CZ590489A3 - Process of continuous polymerization of one or more alpha olefins in gaseous phase - Google Patents

Description

The present invention relates to a process for the gas-phase polymerization of alpha-olefins in a fluidized bed reactor.

| agitated bed, in the presence of a catalyst on the basis of the transition elements.

& _{U £} ^ Ajne polymerize continuously one n «BO Aixam-olefins such as ethylene neoo propylene in gaseous phase in a reactor ε íluidním and / or mechanically agitated bed, in the present of a transition element of Group IV, V or VI periodic table of elements; in particular in the presence of a Siegler-typeatt catalyst or a chromium oxide catalyst. The polymer particles, when formed, are in the fluidized and / or agitated state in the gaseous reaction mixture containing the alpha-olefin somewhat alphaolefins, which are continuously fed into the reactor.

The catalyst is introduced continuously or intermittently into the reactor, while the polymer formed in the fluidized and / or stirred bed is also withdrawn continuously or intermittently from the reactor. The heat of the polymerization reaction is substantially removed by the gaseous reaction mixture that passes through the heat exchanger before. before being recycled to the Eeactor. ^; ', - *, / 1 · · “£' v ^{, r}

If the process of polymerization of alpha-olefins in gaseous s ^- '/''¢.<·<· · I * «· runways' ⁴ phase in the presence of catalyst at a higher efficiency,

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effect on polymer bed particles. These small variations are known. They have an adverse effect in the gas phase polymerization process, since the heat exchange capacity in the gas phase is much lower than in the liquid phase. In particular, these small variations may cause an undesirable increase in the amount of heat generated by the reaction and which cannot be removed sufficiently quickly and efficiently by the gaseous reaction mixture passing through the bed and may cause hot spots to occur in the bed and molten polymer agglomerates. If hot spots appear in the bed, it is usually too late to prevent agglomerate formation. however, if the reaction conditions are corrected in a timely manner, in particular by lowering the polymerization temperature or pressure, or by reducing the rate at which the catalyst is fed to the reactor to reduce the adverse effects of unexpected superactivation, it may. however, the amount and size of the agglomerates formed may be reduced to a certain extent, however, during this period, losses in polymer production and quality deterioration cannot be avoided. Consequently, it is desirable to avoid these problems in general. polymerization conditions are chosen i

so as to ensure that hot spots and gglomerates do not

-. They may, however, ... Application, such conditions, however, will result in a substantial reduction of the product or a deterioration in the quality of the produced polymer: particularly to increase the proportion of catalyst catalysts.

residues in the polymer

HA using a high yield catalyst whose polymerization efficiency can be influenced by small variations in the impurity content of the polymerization medium, as is the case in particular of Ziegler-hatty catalysts based on magnesium, halogen and transition elements such as titanium, vanadium or zirconium · This euperactivation phenomenon may also occur when comonomers are capable of activating the polymerization of alpha-olefins, especially in the case of copolymerization of ethylene and alpha-5-C8 alpha-olefins / Eolymer Science LfíSR, vol. 22, 1580, pp. 446- 454 / *

Soviet Patent No. 1249025 discloses a method for controlling the gas phase polymerization of alpha-olefin in the presence of catalyst, hydrogen and carbon dioxide. The method essentially consists in adjusting the melt index of the polyolefin, which is a physical property characterizing the distribution, the molecular weight of the polymer, adjusting the melt index by measuring the relatively high concentration of carbon dioxide in the reactor and changing the flow rate of the carbon dioxide being fed. induces a change in the specific property of the catalyst, the polymerization. However, this method does not describe a method for maintaining a substantially constant bull. catalyst content in the produced polyolefin or polymerization rate · fa? The gas-phase polymerization process of alpha-olefin found has made it possible to overcome or at least alleviate the above-mentioned problems.

The production of a polymer with high productivity and low catalyst residue content, independent of the incurable minor changes in the quality of the aliasesins or catalyst, or when introducing the catalyst into the r-actor.

It has been found that as a result of this process it is now desirable to produce continuously continuous quality and consistency, with a high degree of reproducibility and high yield, without the formation of agglomerates.

Thus, the present invention relates to a process for the continuous gas phase polymerization of one or more α-α-olefins in an ε illuidic and / or mechanically stirred lot using a catalyst and an activity retarder, characterized in that the polymerization is carried out by introducing a transition catalyst. of metals. IV- ^ Y. or VX. groups of the periodic classification of elements in contact with an alpha-olefin (s) and a very small amount of retarder, efficacy being introduced continuously into the reactor at a flow rate that varies with time to substantially maintain a constant polymerization rate or content transition metals in the produced polymer. Retarder efficiency is chosen from a wide range of ^products: are. capable of reducing the polymerization rate of alpha-olefins in the presence of a catalyst and a transition metal base. Effective retarder, can be selected in particular *

z. Polymerization inhibitors or poisons which are for

(γτy *! · 'u? ø * t · ... Λρ <·, ^: .

,. ·., -R; -φ yt-.kr ,, '5 / <r ;; - y * · _h and calf to zvcieny are mainly carbon monoxide, carbon. carbon dioxide, carbon dioxide, carbon oxysulphides, nitrogen oxides and peroxides, oxygen, alcohols, aldehydes, ketones, thiols and water. the hetarder of activity may also be selected with electron donor compounds capable of complexing the catalyst and reducing the polymerization rate, in particular from organic compounds containing at least one oxygen, sulfur, nitrogen and / or phosphorus atom, the skin may be selected from a wide variety electron-donating compounds such as amines, amides, phosphines, sulphoxides, sulions, esters, ethers, or thioethers should be particularly pointed out in the use of an activity retardant in an amount capable of reducing the polymerization rate without substantially affecting the quality and properties of the polymer produced index, melt flow index, average molecular weight, molecular weight distribution, or stereospecificity of the polymer, since it is very important in the present invention that the rate of introduction of the efficiency retarder into the reactor may vary with time, the properties of the produced polymer may vary. during the reaction to change, since, the activity retarder used has considerable h.

^{1 1} '·' in trliv on polymer properties · Such a result would be pro- (tikladu the subject of the present invention, ·. ^X owever the zře-

, .¼ ''>-> * · l · .g, · ^r -. u * *. i,. ''.

conditions, in which the effectiveness of the process is effective ;; ·; · · · · · · · · · · · · · · · · · · · · · · · · · . · »·,. <. 'Ϊ́

-6a electron donor compounds. However, it is preferred to use conventional oolvmerization poisons, especially alcohols, carbon monoxide, carbon dioxide or oxygen, as well as electron donating compounds, especially amides and ethers. It has been found that emerging results are obtained with oxygen and amides.

The activity retarder may be used in a pure state or preferably diluted with a gas such as nitrogen or dissolved in readily volatile, caustic hydrocarbons. Another possibility is to coexist a mixture of two or more activity retarders. If oxygen is used as the activity retardant, it can be used in admixture with nitrogen. In certain cases, atmospheric air or oxygen depleted air may also be used.

An efficiency retarder is introduced in accordance with the present invention

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continuously into the polymerization reactor. The nraxi is introduced into the reactor at the same time as the alpha-olefin (s) in a continuous or near-continuous, intermittent manner so that the break time is so short that it cannot affect the polymerization rate that is maintained. constant. If the introduction of the activity retarder is interrupted, or if the duration of the interruption is too long, the efficiency of the polymerization catalyst in the reactor is increased due to the absence of the efficiency retarder, the polymerization rate is then uncontrollable and can change rapidly depending on the reagent quality or

The efficiency retarder is much less than 1 part by weight per million (ppm) and is generally less than 0.1 ppm. The amount of activity retarder in the gaseous mixture circulating through the reactor is generally not measurable using a device such as an oxygen analyzer with an electrochemical sensor or an analyzer. Carbon monoxide / carbon dioxide Gas chromatography with a 5-methane combustion detector or analyzer of organic compounds and a thermoionic sensor. In practice, the amount of efficiency retarder introduced into the reactor is such that the solar ratio of the amount of efficiency retarder that is introduced to

-6 -of the amount of alpha-olefins introduced (u) is 10 to 10 &quot;, higher, -8 &quot; x &quot; 7 much 5.10 ^- &quot; to 2.10 &quot; *. It was found by 3 surprises that very small. the amount of activity retardant used is capable of providing a polyolefin gas phase process with high efficiency and high reproducibility without formation of agglomerates. The amount of activity retarder generally depends on the type of gas phase polymerization system and the type of ketor used. The lowest amount of efficiency retarder used and, consequently, the minimum flow rate of introduction of the efficiency retarder into the reactor can be readily determined by maximum heat exchange in the polymerization system, in the gas phase, or by maximum polyolefin production without agglomerate formation. in addition, the largest amount of efficiency retarder to be used and hence the maximum flow rate of introduction of the efficiency retarder into the reactor can be directly associated with the highest concentration of impurities entrained in the reactor * if the quality of the reactants changes. Effective retarder flow rate too low, tulle during polymerization Observed that there was such a decrease in production that the efficiency retarder introduction had to be discontinued. In such a case, it is not possible to avoid a decrease in production and the content of catalyst residues in the polymer can be significantly increased.

It has also been found that if the retarder feed flow rate is too high, i.e. the molar ratio of the amount of retarder introduced to the amount of alpha-olefins is too high, the polymer production decreases or the catalyst residue content in the polymer significantly increases.

In accordance with the present invention, it has also been found that the rate of introduction of the activity retarder may vary with time to maintain the polymerization rate substantially constant if there are minor changes in the quality of the reactants or catalyst or in the feeding of the catalyst to the reactor.

The oscillation rate is considered to be substantially constant over time if the amount of nolynlefin produced per hour does not change by more than 5% by weight, preferably by no more than 3% by weight.

In another process variant, it has also been found that the flow rate of retarder introduction efficiency. it may be modified with time to maintain a substantially constant content of transition metals in the polymer being produced if it changes during polymerization. the quality of the reactants or the catalyst or the catalyst feed to the reactor. This content is considered 2a. Essentially constant if weight

The transition metal in the polymer does not change by more than 10, preferably by no more than 5.

The A.vnn phase of the colvmercce process is generally carried out by maintaining substantially coffin conditions, such as the composition of the reaction mixture, the overall rate of introduction of the catalyst, the height or weight of the bed, the temperature of the polymerization, and the rate of gas. and also calculated because it directly corresponds to the production of the nolvmer, i.e. the velocity of the polymer output, or the feed rate of the allylolefin (s), or the difference between the gas temperature at the inlet and the outlet, taking into account that the rate of heat in the creation of the polymer.

For example, if it is observed that during polymerization, the production of polyolefins tends to increase, or that the transition metal content of the polymer being produced tends to decrease due to unexpected loss of impurities in the alpha-olefins introduced into the reactor, or will use a new catalyst that is somewhat more efficient than the previous one, or further. As more catalyst was introduced into the reactor, the efficiency retarder feed rate would be reduced to maintain a constant polymerization rate, especially polymer production or transition metal content oolvmeru. If the flow rate does not change, or if the change> No / too little, docház1 ^ £ ^h non-desired effect of "super-activation .- ^ ^ T ^ gQyyjjg Qg-yj-g-hot-spot ^';

