DE2609527A1 - ETHYLENE COPOLYMERS AND METHOD FOR PREPARING THE SAME - Google Patents

Description

Ethylene copolymers and processes for. Manufacture of the same

The invention relates to ethylene-based polymers and the production of the same.

Specifically, according to the invention, a copolymer of ethylene with a comonomer is provided which is formed by at least one mono-aL-olefin, at least 50 mol of the mono-oc-olefin forming the comonomer having 5 or more carbon atoms and the copolymer one normalized density (as defined below) in the range of 918 up to 940 kg / m *; one at 200 ⁰ C and one

• _i

Shear rate of 100 s measured effective viscosity (as defined below) of 0.5 χ 10 to to 3.0 10 Nsm "and 'one at 200 C and a voltage

609838/0888

Dresdner Bank (Munich) Account 3939 844 Postscheck (Munich) Account 670-43-804

has a viscosity measured at 10 N / m of at least 2Ae ^ ' ^x ' and not more than 1000 A, where A is the effective viscosity at 200 C and a shear rate of 100 s.

In addition to 5 or more carbon atoms and having a mono-olefin and the Coraonomere can not than 50 MoIJo a mono- oL-olefin having less than 5 carbon atoms such as, for example, include butene (1). The comonomer preferably comprises no more than 20 mol / o of a mono-ot-olefin having fewer than 5 carbon atoms and in particular 0 mol / j. For example, preferred copolymers contain only mono- <x-olefins with at least 5 carbon atoms as comonomers. Suitable comonomers include monocarbon olefins having at least 5 and no more than 12 carbon atoms. The comonomer is preferably a mono-otolefin with not more than 10 carbon atoms, in particular with not more than 8 carbon atoms. It is also preferred that the comonomer is a mono- oc -olefin having at least 6 carbon atoms. The mono-06-olefin comonomer is expediently a linear mono-ot-olefin, in particular hexene (1).

Copolymers according to the invention preferably have a normalized one Density (as defined below) in the range of 920 to 935 kg / m. The term "normalized density"

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refers here to the density measured according to ASTM 1928/70, method A. The density is measured in a density gradient column at 23 ⁰ C and corrected for the presence of residual amounts of catalyst, whereby the "normalized density" using the following relationship

c =

is obtained, where P is the '^ normalized density ",

ο the density measured on the overall copolymer product including the catalyst residues,

y is the density of the catalyst support and / or catalyst and

A is the weight fraction of the catalyst support

and / or catalyst in the copolymer (determined from the ash content).

The copolymers preferably have an effective viscosity

sity at 200 C and a shear rate of 100 s "* in the range from 1.3 10 · ⁵ to 2.4 χ 10 * Nsm" ² . The viscosity at 200 ⁰ C and a voltage of 10 N / m is pre-

(1 6a χ 10-3} preferably is at least 3> 5 Ae ^v '' and not more than 500A, wherein A is as defined above. The viscosity of the copolymer at 20O ⁰ C and a voltage of 10 ^ N / m expediently in the range of 2.2 χ 10

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up to 3 x 10 ⁶ , in particular 3.8 10 ⁴ to 1.2 χ 10 ⁶ Nsm " ² .

ο

The one at 200 C and a shear rate of 100 s

measured "effective viscosity" is with a capillary viscometer and it is defined by the following relationship:

TT

r ⁴ P

8 Ql where

η the effective viscosity in Nsm "²; r the outlet or nozzle radius in mm; P the pressure drop across the nozzle in Nm"²;

3 -1 Q is the volume velocity in mm s; and

1 is the length of the nozzle (or capillary) in mm,

The principles of the capillary viscometer are detailed, for example, in Chapter Four of "Viscosity and Flow Measurement "by Van Wazer, Lyons, Kim and CoI-well, Interscience Verlag, 1963.

The viscosity at a tension of 10 N / m is more expediently measured according to the plate-cone technique, for example as described in Chapter Two of the aforementioned book.

The present in the copolymers according to the invention 609838/0888

The amount of comonomer depends on the particular comonomer or comonomer mixture present. However, in general the amount of comonomer in the range of 6.5 to 30 wt.% Of the copolymer, preferably from 8.0 to 27 Ge \ f.% Of the copolymer s. When the comonomer is formed by hexene (1), the amount of hexene (1) present in the copolymer is generally in the range of 6.5 to 16.5 percent by weight of the copolymer and preferably in the range of 8.0 to 15% by weight of the copolymer. When the comonomer is formed by pentene- (i) or 4-methyl-pentene- (i), the amount of comonomer present in the copolymer is very similar to that present when the comonomer is formed by hexene- (1). More specifically, the amount of pentene- (i) present in the copolymer, when this is the comonomer, is in the range from 6.5 to 20 %, preferably 7.2 to 16.5% by weight. and if the comonomer is formed by 4-methyl-pentene- (i), the amount of the latter in the copolymer is in the range from 6.5 to 18.0 %, preferably 7.2 to 16.5% by weight. If the comonomer is formed by decene (1), somewhat larger amounts are required and specifically the amount of decene (1) is in the range from 7.5 to 23 %, preferably 9 to 21.5% by weight.

Copolymers according to the invention are tough as shown by the results of high speed tensile tests on molded Railway materials is shown. Typically he

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copolymers according to the invention have an elongation at break of at least 400 % and not more than 1500 %, preferably of at least 800 %. As used herein, the term "high speed tensile test" refers to a tensile test with a hydraulic tensile testing machine according to the procedure of ASTM D 2289 "at a pulling speed of 51 cm / s using test specimens cut with a cutter of the British standard 903 part A2 were formed specified type using an effective gauge length of 1.91 cm (instead of 1ZoIl), the samples "tempered" by one-hour immersion in water at 100 ⁰ C were and remained in the water up to its cooling to room temperature the temperature at which the test was carried out.

Copolymers according to the invention have a relatively high molecular weight, and typically has a melt index (measured according to ASTM 1238-62 T with a 2.16 kg weight at 190 ⁰ C) in the range of 0.05 to 1.0 and preferably from 0.08 to 0 , 30.

Copolymers according to the invention typically have an ethyl content (determined by IR analysis) of 12 up to 40, preferably 15 to 30 methyl groups per 1000 carbon atoms. The copolymers have a vinyl content that typically ranges from 0.15 to 0.55 vinyl groups per 1000 carbon atoms, and generally does not

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is greater than 0.45 vinyl groups per 1000 carbon atoms.

