NO155057B - PROCEDURE FOR PREPARING POLYMERS OF 1-OLEFINES WITH 2-8 CARBON ATOMS AND COPOLYMERS OF THESE OLEFINES AND 1-OLEFINES WITH 2-20 CARBON ATOMS. - Google Patents

Description

The present invention relates to a method for producing

ling of polymers of 1-olefins with 2-8 carbon atoms and copolymers of such olefins and 1-olefins with 2-20 carbon atoms

atoms. In this method, a new type of catalysis is used

tor produced by, on a finely divided inorganic oxide carrier material"

to distribute a reaction product between a more specific chromium carboxylate and an organic nitrogen compound which can form a complex with trivalent chromium.

In US patent 3,953,413 chromium chelates of beta-dicarbonyl compounds are described as catalyst components, and in US patent 4,196,098 catalysts and methods for the production of such with low-valent chromium surface molecules as active components and which are produced especially from chromium carboxylates are described , aminocarboxylates or nitrogen-hetero-

cyclic carboxylates.

According to the present invention, a

process for the production of polymers of 1-olefins -

with 2-8 carbon atoms, and copolymers of these olefins and 1-olefins with 2-20 carbon atoms, where the olefins polymeri-

are under polymerization conditions with a catalyst prepared by dispersing on a finely divided, difficult to reduce

bare, inorganic supports, which are silicon dioxide, aluminum oxide, thorium dioxide, zirconium oxide, titanium oxide, magnesium oxide or a mixture or combination thereof, of a reaction

product based on a chromium carboxylate with the formula:

where R is hydrogen, an alkyl, alkenyl, aryl, or aryl

alkyl, cycloalkyl or cycloalkenyl radical or a combination of these radicals, the group R having 0-30

carbon atoms and a corresponding amount of valence-saturating hydrogen atoms, m is an integer of 1-3, n is an integer of

0-2, m + n is 2 or 3, and X is a negative group in ratio

to chromium, and this method is characterized by the fact that the reaction product is formed by reacting the chromium carboxylate with an organic nitrogen compound which can form a complex with trivalent chromium, with the formula:

where R' is hydrogen or a lower hydrocarbon substituent, j is an integer of 1-3, and Y is a divalent radical,

and by activating the mixture obtained after the dispersion on said carrier by heating to a temperature of 316-1094°C in a non-oxidizing gas atmosphere.

Chromium carboxylate is preferably used as chromium (III) formate, chromium (III) acetate, chromium (III) propionate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) benzoate, chromium naphthenate or chromoleate. Ethylenediamine, propylenediamine, 1,3-diaminepropane, diethylenetriamine, triethylenetetramine, 3,4-diaminotoluene, 2,2<1->bipyridine,

2,2'-dipyridylamine, di-2-pyridyl ketone, aniline and diphenylamine.

An appropriate and general method for producing said reaction products for use as a catalyst component in the present invention is to heat and evaporate to dryness an aqueous solution containing a nitrogen compound as described and a chromium carboxylate as defined above, preferably in the molar ratio that corresponds to their coordination stoichiometry. For example, in a system using ethylenediamine and chromium(III) acetate the preferred molar ratio would be 3:1. Similarly, non-aqueous media can be used in place of an aqueous mixture when one or both of the reactants are not soluble in water,

or when the presence of water interferes with or unnecessarily complicates the formation of the desired reaction product.

In certain cases, a mixture of the reactants can be heated without solvent to or above the melting point to form a desired reaction product which is used as a catalyst component. In general, the formation of chelates or complexes can be detected by color changes or by the heat of reaction. The raw product, which is produced according to various methods, is usually purified by known methods such as washing, rinsing, extraction, recrystallization, etc.

