml of toluene solution of ethylene bis(indenyl) zirconium dichloride (Zr: 0.00150 mol/liter) as the catalyst component, and the homopolymerization of ethylene is carried out for 80 minutes, thus the polymerization reaction It is carried out in a turbid state. After the polymerization reaction was completed, the obtained polymer was precipitated in a large amount of methanol and recovered by drying under reduced pressure at 80° C. overnight, thereby obtaining 8.2 g of ethylene copolymer with MFR 0.72 g/10 min and melt tension 2.9 g.

<u style="single">Example 12</u>

Preparation of prepolymerized catalyst

55.4g of silica (TG-20643, manufactured by Fuji Davison) was charged into an 8 liter flask thoroughly washed with nitrogen, which was fired at 700°C for 6 hours and charged with 1 liter of decane to form a suspension before feeding. liquid. 46 millimoles of triisobutylaluminum diluted with 50 ml of decane was added to the suspension, and the mixture was stirred at room temperature for 10 minutes.

Subsequently, 140 ml of a toluene solution (Al: 1.65 mol/liter) of the catalyst component (ii) (manufactured by Schering) prepared as above was added, and the mixture was stirred at room temperature for 10 minutes. Then, 36.9 ml of a toluene solution of bis(methylcyclopentadienyl) zirconium dichloride (Zr: 0.05 mol/liter) was added, and the mixture was stirred for another 15 minutes. Then, the pre-polymerization reaction was carried out at 30°C for 3.5 hours by continuously introducing ethylene under normal pressure.

Then, add 2 liters of decane, 279 ml of catalyst component (ii), 2.79 liters of catalyst component (i) prepared in Example 1 (Zr: 0.00264 mol/liter), and 23.4 ml of 50 ml of decane The diluted triisobutyl aluminum was pre-polymerized at 30°C for 4 hours.

After the pre-polymerization reaction was completed, the solvent was removed by decantation, and washed 3 times with 5 liters of hexane at 60°C, and 3 times with 5 liters of hexane at room temperature, thus obtaining a pre-polymerization catalyst containing 11 mg of Zr. 190mg Al and 16g polyethylene (based on 1g silica).

Polymerization

The copolymerization of ethylene and 1-hexene uses continuous fluid bed gas phase polymerization equipment at a polymerization temperature of 80°C and 20kg/cm²-G is carried out under the total pressure, and the method is to continuously feed the aforementioned prepolymerized catalyst at a flow rate of 0.1 millimoles/hour in terms of zirconium and 15 millimoles/hour in terms of triisobutylaluminum In the reaction system, ethylene, 1-hexene, hydrogen and nitrogen are continuously supplied at the same time while maintaining the following constant gas composition during the polymerization reaction: 1-hexene/ethylene volume ratio 0.015 and H₂/Ethylene volume ratio 6.3×10^-3. The polymer yield was 6.0 kg/hr.

The polymer thus obtained contains 10.7% by weight of 1-hexene unit and 0.53% by weight of decane soluble components, measured at 23°C, has MFR 1.60g/10min, density 0.922g/cm³, Melt tension (MT) 6.6g, and volume specific gravity 0.38g/cm³, And showed that the endothermic curve (determined by DSC) has the highest peak at 112.1°C.

The results are shown in Tables 1 and 2.

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<u style="single">Comparative example 4</u>

Preparation of prepolymerized catalyst

Repeat Comparative Example 1, but use 13.1ml of toluene solution of bis(cyclopentadienyl) zirconium dichloride (Zr: 0.04 mol/L) instead of toluene of bis(methylcyclopentadienyl) zirconium dichloride From the solution, a pre-polymerized catalyst was obtained, which contained 8.7 mg of zirconium, 290 mg of aluminum and 7.7 g of polyethylene, based on 1 g of silica.

Polymerization

Repeat the polymerization procedure similar to Example 1, but use a gas mixture containing 6.7 mol% 1-butene and the aforementioned pre-polymerization catalyst. The amount is 0.01 milligram atoms based on zirconium and 0.25 millimoles based on triisobutyl Aluminum meter, and polymerization reaction system at 85°C and 8kg/cm²-G total pressure for 1 hour, thus obtaining 75g of ethylene/1-butene copolymer, which contains 6.9% by weight of 1-butene unit and 1.5% by weight of decane soluble components, with MFR 2.63g /10min, density 0.922g/cm³And the melt tension is 1.3g, and the endothermic curve (measured by DSC) has the highest peak at 114°C.