Copolymers according to the invention have a broad molecular weight distribution as indicated by gel permeation chromatography elution curves used for the polymers can be obtained. Typical gel permeation chromatography elution curves are shown in the attached drawings, namely, the following figures show curves for products of the following examples:

FIG. 1 for products of Examples 1, 2 and 3; FIG. 2 for products of Examples 4, 5 and 6; Figure 3 for products of Examples 7, 8 and 9 and

Figure 4 for products of Examples 10 and 11 and for a typical radical polyethylene of Film quality and for the linear polyethylene SRM 1475 from the National Bureau of Standards.

All of the curves shown in FIGS. 1 to 4 have been "standardized" to the same area under the elution curve.

Copolymers according to the invention have such a viscosity at 200 ° C. and a shear rate of 100 s that the copolymer can be processed smoothly using conventional techniques to achieve tough or solid products, while the viscosity is at 200 ^° C. and a tension

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of 1Cr N / m is such that a stable "bubble" is obtained when the copolymer is used to produce films by a blown technique. The copolymers according to the invention are accordingly particularly suitable for the production of blown films. Furthermore, the films formed from the copolymers according to the invention have desirable properties and in particular a combination of high impact strength, good tear strength, good tensile properties and good stiffness. It should be noted that the copolymers - although the polymer viscosities ^{were measured at 200 0} C at temperatures above or below 200 ⁰ C can be processed; the temperature of 200 ^° C. is merely an expedient temperature within the broad temperature range which can be used for processing the copolymer.

According to a further aspect of the invention there is provided a film formed from a copolymer of the type defined intended.

More specifically, a Äthylencopolymeres of the type described is extruded through a at a temperature in the range 170-300 ⁰ C, preferably 200 to 250 ⁰ C held annular die and the extrudate is inflated and drawn to obtain a circumferential expansion of 1.2 to 10 , 0 times, expediently up to 5.0 times, especially 1.3 to 3.0 times

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Fold and pulled down (as defined below) 2.5 to 50 times, preferably 5 "to 30 times.

"Pull down" is the ratio of die gap: final film thickness.

The general technique for producing blown films from ethylene polymers is described, for example, in Chapter 20 of "Polythene" by Renfrew and Morgan, 2nd ed., Published 1960 by Iliffe and Sons.

Copolymers according to the invention can by bringing together ethylene and a comonomer of the above Art can be made with a transition metal olefin polymerization catalyst. The term "transition metal olefin polymerization catalyst" as used herein is intended to include any catalytic systems related to polymerization or copolymerization of monoolefins are effective and have a transition metal of groups IVA to VIII, in particular groups IVA to VIA. the Designation includes the Ziegler catalyst systems, catalysts based on chromium or molybdenum oxides and Catalysts based on organometallic compounds of transition metals.

More in detail belong to the transition metal oils-609838/0888

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fin polymerization catalysts the Ziegler catalyst systems) the a mixture of a compound of a transition metal of Groups IVA to VIII, especially the Groups IVA to VIA and an organo compound of a non-transition metal of groups IA to IIIA and in particular Include organoaluminum compounds. Other transition metal olefin polymerization catalysts are based on the oxides of chromium or molybdenum, which are typically on support materials such as silica or aluminum oxide are deposited. Still other transition metal catalyst systems include the organic compounds of transition metals with Tl-allyl, cyclopentadienyl, norbornyl, benzyl and Arylene groups (arene groups) and also compounds, the groups include of the type such as neopentyl and substituted silylmethyl compounds. Generally will the organic compounds of transition metals applied as catalysts when they are on a suitable matrix material such as aluminum oxide, silica or magnesium oxide are deposited.

Ziegler catalyst systems are generally known and are described extensively in the literature. Benzyl compounds and their use as polymerization catalysts are described in GB-PS 1,265,7 ^ 7. links of the zirconium tetrakis (trimethylsilylmethyl) type are given in GB-PS 1,265,564. Organo with a carrier

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Transition metal compounds, such as the compounds of GB-PS 1,265,747 and 1,265,564 and their use as Polymerization catalysts are described in GB-PS 1,314,828. The use of supported chromium compounds as polymerization catalysts is disclosed in GB-PS 1,253,063, 1,264,393 and 1,298,220 and the US-PS 3 123 571 and 3 157 712.

Along with some transition metal olefin polymerization catalysts, it is in order to obtain copolymers having the required effective viscosity at 200 ⁰ C and a seer rate of 100 sec and the required viscosity at 200 ⁰ C and a voltage of 10 N / m necessary, the polymerization in at least two carry out different polymerization zones in which different polymerization conditions are maintained, such as different temperatures and / or different concentrations of a chain transfer agent such as hydrogen. However, it is preferred to carry out the polymerization using catalyst systems which are capable of forming a copolymer with the desired properties in a single zone.

It is particularly preferred to use a catalytic composition as the polymerization catalyst, such as it is described in GB-PS 1,314,828. A suitable one

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Catalyst of this type is zirconium tetrabenzyl on one Alumina carrier.

The polymerization can be carried out under any suitable conditions for the polymerization of monoolefins, for example in the absence of an inert diluent when the polymerization is typically carried out by contacting the gaseous monomers with a solid catalyst system on which a solid copolymer is formed or in the presence of an inert liquid Diluent when the polymerization is carried out to form a solution or suspension of the copolymer in the diluent. If a copolymer solution is to be formed in the diluent, the polymerization temperature is such that the copolymer dissolves in the diluent and is typically 120 ^° C. and above, e.g. B. at up to 300 ⁰ C (depending on the nature of both the copolymer and the diluent) and the pressure is such that the diluent is kept in the liquid state and is for example above atmospheric pressure at up to 1000 atm or above. If the formation of a suspension of the copolymer in the diluent is desired, the polymerization temperature should be such that the major part of the copolymer is not dissolved in the diluent and it is typically below 100 ^° C., but preferably above 20 ^° C., especially 50

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can be applied to 9O ⁰ C and although in conjunction with a suitable diluent pressures below atmospheric pressure, the use is preferred of a pressure above atmospheric pressure, typically at from 0.35 to 35.2 atmospheres (5 to 500 psig), preferably up to 14 , 1 atü lies. The polymerization conditions are controlled to achieve a copolymer with the required properties. The copolymers have a broad molecular weight distribution and this property can be achieved either by polymerization in two or more separate zones or by polymerization using a catalyst capable of providing the desired properties in a single zone. The molecular weight of the copolymer (as indicated by the melt index) is relatively high and is conveniently controlled by the use of a chain transfer agent such as hydrogen. When hydrogen is used as a chain transfer agent, its amount is controlled depending on the desired molecular weight of the copolymer (as indicated by the melt index). The melt index of the copolymer product is thus monitored and the rate of addition of hydrogen accordingly. adjusted if the melt index is outside the required range. It should be noted that the hydrogen addition rate should be increased if the melt index is too low so as to increase the melt index and, conversely, should the hydrogen addition rate be increased.