The reaction product obtained as indicated above is assumed

to generally contain a mixture of closely related N,N chelates or arylamine complexes of trivalent chromium of different composition, essentially of the formula

where Z denotes one of the previously indicated nitrogen compounds which can complex the trivalent chromium, p is an integer of 1-3 if Z is a bidentate, but can be up to 6 if Z is an arylamine, q is an integer of 0-3 depending on Z, p, R and the conditions to which the reaction product is exposed, and X, R, m and n have previously indicated meanings. A typical reaction product produced by heating and evaporating to dryness an aqueous solution of ethylenediamine and chromium triacetate with a molar ratio of 3:1 appears to contain, among other things, tris(ethylenediamine)-chromium triacetate, bis(ethylenediamine)-chromium triacetate, bis(ethylenediamine)-aquachromium triacetate, ethylene -diaminediaquachromium triacetate etc. Logically, all or some of the complexed compounds found in the reaction product should also be suitable as catalyst components, regardless of their origin or method of their preparation. Among all the possible variants described above, those which are strongly complexed by the nitrogen compound but less strongly complexed by the water molecule and which essentially have the formula are preferred

where Z, R and X are compounds and groups defined earlier in connection with the reactants, p' denotes an integer of 2 or 3 if Z is a bidentate such as ethylenediamine, but 1 or 2 if Z is a tridentate such as diethylenetriamine, q ' denotes an integer of 0 or 1, m an integer of 1-3, n an integer of 0-2 and m plus n an integer of 2 or 3. Ideally, both q' and n will be equal to O , p' is equal to 3 if Z is a bidentate, and a typical compound in this case is tris(ethylenediamine)chromium triacetate.

When producing the catalyst used according to the present invention, a number of steps are used which

follows, some of which are optional as indicated.

Pretreatment of the carrier material.

The catalyst support selected from silicon oxide, aluminum oxide, zirconium oxide, thorium oxide, magnesium oxide, titanium oxide or mixtures and combinations thereof resulting from co-precipitation, impregnation, vapor phase deposition etc.,

may have surface areas ranging from a few m<2>/g to over 700 m<2>/g, but preferably higher than 150 m<2>/g. The pore volume is preferably above 0.5 cm<2>/g if the surface area is mainly associated with micropores. A finely divided non-porous carrier with a relatively high surface area such as "Cab-O-Sil" can also be used in the present invention.

Although it is not necessary, a pretreatment of the support before impregnation with the selected organic chromium compound is often preferred. Such pretreatment typically consists in adjusting the carrier's moisture content by drying at an elevated temperature or chemical modification with compounds containing metals such as zirconium, titanium, boron, vanadium, tin, molybdenum, magnesium, hafnium or the like. Such chemical change can consist of introducing compounds such as ammonium hexafluorosilicate which can react with the carrier or with the organic chromium compound during activation. Chemical modification with metal alkyls that react with the carrier can also be used.

The chemically modified carrier, especially when used

aqueous solution impregnation, is usually calcined at an elevated temperature to bind the modifying compound to the support and to drive off excess moisture, in much the same way as setting the moisture content of unmodified support. The calcination or drying step is normally carried out at temperatures of 149-1094°C and can be done by any known method such as e.g.

in a muffle furnace or in a heated fluidized bed with gases such as nitrogen, air, carbon monoxide or other suitable reactive or inert gases as fluidizing agents.

Dispersion of the chromium-containing compound on the support. Dispersion of the chromium-containing compound or mixture

on the carrier can be done in a simple way by ordinary impregnation with an aqueous or organic solvent such as e.g. methanol, acetone, toluene or hexane. Equally satisfactory dispersion or distribution is often achieved by an easier method which uses dry mixing of the chromium-containing compound or mixing with the carrier and carries out final dispersion during the initial stages of activation. If such a dry mixing method is used, the subsequent activation is best carried out in a fluidized bed. The optimum chromium content in the catalyst depends on the type of support, surface area and pore structure. With a typical carrier with a surface area of 100-800 m<2>/g and a total pore volume of 0-3.0 cm<3>/g, the chromium content can be in the range of 0.05-10%, preferably 0.1-2.0 wt. -% on a dry basis.