<u style="single">Comparative example 5</u>

Preparation of prepolymerized catalyst

20ml of decane was added to 1.05g of the same silica as used in Example 1, and a suspension was formed in a 400ml glass bottle. 2.62ml of triisobutylaluminum in decane solution (Al:1 mol/L) was added to the suspension, and the resulting mixture was stirred at room temperature for 30 minutes.

Then, 4.87 ml of the toluene solution of the organoaluminum oxy compound was added to the suspension (the toluene was removed from the toluene solution of methylaluminoxane prepared by Schering) and the residue was re-dissolved in toluene to prepare (Al: 1.79 mol /L)], the resulting mixture was stirred at room temperature for 35 minutes.

Subsequently, 16.2 ml of a toluene solution of bis(n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0108 mol/L) was added to the suspension, and the mixture was stirred for 30 minutes. Then, 75ml of decane was added to the mixture, and prepolymerization was carried out at 30°C for 4 hours through continuous introduction of ethylene under normal pressure. Subsequent operations were similar to Example 1, and a pre-polymerized catalyst was obtained, which contained 9.3 mg of zirconium, 150 mg of aluminum, and 18 g of polyethylene.

Polymerization

Repeat the polymerization procedure similar to that of Example 1, but use the pre-polymerized catalyst containing 6.9 mol% 1-butene and the aforementioned pre-polymerization catalyst, the amount of which is 0.005 mg atoms (calculated as zirconium atoms) and 0.5 millimoles (as triisobutyl aluminum) Meter), and at 85°C and 8kg/cm²The polymerization reaction was carried out under the total pressure of -G for 1 hour, thus 147g of ethylene/1-butene copolymer was obtained, which contained 9.6% by weight of 1-butene unit and 1.5% by weight of decane soluble components, with MFR 2.45g/10min, density 0.910g/cm³, The melt tension is 0.95g, and the highest peak of the endothermic curve is at 109°C (measured by DSC).

<u style="single">Comparative example 6</u>

A glass autoclave containing 1.5 liters and thoroughly washed with nitrogen is fed with 1 liter of toluene, and the mixture of ethylene, 1-butene and hydrogen at 285 liters/hour, 15 liters/hour and 2 liters/hour respectively The rate of introduction into it. The temperature of the system was increased to 70°C, 0.5 millimoles of triisobutylaluminum and the pre-polymerization catalyst prepared in Example 1 were introduced, the amount of which was 0.005 mg atoms in terms of zirconium atoms, and the polymerization reaction was started.

The polymerization reaction was carried out by continuously introducing the aforementioned gas mixture at 75°C and atmospheric pressure for 20 minutes, so that the resulting polymer was dissolved in toluene as the reaction progressed. After the completion of the polymerization reaction, the resulting polymer was precipitated by pouring the polymer solution into methanol.

Then, the precipitated polymer was recovered by filtration, and dried under reduced pressure at 80°C overnight, thereby obtaining 33.1g of ethylene/1-butene copolymer with MFR 1.44g/10min and density 0.922g/cm³And melt tension (MT) 2.1g.

<u style="single">Comparative example 7</u>

A glass autoclave with an inner volume of 1.5 liters and thoroughly washed with nitrogen is fed with 1 liter of toluene, and the mixture of ethylene, 1-butene and hydrogen at 285 liters/hour, 15 liters/hour and 5 liters/hour respectively The flow rate is introduced into it. The temperature of the system was increased to 70°C and started by introducing the organoaluminum oxy compound prepared in Example 1 in the amount of 5.0 mg atoms in terms of aluminum atoms and the catalyst component (i) of 0.0005 mg atoms in terms of zirconium atoms Polymerization.

The polymerization reaction is carried out at 75°C and normal pressure for 20 minutes, while continuously introducing the aforementioned gas mixture, whereby the resulting polymer is dissolved in toluene as the reaction progresses. The subsequent operations are similar to Comparative Example 4. Repeat the procedure to obtain 44.1g of ethylene/1-butene copolymer with MFR 1.08g/10min and density 0.928g/cm³And melt tension (MT) 2.0g.

<u style="single">Example 13</u>

Preparation of prepolymerized solid catalyst (zirconium catalyst)

A 400ml glass bottle thoroughly washed with nitrogen was fed with 1.38g of silica (F-498, manufactured by Fuji Davison), which was fired at 700°C for 6 hours before feeding, and fed with 20ml of decane to form a suspension . 3.24ml of triisobutylaluminum in decane solution (Al: 1 mol/liter) was added to the suspension, and the contents were stirred at room temperature for 30 minutes.