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to lower the melt index, if this turns out to be too high. If the geometry of the polymerization reactor is such that a Gas space exists above the liquid polymerization mixture, so alternatively the relationship between the melt index of the copolymer and the composition of the gas mixture in the gas space can be determined experimentally and then by monitoring and controlling the composition of the gas roughness, a copolymer having a desired melt index can be obtained. The relationship between the composition in the headspace and the melt index of the copolymer product depends on the Geometry of the polymerization reactor and the polymerization conditions and a given relationship is thus only for a given reactor operating under specific conditions works, be applicable. In general, however, copolymers having a melt index in the range of 0.05 to 1.0 can be obtained if the gas space in the reactor is hydrogen and ethylene in the relative amounts (in volume) in the range contains from 0.1: 1 to 2.0: 1.

The amount of comonomer present is similar depend on the polymerization conditions and also on the particular monomer used. The amount of comonomer is from depend on the ethylene concentration and it will be necessary to increase the amount of comonomer when the partial pressure of the Ethylene (and thus the ethylene concentration) is increased.

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In general, suitable comonomer concentrations will range from about 0.25 to about 4.0 moles per liter of the liquid Polymerization medium and more particularly at 0.5 Ms 2.0 mol / l if the comonomer is formed by hexene (1) and at 1.5 to 3.5 mol / l when the comonomer is decene (1). It should be noted, however, that at high ethylene partial pressures to achieve a sufficiently high concentration of the comonomer may be necessary, the comonomer as the liquid Use polymerization medium in the absence of any inert liquid diluent. During operation using liquid comonomers as the liquid polymerization medium, the ethylene addition rate can can be used as a control parameter. It should be noted that when the polymerization is carried out on a continuous basis Basis of the amounts and relative proportions of ethylene and the comonomer to be added - if once equilibrium conditions are set - will be substantially equal to the amounts removed with the product mixture.

The polymerization process is expediently carried out in the presence of an inert diluent and preferably becomes the solution or suspension of the copolymer in the inert diluent at the end of the polymerization process subjected to an overall work-up procedure to fully recover the polymer formed, including the proportions dissolved in the polymerization diluent. A complete work-up can be done by adding a large over-

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Shot of an alkanol such as methanol can be made to the polymer suspension. Preferably, however, water vapor of about 100 ^° C. is passed through the copolymer suspension, to which a small amount of a surface-active compound has been added and the steam passed through the copolymer suspension for a sufficient time to distill off all of the polymerization diluent. This procedure allows the copolymer to be obtained as a copolymer powder with satisfactory flow properties.

According to a further aspect of the invention, a method for producing an ethylene copolymer is thus provided, in the case of ethylene and a comonomer which is formed by at least one mono-Oc-olefin, of which in turn have at least 50 mol ^ 5 or more carbon atoms in Brought into contact with a polymerization catalyst in the presence of an inert hydrocarbon liquid, by the product of a reaction of a transition metal complex of the general formula:

with a practically inert matrix material with a hydroxylic Surface (as defined below) free of adsorbed water is formed, wherein

M a transition metal of groups IVA to VIA of 60983B / ÜB 88

Periodic table of elements;

R is a hydrocarbon group or a substituted hydrocarbon group;

X is a singly charged anionic ligand or a monovalent neutral ligand;

m is an integer from 2 to the valence of the metal M; and

ρ is 0, 1 or 2;

and in the subsequent to the product mixture of copolymer and hydrocarbon liquid 0.005 to 0.1 % and preferably 0.02 to 0.06 wt. ^ j (based on the hydrocarbon liquid) surface-active compound added and water vapor at a temperature of at least 100 ⁰ C is sent through the mixture of copolymer, hydrocarbon liquid and surface-active compound for a sufficient time to distill off practically all of the inert hydrocarbon liquid.

Liiter of a "hydroxylic surface" becomes a surface understood, in which a plurality of -OH groups adhere to the surface, the hydrogen atoms of which are able to act as a proton source, i.e. have an acidic function. A matrix material with such a surface is essentially inert in such a way that the bulk of the matrix material is chemically inert. Examples of such matrix

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materials are silica, alumina, mixtures thereof, and silica-based materials and alumina containing minor amounts of other suitable inorganic oxides such as magnesia and zinc oxide. A particularly preferred matrix material is aluminum oxide, in particular / aluminum oxide.

To suitable hydrocarbon groups R, the same or may be different, include alkyl and alkenyl groups (including Tt-alkenyl groups such as Tl-allyl) or substituted derivatives thereof. However, a preferred class of hydrocarbon groups are those that are substituted Alkyls of the general formula

-CH ₂ Y,

where Y is an aromatic or polyaromatic group such as phenyl or naphthyl; or a ring substituted derivative how p-methyl-phenyl can be. Y can also be a group of general formula

where Z is an element of Group IVB of the Periodic Table of the elements including silicon, germanium, tin or lead and the individual radicals R are independent hydrocarbon groups or hydrogen can mean one another.

A particularly suitable metal complex is zirconium-609838/0888

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tetrabenzyl. Other suitable complexes include zirconium tetra (trimethylsilylmethyl) and zirconium tetra (U-allyl).

The transition metal composition employed as the polymerization catalyst is expediently carried out by Implementation of a suitable transition metal complex with finely divided aluminum oxide according to one of the methods described in GB-PS 1,314 procedures described in detail. The alumina is preferably a ^ -alumina with a Particle size in the range from 20 to 150 yu, especially im Range from 20 to 120/1 and has essentially spherical shape Particles as described in the published German patent application P 23 35 537.5.

The inert hydrocarbon liquid employed as the polymerization medium is preferably an aliphatic one Hydrocarbon that is easily evaporated by passing water vapor through it. To suitable aliphatic Hydrocarbons include pentane, hexane, heptane, and octane. Impurities in the polymerization medium preferably (per impurity) maintained at a level of 1 ppm (by weight) or below. Such impurities are those materials that would otherwise use the transition metal complex used as a polymerization initiator react and deactivate this and they

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are hereinafter referred to as "catalyst poisons". Examples of such catalyst poisons are water vapor, oxygen, Carbon dioxide and carbon monoxide.