-10a bed agglomerates. N ^and to the contrary, if during the polymerization observed., The production of polyolefin tends to decrease · or the content of transition elements in the produced polymer tends to increase, reduce ^n, and the flow rate of introduction of the retarder efficiency so as to maintain a constant polymerization rate, in particular, the oolvmer production or the content of transition elements in the produced polymer. If the flow rate does not change or if its change is too small, polymer production decreases in an undesirable manner and the content of transition elements in the polymer increases. It has been observed, surprisingly, that as a result of the process of the present invention it is now possible to carry out gas phase polymerization at higher temperatures and at a higher alpha-olefin pressure than before. One of the unexpected advantages of this process is that polyolefin production can be increased by 20% without the risk of hot spots and agglomerates. "Significant and unexpected changes in the quality of the reactants, the efficiency of the catalyst" or in the catalyst feed to the reactor. ..

Another unexpected advantage of the present invention is that the polyolefins so produced have a considerably reduced content of transition elements and consequently are of excellent quality without agglomerate formation. Another advantage of the method is that. *> ·· * - - 'h. 4-Jt ·. ·, 1, 4 ~ '· _to control the polymerization is not associated with measurement -koncentrace ^1' re-11tardéru efficiency in the polymerization that the production of honey and poly-

be regulated directly orútokovo without efficiency ond's changes conditions. ypAirl · ’ is also possible), that way j e, j r o already p o ',' ϊ mt. Efficiency efficiency j

iv Xzie in C _ ν, ί, Χ in c.

to small changes in the conditions. These catalysts can be introduced into the reactor continuously or intermittently.

More efficient catalysts may be used, in particular Siegler-Ratt type catalysts based on magnesium, halogen, titanium or vanadium and / or zirconium. It is also possible to increase the efficiency of these catalysts / catalysts by adding a larger amount of co-catalyst selected from organometallic compounds 1.11 or 111 scurine of the Periodic Table of the Elements, in particular organoaluminum compounds.

It is also possible to use ^a modifier agent of the catalyst rises, especially selektivtíní agent such as an aromatic ester or a silicon compound, which is introduced into the reactor continuously at a constant flow rate and in a determined constant molar ratio with the transition metal catalyst. It is also possible to use a high efficiency catalyst based on chromium (III) alloys with a gelled catalyst. a carrier based on a refractory oxide such as silica, alumina or aluminum silicate, and activated at a temperature of at least 250 ° C and at most at a temperature at which the granules of the carrier can start to glass, preferably at a temperature between. 350 ° C and 1000 ° C.

The high performance catalyst can be used directly as such or in the form of a prepolymer to be converted to a prepolymer with a municipality

The catalyst is contacted by contacting the catalyst with one or more Ifa-olefins in an amount such that the prepclymer thus obtained contains between. -0.002 and 10 mile transient pxxx. metal per gram. These reactants may also be contacted with an orgauometallic compound of the metal I, II or III of the nrriodic table of elements, in an amount such that the ratio of metal in said organometallic compound to the amount of transition metal is between G, 1 and 50, preferably between 0.5 and 20. The highly efficient catalyst used directly or after the pre-polymerization stage is introduced continuously or intermittently into the fluidized and / or mechanically stirred bed of the reactor.

The polymerization is carried out continuously in a fluidized and / or mechanically stirred bed by known techniques and using equipment such as described in French Patent No. 2207145 or French Patent No. 2335526. The process is particularly suitable for very large industrial reactors in which the smallest polymerization change speed can; very quickly lead to undesirable effects such as agglomerate formation. The gaseous reaction mixture containing alia-olefin (s) to be polymerized is generally cooled in at least one heat exchanger located outside the reactor before being recycled. Retarder efficacy can be. fed directly into the reactor, preferably within the reactor zone, where the efficiency retarder disperses rapidly, for example under a fluidization grid. It can also be introduced into the line for recycling the gaseous reaction mixture or into the line for filling the reactor with alpha-olefin (s). If the recycle line comprises means for separating gas from fine particulate entrained solids, such as a slope, and means to recycle these fine particles directly to the polymerization reactor, the efficiency retarder can be introduced at any point in the composition. For gas / solid separation or for a fine particle recycle means.

