JPH06511035A - Catalyst activation in high temperature ethylene polymerization - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] name of invention Activation of Catalyst in High Temperature Ethylene Polymerization The present invention is directed to the activation of catalysts in high temperature ethylene polymerization. Methods for producing homopolymers of ethylene and copolymers of ethylene and higher α-olefins and production catalysts. The invention particularly provides for Also using methods of working at degrees and alcokylalkyl aluminum compounds Concerning activated catalysts.

Polymers of ethylene, such as homopolymers of ethylene and ethylene and higher α-ols. Copolymers with lefins have a wide range of end uses, such as films, fibers, and molding. It is used in large quantities for forming molded or thermoformed products, vibrator coatings, etc.

The production of polyethylene involves monomers in an inert liquid medium in the presence of a coordination catalyst. Two types of methods encompass the polymerization of the polymer, i.e., at temperatures below the melting point or melting temperature of the polymer. and at temperatures above the melting or dissolution temperature of the polymer. There is something to work with. The latter is called the "solution" method, an example of which was published in April 1963. Anderson (A, W. Anderson), 7r-Roux, patented on 9th. Elle (E, L, Fal1wel+) and Bruce (J, M, Bruce) It is described in Nadda Patent No. 660°869. In the solution method, monomers and polymers This can be achieved by controlling political change. In the solution polymerization method, for example, The process is operated at extremely high temperatures of 250°C and the heat of polymerization is used to control the resulting polymerization. It is advantageous to flash off the solvent from the body solution.

This method involves a step of removing the catalyst from the polymer following the polymerization step. Although solution polymerization methods are preferably operated without a catalyst removal step, . The catalyst will therefore remain in the polymer.

This type of catalyst, which may also be called “catalyst residue”, is responsible for the coloration of the resulting catalyst. Possible sources of polymer degradation during or following the processing step of the polymer. There is a possibility that this could be the cause. The amount of catalyst residue depends, at least in part, on the process. It is related to the total activity of the catalyst used in the synthesis step, and generally speaking, the higher the total activity of the catalyst, the lower the tolerance. Less catalyst is required to carry out the polymerization at an acceptable rate. Therefore, the melt Catalysts with relatively high total activity are preferred for liquid polymerization processes.

Two important factors in determining the total activity of a catalyst are the instantaneous activity of the catalyst and the operating conditions. The stability of the catalyst at low temperatures, especially at operating temperatures. Extremely active in low temperature polymerization methods Many catalysts that are described as having a Although it also shows high instantaneous activity, it tends to decompose within an extremely short period of time in solution methods. with disappointingly low overall activity. This type of catalyst is There is no commercial interest in the law. Other catalysts are acceptable even at high temperatures in the solution process. Polymers with acceptable overall activity but with a broad molecular weight distribution or wide dry range are useful. to provide polymers with molecular weights that are too low to be commercially useful in the manufacture of products. It's completely different.

The production of ethylene polymers by solution polymerization is described in the publication dated November 14, 1991. Ground squirrels (D, J, G11lis), Huran (M, C).

Hugheson) and Zporil (V, G, Zbor i1) Public PCT Patent application number W091/17193 and the patent publications cited therein. stated in the application. Catalysts activated by siloxalane are exposed to extremely high temperatures. Although it is possible to polymerize ethylene at The run residue is removed from the solvent in the solvent recovery section and recirculation section accompanying the polymerization method. tend to have a significant detrimental effect on the performance of the adsorbent used for purification. has a direction.

Catalyst activity and Additions to Ziegler-Natsuta catalysts to increase stereospecificity and/or stereospecificity. Extensive prior art exists regarding the use of various electron donors as additives. Yoshi Esters, ethers and alcohols of aromatic acids such as toluic acid or benzoic acid metals are often used for this purpose, but most electron donors are useful at low temperatures. The body destroys catalytic activity as the polymerization temperature increases. As an example of the use of electron donors Creamers (H, M, J, C, C) patented on June 27, 1978. U.S. Pat. discloses a low temperature polymerization process operating at temperatures in the range of 00°C and includes examples of activators thereof. The list includes dimethyl monobutoxyaluminum, monodecylpropoxyal chloride Contains aluminum and hydrogenated monobutoxyaluminum.

As exemplified below, trialkylaluminum can be partially added to U.S. Pat. Replaced by alkoxyalkylaluminum of the type used in 97659. For example, at a temperature of no more than 130°C, i.e. at the lower temperature limit of solution polymerization, This also results in a considerable decrease in catalytic activity.

