PL161960B1 - Method of polymerizing and copolymerizing olefins - Google Patents

Abstract

1. Method for polymerization or copolymerization of olefins in the presence of a catalyst containing a compound of a transition metal from group IV B of the periodic table and alumoxane, characterized in that the catalyst used is made from A) a compound of a transition metal with general formula 1, where R<1> denotes a cyclopentadienyl group, possibly substituted with C1-C4-alkyl, or an indenyl group, R<2>, R<3> and R<4> independently denote a cyclopentadienyl group, possibly substituted with C1-C4-alkyl, an indenyl group or a halogen atom, where if two of the symbols R<1>-R<4> denote indenyl groups they may be connected by C1-C4-alkylene, and at least one of the symbols R<2>, R<3> and R<4> denotes a halogen atom, M denotes a zirconium or hafnium atom, k is 1 or 2, l, m and n are 0, 1 or 2, and k+l+m+n is equal to 4; B) alumoxane; C) water; and D) trialkylaluminium, where the molar ratio of aluminium atoms from alumoxane to water is from 0.5 to 50, the number of aluminium atoms from trialkylaluminium is 30-99% of the total number of aluminium atoms from alumoxane and trialkylaluminium, and the ratio of aluminium atoms from alumoxane and trialkylaluminium to transition metal atoms is in the range 20 to 1x10<4>.

Description

The present invention relates to a method of olefin polymerization 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 when producing olefin homopolymers, and allows the production of olefin copolymers with a narrow molecular weight distribution and a narrow composition distribution when producing copolymers of two or more olefins.

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 are copolymerized in the presence of a titanium-based catalyst consisting of a titanium compound and a compound an organoaluminum or vanadium catalyst composed of a vanadium compound and an organoaluminium compound.

In general, ethylene-α-olefin copolymers prepared with titanium-based catalysts have a wide molecular weight distribution and, moreover, have unsatisfactory properties such as transparency, surface non-stickiness, and dynamic mechanical properties. Ethylene-α-olefin copolymers made using catalysts based on vanadium have a higher molecular weight distribution and a narrower composition distribution compared to ethylene-α-olefin copolymers made with titanium catalysts, and also show slightly better properties such as transparency, non-sticky surface and dynamic mechanical properties, but it has been found that these properties are not satisfactorily met. Therefore, it is desirable to develop a process for the preparation of ethylene-α-olefin copolymers having even better the above-mentioned properties.

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With this in mind, recently, methods have been developed to make ethylene-α-olefin copolymers using zirconium-alumoxane catalysts, a new type of Ziegler olefin polymerization catalyst. For example, published Japanese Patent Application No. 19 309/1983 discloses a process for the production of ethylene-α-olefin copolymers by polymerizing ethylene and one or at least two C3-C12-α-olefins at a temperature of -50 to 200 ° C, in the presence of a catalyst consisting of a transition metal compound represented by the formula (cyclopentadienylhMeRHHal, where R is a cyclopentadienyl group, a C1-C6-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 , where R is a methyl or ethyl group, and n is a number from 4 to 20, or a cyclic alumoxane represented by the formula 7 in which R and n are as defined above. In order to regulate the density of the resulting polymer, 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.

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

This specification states that if the polymerization of ethylene is carried out in the presence of a mixture containing an alumoxane prepared by the described process, 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 is obtained. g of transition metal per hour.

Published Japanese Patent Application No. 35 005/1985 discloses a process for the preparation of an olefin polymerization catalyst by reacting an alumoxane compound represented by formula 9, wherein R ¹ is a C 1 -C 10 alkyl group and R 0 is R 1 or an oxygen bond, with with a magnesium compound followed by chlorination of the reaction product and treatment with a Ti, V, Zr or Cr compound. It is found in this specification that the catalyst prepared by the disclosed process is particularly suitable for use in the copolymerization of ethylene with α-C3-C12-olefins. Published Japanese Patent Application 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 making polymers in the form of reactor blends.

In Example 1 of this description, ethylene and propylene are polymerized in the presence of a bis (pentomethylcyclopentadienyl) dimethyl zirconium alumoxane catalyst to produce a 15,300 number average molecular weight polyethylene with a weight average molecular weight of 36,400 and a propylene content of 3. 4%. In Example 2 of this specification, ethylene and propylene are polymerized in the presence of a catalyst consisting of bis (pentomethylcyclopentadienyl] zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and alumoxane to give a mixture of polyethylene with an ethylene-propylene copolymer having a molecular weight fraction of 2% soluble in tolu 200 with a weight average molecular weight of 11,900 and a propylene content of 30 mol%, 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 content of 4.8 mol%.

For the entire blend, the number average molecular weight was 2,000, the weight average molecular weight was 8,300 and the propylene content was 7.1 mol%. In Example 3, a blend of LLDPE (linear low density polyethylene) and ethylene propylene copolymer 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%.

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

Published Japanese Patent Application No. 35,008/1985 discloses that polyethylene or copolymers of ethylene with C3-C10 olefins having a broad molecular weight distribution are produced using a catalyst system comprising at least two metallocenes and an alumoxane. In this specification it is stated that the copolymers obtained in this way have a molecular weight distribution (Mw / Mn) in the range of 2-50. Published Japanese Patent Applications Nos. 260 602/1985 and 130 604/1985 propose methods of olefin polymerization using mixed organoaluminum catalysts containing a transition metal compound, alumoxane and an organoaluminum compound, and disclose that the catalytic activity per transition metal unit it is increased by adding the organoaluminium compound.

A drawback of all of the above-mentioned processes, however, is that the activity per alumoxane unit in the catalyst used is still low. Another problem is that it is difficult to obtain polymers of sufficiently high molecular weight if olefins, e.g. ethylene and propylene, are copolymerized in the presence of catalysts made of transition metal compounds and heretofore known alumoxanes.

The object of the invention was to solve the problems associated with the known processes 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, moreover, having excellent catalytic activity even when the amount of alumoxane used therein is low, and such in the presence of which polymers of high molecular weight olefins can be readily obtained.

The main object of the invention was to develop an olefin polymerization process using the above-mentioned olefin polymerization catalyst. Thus, according to the invention, a method for the polymerization or copolymerization of olefins in the presence of a catalyst comprising a transition metal compound belonging to group IV B of the periodic table and an alumoxane has been developed, and a feature of this process is that a catalyst made of A) a transition metal compound of general formula 1 is used. where R? ^ is a cyclopentadienyl group optionally substituted by Ci-C4-alkyl group or a indenylową.R ^2, R 3 and R ⁴ independently represent a cyclopentadienyl group optionally substituted Ci-C4 alkyl, an indenyl group or a halogen, wherein when two of the symbols R1 - R4 indenyl groups, they are optionally linked via C 1 -C 6 -alkylene, and at least one of the symbols R 2, R 3 and R 4 is a halogen atom, M is a zirconium or hafnium atom, k is 1 or 2.1, m and n are 0, i or 2, ak + 1 + m + n is 4, B) alumoxane, C) water and D) aluminum trialkyl, the molar ratio of aluminum atoms derived from alumoxane to water being 0.5 to 50, preferably 1 to 40, 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 1 x 104. The polymerization catalyst is detailed below olefins, and a method of olefin polymerization using such a catalyst.

In the description of the invention, the term polymerization is sometimes used to mean that it includes not only homopolymerization but also copolymerization, and the term polymer is sometimes used to mean not only homopoEmer but also copolymer. The olefin polymerization catalytic converter prepared from the catalyst components A), B), C) and D) mentioned above is described in detail below.

Catalyst 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 conjugated π electrons as ligand.

A C 1 -C 4 -alkyl substituted cyclopentadienyl group is, for example, methylcyclopentadienyl, ethylcyclopentadienyl, Πζ-γζ. butylcyclopentadienyl, dimethylcyclopentadienyl or pentomethylcyclopentadienyl. The halogen atom can be, for example, a fluorine, chlorine or bromine atom.

Examples of zirconium compounds having a π-conjugated group as a ligand include: bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (methylcyclopentadienyl) zirconium dichloride, bis (tertiary: bis (tertiarybutyrylcyclopentyl) cyclopentylcyclopentide) pentamethylcyclopentadienyl zirconium, bis (indenyl) zirconium dichloride and bis (indenyl zirconium) dibromide Zirconium compounds used as catalytic component A) of the olefin polymerization catalyst may also include zirconium compounds having as a ligand via a polynuclear compound in which at least two indenyl groups are linked together a lower alkylene group. Examples of such zirconium compounds are ethylene bis (indenyl) zirconium dichloride and ethylene bis (indenyl) zirconium dibromide. Transition metal compounds can also be used in which the zirconium atom in the above-mentioned zirconium compounds has been replaced by hafnium.

The catalytic component B) used in the olefin polymerization catalyst is alumoxane. The alumoxane used as this component can be, for example, an organoaluminum compound represented by the general formula 2 or 3.

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

The alumoxane presented above may consist of mixed alkoxy aluminum groups, contain an alkoxy group of formula 4 and an alkoxy aluminum group of formula 5, where in these formulas R 1 and R ² may be the same hydrocarbyl groups as the R group in the formula or 3, except that R ¹ and R2 are different hydrocarbon groups. In this case, those alumoxanes which form mixed alkoxy aluminum groups containing at least 30 mole%, preferably at least 50 mole%, and even more preferably at least 70 mole% of methyloxyaluminum groups of the formula 6 are preferred.

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

The first method is to react a slurry 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 cerave chloride hydrate, in a hydrocarbon medium, with aluminum trialkyl.

The second method is to react the aluminum trialkyl directly with water in an environment such as benzene, toluene, ethyl ether or tetrahydrofuran.

Of the methods mentioned above, the first method is preferable. The alumoxane prepared by the methods described may contain small amounts of organometallic components.

Component C) used in the olefin polymerization catalyst is water, which water can be, for example, 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), trialkyl aluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri (2-methylbutyl) aluminum, tri (3-methylbutyl) aluminum, tri (2-methylpentyl) aluminum, tri (3-methylpentyl) aluminum, tri (4) -methiopentyl) aluminum, tri (2-methylhexyl) aluminum, tri (3-methylhexyl) aluminum etc.

Of the compounds mentioned above, trialkylaluminum compounds containing hydrocarbon groups other than n-alkyl groups are preferred. Particularly preferred compounds include triisopropyl aluminum, triisobutyl aluminum, trimethylbutylj aluminum, tri (3-methylbutyloyl), 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 abovementioned organoaluminum compounds are formed in the polymerization system, for example aluminum halides and alkyl lithium compounds or aluminum halides and alkylmagnesium compounds, can also be used as catalyst component D).

This type of catalyst can be prepared by a method of simultaneous mixing of all catalyst components, A, B, C and D, 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 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 premix catalyst component B with catalyst component C.

The concentration of alumoxane, calculated as aluminum atoms in pre-mixing components B and C of the catalyst, is usually from 5 × 10 ' ⁴ to 3 gram atoms / Utr, preferably from 1 × 10' ³ to 2 gram atoms / liter, and the water concentration is usually from 2. 5 x 10 ⁵ to 2 mol / liter, and preferably from 5 χ 10 ⁵ to 1.5 mole / liter. with a molar ratio of aluminum atoms to water (Al / H20) of 0.5 to 50, preferably 1 to 40. The temperature at which premixing is carried out is usually -50 to 100 ° C and the mixing time is from 0.1 minutes to 200 hours.

When mixing catalyst component A with premixed catalyst components B and C, catalyst component A is used in such an amount that the concentration of the transition metal component of component A of the catalyst is typically 5 × 10 ' ⁶ - 1.5 × 10 "gram atom / liter, and preferably lxl0 ⁵ - 1x10 ^_1 gram atom / Utr. The temperature at which catalyst component A is mixed with the pre-mixed catalyst component B and C is typically -50-100 ° C and the mixing time is from 0.1 minutes to 50 hours.

The catalyst component D is used in such an amount that the amount of aluminum atoms derived from component D of the catalyst 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 organoaluminum compound as component D of the catalyst. In other words, the catalyst component B is used in such an amount 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 an olefin polymerization catalyst, the ratio of the sum of the aluminum atoms derived from catalyst components B and D to the transition metal atoms derived from component A of the catalyst is typically 20-10,000, preferably 50-5,000, and even more preferably 100-2,000. using the aforementioned olefin polymerization catalyst, catalyst component A in the polymerization system is used in such amounts that the concentration of the transition metal derived from that catalyst component A in the polymerization system is 1 × 10 ' ⁸ to about 1 × 10 × ² gram atom / liter , and preferably from 1 x 10 ' ⁷ to about 1 × 10' ³ gram atom / liter, and that the catalyst component B is present in the polymerization system in such an amount that the concentration of aluminum atoms derived from that catalyst component B in the polymerization system is less than 3 milligramatoms / liter, preferably 0.01-2 milligramatoms / liter, even more preferably 0.02-1 milligramatoms / liter.

The above-described olefin polymerization catalysts can be used as solid catalysts by depositing the 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 which can be polymerized using such catalysts include ethylene and 3-20 carbon alpha-olefins, such as propylene, butene-1, pentane-1, hexene-1,

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

The olefin polymerization reaction using such new olefin polymerization catalysts is generally carried out in the gas phase or in a liquid phase, e.g. in solution. When the polymerization reaction is carried out in the liquid phase, a neutral hydrocarbon can be used as the solvent, or the olefins themselves can 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 novel olefin polymerization catalyst is usually -50-200 ° C, preferably 0-120 ° C. The pressure used during the polymerization is generally from 0.1 MPa (atmospheric pressure) to 10 MPa, preferably 0.1-5.0 MPa, and the polymerization may be carried out batchwise, semi-continuously or continuously. The reaction can also be carried out in two or more steps under different conditions. The molecular weight of the olefinic polymers produced can be adjusted with hydrogen and / or by changing the polymerization temperature.

When olefins are homopolymerized with the new olefin polymerization catalysts, olefin polymers with a high molecular weight and a narrow molecular weight distribution can be obtained. When two or more olefins are copolymerized using the olefin polymerization catalysts defined above, olefin copolymers having a narrow molecular weight distribution, a narrow composition distribution, and a high molecular weight can be obtained. Moreover, the catalysts according to the invention have a high catalytic activity, so that the amount of alumoxane in them can be reduced.

The following examples illustrate the invention. _

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

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

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

Sample preparation:

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

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

c) Load the filtered o-dichlorobenzene solution into the GPC apparatus.

Conditions for the measurement in GPC

a) 1500-ALC / GPC device by Waters Co.

b) GMH column by Toyo Soda K.K.

c) Sample size 400 μΐ

d) Temperature 140 ° C

e) Flow rate 1 ml / minute.

The value of B for the ethylene copolymer according to the invention is given 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 the α-olefin in the copolymer and Poe is the molar fraction of the a-olefin / ethylene chains in the diads in the chain.

The value of B is an index of the distribution of mers 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, Macromolecules, 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 higher the B index value for a copolymer, the lower the block content in the copolymer chain, and the more even distribution of ethylene and α-olefin units, which means: that copolymers with higher B indexes show a narrow composition distribution.

The size of B is determined from the ¹³ C-NMR spectrum. The sample is prepared by thoroughly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a 10 mm diameter tube. The measurement conditions are generally as follows: measurement temperature 120 ° C, frequency 25.05 MHz, spectral width 1500 Hz, spectral width of the filter 1500 Hz, pulse repetition time 4.2 s, pulse width 7 µs, number of cycles 2000-5000. On the basis of the spectrum obtained, the values of Pe, Po and Poe are determined. The content of the n-decane-soluble ethylene copolymer fraction produced by the method according to the invention is also determined (because the lower the content of the n-decane-soluble fraction, the narrower the distribution of the copolymer composition). About 3 g of the ethylene copolymer is dissolved in 450 ml of n-decane at 145 ° C, cooled to 23 ° C, the n-decane insoluble fraction is filtered off, and the n-decane soluble fraction is separated from the filtrate.

Example I. Preparation of alumoxane.

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

Preparation of the catalyst and polymerization.

57 ml of toluene, 0.94 g of finely divided Al2SO4.3 · I3H2O and 50 ml of toluene alumoxane solution obtained above (Al concentration 2.14 mol / liter) were introduced into a 400 ml glass flask, purged thoroughly with nitrogen, and then the temperature increased to 40 ° C and reacted for 72 hours. The suspension obtained in this way was used in the following polymerization process.

900 ml of 4-methylpentene-1 and 1 mraol of triisobutylaluminum were introduced into a 2-liter stainless steel autoclave, thoroughly purged with nitrogen, and increased to 100 ° C after the autoclave. Then 0.2 ml of a suspension of the obtained mmole of bis (methylcyclopentadienyl) zirconium dichloride was combined in 40 ml of cyclohexane, stirred for 2 minutes at room temperature and introduced with ethylene into the polymerization system to initiate polymerization. The 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 the 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 with a melt index of 1.6 g / 10 minutes, a density of 0.902 g / cm3, Mw / Mn = 2.14 and a n-decane soluble fraction of 1.6% by weight were obtained.

Example Π (comparative). The polymerization was carried out in the same manner as in Example 1 except that the alumoxane obtained in Example 1 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 75 g of polymer with a melt index of 6.2 g / 10 minutes, a density of 0.904 g / cm, Mw / Mn = 2.20 and a n-decane soluble fraction of 1.6% by weight were kept.

; winter temperature above i 8x10 ' ⁴

Table

cr order Component A of the catalyst Alumo- priest (ml) Alumina compound Performance (8) Melt Index (g / 10 minutes) Density ⁽ g ^/ cm ³⁾ Mw / Mn Ilo pink{ in Type Quantity (mmoles) Type Quantity (mmoles) Bis / cyclopentadienyl / zirconium dichloride 2xl0'3 0.2 Triazobutylaluminum 1 74 2.8 0.903 2.29 Bis / cyclo pentadienyl / zirconium dichloride 2xl0'3 0.2 Tri (2-ethylhexyl) aluminum 1 69 2.5 0.902 2.34 Bis / indenyl / zirconium dichloride 8xl0 ' ⁴ 0.2 Triazobutylaluminum 0.5 76 4.1 0.904 2.45

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Examples IH-V. The polymerization of 4-methylpentene-1 was carried out in the same manner as in Example 1, except that in each case a catalyst containing the ingredients listed in the table was used to give the polymers shown in the table.

EXAMPLE 5 57 ml of toluene prepared in Example 1 were introduced into a 400 ml glass flask, thoroughly purged with nitrogen, followed by reaction at 40 ° C for 48 hours. To 10 ml of the suspension thus obtained were 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 suspension treated as described above and 1 mmol of triisobutylaluminum. 88 g of polymer with a melt index of 2.1 g / 10 minutes, a density of 0.903 g / cm ³ , Mw / Mn = 2.31 and a n-decane soluble fraction of 1.6% by weight were obtained.

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

Example VII. Polymerization was carried out in the same manner as in Example 1 except that bis (cyclopentadienyl) hafnium dichloride was used in place of bis (methylcyclopentadienyl) zirconium dichloride. 15 g of a polymer with a melt index of 1.3 g / 10 minutes, a density of 0.906 g / cm3 and Mw / Mn = 2.41 was obtained.

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Publishing Department of the UP RP. Circulation of 90 copies. Price: PLN 10,000

Claims (3)

Patent claims A method of polymerization or copolymerization of olefins in the presence of a catalyst comprising a transition metal compound belonging to group IV B of the periodic table and an alumoxane, characterized by the use of a catalyst prepared from A) a transition metal compound of general formula 1, in which R ¹ is a cyclopentadienyl group optionally substituted Ci-CU-alkyl or indenyl group, R ^2, R ³ and R ⁴ independently represent a cyclopentadienyl group optionally podstawionąCi-CU-aikilem, an indenyl group or a halogen, wherein when two of the symbols Ri - R4 are indenyl that optionally they are linked via Ci-C4-alkylene, and at least one of R2, R3 and R4 is halogen, M is zirconium or hafnium, k is 1 or 2.1, m and n are 0.1 or 2, and k + l + m + n is 4, B) alumoxane, C) water and D) trialkylaluminum, where the molar ratio of aluminum atoms derived from alumoxane to water is 0.5 to 50, the number of aluminum atoms derived from trialkylaluminum u represents 30-99% of the total number of aluminum atoms derived from alumoxane and aluminum trialkyl, and the ratio of aluminum atoms derived from alumoxane and trialkyl aluminum to transition metal atoms is 20 to 1 × 104. 2. The method according to p. The process of claim 1, wherein the catalyst has a molar ratio of aluminum atoms to water of 1 to 40. 3. The method according to p. 3. The process of claim 1, wherein the catalyst is prepared with aluminum trialkyl, in which the alkyl group is isopropyl, isobutyl, 2-methylbutyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl or 2-ethylhexyl, especially isobutyl or 2-ethylhexyl.