The efficiency hetarder can be introduced into the reactor at two or more locations, particularly preferably into a line for recycling the gaseous reaction mixture and into the Pseyn / solids seoant, or into the reactor, particularly the soda part of the reactor.

* The polymerization reaction is generally carried out at a pressure of 0.5 to 5 ° C and at a temperature of 0 to 135 ° C. The method is suitable for half-directing one or more alpha-olefins containing from 2 to 8 carbon atoms, especially for the ethylene or crooylene polymerization. . It is particularly suitable for co-polymerization. ethylene with at least one alpha-olefin containing 3 to 8 carbon atoms or oro kooolymeraci propylene with at least one alpha olefin containing 4 ^and 6 carbon atoms such as ethylene and / or conjugated diene NEI. The gaseous reaction mixture may contain hydrogen and an inert gas such as nitrogen, methane, ethane, propane, butane, isobutane or isopentane. When a fluidized bed reactor is used, the fluidization rate of the gaseous reaction mixture passing through the bed is 2 to 10 times. fluidization velocities. The polymer produced is. withdrawn from the reactor continuously or, preferably, intermittently.

Example

The process is carried out on a fluid bed, the gas phase polymerization reactor having a vertical cylinder of 4.5 π diameter and equipped with a velocity reduction chamber. In its easy part there is a fluidization grate and an external gas recirculation line connecting the top of the speed reduction chamber to the bottom of the reactor below the fluidization grate, the gas recycle line being equipped with a circulating gas compressor and heat transfer means. Preferably, the oro feed lines are connected to the gas recycle line through the supply of ethylene, 1-butene, hydrogen and nitrogen, which are the main components of the gaseous reaction mixture passing through the fluidized bed.

Above the fluidization grate, the reactor contains a fluidized bed containing 52 tons of a powder of linear low density polyethylene containing particles having a diameter of 0.7 mm on average. The gaseous reaction mixture, which contains 42% by volume of ethylene, 1% butene, 8% hydrogen and 12% nitrogen, is passed through the fluidized bed at 20 bar and 80 ° C and at a fluidization rate of 0.5 m / s.

The catalyst is identical to the catalyst described in Example 1 of French Patent No. 2405561 which contains magnesium, chlorine and titanium and which has been converted to a prepolymer containing 40 g of polyethylene per millimol of titanium and such an amount of tri-n-octylalaminium (TnOA). that the Al / Ti molar ratio is 0.85 + 0.05 are fed to the reactor intermittently over time. The feed rate of the prepolymer to the reactor was 150 kg / h.

AND

The gaseous mixture containing 9% of nitrogen ^and 2 hours of oxygen (by volume) is continuously fed during polymerization to the ethylene feed line connected to the polymerization reactor. to maintain a linear low-density polyethylene output at a constant value of 13.5 ± 0.4 tonnes per hour, due to undesirable changes in the quality of the catalyst and the reactants used in the process.

Under these conditions, the oxygen content of the ethylene entering the reactor changes with time. 0.1 to 0.3 volumes per million (vpm) and the molar ratio of the amount of oxygen introduced to the amount of ethylene and 1-butene introduced varies from 1.10 to 7.10 It has been found impossible detect the presence of oxygen in the gaseous reaction mixture circulating through the fluidized bed (oxygen content is below 0.1 vpm). * over a number of days of continuous polymerization under these conditions, the emerging polymer remains constant, without agglomerate formation, and the quality of the linear low density polyethylene prepared in this way remains constant and guaranteed, despite accidental changes in efficiency. catalyst and fluctuations. which are unpredictable and difficult to detect in impurities introduced by ethylene, butene and other components of the gaseous reaction mixture. In particular, the carbon monoxide content of the ethylene introduced into the reactor varies. nod or 0.1 vpm.