Surprisingly, this trend of decreasing catalytic activity at higher temperatures is reversed. , the alkoxyalkyl aluminum activated catalyst is heated to a temperature of about 180°C or higher. It has now been found that this compound exhibits excellent activity.

Therefore, the present invention provides ethylene and/or ethylene and Cs-C1z higher α- of a catalytic amount of titanium-containing coordination catalyst in an inert solvent in a mixture with an olefin. homopolymers of ethylene by polymerization at temperatures above 105°C in the presence of and a glue made of a copolymer of ethylene and a C3-CI2 higher α-olefin. In a solution process for the production of high molecular weight polymers of α-olefins selected from (a) The catalyst is prepared by a solution of alkoxyalkylaluminum in an inert solvent. It is activated by: (b) operating the process at least partially at a temperature of at least 180°C; Provide improvements featuring:

The present invention further provides the method of polymerizing the monomer at a temperature in the range of 180-320°C; The coordination catalyst is formed from a first component and a second component, the first component being the second component contains alkoxyaluminum alkyl and titanium; Glue made of a mixture of aluminum alkyl and aluminum alkoxyalkyl selected from the loop, and each of RSR' and R' in the formula is the same. Alkyl, which may be present or different, uniquely having 1 to 20 carbon atoms X is halogen, n is 1-3, and , m is 0-2, and ethylene and at least 1 a monomer selected from the group consisting of mixtures with species of CS-CO and higher olefins; monomer, coordination catalyst, and an inert hydrocarbon solvent to the reactor, and recovering the polymer thus obtained. Homopolymers of ethylene and copolymers of C3-C, □higher α-olefins, etc. A solution method for producing high molecular weight polymers of α-olefins selected from the following groups: It also provides law.

In a preferred embodiment of the process according to the invention, R has 2-8 carbon atoms. alkyl with n=3, and R' and R' each have 2-8 carbon atoms. Alkyl having a child, m=2.

In one embodiment of the method according to the invention, the second component is trialkylaluminium. The form of a mixture of aluminum and alcohol, the amount of alcohol being dialy less than the stoichiometric amount to form the kylalkoxyaluminum (especially if is a trialkylaluminum in which each R3 has 1-10 carbon atoms. AIR's, which are alkyl groups, and alcohols have R4 of 1 to 20 carbon atoms in the formula. Formula R in which the atoms are in particular alkyl or aryl having 1-16 carbon atoms It is of 40H.

In other embodiments of the method, the first component: (i) has a combination of R' and R2; Each may be the same or different (ij) reactive chloride component, and Beauty (ffi) Titanium tetrachloride formed from.

Alternatively, tetrahalide nitrogen optionally containing vanadium oxytrihalide A solution of tanium is added to an organoaluminum compound, such as a trialkylaluminium. or rapidly mixed with a dialkyl aluminum halide at a temperature below 30°C. , the resulting mixture is heated to a temperature of 150-300'C for a period of 5 seconds to 60 minutes. The first component can also be formed by

In other specific examples of the method, the first catalyst component and the second catalyst component are The formation and mixing thereof are carried out in-process at temperatures below 30°C.

The present invention is directed to a method for producing high molecular weight polymers of α-olefins. These types of polymers can be processed into articles by extrusion, injection molding, thermoforming, rotational molding, etc. is intended. The above-mentioned α-olefin polymers are particularly produced by homopolymerization of ethylene. and ethylene and higher α-olefins, i.e. ethylene series α-olefins. In particular, higher α-olefins of this type having 3 to 12 carbon atoms, such as C3'''CI, examples of which are 1-butene, 1-hexene and 1-octene. It is a copolymer with two higher olefins. Preferred higher α-olefins are 4-10 carbon atoms. In addition, cyclic endomethylene In the method described in the present invention, monomers, a coordination catalyst and an inert hydrocarbon solution are used. A medium and optionally hydrogen are fed to the reactor. Monomers include ethylene or ethylene. and at least one C3-cu higher olefin, preferably an olefin. ethylene or ethylene and at least one C4-C+O higher alpha-olefin ethylene Mixtures with olefins are possible; α-olefins are understood to be hydrocarbons. Probably.

The coordination catalyst is formed from two components: a first component and a second component. . The first component is titanium or other transitions thereof with a valence state lower than the maximum valence. Organometallic compositions of the type typically used in solution polymerization processes, containing mixtures with transfer metals. It's a minute. The first component may be in solid form. An example of the first component is given above. be.