18.8ml of toluene solution of organoaluminum oxy compound (prepared by drying methylaluminoxane manufactured by Schering and re-dissolving the residue in toluene, Al: 0.864 mol/L) was added to the suspension, and the mixture was added to Stir at room temperature for 30 minutes.

Subsequently, 1.03 ml of a toluene solution of bis(cyclopentadienyl) zirconium dichloride (Zr: 0.0417 mol/L) was added to the suspension, and the mixture was stirred for 10 minutes. Then, 50 ml of decane was added, and the pre-polymerization reaction was carried out at 30°C for 2 hours while continuously introducing ethylene under normal pressure.

Subsequently, 100.5 ml of a toluene solution of ethylene bis(indenyl) zirconium dichloride (Zr: 0.00172 mol/liter) was added, and the prepolymerization was continued at 30°C for 4 hours.

After the prepolymerization reaction was completed, the solvent was removed by decantation. The residue was washed 3 times with 250ml hexane at 60°C and then with 250ml hexane 3 times at room temperature. Thus, a prepolymerized solid catalyst containing 9.5 mg atomic zirconium was obtained. 0.66 g atomic aluminum and 1750 g polyethylene.

Polymerization

A stainless steel autoclave with an internal volume of 2 liters and thoroughly washed with nitrogen was charged with 150 g of sodium chloride (special grade, available from Wako Junyaku KK), and the contents were dried at 90° C. under reduced pressure for 1 hour. Subsequently, the system pressure was returned to normal pressure by introducing ethylene, and the system temperature was maintained at 70°C. Subsequently, a premix of 0.3 millimoles of triisobutylaluminum and the aforementioned solid catalyst (0.003 milligram atoms in terms of zirconium) was fed into the autoclave.

Then, first introduce 50Nml hydrogen, and then introduce ethylene into the autoclave at a system temperature of 70°C, so the total pressure becomes 8kg/cm²-G, and start the polymerization reaction.

Subsequently, the polymerization reaction was carried out at 85°C for 1 hour while maintaining the total pressure at 8 kg/cm by simply introducing ethylene.²-G. After the polymerization reaction is completed, sodium chloride is removed from the contents by washing with water. The remaining polymer was washed with methanol and dried under reduced pressure at 80°C overnight, thus obtaining 142 g of polymer with a volume specific gravity of 0.43 g/cm³, MFR 0.65g/10min (measured at 190°C and 2.16kg load), melt tension (MT) 10g and average particle size 410μm.

<u style="single">Example 14</u>

20 ml of decane was added to 1.12 g of the same silica used in Example 13 to form a suspension. 2.8 ml of triisobutylaluminum in decane solution (Al: 1 mol/L) was added to the suspension, and the mixture was stirred at room temperature for 35 minutes.

Then, 10.8 ml of the toluene solution (Al: 0.864 mol/L) of the same organoaluminum oxy compound as used in Example 1 was added to the suspension, and the mixture was stirred at room temperature for 25 minutes.

Subsequently, 1.34 ml of a toluene solution of bis(cyclopentadienyl) zirconium dichloride (Zr: 0.0417 mol/L) was added to the suspension, and the contents were stirred for 30 minutes. In addition, 50 ml of decane was added, and a pre-polymerization reaction was performed at 30° C. for 2 hours through continuous introduction of ethylene at normal pressure. Subsequently, 71.3 ml of a toluene solution (Zr: 0.00183 mol/L) of ethylene bis(indenyl) zirconium dichloride) was added to the reaction mixture, and the pre-polymerization was continued at 30° C. for 3.5 hours. Subsequent operations similar to Example 13 were performed to obtain a solid catalyst containing 9.6 milligrams of atomic zirconium, 0.66 grams of atomic aluminum and 2100 g of polyethylene, based on 100 g of silica.

Polymerization

Repeat the procedure of Example 13 to obtain 88g polymer with a volume specific gravity of 0.42g/cm³, MMFR 0.60g/10min and average particle size 380μm.

<u style="single">Example 15</u>

Preparation of solid catalyst (zirconium catalyst)

30 ml of decane was added to 3.0 g of the same silica used in Example 13 to form a suspension. 7.45ml of triisobutylaluminum in decane solution (Al:1 mol/L) was added to the suspension, and the mixture was stirred at room temperature for 25 minutes.

Subsequently, 17.6 ml of the toluene solution (Al: 2.13 mol/L) of the same organoaluminum oxy compound as in Example 13 was added to the suspension, and the contents were stirred at room temperature for 25 minutes.