Thermal activation of the catalyst in a non-activating atmosphere.

The non-oxidizing atmosphere used in the catalyst production is made up either of an inert gas such as nitrogen, helium, argon etc., of a reducing gas such as carbon monoxide, hydrogen etc. or by evacuation to a sufficiently high vacuum. In the latter case, it is advantageous to allow a smaller quantity of non-oxidizing gas to be introduced.

In all cases, mixtures of non-oxidizing gases can be used if desired.

When the activation is carried out in a non-oxidizing (inert or reducing) gas atmosphere, either a stationary layer or a fluidized layer can be used. Experience shows, however, that a fluidized bed is best. For economic reasons, oxygen-free nitrogen is normally used to fluidize the catalyst in an activator. It was found experimentally that even a small contamination with oxygen during activation usually had a destructive effect on the catalyst activity and that such an adverse effect is greatly increased when the chromium level is reduced to approx. 0.15% from a more typical value of 1% by weight, often to the extent that the catalyst is completely deactivated.

The activation step is normally carried out according to a specific heating cycle which consists of heating the catalyst to a specific temperature, usually in the range of 454-1094°C, keeping the catalyst at this temperature for a specific time, usually from 30 minutes to 12 hours, followed by cooling to room temperature in a nitrogen atmosphere. The heating scheme may also include one or more residence periods at temperatures below the maximum temperature to enable diffusion of moisture, solvent or gas products from the catalyst's pores or to enable reactions such as decomposition of the organic chromium compound on the surface. The final activation temperature can usually be chosen on the basis of several factors such as the desired properties of the manufactured polymers, the type of carrier material, pretreatment etc. The heating rate at temperatures above approx. 316°C is usually not critical.

Polymerization processes.

Said catalysts can be used in the present method in liquid phase, solution or slurry or in vapor phase. When prepared in the liquid phase, any C^-C-^ saturated liquid hydrocarbon can be used as reaction medium or diluent. Other types of solvents are aromatic hydrocarbons and chlorinated hydrocarbons. Polymerization of 1-olefins can be carried out batchwise or continuously. The catalyst is usually added to the reactor as a slurry in the case of a continuous process, but as a dry powder in the case of a batch process. The filling method for solvent and olefin on the reactor system can follow any known practice related to batch or continuous operation respectively. Vigorous stirring of the reaction mixture is naturally preferred and likewise the provision of sufficient cooling means for regulating the reactor temperature.

In liquid phase processes, the olefin polymer or copolymer is normally recovered by depressurizing the solvent without an intermediate step to remove the catalyst. The activity of the catalyst used is normally over 300 kg of polymer per kg catalyst so that it is unnecessary for practical reasons to remove the catalyst. The reactor conditions depend on the type of olefin and the desired polymer.

For ethylene, the reactor pressure can be in the range 446.1-6895 kPa, the temperature 66-260°C and dry matter content 5-60% by weight.

The following examples illustrate the invention.

Example 1

The reaction product between chromium (III) acetate and ethylene diamine used in this example was prepared in the following way: 15 g of ethylene diamine and 19 g of chromium (III) acetate were dissolved in 30 ml and 50 ml of deionized water respectively. The two solutions were mixed, heated and evaporated to dryness. The residue was dissolved in 300 ml of methanol to remove insoluble components. Finally, the filtrate was evaporated and 29 g of reddish-brown solid was recovered.

A catalyst was prepared according to the following procedure: (1) Approx. 4.5 kg silicon dioxide gel ("Davison MS-ID") with a surface area of approx. 350 m<2>/g and 1.70 cm<3>/g total pore volume were dried in a pilot-scale activator,

essentially 30 cm inner diameter x 75 cm long cylinder provided with gas dispersion plate and surrounding electric heating coil. The drying took place in a fluidized bed which was maintained at 2,800 l/hour of air at 704°C in

5 hours.

(2) 30 g of silica pre-dried in this way was impregnated with 90 ml of methanol solution containing 2.4 g of the above reaction product of chromium(III) acetate and ethylenediamine.

(3) The solvent was then evaporated at 30-65°C

by nitrogen flushing until the catalyst became free-flowing. The drying step was switched on after impregnation of the carrier with organic solvent and since this was always done, it will not be mentioned in the later

examples.

(4) Approx. 15 g of this impregnated and partially dried catalyst was loaded onto the catalyst activator which consisted of a "Vycor" glass tube 38 mm outer diameter and 68 cm long fitted with a glass fritted disc in the middle of the tube to fluidize the catalyst, and equipped with an electric heating coil around the tube for setting the catalyst temperature. The catalyst was then fluidized with oxygen-free nitrogen in amounts of approx.

400 ml/minute and activated after the following heating cycle: (a) stay at 121°C for 1 hour, (b) stay at 177°C for 1 hour, (c) stay at 287.7°C for 1 hour,

(d) raising by 93°C every 15 minutes up to 871°C,

(e) holding at 871°C for 2 hours and (f) cooling to room temperature under a nitrogen atmosphere. The oxygen-free nitrogen used for this and the following examples was prepared by passing high purity nitrogen through

a layer of reduced copper catalyst.

(5) The catalyst thus activated was transferred to a closed container equipped with hose and clamp in both openings without being exposed to air. This step was also repeated in all the following examples.

Evaluation of the activated catalyst with regard to the ethylene polymerization activity was carried out according to a general procedure as follows: The reactor, which was essentially an autoclave with an inner diameter of 12.5 cm and approx. 30 cm deep was equipped with an agitator with a rotation speed of 560 rpm, a flushing bottom valve and three openings for filling catalyst, isobutane and ethylene, respectively. The reactor temperature was regulated by a heating jacket containing methanol which was kept boiling by an electric heating coil around the jacket. The regulation mechanism included automatic setting of the heating jacket pressure depending on the cooling or heating needs.

To test the catalyst, the reactor was first thoroughly flushed with ethylene at temperatures around 93°C, after which 0.05-0.5 g of catalyst was transferred from a catalyst container under nitrogen to the reactor through a transfer tube without being exposed to air. After the catalyst's filling opening was closed, approx. 2900 ml of isobutane (dried and oxygen-free) was charged to the reactor, trapped ethylene was released, and the reactor heated to 107.2°C. The reactor was then pressurized with ethylene set at 3893.6 kPa and ethylene was allowed to enter the reactor when the pressure fell below 3893.6 kPa. The instantaneous flow rate of ethylene was controlled by rotameters of different capacities. The duration of the experiment was normally from 40 minutes to 4 hours depending on the polymerization rate or productivity.

At the end of each experiment, the ethylene flow was shut off, the flush-bottom valve was opened and the reactor contents were squeezed out into a container measuring approx. 12.5 cm inner diameter x 25 cm depth where isobutane was vented through a 200 mesh sieve to drain. Polymer particles back in the container were recovered and weighed.

In this particular example, the activated catalyst was tested twice. The first experiment consisted of filling the catalyst in an amount of 0.2228 g, the experiment lasted 60 minutes and gave 104 g of polymer with a melt index equal to 0.11

for unkneaded resin. The second experiment used a catalyst quantity of 0.1830 g, was terminated after -60 minutes and gave 80 g of polymer with a melt index of 0.10 for unkneaded sample. The resins in both experiments appeared white to the naked eye.

Example 2-5

Catalysts used in these examples were prepared in the same manner as in Example 1 except that the final residence temperature during the activation process was 927 and 816°C, respectively, instead of 871°C.

According to the general procedure as described

in Example 1, the catalysts were tested and the following results were obtained:

Example 6-7

The examples illustrate the preparation of a reaction product between chromium(III) pentanoate and ethylenediamine.

The reaction product between chromium(III)pentanoate and ethylenediamine was prepared by mixing 19.7g of chromium(III)pentanoate dissolved in 70ml of acetone and 10g of ethylenediamine dissolved in 30ml of mineral-free water, heating and concentrating by evaporation to a sticky, dark red, semi-solid mass. After the evaporation residue had been dissolved in 400 ml of acetone, insoluble substances were filtered off and the filtrate was again evaporated to a sticky, dark red material weighing approximately 15 g. The above chromium(III) pentanoate was again prepared by an exchange reaction between the intermediate sodium pentanoate and chromium trichloride as follows: 200 g of valeric acid was first neutralized to about pH 9 with 500 ml of aqueous solution containing about 78 g of sodium hydroxide 174 g of chromium trichloride was dissolved in 500 ml of water and mixed with the solution to form a precipitate. The precipitate was dissolved in 2100 ml of benzene and washed in solution with a total of 1000 ml of water. After filtration, the filtrate was evaporated to about 203 g of thick, sticky, greenish-blue that connection was made.

A catalyst was prepared by dispersing 3.1 g of the above reaction product on 30.0 g of pre-dried silicon dioxide of the type "952 MS-ID" as described in example 1 by solution impregnation with 90 ml of acetone as solvent. About. 15 g of this impregnated and partially dried catalyst was activated in the same way as described in example 1.

The thus activated catalyst underwent two trials

according to the method described in Example 1. For catalyst additions of 0.1797 g (Example 6) and 0.1589 g (Example 7) and a reactor run time of 60 minutes in both cases, 117 and 88 g of polymer were obtained in the two cases, corresponding to reactivities of 651 and 553 g/g catalyst/hour, respectively. The melt indices of the resin for the unkneaded sample were 0.20 and 0.26, respectively. The resin color was relative

white in both cases.

Example or 8

The example illustrates the production of a reaction product between chromium(III) formate and ethylenediamine.

The reaction product between chromium (III) formate and ethylene diamine used in this example was prepared by mixing two solutions, 15.7 g of chromium (III) formate dissolved in 30 ml of water and 15.0 g of ethylene diamine dissolved in 50 ml of water, heating and concentrating the mixture to a sticky, reddish evaporation residue. After the residue had been dissolved in 200 ml of methanol, insoluble substances were filtered off and the filtrate evaporated again to a slightly sticky red substance weighing approx. 16 g.

2.2 g of the reaction product was dissolved in 90 ml of methanol

for impregnation of 30.0 g of pre-dried silicon dioxide "952 MS-ID" described in example 1. Approx. 20 g of the impregnated and partially dried catalyst was activated as described in example 1.

According to the general experimental process as described in example 1, 92 g of polymer were obtained after 1 hour of reaction with 0.2179 g of catalyst. The melt index of the resin unkneaded was 1.59.

Example 9-10

The examples show execution of the invention with higher homologues of ethylenediamine including 1,2-diaminoalkanes (e.g. propylenediamine) and 1,3-diaminoalkanes (e.g. 1,3-diaminopropane).

The reaction product between propylenediamine and chromium(III) acetate which was used as a catalyst ingredient for Example 9,

was prepared by heating and evaporating to dryness a mixture of two solutions, one prepared by dissolving 15 g of 1,2-diaminopropane in 30 ml of water and the other by dissolving 15.5 g of chromium(III) acetate in 50 ml water. The resulting residue was dissolved in 200 ml of methanol. After removal of insoluble substances, the filtrate was evaporated, recovering 23 g of red substance.

The catalyst used in Example 9 was prepared

by dispersing 2.6 g of the reaction product on 30.0 g of pre-dried silica of the type "952 MS-ID" as described in example 1, with 90 ml of methanol as solvent.

About. 15 g of this impregnated and partially dried catalyst

was then activated in the same way as in example 1.

The reaction product between 1,3-diaminopropane and chromium(III) acetate used as a catalyst component in example 10 was prepared in the same way as in example 9 except for minor differences in the amount of solvent.

About. 18 g of slightly sticky and purplish red material was produced.

The catalyst used in Example 20 was prepared using 2.7 g of this reaction product and 30.0 g of pre-dried silica "952 MS-ID" as described in Example

1. The method of manufacture including non-oxidative activation

was identical to the procedure described under example 9.

The two catalysts under examples 9 and 10 were tested as described in example 1 and the following results were obtained:

Example 11

The example illustrates the invention using an aromatic diamine instead of the aliphatic diamines used in the previous examples.

The reaction product between 3,4-diaminotoluene and chromium(III) acetate was prepared by mixing two solutions, one of which contained 20 g of 3,4-diaminotoluene in 50 ml of water and the other 12.5 g of chromium(III) acetate in 50 ml of water, followed by heating and evaporating the mixture to dryness. The residue was dissolved in 200 ml of acetone and the filtrate evaporated to approx. 25 g dark brown compound.

A catalyst was made by impregnating 30 g of pre-dried "952 MS-ID" silica as described in Example 1

with 90 ml of acetone solution containing 3.2 g of this reaction product. About. 15 g of impregnated and partially dried catalyst was activated in nitrogen in the same way as in example 1.

For a catalyst amount of 0.1887 g and a run time of

60 minutes, according to the general experimental process as described in example 1.55 g of polymer with a resin melt index (unkneaded) of 1.0 was obtained.

Example 12

The example shows application of the invention with polyamines or condensed diamines such as diethylenetriamine.

The reaction product between diethylenetriamine and chromium(III) acetate used for this example was prepared by mixing two solutions, one of which contained 15 g of diethylenetriamine in 50 ml of water and the other 11.1 g of chromium(III) acetate in 40 ml of water , followed by heating and evaporating the mixture to an oily and purplish, glue-like residue. This residue was dissolved in 300 ml of methanol and, after removal of insoluble substances, the filtrate was again evaporated to an oily and glue-like, purple colored compound weighing approx. 18 g.

A catalyst was made by dispersing 3.2 g of the reaction product on 30 g of pre-dried silica "952 MS-ID" as described in example 1 by impregnation with 90 ml of methanol as solvent. About. 15 g of impregnated and partially dried catalyst were activated in oxygen-free nitrogen essentially as in example 1.

The above catalyst was tested in that way

which is described in Example 1. 34 g of polymer was recovered and had a melt index of 0.69 (unkneaded) over a 1 hour period with a catalyst charge of 0.1335 g.

Example 13-15

These examples demonstrate the invention with a reaction product between a chromium (III) carboxylate and a heterocyclic nitrogen base which can complex (chelate) the trivalent chromium, e.g. 2,2<1->bipyridine and 2,2'-dipyridylamine The chromium-containing reaction product used as a catalyst component for examples 13 and 14 was prepared by mixing two solutions, the first of which contained 10 g of 2,2<1->bipyridine in 40 ml of water and the other 4.9 g of chromium(III) acetate in 30 ml of water, followed by heating and concentrating the mixture to a slightly sticky residue of a brown material. This residue was dissolved in 300 ml of methanol to remove insoluble substances. By evaporating the filtrate, approx. 9 g brown residue. 4.0 g of this reaction product was then used to impregnate 30 g of pre-dried "952 MS-ID" silica as described in Example 1 with 90

ml methanol as solvent. About. 15 g of impregnated and partially dried catalyst was activated as in example 1.

The chromium-containing product used as catalyst component for Example 15 was prepared by mixing two solutions, the first of which contained 10 g of 2,2'-dipyridylamine in 50 ml of water and the second 4.5 g of chromium acetate also in 50 ml of water, followed by heating and evaporating the mixture to dryness. A violet colored compound was precipitated from the hard evaporation residue with a total of 500 ml of water. After evaporation of the water, 4.6 g of a violet compound were obtained. A catalyst was then made by impregnation

30 g in silica "952 MS-ID" without pre-drying with a 90 ml aqueous solution of 4.39 g of reaction product as above. The impregnated catalyst was dried in an oven at 110°C for 2 hours and then at 205°C for a further 4

hours in the same oven. About. 15 g of this impregnated and dried catalyst was then activated as described in example 1.

The catalysts from examples 13, 14 and 15 were tested

according to the general process as described in example 1. The following results were obtained:

Example 16

The example shows application of the invention with the reaction product between an aromatic amine, e.g. aniline, and chromium (II) acetate.

The reaction product used as a catalyst component according to this example was prepared by mixing 12.3 g of chromium acetate, 100 ml of water and 15 g of aniline and heating the mixture to precipitate a black sticky compound. The precipitate was washed with 100 ml of water five times and then dissolved in 200 ml of acetone to remove insoluble substances. The filtrate was evaporated to a black sticky substance weighing about 13 g.

A catalyst was prepared by dispersing 2.9 g

of this reaction product on 30 g of pre-dried silicon dioxide "952 MS-ID" as described in example 1 by impregnation in solution with 90 ml of acetone as solvent. About. 15 g of impregnated and partially dried catalyst was activated in the same way as described in example 1.

An experiment to find the ethylene polymerization activity

in the manner described in Example 1, showed that the reactivity was 261 g/g catalyst/hour and the melt index of the resin (unkneaded) 0.80.

Claims (7)

1. Process for the production of polymers of 1-olefins with 2-8 carbon atoms, and copolymers of these olefins and 1-olefins with 2-20 carbon atoms, where the olefins are polymerized under polymerization conditions with a catalyst prepared by dispersing on a finely divided, difficult reducible inorganic carrier, which is silicon dioxide, aluminum oxide, thorium dioxide, zirconium oxide, titanium oxide, magnesium oxide or a mixture or combination thereof, of a reaction product based on a chromium carboxylate with the formula: where R is hydrogen, an alkyl, alkenyl, aryl, or aryl-alkyl, cycloalkyl, or cycloalkenyl radical or a combination of these radicals, the group R having 0-30 carbon atoms and a corresponding amount of valence-saturating hydrogen atoms, m is an integer of 1-3, n is an integer of 0-2, m + n is 2 or 3, and X is a negative group in relation to chromium, characterized in that reac the cation product is formed by reacting the chromium carboxylate with an organic nitrogen compound that can form a complex with trivalent chromium, with the formula: where R' is hydrogen or a lower hydrocarbon substituent, j is an integer from 1-3, and Y is a two-valued radical, and by activating the mixture obtained after the dispersion on said carrier by heating to a temperature of 316-1094°C in a non-oxidizing gas atmosphere. 2. Method according to claim 1, characterized in that a catalyst is used whose carrier is pretreated before application of the reaction product by heating at a temperature in the range 149-1094°C until volatile components are at least partially driven off. 3. Method according to claim 1, characterized in that the catalyst reaction product is dissolved in a solvent and the resulting solution is used for impregnation of the carrier. 4. Method according to claim 1, characterized in that the dispersion of the catalyst reaction product takes place by dry mixing with the four-part carrier material followed by heating in a fluidized bed which is suspended by a non-oxidizing gas flowing through the carrier during the heating. 5. Method according to claim 1, characterized in that the activation of the catalyst is carried out in a fluidized bed which is kept in suspension with the flow of a non-oxidizing gas, such as nitrogen, hydrogen, carbon monoxide, a noble gas, or a mixture of such gases. 6. Process according to claim 1, characterized in that chromium (III) formate, chromium (III) acetate, chromium (III) propionate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III)- benzoate, chromium naphthenate or chromoleate. 7 . Method according to claim 1, characterized in that ethylenediamine, propylenediamine, 1,3-diaminepropane, diethylenetriamine, triethylenetetramine, 3,4-diaminotoluene, 2,2'-bipyridine, 2,2'-dipyridylamine, di- 2-pyridyl ketone, aniline and diphenylamine.