-16Iříklsd 2 / comparative /

The process is carried out under the same conditions as described in Example 1, except that the gas mixture containing the cartridge is not fed to the ethylene fed to the polymerization reactor.

even these conditions bvio very quickly found that the output of the linear low density polymer varies with time from about 11.5 to 14.5 tons per hour and cannot be essentially maintained / constant that the quality of the prepared polymer varies significantly and that agglomerates are formed molten polymer.

Example 3

The process is performed on a fluidized bed. in a gas-phase polymerization reactor comprising a vertical cylinder having a diameter of 0 mm and a height of 6 m and equipped with a speed reduction chamber. In its lower part, the reactor is provided with a fluidization grate and an external gas recycle line connected to the top of the velocity reduction chamber and the bottom of the reactor.

This pipe is located about from. The gas recycle is also provided with a circulating gas compressor and heat transfer means. Advantageously, an inlet of ethylene, but-butene, hydrogen and nitrogen, which are the main components of the gaseous reaction mixture passing through the fluidized bed, is introduced into the gas recycle line.

Above the fluidization grate, the reactor comprises a fluidized bed containing 400 kg of linear low density polyethylene powder having an average particle diameter of 0.7 mm 2. fteactive gas mixture,

-17containing 50% ethylene by volume, -12% 1-butene, 6% hydrogen · 51% nitrogen and 1% ethane is passed through the fluidized bed at a pressure and κ fluidization rate upward, 6 r? 0.5 m / min.

A catalyst which is idanoic to the catalyst described in Example 1 of the French Chloro-24-C5-containing catalyst, which contains magnesium, chlorine and titanium, and which has been previously converted to a catalyst containing 40 g of polyethylene per miol. titanium, and tri-n-octylsiuminium (OO ^ň ) in an amount such that the molar ratio A / /,, equal to 1.65 + 0.05, is fed to the reactor intermittently over time. The flow rate of the feed to the reactor was 0.7 kg / h.

A solution of dimethylformamide (TW) in isopentane containing 0. CC4 mol DL-IR on Htr is continuously introduced into the gas recycle line during the polymerization. With Sax, the flow rate of this solution varies between 125 ml / h and 300 m'i / h to maintain the linear low-density polyethylene output at a constant value of 100+ 3 kg- per hour, due to undesirable fluctuations in catalyst and reactant quality. used in the process.

Under these conditions. the mole ratio of the amount of DMF that is fed to the amount of ethylene fed and 1-butene fed varies from 1.5 [deg.]? do 5.10 ?. It has been found that it is impossible to detect the presence of DKK in the gaseous reaction mixture that circulates through the fluidized bed (DO content below 0.1 vem). A few days of credit

-18nual ^ olymersce Executed from? under these conditions, the polymer output is constant without agglomerate formation and the quality of the linear low-density polyethylene produced in this way remains constant, regardless of accidental changes in catalyst efficiency and fluctuations that are unpredictable and difficult to detect in ethylene introduced impurities. , 1-butene and other components of the gaseous reaction mixture. From names? the carbon monoxide content of the ethylene introduced into the reactor is generally below. or C value, 1 vr> m *

-18aExample 4

The process is carried out in a fluidized bed gas phase polymerization reactor containing a vertical cylinder of 0.9 ar diameter. and 6 m high and equipped with a speed reduction chamber. At its lower end, the reactor is provided with a fluidization grid and an external gas recycling line connecting the upper portion of the speed reduction chamber to the lower portion of the reactor located below the fluidization grid. The gas recirculation bucket is connected to a gas circulating compressor and heat transfer means. Preferably, ethylene, hydrogen and nitrogen lines are connected to the gas recycle lines, which are the main components of the gaseous reaction mixture passing through the fluidized bed.

Above the fluidization grid, the reactor comprises a fluidized bed containing 400 kg of high density polyethylene powder, which is formed to contain particles having an average weight diameter of 0 ₍ 8 mm). The gaseous reaction mixture contains 35% ethylene, 15% hydrogen and 40% by volume of nitrogen, passes through the fluidized beds at a pressure of 2.0 MPa at 100 ° C and with a fluidization rate of up to 0.4 ms-1.

Chromium oxide catalysts prepared by treating a catalyst available under the trademark EP 30 * from Joseph Crosfield and Sons (England), containing 1 wt. % chromium and 3.8 wt. The titanium, coupled to the silica support, was heat treated at 550 ° C for 4 hours, and converted to an ethylene prepolymer containing 40 g of polyethylene per millimole of tremor. The prepolymerized catalyst thus obtained is simultaneously fed into the reactor at a feed rate of 0.21 kg of prepolymer per hour.

The gaseous mixture containing nitrogen and 262 vpm of oxygen is continuously introduced throughout. polymerization into ethylene feed line; connected to the polymerization reactor. The flow rate of the oxygen-containing gas mixture varies with time between 60 and 120 NlA so as to maintain the output of high density polyethylene at a constant value of 90 kg / h despite undesirable fluctuations in the quality of the catalyst and the reactants used in the process. Under these conditions, the molar ratio of the amount of oxygen introduced to ethylene-7-yne varies from 2 x 10 to 4 x 10. It should be noted that after many days of continuous polymerization under these conditions, the polymer output is kept constant without agglomerate formation. The quality of the high-density polyethylene thus produced remains constant and guaranteed, despite various random variations in catalyst activity and fluctuations in impurities introduced by ethylene, hydrogen and nitrogen. "

Claims (8)

CLAIMS 1. A process for the continuous gas phase polymerization of one or more alpha-olefins in a fluidized bed and / or mechanically stirred bed reactor with the aid of a catalyst and an activity retarder, characterized in that: The process according to claim 1, characterized in that the polymerization is carried out by introducing a transition metal catalyst IV, V. or VI. a periodic classification of the elements in contact with the alpha-olefin (s) and continuously introducing into the reactor an activity retarder in an amount such that the molar ratio of the efficacy retarded to the amount of alpha-olefin (s) introduced is between 10 and 10, flow rate; which varies with time to maintain constant: ¹ % either the polymerization rate or the preferred metal content of the polymer produced, wherein said activity retardant is capable of reducing the rate of alpha-olefin polymerization in the presence of said transition metal catalyst. 2. A process according to claim 1, wherein the efficiency retarder is introduced into the reactor in an amount such that the molar ratio of the introduced retarder is θ. efficiency to the amount of alpha-olefin introduced is 5 x 10 'to 2 x 10' 6, more preferably 10 "? Up to 10O \ Method according to claim 1, characterized in that: that the activity retarder is selected from polymerization inhibitors and electron donor compounds. 4. The method of claim 3 wherein the polymerization inhibitor is selected from the group consisting of carbon monoxide, carbon dioxide, carbon dioxide, carbon oxysulfide, nitrogen oxides and peroxides, alcohol in, thin, aldehydes, ketones. , oxygen ^Λ water, fich 5. The method of claim 5 wherein the electron donor compound is selected from the group consisting of amines, amides, fossils, sulfoxides, sulions, esters, ethers, and thioether. Method according to claim 1, characterized in that the catalyst is a Ziegler-Nattovs n-type catalyst based on magnesium, halogen, titanium and / or vanadium and / or zirconium. 7. The method according to claim ¹ , characterized in that it is a catalyst. the flood is a catalyst for. chromium oxide base · combined with granulated carrier based on radiant / resistant oxides and is heat activated. 8. Method according to ¹ '; 1, characterized in that the alpha-olefin (s) contain from 2 to 5 carbon atoms. * 9. Process according ^to · -'- 1, characterized in that polymeřade Se 'Performs-pressure at ^ \ Q, SZ 5 5 -KFa · - and - ^{Ώ ϋ} temperature .. transversely from 0 to 155 ° C . ·