The second component is alkoxyalkylaluminum or aluminum alkyl. is a solution in an inert solvent of a mixture with an alkoxyalkylaluminum: a mixture The ratio of aluminum alkyl to alkoxyaluminum alkyl in the product is Can be used for process control. Aluminum alkyl has the formula AIR,X, - , later, and the alcoquine aluminum alkyl has the formula AIR', ○R'31. in which R, R' and R' each have 1-20 carbon atoms. alkyl or aryl having a halogen, especially fluorine, chlorine or n is 1-3 and m is 2. A preferred halogen is chlorine.

The above alkoxyaluminum alkyls correspond to the corresponding alkylaluminums. The corresponding alcohol and alkoxyaluminum alkyl form. In fact, the A preferred method of forming component 2 is to convert all alkyl aluminum into alkoxy less than the stoichiometric amount required for conversion to sialumium alkyl. Alcohol is added to aluminum alkyl. This mixing is done in-process. , the reaction can be conveniently carried out at temperatures below 30°C, allowing the reaction to occur for several minutes. child The time will vary depending on the type and reactivity of each component used to make a particular catalyst. Ru. As illustrated below, it is possible to feed alcohol directly into the reactor during the polymerization process. is disadvantageous to the polymerization process.

Alkyl aluminum versus alcohol used to achieve control of the polymerization process. The ratio is in the range 0.1-1 (alcohol/aluminum).

The concentration of each component in the solution used to manufacture the catalyst is not critical, and is mainly determined by actual conditions. Governed by the above considerations. Concentrations as low as 25 ppm by weight are also used. higher concentrations, e.g. 1100 pp and above, are preferred. Yes.

As exemplified below, a series of steps in the production of a catalyst are used to obtain a highly active catalyst. It is important for

The coordination catalyst described in this specification does not allow separation of any components of the catalyst. used in the method described in the present invention. In particular, the liquid fraction is also The solid fraction is also not separated from the catalyst. In addition, the catalyst and its components are slurry isn't it. All components are shelf-stable liquids that are easy to handle.

For example hexane, heptane, octane, noclohexane, methylcyclohexane and hydrogenated naphtha. The solvent used in the production of the present catalyst is preferably is the same as that supplied to the reactor for the polymerization process.

The first component of the catalyst described herein is prepared in solution according to the method described in the invention. over a wide temperature range that can be used in alpha-olefin polymerization processes operating under It can be used as For example, this polymerization temperature includes 105-320°C. Ranges are possible, particularly from 105-310'C, but as exemplified below. This deactivator is particularly efficient at temperatures of 1800C and therefore The methods described are limited (and partly work at high temperatures of this type).

The pressures used in the process according to the invention are those known for solution polymerization, e.g. The pressure is in the range 4-24-2O.

In the process according to the invention, α-olefin monomers are introduced into a reactor in the presence of a catalyst. Polymerize below. Pressure and temperature are controlled so that the polymer formed remains in solution. control

Improved control of melting index and/or molecular weight distribution, resulting in more uniform production To aid in the production of the compound, as disclosed in Canadian Patent 703.704, 1-100% by weight based on the total amount of solution fed to the reactor. Amounts of ppm of hydrogen can be added to the feedstock.

The solution exiting the polymerization reactor typically deactivates any catalyst remaining in the solution. processed for. Various catalyst deactivators are known, including fatty acids, Alkali metal salts of group carboxylic acids, alcohols, and hydrocarbon solutions used as deactivators. The medium is preferably the same as the solvent used in the polymerization step. using different solvents If used, it is miscible with the solvent used in the polymerization mixture and is compatible with the polymerization process. must not cause adverse effects on the solvent recovery system associated with .

After deactivating the catalyst, the solution containing the polymer is passed through a bed of activated alumina or voxel. to partially remove deactivated catalyst residues and/or other impurities. It is also possible to remove the deactivated catalyst completely, but it is also possible to carry out the process without removing the deactivated catalyst. It is preferable to activate it. The solvent can then be flashed off the polymer. This can then be extruded into water and cut into suitable fine shapes such as pellets. Can also be done. The recovered polymer was then treated with saturated steam at atmospheric pressure to For example, the amount of volatile substances can be reduced and the hue of the polymer can be improved. This place The treatment can be carried out for about 1 to 16 hours, followed by passing the polymer through a stream of air for about 1 to 16 hours. Allow to dry for 4 hours and cool. The polymer is first formed into fine shapes such as pellets. Pigments, antioxidants, UV blockers, and shielding amino acids can be added to the Additives such as light stabilizers can be added to the polymer.