Subsequently, 2.14 ml of a toluene solution of bis(methylcyclopentadienyl) zirconium dichloride (Zr: 0.0465 mol/L) was added to the suspension, and the contents were stirred for 5 minutes. 100ml of decane was added to the mixture, and the pre-polymerization reaction was continuously carried out at 25°C for 2.5 hours by continuously introducing ethylene at normal pressure. Then, 166.4 ml of a toluene solution of ethylene bis(indenyl) zirconium dichloride (Zr: 0.0024 mol/liter) was added, and the prepolymerization reaction was continued at 30°C for 5 hours. Subsequent operations similar to Example 13 were performed to obtain a pre-polymerized solid catalyst containing 9.0 milligrams of atomic zirconium, 0.55 grams of atomic aluminum and 2000 g of polyethylene, based on 100 g of silica.

Polymerization

Repeat the polymerization procedure of Example 13, but use 0.54 millimoles of triisobutyl aluminum, and the catalyst component together with ethylene. The internal pressure is 6.5kg/cm²In the autoclave, 124g of polymer is obtained with a volumetric specific gravity of 0.41g/cm³, MFR 0.58g/10min, melt tension (MT) 13g and average polymer particle size 400μm.

<u style="single">Comparative example 8</u>

Preparation of prepolymerized solid catalyst (zirconium catalyst)

20 ml of decane was added to 3.05 g of the same silica used in Example 13 to form a suspension. 7.61ml of triisobutylaluminum in decane solution (Al:1 mol/L) was added to the suspension, and the mixture was stirred at room temperature for 30 minutes.

Subsequently, 11.9 ml of the toluene solution (Al: 2.13 mol/L) of the same organoaluminum oxy compound as in Example 13 was added to the suspension, and the contents were stirred at room temperature for 30 minutes.

Subsequently, 10.9 ml of a toluene solution of bis(methylcyclopentadienyl) zirconium dichloride (Zr: 0.0465 mol/L) was added to the suspension, and the mixture was stirred for 30 minutes. 100ml of decane was added to the mixture, and the pre-polymerization reaction was continuously carried out at 30°C for 3.5 hours by continuously introducing ethylene under normal pressure. Subsequent operations similar to Example 13 were performed to obtain a solid catalyst containing 12.0 mg atomic zirconium, 0.71 grams atomic aluminum and 790 g polyethylene, based on 100 g silica.

Polymerization

Repeat the polymerization procedure of Example 15, but use the pre-polymerized solid catalyst obtained as above, the amount of which is 0.015 mg atoms in terms of zirconium atom, to obtain 70 g of polymer with a volume specific gravity of 0.42 g/cm³And MFR 0.69g/10min.

<u style="single">Comparative example 9</u>

Preparation of prepolymerized solid catalyst (zirconium catalyst)

20 ml of decane was added to 1.16 g of the same silica used in Example 13 to form a suspension. 4.05 ml of triisobutylaluminum in decane solution (Al: 1 mol/L) was added to the suspension, and the mixture was stirred at room temperature for 30 minutes.

Subsequently, 3.17 ml of the toluene solution (Al: 2.13 mol/L) of the same organoaluminum oxy compound as in Example 13 was added to the suspension, and the contents were stirred at room temperature for 30 minutes.

Subsequently, 80.5 ml of a toluene solution of ethylene bis(indenyl) zirconium dichloride (Zr: 0.0024 mol/L) was added to the suspension, and the mixture was stirred for 30 minutes. Then, 50 ml of decane and 90 ml of toluene were added, and the pre-polymerization reaction was continuously carried out at 30° C. for 3 hours through continuous introduction of normal pressure ethylene. Subsequent operations similar to Example 13 were performed to obtain a pre-polymerized solid catalyst containing 8.9 milligrams of atomic zirconium, 0.56 grams of atomic aluminum and 1000 g of polyethylene, based on 100 g of silica.

Polymerization

Repeat the polymerization procedure of Example 15 to obtain 123g of polymer with a volumetric specific gravity of 0.36g/cm³, MFR 0.44g/10min and polymer average particle size 370μm.

Example 16

Polymerization

Repeat the polymerization procedure of Example 13, but use a gas mixture of ethylene and 1-butene (1-butene content 3.9 mol%) instead of ethylene, 30 Nml hydrogen, 0.75 millimoles of triisobutyl aluminum, and Example 3 The amount of the prepared solid catalyst component is 0.0075 mg atom in terms of zirconium atom, and the polymerization temperature and total pressure are set to 80°C and 2.5kg/cm, respectively²-G, so 172g of polymer obtained has a volume specific gravity of 0.38g/cm³, MFR 0.82g/10min, melt tension (MT) 9g and density 0.918g/cm³。

<u style="single">Example 17</u>

Preparation of prepolymerized solid catalyst (zirconium catalyst)

25ml of decane was added to 1.49g of the same silica used in Example 13 to form a suspension. 3.72ml of triisobutylaluminum in decane solution (Al:1 mol/L) was added to the suspension, and the mixture was stirred at room temperature for 45 minutes.

Subsequently, 8.09 ml of the toluene solution of the same organoaluminum oxy compound as in Example 13 (Al: 2.30 mol/L) was added to the suspension, and the contents were stirred at room temperature for 45 minutes.

Subsequently, 2.13 ml of a toluene solution of bis(methylcyclopentadienyl) zirconium dichloride (Zr: 0.0465 mol/L) was added to the suspension, and the contents were stirred for 10 minutes. 75ml of decane was added to the mixture, and the prepolymerization reaction was continuously carried out at 30°C for 1.5 hours through continuous introduction of normal pressure ethylene. Then, 51.9 ml of a toluene solution of ethylene bis(indenyl) zirconium dichloride (Zr: 0.00287 mol/liter) was added, and the pre-polymerization reaction was continued at 30°C for 4 hours, thereby obtaining a pre-polymerized solid catalyst It contains 11.5 milligrams of atomic zirconium, 0.71 grams of atomic aluminum and 1700 grams of polyethylene, based on 100 grams of silica.

Polymerization

Repeat the polymerization procedure of Example 13, but use a gas mixture of ethylene and 1-butene (1-butene content 4.4 mol%) instead of ethylene, 30 Nml hydrogen, 0.5 millimoles of triisobutyl aluminum, and prepare as above The amount of pre-polymerized solid catalyst component is 0.005 milligram atoms in terms of zirconium atoms, so 137g of polymer is obtained with a volumetric specific gravity of 0.39g/cm³, MFR 0.53g/10min, melt tension (MT) 12g and density 0.917g/cm³。

[Preparation of Aluminoxane]

Add 50g of copper sulfate pentahydrate to 565ml of a toluene solution containing 48.2g of trimethylaluminum at 0°C, 5g each time at 5 minutes intervals, and stir while mixing. After mixing, slowly raise the temperature to 250°C and maintain at 250°C for 2 The reaction time is hours, and then the temperature is raised to 35°C for 2 days. The remaining solid copper sulfate is separated to obtain a toluene solution of aluminoxane. The concentration of methylaluminoxane is 273mg/ml (2.7w/v%).

[Reaction of Silicon Dioxide and Methyl Aluminoxane]

In the nitrogen-oxygen circulation, 100g of silicon dioxide [Davidson produced #952] dried at 600°C for 4 hours was added to 120ml of the aluminoxane-toluene solution prepared by the above method (3.3g aluminoxane). After reacting at °C for 1 hour, it was sufficiently washed with toluene to remove unreacted aluminoxane.

[The reaction of silicon dioxide treated with the above-mentioned methylaluminoxane and bis(cyclopentadienyl) zirconium dichloride]

Add 0.25 g of bis(cyclo-pentadienyl) zirconium dichloride to the above-mentioned methylaluminoxane-treated alumina-toluene slurry, and react at 25°C for 2 hours , And then washed with toluene, and dried under reduced pressure at 40 °C. The obtained solid catalyst was stored under nitrogen. The solid catalyst contains 60mg of Al and 2.4mg of Zr in 1g,

[Copolymerization of Ethylene and Butene]

150g of sodium chloride (Wako Pure Chemical Industries, Ltd., special grade) was used as seed crystals, placed in an autoclave with a volume of 21, and 7.1ml of the above-mentioned aluminoxane solution (193mg of aluminoxane) was added to it at 60°C. Disperse for 10 minutes. Then 0.19 g of the above-mentioned solid catalyst was added to it, and dispersed for 5 minutes. Then press 6cc of liquefied butene into it, and increase the pressure to 9kg/cm with ethylene containing 2.5 mol% of butene²-G. The polymerization reaction started immediately, and the polymerization reaction was carried out for 2 hours while compensating the absorption of the above-mentioned butene-containing ethylene. After the polymerization is completed, the sodium chloride is washed with water, and the remaining polymer is washed with methanol, and then dried under reduced pressure at 80°C overnight. As a result, the melt index (melt index) is 1.5g/10 points, and the density is 0.925g/cm.², 50g of polymer with a melt tension of 1.5g.