Method of polymerizing and copolymerizing olefins

The present invention relates to an olefin polymerization process using a new olefin polymerization catalyst. The new catalyst has excellent catalytic activity, enabling the production of high molecular weight olefin polymers. In particular, the olefin polymerization catalyst enables the production of olefin polymers with a narrow molecular weight distribution in the case where olefin homopolymers are produced and enables the production of olefin copolymers with a narrow molecular weight distribution and with a narrow composition distribution when copolymers of two or more olefins are produced.

It is known that polymers of α-olefins, in particular polymers of ethylene or copolymers of ethylene with α-olefins are prepared by a method in which ethylene is polymerized or ethylene and α-olefin is copolymerized in the presence of a titanium-based catalyst composed of a titanium compound and a compound an organoaluminium or vanadium based catalyst consisting of a vanadium compound and an organoaluminium compound.

In general, copolymers of ethylene and α-olefins obtained using titanium-based catalysts have a broad molecular weight distribution, and in addition have unsatisfactory properties such as transparency, surface non-stickiness and dynamic mechanical properties. Copolymers of ethylene with α-olefins obtained using vanadium-based catalysts have a higher molecular weight distribution and narrower composition distribution as compared to copolymers of ethylene with α-olefins obtained using titanium catalysts, and also have slightly better properties such as transparency, surface non-stickiness and dynamic mechanical properties, but it was found that such properties are not satisfactorily met. For this reason, it is desirable to develop a method for producing copolymers of ethylene and α-olefins having even better above-mentioned properties.

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With this in mind, methods have recently been developed for producing ethylene α-olefin copolymers using zirconium and alumoxane catalysts, a new type of Ziegler catalyst for olefin polymerization. Yes e.g. Japanese Patent Application Publication No. 19 309/1983 discloses a method of producing copolymers of ethylene with α-olefins, consisting of polymerizing ethylene and one or at least two C3-C12-α-olefins at a temperature from -50 to 200 ° C in the presence of a catalyst consisting of a transition metal compound, represented by the formula (cyclopentadienylhMeRHHal, in which R is a cyclopentadienyl group, a C 1 -C 6 -alkyl group or a halogen atom, Me is a transition metal atom, and Hal is a halogen atom and a linear alumoxane represented by the formula Al2 [A / R / -O]_n, wherein R is a methyl or ethyl group, and n is a number from 4 to 20, or a cyclic alumoxane represented by formula 7, wherein R and n are as defined above. In this specification, it is stated that in order to control the density of the polymer obtained, the polymerization of ethylene should be carried out in the presence of small amounts, up to 10% by weight, of relatively long chain α-olefins or mixtures thereof.

Japanese Patent Application Publication No. 95 292/1984 discloses an invention regarding methods for producing linear alumoxanes represented by formula 8, wherein n is a number from 2 to 40 and R represents a C1-C6-alkyl group, and cyclic alumoxanes represented by formula 7, wherein and R are as defined above.

This description states that if the polymerization of ethylene is carried out in the presence of a mixture containing alumoxane prepared as described, e.g. methylalumoxane, and a bis (cyclopentadienyl) zirconium compound or a bis (cyclopentadienyl) titanium compound, at least 25,000,000 g of polyethylene per 1 are obtained. g of transition metal for 1 hour.

Japanese Patent Application Publication No. 35 005/1985 discloses a method of producing an olefin polymerization catalyst by reacting an alumoxane compound represented by formula 9, wherein¹ is a C 1 -C 10 -alkyl group and R 0 is R 1 or a bond through an oxygen atom to a magnesium compound followed by chlorination of the reaction product and treatment with a Ti, V, Zr or Cr compound. In this specification, it has been found that the catalyst prepared by the disclosed method is particularly suitable for use in the copolymerization of ethylene with α-C3-Ci2-olefins. Japanese Patent Application Publication No. 35 006/1985 discloses a mixture of (a) two or more different transition metal compounds containing one, two or 3 cyclopentadienyl rings or derivatives thereof, and (b) alumoxane as a catalyst for producing polymers in the form of reactor mixes.