In each specific example, the antioxidant mixed into the polymer obtained from the process described in the present invention A single antioxidant, e.g. a shielding phenolic antioxidant, can also mixtures, e.g. shielding films in combination with secondary antioxidants e.g. phosphites. Enolic antioxidants are also possible. A range of 5:1 is possible for both, and antioxidant The total amount of inhibitor ranges from 200 to 3000 ppm.

The process according to the invention comprises a homopolymer of ethylene and, for example, about 0.900-0 ．． 970 g/cm3, especially in the range 0.915-0.965 g/cm" Can be used to produce copolymers of ethylene and higher α-olefins with : having a density of more than this, for example about 0.960 g/cm3, or more The polymer is a homopolymer.

This type of polymer was measured by the method of ASTM D-1238, Condition E. For example, it can have a melting index in the range of about 0.11-120 d/min. Polymerization The body can be produced with either a narrow or wide molecular weight distribution. Can be done. For example, the subject polymers may range from about 1.1-2.5, particularly about 1.3- It can have a stress index, which is a measure of molecular weight distribution, in the range of 2.0.

The stress index was calculated using the A37M Melt Index Test Method procedure and the following formula: Measuring flow rate of melt indexer by force (load of 2160g and 6480g) and decide. Values of stress index below about 140 indicate a narrow molecular weight distribution; Values above indicate a wide molecular weight distribution.

The polymer produced by the method described in the present invention is a homopolymer of ethylene or the following method. In the examples, the following method was used unless otherwise noted.

The reactor has a free volume of 8, equipped with 6 regularly spaced internal baffles. In a pressure vessel of 1 m1 (regular internal shape with dimensions of approximately 15 x 90 mm) there were. The vessel consists of a six-blade turbine-type impeller, a heating jacket, and a pressure Equipped with controller and temperature controller, three supply lines and a single discharge It was. The supply pipes are connected to the top of the container at intervals of 4Qmm in the radial direction from the shaft. The discharge pipe was located in the axial direction of the stirrer drive shaft. catalyst precursor The reactants, such as the Activated alumina bed, molecular alumina bed and silica bed before ripping. It was purified by passing it through a double bed.

A cyclohexane solution produced by dissolving purified gaseous ethylene in a purified solvent. of ethylene was metered into the reactor. By adjusting the feed rate of catalyst components, The desired conditions were prepared within the same period. The desired retention time in the catalyst piping is determined by the amount of time each component passes through. This was achieved by adjusting the length of the piping. The retention time in the reactor depends on the solvent flow into the reactor. The volume was adjusted and kept constant so that the total flow rate remained constant. Reactor pressure is 7.5M Temperature and flow rate were kept constant throughout each experiment.

The initial (unconverted) monomer concentration in the reactor was 3-4% by weight.

Toluene or cylindrical deactivators i.e. triisopropanolamine or nonanoic acid When the solution in chlorohexane is introduced into the reactor discharge piping, the reactor outflow is as follows: Kp = (Q/(1-Q)Xi/HUT) (1/catalyst concentration) defined as .

In the above formula, Q is the fraction of ethylene (monomer) converted to polymer, and HUT is the reactor retention time in minutes, the catalyst concentration is in mmol/1, and the impurity This is the concentration in the reaction vessel corrected for that. Catalyst concentration is based on the total amount of transition metals This is the value. Polymerization activity (Kp) was calculated.

The invention will be illustrated by the following examples. Unless otherwise noted, each example The solvent used was cyclohexane, the monomer was ethylene, and the reaction The vessel holding time was kept constant at 30 minutes.

Example I Dibutylmagnesium, triethylaluminum, tert-butyl chloride and tetrachloride Each cyclohexane solution of titanium was injected into the process at ambient temperature (approximately 30°C). Mix to produce a catalyst, followed by further addition of triethylaluminum cyclohexane. solution was added. The concentration and flow rate of each species were determined to give the following molar ratios: Adjusted to: Chlorine (from tert-butyl chloride)/Magnesium = 2.4 + Mag. Netium/Titanium = 5. O; Aluminum (first triethyl aluminum)/titanium = 09 aluminum (second triethylaluminum)/titanium = 3.0° Reactor polymerization Work was carried out at a temperature of 230°C as measured in the reactor. To the above Mg and AI2/Mg The ratios reported for Mg/Ti and A, ]l/Mg are as follows: This is the optimized ratio required to obtain maximum catalytic activity.