Moisture or water vapor can be removed from the diluent by contact with any suitable solid desiccant be removed; however, preferably the diluent is passed through a 4A or 5A molecular sieve column. Oxygen and oxygen-containing impurities can be removed by contacting the diluent with a suitable solid oxygen scavenging medium such as finely divided copper (e.g. BTS catalyst, now also referred to as "R3-11" from BASF) or manganese (II) oxide.

Using such means it should be possible to achieve contaminant concentrations of less than 1 ppm; however, it is also desirable to regularly monitor the diluent impurity concentration, especially when a polymerization is carried out in a continuous process.

Preferably the purity is that used to make the supported transition metal composition Transition metal complex is very high, especially when a Group IVA transition metal complex is used will.

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Since the transition metal complex is usually formed by reacting a compound of a Group IVA metal such as of a halide with a hydrocarbyl compound of a metal of groups I to III is generated, the "purity" of the organometallic compound considered here can expediently can be expressed as the residual amount of the metal of groups I to III contained. As a "purity ratio" thus becomes the molar ratio of the transition metal (especially the group IVA metal) to the group I to III metal understood in the transition metal complex.

When a complex of a Group IVA transition metal nach.dem previously used method is produced, for example as in GB-PS 1 265 74-7 and GB patent application 1 403 746 of the applicant is described, so is the purity ratio of the product usually in the Area of 50/1 or below. However, if such products are further purified to achieve a purity ratio of at least 100/1 or preferably 500/1, in particular 1000/1 and above, one finds - if from such Compounds prepared, provided with alumina support compositions are used - in the copolymerization of ethylene, an increase in the incorporation of the comonomer into the copolymer obtained.

Complexes of Group IVA transition metal with the ge-609838/0888

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required high levels of purity can be obtained by any suitable method; some suitable procedures but can be given as an example:

(1) The transition metal complex can reasonably often be obtained from a suitable ethereal or hydrocarbon solvent, such as hexane or diethyl ether, are recrystallized.

(2) A hydrocarbon solution of the transition metal complex can be mixed with a small amount of the moisture-free Alumina, which is to be used as a carrier, partially converted and to achieve a solution of the purified transition metal complex can be filtered.

(3) A hydrocarbon solution of the transition metal complex can be filtered through a bed, which contains a small amount of dried alumina, after which the transition metal complex is crystallized from the filtrate.

After the completion of the polymerization, the formed copolymer is removed from the polymerization diluent and any unreacted monomers by contact with Vapor emitted in the presence of a surface-active compound. A wide range of surface active compounds can be applied and satisfactory effects can be obtained with both water-soluble and water-insoluble ones surface-active compounds are obtained. Preferably, water-soluble surface-active compounds are

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fertilize used to prevent contamination of the copolymer with the surface-active compound as low as possible and also the return of the surface-active Support connection. Particularly preferred Ϊ3φβη of surface-active compounds are water-soluble wetting agents. Suitable water-soluble wetting agents include the following water-soluble materials: salts of sulfosuccinic acid, particularly those of dihydrocarbylsulfosuccinic acid; Adducts of linear alcohols with ethylene oxide, such as adducts of alcohols having 13 to 15 carbon atoms with 6 to 14 moles of ethylene oxide; Adducts of phenols with ethylene oxide, such as adducts of nonylphenol with 6 to 30 mol ^ ethylene oxide; Block copolymers of ethylene oxide and propylene oxide, such as those containing 20 to 70 moles of ethylene oxide; Derivatives of tetrafunctional polyoxyalkylene block copolymers with alkylenediamines such as Derivatives of ethylene oxide / propylene oxide block copolymers with Ethylenediamine; Polyoxyethylene derivatives of fatty acids and Polyethylene oxides that are in branched fluorocarbon groups end up.

The water vapor is expediently introduced into a stirred polymer suspension through a dip tube at AT-HD sphere pressure. If the polymerization diluent has a boiling point below 100 ⁰ C, the temperature of the mixture rises rapidly to 100 ⁰ C, if everything

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Diluent is removed. If desired, the steam flow can be interrupted when the temperature of the mixture has reached 100 ^° C., but this is not necessary and the steam flow can be maintained for a certain time after a temperature of 100 ^° C. has been reached. While it is appropriate to use water vapor at atmospheric pressure, higher or lower pressures and correspondingly higher or lower steam temperatures can be used. If desired, the steam treatment can be done on a continuous basis in a series of vessels or zones.

For a better understanding of the invention, different Aspects of the same are illustrated by the following examples.

Production of zirconium tetrabenzyl on alumina - Production of zirconium tetrabenzyl

130 grams of zirconium tetrachloride was placed in a dry 250 ml flask purged with nitrogen. In addition, 2,932 1 were added to a solution of Magnesiumbenzylchlorid (prepared by reacting 53.5 g of magnesium turnings with 232 ml benzyl chloride) cooled in diethyl ether to -20 ⁰ C and stirred with 126 g of zirconium tetrachloride from the 250ml flask over a period of 30 to 45 minutes moved away, with the addition via a flexible nitrogen-filled

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flushed connector took place. The reaction temperature was maintained during the addition between -15 and -1O ⁰ C and worked by wrapping with aluminum foil des.Reaktionsgefäßes the absence of light. The cold bath was left in place while the reaction mixture was heated to ⁰ ° C. and then removed. The reaction mixture was stirred at room temperature overnight.

The ethereal solution was Zirkoniumtetrabenzyl from ZrCl ^ and precipitated by filtration through MgCIp ^ ■ 20 g of Ketjen Grade B alumina (the above 2 hours was at 500 ⁰ C dried) separated on a G3 / G4 frit. Another liter of dry ether was added to the remains of the reaction vessel and, after stirring for 30 minutes, filtered through the same frit. The combined filtrates were then concentrated in vacuo to about half the original volume, whereupon orange crystals of zirconium tetrabenzyl separated out. The crystals and mother liquor were left to stand at -20 ° C. overnight.

After decanting the essential mother liquor, the crystals were pumped dry (about 1 hour) before they are dissolved in hexane by contacting the crystals (3 times) with 1 liter of boiling hexane for one hour per contact period became. Using nitrogen pressure, the

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hot hexane solutions rapidly by a ~ 10 g of Ketjen Grade B alumina (the above 2 hours been dried at 500 ⁰ C was) containing pressed G2 frit. On cooling, crystals secreted from Zirkoniumtetrabenzyl from the filtrate, which was in turn allowed to stand for a complete crystallization overnight at -20 ⁰ C.

The hexane was then decanted off and the crystals were pumped dry before being put into 500 ml of dry oxygen freed toluene were dissolved. At this point in time, a check was carried out by IR spectroscopy to

—I know the absence of ether residues (1120 cm) and those containing oxygen Products (1100 cm "). Finally, was the solution made up to 1 liter with toluene and analyzed for zirconium, magnesium and chlorine. The molar ratio of Zr / Mg was higher than 2000: 1.

Supported catalyst

80 (20-60 s) to 100 g Ketjen Grade B alumina were dried for 2 hours in nitrogen purged tubes at 500 ⁰ C. After cooling, the alumina was transferred to a dry 2 liter round bottom flask purged with nitrogen and slurried in about 500 ml of hexane. Sufficient zirconium tetrabenzyl solution in toluene was then added with shaking to achieve a loading of the catalyst with 0.5 mg atom (0.5 m atom) Zr / g

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The final volume was adjusted to about 1 liter.

All manipulations were carried out throughout the preparation carried out under dry, oxygen-free nitrogen. All glassware was removed from an oven before assembly and the solvents over molecular sieves dried and deoxygenated prior to use by passing dry nitrogen through it.

example 1

In a 6 l stainless steel autoclave fitted with a pipe Stahl was continuously fed the following reagents:

Hexane 1.65 l / 3td.

Hex- (1) 0.35 l / h Ethylene 310 l / 3td.

Hydrogen was fed slowly to maintain a predetermined polymer melt index.

A suspension containing zirconium tetrabenzyl on an alumina support (prepared as described above) was injected intermittently from a "diaper" which itself was in turn held in a glass tank stirred ICatalyst suspension was fed.

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A suspension of the polymer formed was continuously removed from the autoclave at one of the rate of addition Reagents withdrawn at the appropriate rate. The volume of the polymer suspension present in the autoclave was held at 3 1 and the suspension stirred continuously.

Hexane and ethylene were passed through a 5Λ Ilolekularsiebsaule and a "BTS" column (new name "Po-H"; finely divided copper) cleaned. Hexene-(1) was made by passing it through a 3A molecular sieve column and purified a "BTS" column.

The catalyst was added at a rate of 0.21 mg-atom Zr / hour. The autoclave and its contents were kept at a temperature of 8O ⁰ C. The pressure in the autoclave was 6.7 atmospheres (95 psig) and the composition in the gas space of the autoclave corresponded to:

Hydrogen 38.7 ethylene 49.3 vol

Ethane 12.0 tf

The polymer suspension withdrawn from the autoclave (2.3 l / hour) was mixed with 1 l of water, the 0.5 g of sodium dioctyl sulfosuccinate contained.

Steam was introduced into the stirred mixture at a

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Introduced a temperature of 100 ⁰ C at atmospheric pressure at a rate of about 25 g / min until all of the hexane and remaining hexene (1) had been removed. This process took about 1 hour. The polymer suspension in water was filtered and the polymer at a pressure of 25 mm was dried at 7O ⁰ C.

Further details of the polymerization are given in Table 1.

Examples 2 to 11

The procedure of Example 1 was repeated, but using different proportions (as indicated in Table Λ ) and with the exception that the volume of the polymer suspension present in the autoclave was kept at 41 in Examples 3 to 11 and a mixture in Example 9 of hexene (1) and butene (1) was used as comonomer.

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Table 1

cn ο in co

cc

co co approx

example
or
VgI.-
example Reagent flow rate. Hexane
(lit er / style) Coroonomer & s
(liter / Sta)
(b) (m-3-A-tom,
zr / sta) In addition in the gas compartment
(VoI %) Ethylene Athan Autoclave »;
pressure
(P ^si 8).
atü Rüfrrrge-
schwii> -
digks.
(Rpm) Discharge
ffisctrwind,
t'cs polymer ..
Mud
(lit er / 5t d) Polymer·
yield
(g / hr) 1 AHylen
(liter / StA)
(a) 1.65 0.35 0.21 H ₂ 49.3 12.0 (95) 0.7 1000 2.5 555 2 510 2.0 0.40 0.27 58.7 56.8 11.1 I 80) 5.6 1000 2.6 552 5 500 3.2 0.75 0.67 52.1 47.5 7.5 175) 5.3 1500 4.1 530 4th 380 5.2 0.75 0.67 45.2 45.8 7.7 (75) 5.5 1500 4.2 551 5 580 3.1 0.54 0.67 46.5 47.5 11.7 (75) 5 ,? 1500 4.0 553 6th 500 3.0 0.57 0.67 41.0 44.1 13.7 (80 \ 5.6 1500 4.1 578 7th 500 3.1 0.80 0.67 42.2 55.2 11.1 (7515.5 1500 4.0 • 550 8th 500 0.50 0.60 53.7 '46, 6 18.5 (75 b "; 5 1400 3.7 545 9 500 3.0 0.44 1
0.095J 0.65 32.9 57.6 14.7 (80) 5, _fa 1500 3.6 575 10 520 3.0 0.50 0.72 27.7 57.1 9.7 1500 4.0 535 11 500 3.1 0.50 0.72 35.2 50.6 6.1 (65) k, 6 1500 4.1 595 λ 500 V 0.15 0.76 43.3 45.7 I4 _r 3 1ΊΟΟ 3.87 586 580 42.0

K?

cn ro

26Ü9527

Comments on Table 1

a) Ethylene volume, measured at 760 mm pressure and 20 ⁰ C;

b) the Comonoinere was in all examples only Hexen-d), apart from example 9 (0.44 l / h Hexene- (1) and 0.095 l / h butene- (1)) in Comparative Example A, the comonomer was through 0.15 l / h of butene- (1) formed;

c) Yield of the polymer isolated after treatment with steam.

The properties of the poles obtained are in Table 2 reproduced.

B 09S3 8 / ÜÜÖ8

• Ι

Λϊ 8 U

-P 3 ο <c · SE ^ f- CJ

8 O

Ul KN .HO

K
νθ

4!

OI

• Η

.a

It " I.

• ώ ώ

KN I. U.N. νθ Γν co σ> I. CVJ I. I. I. I. ι τ- Fig OI OJ KN KN KN i? S. Fig 'S Fig Fig Fig Sn CV
OI P, CV
CM 5 ?,

CO

36

OI

a Ri Jm

Cv

τ-

53

KN

CVJ

co

⁰ RS

σ * σ »* ö

ο ° ο X ^ o ° ο ° ο "Ό ^ o ^ o χ
KN
VO ° ο VD X
S. X
T-
VD , 27 χ ' χ , 17 χ ' χ
SR χ , 57 χ ' , 17 χ ' K
ίν

O X

O X

Cv KN

U.N.

O X

O X

O X

"b

O X

"ο

^ o

OI Cv "

X X

KN CO

TT * -ί ~

ΟΟΟΟΟΟΟΟ OO

T-T-T-T-T-T-T- τ- T-T- XXXXXXX X XK

[V - * KN -rf- CO Ol VO KN

ιΛΟΝνΟιΛΟνΟί CO ^ i

Oil

OI

Τ "KN

KN

KN

KN O

b KN
O KN
O κ \ KN
O KN
O KN
O KN
O KN
O χ X X X X X X X X S? CV
CM Cv
r- SR j? CV
U.N. KN
VO Cv
τ-

ΙΛ KN KN JD CM OJ O O O ON cn KN CM ο

Cv νθ CO νθ Cv Ol Ol Κ \ τ- T-

νθ

KN O

KN Jl · Cv KN

τ * σ »ο * ο csi co σ *

■ * SP O ΙΛ t "O C ^

Oi OJ g Κ \ κ \ Κ \ (SJ

O ^ O ^ O * O * W * O ^ O ^

609838/0888

2BÜ9527

Comments on Table 2

d) The normalized density was measured according to ASTM 1928/70, Method A, at 23 ⁰ C and includes a correction for the presence of catalyst residues;

e) measured by an IR technique using a mathematical comparison of the extinction curve at 1310 to 1430 cm "" with two standard polyethylenes of known methyl number. A correction was then made to account for those methyl groups attached to the molecule ends form by the methyl number of a linear ethylene homopolymer that was made using the same catalyst system and had practically the same molecular weight distribution and MFI. Contained in Example 9 the product hexene (1) (7.3 wt.? 0 and butene-O) (3.4 wt. 70) and in comparative example A only Butene- (1) (10.2 wt.? S). In all other examples the comonomer was only formed by hexene (1).

f) Measured at 190 ° C with a weight of 2.16 kg according to ASTM 1238-62T;

g) measured at 20O ⁰ C with a capillary viscometer with a nozzle or capillary of 32 mm length and 2 mm diameter and a viscometer cylinder diameter of 22.2 mm using the relationship:

Tt r ⁴ P

SQl

609838/0888

26U9527

h) Measured at 200 C * using a cone and plate device with a cone of 5 cm in diameter and a cone angle of 4 on a Weissenberg Rheogoniometer type R 18;

i) measured according to ASTM D 2289 at a pull rate of 51 cm / s with a test sample according to British Standard 903 Part A2, but with an effective gauge length of 1.91 cm (instead of 1 inch); the test sample was heat-treated by dipping for one hour in ¥ ater of 100 ⁰ C and allowed to cool, water and sample to room temperature;

j) determined as specified under (e), but without

Correction for the methyl groups that make up the ends of the molecule;

k) the optical density per cm of a shaped resp.

cast sample approximately 0.05 cm thick was measured at 910 cm "" ^. The sample was through 20 minutes long immersion in liquid bromine at room temperature "brominated" and then dried overnight. The optical density per cm of sample was again determined at 910 cm "" "". The difference between the Both optical densities are due to unsaturated components and this difference χ 0.126 results in the "Vinyl groups per 1000 carbon atoms".

l) The indication "Figure 1-1" means curve 1 of Figure In Figure 4, curve A was made with polyethylene from

609838/0888

26U9527

ringer density with an ILFI of 0.3 and a "normalized density" of 924 kg / m ^.

All elution curves were standardized to the same area. The curves were obtained using the following equipment and technique: The column set had dimensions of 487 cm in length and 7.93 mm nominal inside diameter. "Spherosil" (from Pechiney Saint Gobain) with a size (diameter) between 75 and 105 μ was used as the column packing material. The different grades of packing material and the proportion thereof corresponded to the following fourths:

XOA 600 27 wt. ^C / o

XOA 400 8% by weight.

XOA 200 8 wt

XOB 075 8 wt

- XOB 030. 8 wt

XOB 015 8% by weight.

XOC 005 33 wt.

A detector was used to determine the concentration of the individual bodies in the eluted materials Differential refractometer used.

The polymer samples were dissolved in 1-methylnaphthalene at 165 ° C. to give a concentration of 0.25% by weight and the injected solution had a volume of 2 ml. The sample solution was passed through a pre-injection filter with a pore size of 76 μ . That as a carrier

609838/0888

" ^3β " 2BU9527

The final solvent was 1-methyl-naphthalene with a Content of 0.1 / S Topanol OC. The flow rate of the carrier solvent was about 1 ml per minute and the columns, detector and solvent were "held at 165 C. The void volume of the system corresponded a Slution number of about 83. For all curves in Fig. 1 up to 4 the elution number is plotted against the change in the refractive index (^ Rl).

Foil production

The polymers from Examples 2, 3, 8 and 10 and from Comparative Example A were processed into films under Use of a laboratory tubular film upward extrusion unit with conventional air cooling devices for the blown film using the following conditions :

The extruder had a screw diameter of 3.82 cm at a ratio of length to diameter of 18: 1 and was operated at a melt and die temperature of 230 ⁰ C. The nozzle had a diameter of 76.2 mm and an annular gap of 1 mm. The film was inflated to give a circumferential expansion of 2.5 μl and films 30, 90, 100 and 150 μ thick were produced. The unit was operated at a throughput of 10 kg / hour.

60983 8/08 88

26U9527

The properties of the films obtained are shown in table 3 "reproduced together with properties of foils, which were obtained in a similar way, but using a radical polyethylene with a melt index of 0.3 and a normalized density of 924 kg / m.