Example 1 in this specification states that ethylene and propylene are polymerized in the presence of a catalyst consisting of bis (five-methylcyclopentadienyl) dimethyl zirconium and alumoxane to give polyethylene with a number average molecular weight of 15 300, a weight average molecular weight of 36 400 and a propylene content of 3, 4%. In Example 2, in this specification, ethylene and propylene are polymerized in the presence of a catalyst consisting of bis (pentylmethylcyclopentadienyl diammonium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and alumoxane, to obtain a mixture of polyethylene with a copolymer of ethylene with a propylene-containing molecular weight fraction 200 and having a weight average molecular weight of 11,900 and a 30% molar propylene content, and a toluene insoluble fraction, with a number average molecular weight of 3,000, a weight average molecular weight of 7,400 and a propylene component content of 4.8 mol%.

For the entire blend, the number average molecular weight was 2000, the weight average molecular weight was 8 300 and the propylene component content was 7.1 mol%. In Example 3, a blend of LLDPE (linear low density polyethylene) and a copolymer of ethylene with propylene was prepared containing a soluble fraction with a molecular weight distribution (Mw / Mn) of 4.57 and a propylene component content of 20.6 mol% and an insoluble fraction with a molecular weight distribution of 3 , 04 and a propylene component content of 2.9 mol%.

Japanese Patent Application Publication No. 35 007/1985 discloses a method of polymerizing ethylene alone or copolymerizing ethylene with an α-olefin having 3 or more carbon atoms in the presence of a catalyst system containing metallocene and a cyclic alumoxane represented by formula 7, wherein R is an alkyl group of 1 -5 carbon atoms, an is an integer from 1 to about 20, or a linear alumoxane represented by formula 10, wherein R and n are as defined above. The polymers thus obtained had a weight average molecular weight from about 500 to about 1,400,000 and a molecular weight spread in the range of 1.5-4.0.

Japanese Patent Application Publication No. 35 008/1985 discloses that polyethylene or copolymers of ethylene with C3-C10-olefins with a broad molecular weight distribution are prepared using a catalyst system containing at least two metallocenes and alumoxane. In this specification it was found that the copolymers thus obtained have a molecular weight (Mw / Mn) distribution in the range of 2-50. Published Japanese Patent Application Nos. 260 602/1985 and 130 604/1985 proposed methods for polymerizing olefins using catalysts made from a mixed organoaluminium compound containing a transition metal compound, alumoxane and an organo aluminum compound, and disclosed that catalytic activity per transition metal unit is increased by the addition of an organoaluminium compound.

The disadvantage of all the above-mentioned methods, however, is that the activity per alumoxane unit in the catalyst used is still low. Another problem is that there are difficulties in obtaining polymers with a sufficiently high molecular weight if olefins, e.g. ethylene and propylene, are copolymerized in the presence of catalysts made from transition metal compounds and alumoxanes known to date.

The object of the invention was to solve the problems associated with the known methods described above, and to develop an olefin polymerization catalyst in the presence of which olefin polymers with a narrow molecular weight distribution can be obtained when olefin homopolymers or olefin copolymers with a narrow molecular weight distribution and narrow distribution are produced. composition when copolymers of two or more olefins are produced, and furthermore exhibiting excellent catalytic activity even when the amount of alumoxane used in them is low, and one in which high molecular weight olefin polymers can easily be obtained.

The main object of the invention was to develop a method for olefin polymerization using the above-mentioned olefin polymerization catalyst. Thus, according to the invention, a process for the polymerization or copolymerization of olefins in the presence of a catalyst containing a transition metal compound belonging to group IV B of the periodic table and alumoxane was developed, and the feature of this method is that a catalyst made from A) a transition metal compound of general formula 1 is used in which R? is a? cyclopentadienyl group optionally substituted with C 1 -C 4 -alkyl or an indenyl group², R3 and R⁴ independently represent a cyclopentadienyl group optionally substituted with C 1 -C 4 -alkyl, an indenyl group or a halogen atom, wherein when two of the symbols R 1 - R 4 represent indenyl groups, they are optionally connected via C 1 -C 4 -alkylene, and at least one of the symbols R2, r3 and R4 is a halogen atom, M is a zirconium or hafnium atom, k is 1 or 2.1, min is 0, ł or 2, ak + 1 + m + n is 4, B) alumoxane, C) water and D) trialkyl aluminum, wherein the molar ratio of aluminum atoms derived from alumoxane to water is 0.5 to 50, preferably 1 to 40, the number of aluminum atoms derived from trialkylaluminum accounts for 30-99% of the total number of aluminum atoms derived from alumoxane and trialkylaluminum, and the ratio of aluminum atoms derived from alumoxane and trialkylaluminum to transition metal atoms is 20 to 1x104. The following describes in detail the olefin polymerization catalyst and the olefin polymerization method using such a catalyst.

In the description of the invention, the term polymerization is sometimes used in the sense that it includes not only homopolymerization but also greater polymerization, and the term polymer is sometimes used in the sense that it means not only homopoEmer but also a copolymer. The following describes in detail the olefin polymerization catalyst prepared from the catalyst components A), B), C) and D) mentioned above.

The catalytic component A) used in the olefin polymerization catalyst is a transition metal compound belonging to group IV B of the periodic table selected from the group consisting of zirconium and hafnium, and preferably a zirconium compound containing a group with π-linked electrons as a ligand.

The C 1 -C 4 -alkyl substituted cyclopentadienyl group is, for example, methylcyclopentadienyl, ethylcyclopentadienyl, ΠΙ-γζ. butylcyclopentadienyl, dimethylcyclopentadienyl or five-methylcyclopentadienyl. The halogen atom may be e.g. fluorine, chlorine or bromine atom.

Examples of zirconium compounds containing as a ligand a group with π-linked electrons include: bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (methylcyclopentadienyl) zirconium dichloride, bis (III-cyclocyclic di-zirconium dichloride) pentamethylcyclopentadienyl diammonium, bis (indenyl) zirconium dichloride and bis (indenyl zirconium) bromide. Zirconium compounds used as the catalytic component of A) olefin polymerization catalyst may also include zirconium compounds having as a ligand a multi-core compound in which at least two indenyl groups are connected to each other via a lower alkylene group. Examples of such zirconium compounds include ethylene bis (indenyl) zirconium dichloride and ethylene bis (indenyl) zirconium dichloride. It is also possible to use transition metal compounds in which the zirconium atom in the above-mentioned zirconium compounds has been replaced by a hafnium atom.

The catalytic component B) used in the olefin polymerization catalyst is alumoxane. The alumoxane used as this component may e.g. be an organo aluminum compound represented by general formula 2 or 3.

In an alumoxane of formula 2 or 3, R is a hydrocarbon group such as a methyl, ethyl, propyl or butyl group, preferably a methyl or ethyl group, and even more preferably a methyl group, and m is an integer equal to at least 2, and preferably 5-40.

The above-described alumoxane may consist of mixed α-Aloxy aluminum groups containing an alkoxy group of formula 4 and an alkoxy aluminum group of formula 5, wherein in the formulas R 1 and R² may be the same hydrocarbon groups as the R group in the formula or 3, with the proviso that R¹ and R2 are different hydrocarbon groups. In this case, those alumoxanes that form mixed alkoxyaluminum groups containing at least 30 mole%, preferably at least 50 mole%, and even more preferably at least 70 mole% methyloxy aluminum groups of formula 6 are preferred.

Alumoxane as described above can be prepared, e.g., by the methods described below.

The first method involves reacting a suspension of a compound containing adsorption water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerium chloride hydrate, in a hydrocarbon medium with trialkylaluminum.

The second method involves reacting trialkylaluminum directly with water in an environment such as benzene, toluene, ethyl ether or tetrahydrofuran.

Of the methods mentioned above, the first method is preferred. The alumoxane produced by these methods may contain small amounts of organometallic components.

Component C) used in the olefin polymerization catalyst is water, which water may be, e.g., water dissolved or dispersed in the polymerization solvents listed below, or water contained in the compounds or salts used to prepare component B) of the catalyst.

As component D), trialkylaluminum compounds, such as trimethylaluminum, triethylaluminum, trisobutylaluminum, tri (2-methylbutyl) aluminum, tri (3-methylbutyl) aluminum, tri (2-methylpentylaluminum, tri (3-methylpentyl) aluminum, tri (4) are useful -methylpentyl) aluminum, tri (2-methylhexyl) aluminum, tri (3-methylhexyl) aluminum, etc.

Of the compounds mentioned above, trialkylaluminum compounds having hydrocarbon groups other than n-alkyl groups are preferred. Particularly preferred compounds include triazopropylaluminum, triazisobutylaluminum, tri-methylbutylaluminum, tri (3-methylbutylaluminum, tri (2-methylpentyl) aluminum, tri (3-methylpentyl) aluminum, tri (4-methylpentyl) aluminum, tri (2-methylhexyl) ) aluminum, tri (3-methylhexyl) aluminum and tri (2-ethylhexyl) aluminum.

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Compounds from which the above-mentioned organo-aluminum compounds are formed in the polymerization system can also be used as component D) of the catalyst, e.g. aluminum halides and alkyl lithium compounds or aluminum halides and alkyl magnesium compounds.

This type of catalyst can be prepared by a method of mixing all catalyst components, A, B, C and D simultaneously, in a hydrocarbon or olefin medium, by a method of pre-mixing two catalyst components to obtain a mixture, and then mixing this mixture with the other two components catalyst, or by a method of pre-mixing the three catalyst components to form a mixture, and then mixing this mixture with the remaining fourth catalyst component. In these cases, it is preferable to pre-mix the B component of the catalyst with the C component of the catalyst.

The concentration of alumoxane, calculated as aluminum atoms, in the initial mixing of catalyst components B and C is usually from 5 5 10 '⁴ up to 3 grams / Utr, preferably from 1 χ 10 '³up to 2 gram / atoms and the water concentration is usually from 2.5 x 10 '⁵ up to 2 moles / liter, preferably from 5 χ 10⁵ up to 1.5 mole / liter at a molar ratio of aluminum to water (Al / H2O) 0.5 to 50, preferably 1 to 40. The temperature at which pre-mixing is carried out is usually -50 to 100 ° C, and the mixing time from 0.1 minutes to 200 hours.

When mixing component A of the catalyst with the premixed components B and C of the catalyst, component A of the catalyst is used in such an amount that the concentration of transition metal contained in component A of the catalyst is usually 5 χ 10 '⁶ - 1.5 x 10 '' gramoatom / liter, preferably 1x10⁵ - 1x10^_1 gram atom / Utr. The temperature at which the catalyst component A is mixed with the pre-mixed mixture of catalyst components B and C is typically -50 - 100 ° C, and the mixing time from 0.1 minutes to 50 hours.

Catalyst component D is used in an amount such that the amount of aluminum atoms derived from catalyst component D is 30-99%, preferably 40-99%, and even more preferably 50-99% of the total amount of aluminum atoms derived from alumoxane as component B of the catalyst and atoms aluminum derived from an organo aluminum compound as component D of the catalyst. In other words, component B of the catalyst is used in an amount such that the aluminum atoms derived from component B of the catalyst constitute 1-70%, preferably 2-60%, and even more preferably 5-50% of the total sum of atoms derived from components B and D of the catalyst.

In the olefin polymerization catalyst, the ratio of the sum of aluminum atoms derived from catalyst components B and D to transition metal atoms derived from catalyst component A is usually 20-10,000, preferably 50-5000, and even more preferably 100-2000. When olefin polymerization is carried out using the above-mentioned olefin polymerization catalyst, the catalyst component A in the polymerization system is used in amounts such that the concentration of transition metal derived from this component A catalyst in the polymerization system is 1 χ 10 '⁸ up to about 1 χ 10 '²gramoatom / liter, preferably from 1 x 10 '⁷ up to about 1 χ 10 '³ gramoatom / liter, and that the B component of the catalyst is present in the polymerization system in such an amount that the concentration of aluminum atoms derived from this B component of the catalyst in the polymerization system is less than 3 milligramatoms / liter, preferably 0.01-2 milligramatoms / liter, and more preferably 0.02-1 milligramatomatom / liter.

The olefin polymerization catalysts described above can be used as solid catalysts, depositing catalyst components on particulate inorganic compounds such as silica or alumina, or on organic compounds such as polyethylene, polypropylene and polystyrene.

The olefin polymerization catalysts described above are used to prepare olefin polymers. Olefins that can be polymerized using such catalysts include ethylene and α-olefins containing 3-20 carbon atoms, such as propylene, butene-1, pentan-1, hexene-1,

4-methylpentene-1, octene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecene-1 and eicocene-1. If desired, pollenes such as diene can be copolymerized with the aforementioned olefins.

The olefin polymerization reaction using such new olefin polymerization catalysts is usually carried out in the gas phase or in the liquid phase, e.g. in solution. If the polymerization reaction is carried out in the liquid phase, an inert hydrocarbon may be used as the solvent, or the olefins themselves may serve as solvents.

The hydrocarbons used as solvents in the above polymerization reaction include, in particular, aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene and xylene, and petroleum fractions such as gasoline, kerosene and light oil.

The temperature at which olefin polymerization is carried out using the new olefin polymerization catalyst is usually -50-200 ° C, preferably 0-120 ° C. The pressure used during the polymerization is usually from 0.1 MPa (atmospheric pressure) to 10 MPa, preferably 0.1-5.0 MPa, wherein the polymerization can be carried out in a batch, semi-continuous or continuous manner. The reaction can also be carried out in two or more steps, under different conditions. The molecular weight of the olefin polymers produced can be controlled by means of hydrogen and / or by changing the polymerization temperature.

In the case where olefins are homopolymerized using new olefin polymerization catalysts, olefin polymers with high molecular weight and narrow molecular weight distribution can be obtained. When two or more olefins are copolymerized using the olefin polymerization catalysts set out above, olefin copolymers with narrow molecular weight distribution, narrow composition distribution and high molecular weight can be obtained. The catalysts according to the invention also have high catalytic activity, whereby the amount of alumoxane can be reduced.

The invention is illustrated by the following examples. _

In the examples below, Mw / Mn was determined as follows, according to the method of Takeuchi, Gel Permeation Chromatography, Maruzen, Tokyo.

1. Using standard polystyrene with known molecular weight (monodisperse polystyrene produced and sold by Toyo Soda KK), the molecular weights and the corresponding gel chromatograph (GPC) readings of the sample are measured to determine the correlation diagram of the molecular weight calibration curve M as a function of eluate volume (EV). The polymer concentration in the sample is 0.02% by weight.

2. The sample chromatogram is determined based on GPC measurements, then the number average molecular weight Mn and the weight average molecular weight Mw are calculated in units for polystyrene, based on the calibration curve mentioned in point 1, to determine the size of Mw / Mn. The sample preparation and measurement conditions are as follows:

Sample preparation:

a) The sample is placed in an Erlenmeyer flask together with dichlorobenzene so that the concentration of the sample is 0.1% by weight.

b) The Erlenmeyer flask is heated at 140 ° C while stirring its contents for about 30 minutes to dissolve the sample in dichlorobenzene.

c) The filtered solution in dichlorobenzene is introduced into the GPC apparatus.

Conditions for taking measurements in GPC

a) The 1500-ALC / GPC device from Waters Co.

b) GMH column made by Toyo Soda KK

c) Sample size 400 μΐ

d) Temperature 140 ° C

e) Flow rate 1 ml / minute.

The size B for the ethylene copolymer prepared according to the invention is determined by the following formula:

B = P^QE

Po · Pe in which Pe is the molar fraction of the ethylene component in the copolymer, Po is the molar fraction of α-olefin in the copolymer, and Poe is the molar fraction of α-olefin / ethylene chains in the dyads in the chain.

Size B is an indicator of the distribution of mer in the copolymer chain. It is determined based on the aforementioned Pe, Po and Poe values ​​by the method given in the following publications: GJRay, Macro molecules, 10,773 (1977), JCRandall, Macromolecules, 15.353 (1982), J. Polymer Science, Polymer Physics Ed., 11 , 275 (2973) and K. Kimura, Polymer, 25, 441 (1984). The larger the B index for the copolymer, the smaller the content of blocks in the copolymer chain, and the distribution of ethylene and α-olefin units is more even, which means that copolymers with higher B indexes have a narrow composition distribution.

Size B is determined based on the spectrum ¹³C-NMR. The sample is prepared by dissolving exactly 200 mg of the copolymer in 1 ml hexachlorobutadiene in a 10 mm tube. The measurement conditions are usually: measurement temperature 120 ° C, frequency 25.05 MHz, spectrum width 1500 Hz, filter spectrum width 1500 Hz, pulse repetition time 4.2 s, pulse width 7 s, number of cycles 2000-5000. Based on the spectrum obtained, the values ​​of Pe, Po and Poe are determined. The content of the ethylene copolymer fraction prepared according to the invention soluble in n-decane is also determined (since the smaller the content of the soluble fraction in n-decane, the narrower the distribution of the copolymer composition is). About 3 g of ethylene copolymer is dissolved in 450 ml of n-decane at 145 ° C, cooled to 23 ° C, the insoluble fraction in n-decane is filtered off, and then the soluble fraction in n-decane is separated from the filtrate.

Example I. Preparation of alumoxane.

Into a 400 ml flask, thoroughly purged with nitrogen, 37 g of AfSOi 3 · MH2O and 125 ml of toluene were introduced, followed by cooling to 0 ° C. Then 500 mmol of trimethylaluminium diluted with 125 ml of toluene are added dropwise. The temperature of the flask was increased to 40 ° C, after which the reaction was continued at this temperature for 10 hours. After the reaction was completed, the mixture was filtered to separate the solid from the liquid fraction. Toluene was removed from the filtrate to give 12 g of alumoxane as a white solid. The alumoxane thus obtained was redissolved in toluene and the resulting solution was used for the preparation of the catalyst and for polymerization. The molecular weight of alumoxane, determined on the basis of measuring the decrease in the freezing point of benzene, was 870. This means that in component B of the catalyst m is 13.

Catalyst production and polymerization.

Into a 400 ml glass flask purged with nitrogen thoroughly, 57 ml of toluene, 0.94 g of finely divided Al2 SO4.3 · I3H2O and 50 ml of the toluene solution of alumoxane obtained above (Al concentration 2.14 mol / liter) were added, followed by temperature increased to 40 ° C and reacted for 72 hours. The suspension thus obtained was used in the following polymerization process.

900 ml of 4-methylpentene-1 and 1 mraol of trisobutylaluminum were introduced into a 2-liter stainless steel autoclave, thoroughly purged with nitrogen, after being raised to 100 ° C. Then 0.2 ml of the suspension obtained obtained mmol of bis (methylcyclopentadienyl) zirconium dichloride was combined in 40 ml of cyclohexane, mixed for 2 minutes at room temperature and introduced together with ethylene into the polymerization system to initiate polymerization. Polymerization was carried out at a pressure of 2.1 MPa for 40 minutes, continuously introducing ethylene into the system. A small amount of methanol was added to stop polymerization.

The polymer solution was added to a large excess of methanol to precipitate the polymer, which was then dried at 80 ° C for 12 hours under reduced pressure. 111 g of polymer was obtained, with a melt flow index of 1.6 g / 10 minutes, a density of 0.902 g / cm3, Mw / Mn = 2.14 and a soluble fraction content of n-decane of 1.6% by weight.