In trials 2 and 3, catalyst production was carried out at 1 molar equivalent (per mole of A12). 3-butyl alcohol to the second part of triethylaluminum (therefore the alcohol Same as above except that oxide formation) was added.

1 2.4 5.0 0.9 3.0 None 230 13.92 2.2 5 ．． 0 0.9 6.0 t-butanol 230 31.73, 2.4 5 ．． 0 0.9 3. Ot-butanol 230 4.84 2.3 5.0 0 ．． 9 3.0 Phenol 230 30.45 2.2 5.0 0.9 3 ．． 0 Ethanol 230 24.962・3 5.0 0.9 4.5 n- Decanol 230 24,17 2.2 5.0 0.9 3.0 Neopen Chill 230 29.3 alcohol 8 2.3 5.0 0.9 6゜Ot-Butanol” 230 2.7 Note 1 Ratio of triethylaluminum to titanium in the first addition Kp: Calculated polymerization rate constant. 1/mmol/min3 Added to the reactor in addition to the catalyst In t-butanol trials 1.2 and 3, the ratio of catalyst components for the alkoxide system was , the type and composition of other catalyst components, and the mode of operation of the process. has a significant effect on the expected increase in activity. However, it has also been shown that the catalytic activity can be increased by more than twice. This is to clarify. In Trial 3, compared to Trial 2, the catalytic activity was determined by the ratio of the components. It explains that it is sensitive and can be used for process control.

Trials 4.5.6 and 7 also illustrate the use of alcohols other than tert-butanol. It is.

Trial 8 added alcohol directly to the reactor rather than to the second triethylaluminum stream. Explain the disadvantageous effects of adding chlorine. This result shows that the alkoxydialkyl This indicates that prior formation of aluminized type is necessary.

! JL pot■ As a comparison with other known activators for high-temperature polymerization, the active and monomerizing agents shown in Table ① The procedure of Example I was repeated using and reaction temperature. The results obtained are as follows. It was ri.

Table■ 9 2.3 5.0 0.9 6. OBUODEAL200 93.710 2 ．． 2 5.0 0.9 6. OBUODEAL230 31.711 2.3 5.0 0.9 6. OB’UODEAL260 1.412 2.3 5.0 0.9 3.0 DESI 200155.713 2.3 5.0 0.9 3.0 DESI 230 35.414 2.4 5.0 0.9 3.0 DESI 260 9.115 2.2 5.0 0.9 1.5 DIBL O20058,0162,35,00,91,5DIBLO23016,21? , 2.2 5.0 0.9 1.5 DIBLO2602,8182,25, 00,91,5TEAL 230 13.9BUODEAL t-butoxydie Chillaluminum DESI Diethylaluminum Ethyldimethylsiloxane D IBLO diisobutylaluminoxane TEAL triethyl aluminum 1 Molar ratio of triethylaluminum to titanium 2 Titanium as activator Molar ratio Kp to umum 1/mmol/min This example shows a comparison with other activators by t-butoquinone ethylaluminum. shows the relative improvement in catalytic activity at elevated temperatures.

Example■ of titanium tetrachloride, vanadium oxytrichloride and diethylaluminum chloride. The catalyst was prepared from a cyclohexane solution. Add hot cyclohexane solvent to The mixed solution was heat treated at 205-210°C for 110-120 seconds. Then, activate The catalyst was activated by adding a activating agent. The polymerization reactor was operated at the temperatures shown in Table ■. . The solution flowing out of the reactor was deactivated as described above, and the polymer was recovered. catalyst Activity was calculated. The results obtained were as follows. In any trial Also, (number of moles of Ti)/(number of moles of ■)=1.

Table■ 19 1.0 4. OTEAL 200 72.820 1.1 2.0 TE AL　230　20.021　1.1　2. OTEAL 260 5.322 1.1 2.7 DESI 230 33.123 1.0 2.7 DESI 260 11.524 1.0 1.3 DIBLO20071, 7251, 0L3 DIBLO23021,7261,01J DIBLO2606,42 7' 1.0 2. OBUODEAL 200 123.528 1.0 2. OBUODEAL 230 37.929 1.1 2. OBUODEAL 2 60 11.7 BUODEAL t-butoxydiethyl aluminum DESI Diethylaluminum ethyldimethylsiloxane DIBL○ Diisobutyral Molar ratio to total amount of minoxane 2 Ratio to the total amount of titanium and vanadium in the activator This example was obtained using t-butoxydiethylaluminum as the activator. It explains the improvements that can be made.