609838/0888

2 b U 9 5 2 7

■ Ρ ν 3 chi -Ρ ' in -ν α. Φ 325 290 ϋ % 253 315 326 264 310 250 180 R.
τ- • Η • Η
Φ ι 4th S. EH Kant • Η
Φ FiIa φ ^ -ν ι ^ω • Ρ jdick Q
Σ 730 ιη 069 880 825 815 ΙΛ 620 cn W) α. Pj U α rj CJ CTV a. 420 SiS 680 970 835 390 765 ■ ♦ 530 595 ο deh IL O. CM (M 00 νΟ VO CO CM CNi τ- Bru O * tr · * ·
Τ
ΗΝ 28, 26, £ Q
S. • "Ν U β <Μ O τ- τ " σν ο ΙΛ Τ σ » VO ? W. D. O
ε ■ * Κ \ »Λ κ \ ΙΛ ^ ^- ΙΛ Α ΙΛ CM —Ν α. ιη νΟ ιη. ΙΛ »Ο CVl ΙΛ νΟ τ- ■ Ρ. _ • ^: ?: 13th CM ιη ΙΛ O 10, VO ο 00 σ » C * CO σ> CO τ- \ Ο CM I. CL 10 O
τ- τ- τ- 12th σ
τ- r- τ-
τ- O 10. I. ιη νθ CO τ- τ- CO CO O VO ο Q
ε CM CM τ- cr> CM 00 OO ^ · ΙΛ ώ ^ p time νΰ ο CM κ \ C ^ - ιΛ CM V O VO CO C- ςτ { * ~ ιη 00 ΙΛ Ο3 ΙΛ CM ΙΛ • Η Φ 575 1100 I. 1 1000 850 270 T " 174 800 630 ιη 1110 I. S. 1000 1050 092 I. 002 510 150 100 150 150 150 150 100 150 CM CM CM »Λ CO O ο « * CQ

609838 / Q888

26U9527

Notes on the table

This polymer is a commercially available one
Radical polyethylene polymer with a melt index of 0.3 and a normalized density of 924 kg / m ^;

in) the impact resistance was after the British
Standard 2782; 1970, method 306F measured;

n) determination according to British Standard 2782; 1970, method 308B;

p) MD means machine direction; TD means transverse direction to it;

q and r) the tensile tests on the films were carried out on samples 10 mm wide according to the ISO Recommendation 1184, 1970, described method with a stress ratio of 500 mm per minute .

s) The stated values for the film stiffness are the 1 73 secant moduli measured according to ASTM D882-73. Four test samples measuring 10.4 cm by 1.27 cm were used in both the cross direction and the machine direction. A pull rate of 2.54 cm per minute was used. The numeric value reported is the geometric mean of the fourth mean measured in the cross and machine directions.

609838 / 0.8 88

" ⁴⁰ " 26U9527

Examples 12-14

The procedure of Example 1 was followed using a 14 liter stainless steel autoclave and Pentene- (1); 4-methyl-pentene- (1) or decene (1) as comonomers repeated. Further details on the polymerization conditions and the nature of the products obtained are given in "Tables 4 and 5.

6 0 9 B 3 8/0 H Π

Tabel

at
game Reagent flow rate Hexane
(1 H) Comono-
meres
(1 H)
(t) Catal
gate (mg-
atom
Zr / h) In addition in the gas compartment
(Vol.96) Ethylene Ethane automobile
slave
pressure
(psig)
atü Stir
speed
age
(Rpm) Discharge
speed
age
d.Polymer
muddy
(1 H) Poly-
mer-
the end-
prey
(g / hr)
(c) 12th
13th
14th Ethylene
(1 H)
(a) 2.84
2.30
3.2 0.70-P
1.52-D
0.56 MP 0.50
0.45
0.60 H ₂ 58.8
46.2
42.4 14.4
26.0
24.8 (100) 7.03
(58) 4.06
(65) 4.57 1000
900
1200 4.02
4.29
4.22 563
630
612 580
580
580 26.8
27.8
33.8

O CO GO C *> OO

O CO CO CO

Comments on Table 4

(a) and (c)

are then defined in Table 1 (page 30);

(t)

ρ _

D =

MP =

Pentene- (1) decene- (1) 4-methylpentene- (i

he;

2 6 [J 9 527

Table 5

at
game density
(kg / m3)
(d) Comono-
merge.
(Wt.%)
(e) MFI
U) effective
viscosity
at 10Os-MA)
(Nsm-2)
(S) 2Ae (1 , 6A χ 10 ~ ³ ) 12th 927.1 10.1 0.19 1.54 χ 10 ³ 3 , 6 χ 10 ⁴ 13th 927.2 11.3 0.15 1.60 χ 10 ³ 4th ,1 χ 10 ⁴ 14th 928.1 13.1 0.19 1.60 χ 10 ³ 4th ,1 χ 10 ⁴

Viscosity at 1000A Deh
tion
(%) methyl Vinyl- at
game 10 ³ N / m ² (B)
(Nsm-2) (i) groups
per 1000
C atoms groups
per 1000
C atoms (H) 1.54 χ 10 ⁶ 650 (d) (k) 12th 2.2 χ 10 ⁵ 1.60 χ 10 ⁶ 650 21.3 0.51 13th 2.4 χ 10 ⁵ 1.60 χ 10 ⁶ 610 16.0 0.30 14th 1.9 x 10 ⁵ 30.4 0.24

Notes on Table 5i

(d) to (k)

are then defined in Table 2 (page 32)

609838/0888

26U9527

Foil production

The polymers of Examples 12 to 14 were processed into films using the conditions described above and apparatus with the exception that the melt and the die temperatures were 225 ⁰ C and, in the formation of films having 30 μ thick peripheral widenings 3 0: 1 were applied.

The properties of the films obtained are shown in Table 6.

B 0 9 H Ά H / Ü 8 8 8

Tabel

Polyaer Movie
thickness
0-0 Impact
solidifies
(«) (■) Chewed Tear
ability ( g / p) 2-isxestieikeit ι «· /» ι
Tq) TD (p) fracture TD (p) Fraction
strain TD (p) Stiff
speed
(-) ₂
(«</ -) 12th 30th flax 240 KD (p) TD (p) SiBckgr. 14.5 iiD (p) 41.0 W.
(r 65O 320 12th 150 320 890 2.3 18, 6 MD (p) 13.5 52.4 31.6 JU3 (p) 795 270 13th 30th 1170 26O 6.9 10.0 15.2 17.0 31.5 45.1 440 700 380 ■ 13th 150 270 1010 V 18.2 13.0 14.2 ' 5b, b 32.8 780 745 270 14th 150 1170 1060 13.6 15.2 13.5 35; 9 33.8 400 7? 0 300 1290 10.1 13.4 35.6 680 12.7 76O

Notes on the table

(m) to (s) are defined following Table 3.

Claims (27)

Claims 1. Copolymer of ethylene with a comonomer which is formed by at least one mono-cc-olefin, at least 50 mol / ό of the mono- <x.-olefin which forms the comonomer having 5 or more carbon atoms, characterized in that that the copolymer has a normalized density in the range of 918 to 940 kg / m; an effective viscosity measured at 200 ^° C. and a shear rate of 100 s in the range from 0.5 1Cr to 3.0 χ 1Cr Nsm and one at 200 C and has a viscosity measured at a tension of 10 N / m, (λ g / \ _x ] Q3) at least equal to 2Ae ^v '' and not higher than 1000 A, where A is the effective viscosity at 200 ⁰ C and a speed of 100 s seer. 2. Copclymeres according to claim 1, characterized in that the comonomer 0 Mol $ of a mono- o6-olefin with less as 5 carbon atoms. 3. Copolymer according to claim 1 or 2, characterized in that the comonomer is a mono-oc-olefin with at least 5 and not more than 12, preferably not more than 10 carbon atoms and in particular hexene (1). 609838/0888 26U9527 4. Copolymer according to one of claims 1 to 3, characterized by a normalized density in the range from 920 to 935 kg / m ⁵ . . 5. Copolymer according to one of claims 1 to 4, characterized by an effective viscosity at 200 ⁰ C and a shear rate of 100 s ~ in the range from 1.3 x tO ³ to 2.4 χ 10 ³ Nsm " ² . 6. Copolymer according to one of claims 1 to 5, characterized by a viscosity at 20O ⁰ C and a tension of 10 ³ N / m ² of at least 3.5Ae ^ ¹ ' ^{6A x 10} ^ and not more than 500A. 7. Copolymer according to one of claims 1 to 6, characterized by a viscosity at 200 ⁰ C and a tension of 10 N / m in the range of 2.2 χ 10 to 3 x 10, 4 6-2 in particular from 3.8 10 to 1.2 χ 10 Nsm 8. A copolymer according to any one of claims 1 to 7, characterized in that the amount of the comonomer in the range of 6.5 to 30 wt.% Of the polymer, preferably from 8.0 to 27 Gew.Jü of the polymer is. 9. Copolymer according to claim 8, characterized in that the comonomer is formed by hexene (1) which is in 609838/0888 ~ ⁴⁷ ~ 26U9527 an amount in the range of 6 ", 5 to 16.5 wt.% Of the polymer, in particular 8.0 to 15 wt. % Of the polymer is present. 10. Copolymer according to one of claims 1 to 9, characterized by an elongation at break in the high-speed tensile test of at least 400 %, preferably at least 800 Ji and not more than 1500 %. 11. Copolymer according to one of claims 1 to 10, characterized by a melt index (measured at 190 C. weighing 2.16 kg) in the range from 0.05 to 1.0 and preferably in the range from 0.08 to 0.30. 12. Copolymer according to one of claims Λ to 11, characterized by a methyl content of 12 to 40 methyl groups per 1000 carbon atoms. 13. Copolymer according to one of claims 1 to 12, characterized by a vinyl content in the range of 0.15 up to 0.55 vinyl groups per 1000 carbon atoms. 14. Pol} / mer foil, characterized in that it is starting from a copolymer according to any one of the preceding claims. 15. A method for producing a copolymer according to a K098387 0Ö8 8 of claims 1 to 13, characterized in that ethylene and a comonomer, which by at least one mono-odolefin at least 50 moles of which have 5 or more carbon atoms with a transition metal olefin polymerization catalyst be brought into contact. 16. The method according to claim 15, characterized in that the polymerization in an inert liquid diluent is carried out under such conditions that a solution or suspension of the copolymer in the diluent is formed. 17. The method according to claim 16, characterized in that the solution or suspension of the copolymer in the inert The diluent was subjected to an overall work-up procedure for the recovery of all of the copolymer formed will. 18. The method according to claim 17, characterized in that the overall treatment is carried out by passing water vapor at a temperature of about 10O ⁰ C through a copolymer suspension, which is mixed with a small amount of a surface-active compound, the steam through the copolymer suspension is sufficient sent for a long time to distill off all of the polymerization diluent. 6 O 9 B 3 H / O 8 H 8 " ⁴⁹ " 26U9527 19. The method according to claim 17, characterized in that that the monomers in the presence of an inert hydrocarbon liquid with a polymerization catalyst be brought into contact, which is caused by the product of a reaction of a transition metal complex of the general formula: with an essentially inert matrix material with a hydroxylic surface free of adsorbed water is, is formed; that to the product mixture of copolymer and hydrocarbon liquid 0.005 to 0.1 wt. £ 3 (based on the hydrocarbon liquid) a surface-active one Compound can be added and water vapor at a temperature of at least 100 ^ through the mixture of copolymer, hydrocarbon liquid and surface active compound for a sufficiently long time Time is allowed to distill off substantially all of the inert hydrocarbon liquid, wherein: M is a transition metal from groups IVA to VIA of the Periodic Table of the Elements; R is a hydrocarbon group or a substituted one Hydrocarbon group; X is a singly charged anionic ligand or monovalent neutral ligand; m is an integer with a value from 2 to Wer-609838/0888 26U9527 activity of the metal M; and is 0 or an integer that has a value up to 2. 20. The method according to claim 19, characterized in that the essentially inert matrix material is replaced by silica, Alumina, a mixture of silica and alumina, or silica or alumina with a content of small amounts of other inorganic oxides is formed. 21. The method according to claim 20, characterized in that the essentially inert matrix material is formed by ^ -aluminium oxide with a particle size in the range from 20 to 150 μ . 22. The method according to any one of claims 19 to 21, characterized in that the inert hydrocarbon liquid Contains impurities at a concentration level per impurity that is less than 1 ppm (by weight). 23. The method according to any one of claims 19 to 22, characterized in that the transition metal complex is such Has purity that its impurity ratio is at least 100: 1, preferably at least 1000: 1. 609838/0888 " ⁵¹ " 26U9527 24. The method according to any one of claims 19 to 23, characterized in that the transition metal complex by zirconium tetrabenzyl, zirconium tetra (trimethylsilylmethyl) or zirconium tetra ('Tt-allyl) is formed. 25. The method according to any one of claims 19 to 24, characterized in that the surface-active compound is soluble in water. 26. The method according to claim 25, characterized in that the surface-active compound is a water-soluble Wetting agent from the group of salts of suIfosuccinic acid, Adducts of linear alcohols with ethylene oxide, adducts of phenols with ethylene oxide, block copolymers of ethylene oxide and propylene oxide, derivatives of tetrafunctional polyoxyalkylene block copolymers with alkylenediamine, polyoxyethylene derivatives of fatty acids and polyethylene oxides with branched fluorocarbon end groups. 27. The method according to any one of claims 15 to 26, characterized in that the polymerization in the presence of Hydrogen is carried out. ΰ o 9 β 3 c / u a a 8