Example Π (comparative). Polymerization was carried out in the same way as in Example 1, except that the alumoxane obtained in Example I was used in an amount corresponding to 0.2 mg of aluminum atoms, without contacting it with water, i.e. without adding Ah (SO4) 3 · 13H;> O ._J 75 g of polymer with a melt index of 6.2 g / 10 minutes, density 0.904 g / cm, Mw / Mn = 2.20 and a content of soluble fraction in n-decane 1.6% by weight was maintained.

; the temperature above and 8x10 '⁴

Table

<td rowspan="2">cr governance</td><td colspan="2">Component A of the catalyst</td><td rowspan="2">Alumo- xanthan (Ml)</td><td colspan="2">Organo-aluminum compound</td><td rowspan="2">Performance (8)</td><td rowspan="2">Melt flow rate (g / 10 minutes)</td><td rowspan="2">Density⁽g^/cm³⁾</td><td rowspan="2">Mw / Mn</td><td rowspan="2">Ilo pink{ in</td>

<td>Type</td><td>Quantity (Mmol)</td><td>Type</td><td>Quantity (Mmol)</td>

<td></td><td>Bis / cyclopentadienyl / zirconium dichloride</td><td>2xl0'3</td><td> 0,2</td><td>triisobutylaluminum</td><td> 1</td><td> 74</td><td> 2,8</td><td> 0,903</td><td> 2,29</td><td></td>

<td></td><td>Bis / cyclo pentadienyl / zirconium dichloride</td><td>2xl0'3</td><td> 0,2</td><td>Tri / 2-ethylhexyl / aluminum</td><td> 1</td><td> 69</td><td> 2,5</td><td> 0,902</td><td> 2,34</td><td></td>

<td></td><td>Bis / indenyl / zirconium dichloride</td><td>8xl0 '⁴</td><td> 0,2</td><td>triisobutylaluminum</td><td> 0,5</td><td> 76</td><td> 4,1</td><td> 0,904</td><td> 2,45</td><td></td>

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Examples IH-V. Polymerization of 4-methylpentene-1 was carried out in the same manner as in Example 1, except that in each case the catalyst containing the components listed in the table was used to obtain the polymers shown in the table.

Example V. Into a 400 ml glass flask, thoroughly purged with nitrogen, 57 ml of the toluene obtained in Example 1 were added, followed by reaction at 40 ° C for 48 hours. To 10 ml of the suspension thus obtained was added 40 ml of toluene and 0.1 mmol of bis (cyclopentadienyl) zirconium dichloride. Both components were contacted at room temperature for 10 minutes. Polymerization was carried out in the same manner as in Example 1, using 1.0 ml of the treated suspension and 1 mmol of trisobutylaluminum. 88 g of polymer was obtained, with a melting index of 2.1 g / 10 minutes, density 0.903 g / cm³, Mw / Mn = 2.31 and with a content of soluble fraction in n-decane of 1.6% by weight.

Example VI. Polymerization was carried out in the same manner as in Example 1, except that 5x10 'was used instead of bis (methylcyclopentadienyl) zirconium dichloride⁴ mmol of ethylene bis (indenyl) zirconium dichloride, and instead of 900 ml of 4-methylpentene-1, a solution-forming mixture of 300 ml of 4-methylpentene-1 and 600 ml of cyclohexane was used, the polymerization was carried out for 20 minutes J 129 g of polymer with a flow index of 8.9 g / 10 minutes, density 0.907 g / cm3 and Mw / Mn = 2.31.

Example VII. The polymerization was carried out in the same manner as in Example 1 except that bis (cyclopentadienyl) hafnium dichloride was used instead of bis (methylcyclopentadienyl) zirconium dichloride. 15 g of polymer were obtained, with a melting index of 1.3 g / 10 minutes, density 0.906 g / cm 3 and Mw / Mn = 2.41.

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