Example■ To compare the use of aluminum alkoxydialkyl with other activators, 1 The procedure of Example 1 was repeated using a reactor temperature of 30°C.

The results were as follows.

30 1.0 2. OTEAL 130 23131 1.2 2.7 DES I 130 8932, 1.1 2.0 DIBLO130292331, 03,5'BUODEAL 130 75BUODEAL t-butoxydiethyl Aluminum DES I Diethylaluminium Ethyldimethylsiloxane D IBLO diisobutylaluminoxane TEAL triethyl aluminum 2 Molar ratio of activator to the total amount of titanium and vanadium This example demonstrates the use of an alcoquine alkylanobenium as an activator. This also explains the poor low-temperature activity and therefore the surprisingly good high-temperature activity of the combined catalyst. It is.

Copy and translation of amendment) Submission (Article 184-8 of the Patent Law) March 31, 1994

Claims (11)

[Claims] 1. Ethylene and/or mixture of ethylene and C3-C12 higher α-olefin the compound containing a catalytic amount of titanium in an inert solvent in the presence of a catalyst, Homopolymers of ethylene and ethylene and C by polymerization at temperatures above 105°C α- selected from the group consisting of copolymers with 3-C12 higher α-olefins In a solution process for the production of high molecular weight polymers of olefins: (a) the catalyst is activated by a solution of alkoxyalkyl aluminum in an inert solvent; It is something that has been made into; (b) operating the process at least partially at a temperature of at least 180°C; An improvement characterized by: 2. The monomers are polymerized at temperatures in the range of 180-320°C, and the coordination catalyst is It is formed from a first component and a second component, and the first component is titanium. the second component is alkoxyaluminum alkyl and alkyl alkyl. selected from the group consisting of mixtures of aluminum and alkoxyalkylaluminium. and the aluminum alkyl is of formula AlRnX3-n. and the alkoxyalkyl aluminum is of the formula AlR'mOR'3-m. Yes, even if R, R' and R'' in the above two formulas are the same, they are different. independently alkyl or aryl having 1-20 carbon atoms; X is a halogen, n is 1-3, m is 0-2, and ethylene and ethylene and at least one C3-C1, characterized in that A monomer selected from the group consisting of a mixture with two higher α-dimensional olefins, a coordination catalyst, supplying a medium and an inert hydrocarbon solvent to a reactor to polymerize the above monomers, Homopolymer of ethylene by recovering the polymer thus obtained and a glue made of a copolymer of ethylene and a C3-C12 higher α-olefin. A solution process for the production of high molecular weight polymers of α-olefins selected from the following. 3. R is alkyl having 2-8 carbon atoms, n=3, and R ' and R'' are each alkyl having 2-8 carbon atoms, and m= 2. The method according to claim 1 or claim 2, characterized in that: 4. The first component above optionally contains vanadium oxytrihalide. A solution of titanium genide and organic aluminum are rapidly mixed at a temperature of 30°C or less. , the resulting mixture is heated to a temperature of 150-300°C for a period of 5 seconds to 60 minutes. The method according to claim 3, characterized in that the method is obtained by: 5. The above second component is in the form of a mixture of trialkylaluminium and alcohol. The amount of alcohol in the form of dialkylalkoxyaluminum is Claim 3 characterized in that the amount is less than the stoichiometric amount for producing Method described. 6. The above trialkyl aluminum is AlR33 and each R3 is 1-1 is an alkyl group having 0 carbon atoms and the above alcohol has the formula R4OH. alkyl or aryl of which R4 has 1-20 carbon atoms; The method according to claim 5, characterized in that: 7. The first component above is: (i) Each of R1 and R2 may be the same or different; M each independently selected from alkyl groups having 1-10 carbon atoms a mixture of gR12 and AlR23; (ii) a reactive chloride component; and (iii) Titanium tetrachloride 4. The method according to claim 3, wherein the method is formed from: 8. If the above organoaluminum compound is trialkylaluminum or halogen 5. The method according to claim 4, wherein the dialkylalkyl is dialkylalkyl. 9. The method according to claim 7, wherein the halide is a chloride. Law. 10. Forming and mixing the first catalyst component and the second catalyst component in a step of 3 4. Process according to claim 3, characterized in that it is carried out at a temperature below 0<0>C. 11. Use of the above coordination catalysts without separating any of their components 11. A method according to any one of claims 1-10, characterized in that: