FI61197C - FOERFARANDE FOER POLYMERISERING ELLER KOPOLYMERISERING AV OLEFINFOERENINGAR - Google Patents

Description

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Patent- och ragifterttyralfan Antttkin utkgd och utl.tkrWton pubtlcarad 26.02.82

(32) (33) (31) atuolkmi · —teflrt priority i3.O6.7U

USA (US) U78879 (71) Chemplex Company, 3100 Golf Road, Rolling Meadows, Illinois, USA (72) Yu-Tang Hwang, Clinton, Iowa, Howard Lee Grimmett, Clinton, Iowa, USA (US) (7) * 0 Berggren Oy Ab (5M Process for the polymerization or copolymerization of olefinic compounds - Förfarande för polymerisering eller copolymerisering av olefinforeningar (62) Divided by application 751758 and in particular for the polymerization or copolymerization of ethylene and other 1-olefins having a total of 2 to 8 carbon atoms with 1-olefins having 2 to 20 carbon atoms.

The most relevant prior knowledge of the field of which the applicants are aware is as follows: Z. Electrochemie Vol. 63,

Well. 1 (1959) pages 105-in, which discloses a catalyst formed by the reaction between organoaluminum compounds and transition metal complexes, and in particular by the reaction of an organoaluminum compound and a chromium acetylacetonate complex. However, the olefin polymerization activity of this catalyst is somewhat low. U.S. Patents 3,351,623 and 3,635,800 disclose catalysts consisting of a mixture of one component, vanadium-2, U-diketone chelate, rather than the chromium chelate of this invention. These prior art catalyst systems and the results obtained are different from this invention.

2,611 97 The olefinic compounds polymerizable in accordance with the present invention, and in particular the 1-olefins having 2 to 8 carbon atoms, are polymerized or copolymerized with C2-C20 olefins to form solid polymers and copolymers in the presence of new catalysts consisting essentially of low valence chromium surfactants. supported on at least one inorganic oxide which is difficult to reduce, preferably having a moderate surface area. More specifically, the low valence chromium grades are derived from the chromium chelate of the beta-dicarbonyl compound, of which chromium acetylacetonate is a good example of its interaction with the catalyst support and / or thermal decomposition in a substantially oxygen-free atmosphere, e.g., an inert such nitrogen or reducing agent.

The inorganic oxide may be silica, alumina, zirconia, thorium oxide, magnesium oxide, titanium dioxide, or mixtures and combinations thereof obtained by co-precipitation, impregnation, gas phase deposition, etc. The surface area of the support may vary from a few m / g to more than 700 m / g / g, but is preferably 2 3 over 150 m / g. The pore volume is preferably more than 0.5 cm / g if the surface area is mainly due to micropores. A finely divided pore-free carrier having a relatively large surface area, such as "Cab-O-Sil", can also be used in the present invention. Activation and calcination of the catalyst at elevated temperatures, preferably at about 260-1093 ° C, is performed either in a fluidized bed maintained by a flow of non-oxidizing gas or in a solid bed under high vacuum, optionally equipped with a small non-oxidizing gas inlet.

Chromium acetylacetonate can be considered as a derivative of 2, 4-pentanedione. Due to its chelating structure, the six coordination sites of central chromium are efficiently occupied. Suitable chromium compounds suitable for the catalyst used in the process of this invention are inherently all chromium derivatives of beta-diketone, beta-ketoaldehyde or beta-dialdehyde having the formulas: (R - C - CH - C - R) CrX.

„„ Mn 0_0, (Le - CH - C - R '"1) CrX„ or „„ mn 0 0_ (R - C - C - C - R'J) CrX «„ mn 0 0 3 61197 where R is independently selected hydrogen, alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl radicals and combinations of these radicals, each radical R containing 0-10 carbon atoms and a corresponding number of hydrogen atoms satisfactorily valent, Rf is selected from alkylene, alkenylene, arylene, cycloalkyl cycloalkenylene radicals and combinations of these divalent radicals in which the radical R 'contains 1 to 10 carbon atoms and a corresponding number of hydrogen atoms satisfactory to valences, m is an integer from 1 to 3, n is an integer from 0 to 2 and m + n is 2 or 3 and X is a halide, alkyl or For example, instead of chromium acetylacetonate, chromium benzoylacetonate, chromium-5,5-dimethyl-1,3-cyclohexanedione, chromium-2-acetylcyclohexanoate and the like can be used.

The currently known methods for preparing a chromium derivative of 3-diketone appear to lead primarily, though not exclusively, to a chelate where m is 3 and n is 0. However, it is clear that it is possible to prepare a chromium chelate where m is 2 and n is 1 or vice versa. In any case, it is clear that the latter compounds are also useful catalysts for polymerizing or copolymerizing olefinic compounds, since during activation the two most negative ligands of the chelate interact with the hydroxyl group of the support to give the same result regardless of the type of ligand to carbon dioxide and a carbon layer, thereby reducing the chromium compound and forming an active catalyst. Thus, it is quite clear that a catalyst according to the main claim, where m is 1 and n is 2, gives the same result as shown in the examples.

The chromium in the chelate used in the process of this invention has a low valence of three compared to the valence of six chromium oxide-containing catalysts in the art. The new catalysts are dark black if properly activated according to the methods of this invention.

The preparation of the catalysts used in the process of this invention involves the following procedures, some of which are optional as shown. These procedures include pretreatment by heating the support (optional but normally recommended), dispersion of the chromium chelate on the support, and activation of the supported catalyst by heating in a non-oxidizing atmosphere.

Preliminary examination of the applicant

The purpose of the pre-treatment is to adjust the moisture content of the carrier. The pretreatment can be performed in a fluidized bed with any dry non-reactive gas such as air or nitrogen. Alternatively, the pretreatment can be performed in a solid bed, such as a muffle furnace. Pre-treatment in a fluidized bed is preferable to calcination in a muffle furnace, especially if the temperatures are above 427 ° C. The optimum pretreatment temperature depends on the type of support and its physical properties and can vary between 20 ^ -1093 ° ε. The effects of residual moisture or other volatile substances on the course of activation are not yet fully understood.

5,61197

Dispersion of the Chromium Chelate on the Support The dispersion of the chromium chelate of the present invention on the support can be easily carried out by a conventional impregnation method using organic solvents such as toluene or benzene. Equally satisfactory dispersion is often achieved by a more effortless method which provides dry mixing of the chelate with the carrier and accomplishes the final dispersion during the initial stage of activation. If such a dry blending technique is used, subsequent activation is best performed as a fluidized bed operation. The optimum chromium content of the catalyst depends on the type of support, the surface area and the pore structure. In the present invention, the support may have a surface area of 100-800 m / g or more and a pore volume of 0-3, C cm 2 / g, the amount of chromium may vary between 0.05-5% with the preferred amount being somewhere near 0 , 1-1.0 wt.

Activation in a Non-Oxidizing Atmosphere According to the present invention, a non-oxidizing atmosphere is provided either by an inert gas such as nitrogen, helium, argon, etc. with a reducing gas such as carbon monoxide, hydrogen, etc., or by removing the gases substantially to high vacuum. In the latter case, it is desirable to allow deliberate infiltration of a small amount of non-oxidizing gas. In all cases, a mixture 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 fluidized bed or a solid bed process can be used. However, our experience shows that a fluidized bed process is recommended. which normally results in 1 to 3 hours at 149-177 ° C and again at 288-315 ° C. When chromium acetylacetonate is used in the preparation of the catalyst, these two temperature ranges indicate a corresponding interaction between chromium acetylacetonate and the support in two However, it is possible to obtain active catalysts using other activation-temperature control elements.

The final activation temperatures may range from 315 to 1093 ° C depending on factors such as the desired resin properties, type of support, pretreatment, etc. In the case of a chromium acetylacetonate catalyst on silica, the activation temperatures are preferably between 760 and 95 ° C. Heating rates above 315 ° C are generally not critical.

The novel catalysts of this invention can be used in liquid phase, solution or slurry processes or gas phase processes. In the liquid phase operation, any saturated C 1 -C 4 hydrocarbon can be used as the reaction medium or diluent. Other types of solvents such as aromatic hydrocarbons and chlorinated solvents may also be used.

The polymerization of 1-olefins can be carried out as a batch or continuous process. The catalyst is generally fed to the reactor as a slurry in a continuous process, but as a dry powder in a batch process. The method of feeding the solvent and olefin to the reactor system may follow any conventional practice suitable for a batch or continuous process. Vigorous stirring of the reaction medium is, of course, highly recommended, as is efficient cooling to control the temperature of the reactor.

The olefin polymer or copolymer is normally recovered by expansion by distilling off the solvent or diluent without any intervening steps to remove the catalyst. The activity of the novel catalysts described in this invention is normally high enough to omit the catalyst removal steps for all practical purposes. In the case of ethylene, the pressures can range from a normal pressure of about 200 MPa and temperatures between 66-260 ° C.

The following examples illustrate the invention:

Notes to Examples 1-10 Concerning Laboratory Batch Polymerization Work These examples are presented primarily to illustrate various parts of the preparation of new catalysts and their use in the polymerization of olefins.

To give an overall picture of these examples, the purposes of each example and certain features of catalyst preparation are summarized as follows:

Example 1 illustrates a relatively simple catalyst preparation case in which silica is used in the received form by pretreating cloth 7 61197 before impregnating it with chromium acetylacetonate.

Example 2 illustrates a variation of Example 1 in which a larger surface area (600 m / g vs. 350 m / g) is precalcined prior to impregnation with chromium acetylacetonate. Another feature of this invention is the relatively high chromium content (nominally 3% by dry weight compared to a typical 58).

Examples 3 and 4 illustrate the use of a support other than silica. More specifically, titanium dioxide is used in Example 3 and silica-alumina containing 11-14% Al 2 O 2 is used in Example 4.

Example 5 illustrates the use of chromobenzoylacetonate, an aryl variant of chromium acetylacetonate.

Example 6 illustrates the use of helium instead of nitrogen during activation.

Example 7 illustrates activation in a reducing gas, namely a mixture of carbon monoxide and nitrogen, and also the use of high pore volume silica as a carrier.

Example 8 illustrates activation in a mixture of hydrogen and nitrogen.

Example 9 illustrates activation at a relatively low temperature level (538 ° C compared to the more typical 871-927 ° C).

Example 10 illustrates the use of a catalyst to prepare a polymer from propylene.

Catalyst Test Procedure Suitable for Examples 1-9 ·

The ethylene polymerization activity of the given catalyst was tested in a bench-scale reactor using isobutane as the reaction medium. The reactor, consisting essentially of an autoclave with an inner diameter of 12.5 cm and a depth of 30 cm, was equipped with a stirrer running at 560 rpm, a bottom valve and three orifices for charging the catalyst, isobutane and ethylene. The reactor temperature was controlled by a jacket containing methanol, which was kept boiling by an electric heater surrounding the jacket. The control mechanism included automatic control of the jacket pressures according to either cooling or heating needs.

V

8 61197

According to the general test procedure, the reactor was first thoroughly purged with ethylene at temperatures of approximately 93 ° C, followed by the transfer of 0.05-0.5 g of catalyst from the catalyst flask under nitrogen to the reactor via a transfer tube without exposing it to air. After the catalyst inlet was closed, 2900 ml of isobutane (dried and deoxygenated) was charged to the reactor, the closed ethylene was released and the reactor was allowed to warm to 107 ° C. The reactor was then pressurized with ethylene, which was adjusted to a pressure of 3> 8 MPa and allowed to flow into the reactor whenever the reactor pressure dropped below 3.8 MPa. The instantaneous ethylene flow rate was monitored with rotameters of different capacities. The duration of the test run was normally 40 minutes to four hours depending on the polymerization rate or the desired production capacity.

At the end of the test run, the ethylene flow was stopped, the bottom valve was opened and the contents of the reactor were discharged into a recovery vessel approximately 12.5 cm in internal diameter and 25 cm deep, from which isobutane was allowed to leak through a 200 mesh screen into the outlet. The polymer particles remaining in the tank were collected and weighed.

Example 1

The catalyst was prepared by the following steps: (1) 30.0 g of Davison MS-ID silica gel having an area of n.

2. x ...

350 m / g and a total pore volume of 1.70 cnr / g, was saturated with an organic solution prepared by dissolving 3.91 g of chromium acetylacetonate in 100 ml of benzene.

(2) The solvent was evaporated at 29 * 60 ° C under nitrogen ventilation until the catalyst became free-flowing. This step was always followed by impregnation when an organic solvent was used and its mention is omitted from the following examples for simplicity.

(3) About 20 g of this catalyst was charged to a catalyst activator consisting of a Vycor glass tube with an outer diameter of 38 mm and a length of 69 cm and a tubular electric heater. A sinter plate was placed in the center of the tube to fluidize the catalyst. In this particular example, the fluidized bed was maintained at a nitrogen flow of approximately 400 cm 3 / min and the catalyst was activated by a heating cycle as follows: (a) holding at 121 ° C for 1/2 hour, (b) holding at 177 ° C for 1 hour (c ) by holding at 288 ° C for 1 hour, (d) raising 9,61197 to about 55 ° C every fifteen minutes up to 871 ° C, (e) holding at 871 ° C for 2 hours, and (f) cooling to room temperature under nitrogen. atmosphere.

(4) The activated catalyst was transferred to a closed flask equipped with a hose with clamps at both openings without exposing it to air. This step was also applicable to all of the following examples and its mention is omitted below for simplicity.

Thereafter, according to the general experimental procedure described previously, 0.1683 g of catalyst was charged to the reactor. The duration of the run was 120 minutes, including an induction period of about two minutes. The recovered polymer weighed 175.4 g and the melt index of the polymer powder (ASTM D-1238-62 T) was 0.28 g / 10 min.

Example 2

The catalyst was prepared by the following steps: (1) About 400 g of Davison 951 MS silica having an area of n.

600 m / g and a total pore volume of 1.00 cnr / g, calcined in a muffle furnace with a heating cycle in which (a) maintained at 204 ° C for 1 hour, (b) raised to 67 ° C every fifteen minutes up to 871 ° C, ( c) maintained at 871 ° C for 4 hours and (d) cooled to room temperature.

(2) 30 g of this calcined silica base was impregnated with an organic solution prepared by dissolving 6.30 g of chromium acetylacetonate in 100 ml of toluene.

(3) The saturated and partially dried catalyst was activated under a nitrogen atmosphere as in Example 1, except that the heating cycle was as follows: (a) maintained at 121 ° C for 1/2 hour, (b) maintained at 177 ° C for 1 hour, (c) maintained at 288 ° C for 1 hour, (d) raised to 83 ° C every fifteen minutes up to 899 ° C, (e) maintained at 899 ° C for 3 hours, and (f) cooled to room temperature.

As in Example 1, 0.5269 g of this activated catalyst was tested according to the general experimental procedure. The running time was 60 minutes including a 2 minute induction. The recovered polymer weighed 130.0 g.

10 61197

Example 3

The catalyst was prepared by the following steps: (1) 30 g of titanium dioxide in the form of microspheres with a surface area of 112 m / g, a total pore volume of 0.85 cnr / g and an average particle size of 65 microns were saturated with an organic solution prepared by dissolving 1.935 g of chromium acetylacetonate 80 ml of toluene.

(2) The saturated and partially dried catalyst was activated in the apparatus described in Example 1 using nitrogen to fluidize the catalyst bed. The heating cycle was as follows: (a) maintained at 121 ° C for 1 hour, (b) maintained at 177 ° C for 1 hour, (c) maintained at 288 ° C for 1 hour, (d) raised to 55 ° C every fifteen minutes. up to 871 ° C, (e) maintained at 871 ° C for 3 hours and (f) cooled to room temperature under a nitrogen atmosphere.

For the activity test, 0.1285 g of catalyst was charged to the reactor. The test run was terminated after 60 minutes including 8 minutes of induction. 5.0 g of polymer were recovered.

Example A

The catalyst was prepared by the following steps: (1) 50 g of Davison's silica-alumina containing 11-1% Al 2 O 3 was saturated with an organic solution prepared by dissolving 2.8 x 15 g of chromium acetylacetonate in 100 ml: toluene.

(2). This saturated and partially dried catalyst was activated under nitrogen as in Example 1, including holding at a final temperature of 87 ° C for 2 hours.

The catalyst thus prepared was tested according to the general procedure described previously. The net catalyst charge was 0.2889 g and the run was terminated after 60 minutes including 6 minute induction. The polymer was recovered 7.5 g ·

Example 5

The catalyst was prepared by the following steps: 11 61197 (1) Davison 952 MS-ID silica was dried in a pilot plant scale activator at 704 ° C for 5 hours as in Example 11.

(2) 20.0 g of this pre-dried silica was saturated with an organic solution containing 2.1 g of chromobenzoylacetonate dissolved in 90 ml of toluene.

(3) About 15 g of this saturated and partially dried catalyst was activated under nitrogen. The activation cycle was as follows: (a) maintained at 121 ° C for 1 hour, (b) maintained at 177 ° C for 1 hour, (c) maintained at 288 ° C for 1 hour, (d) raised to 110 ° C every fifteen minutes up to 871 ° C, (e) maintained at 871 ° C for 2 hours and (f) cooled to room temperature under a nitrogen atmosphere.

The catalyst thus prepared was tested according to the general procedure described previously. The net catalyst charge was 0.1700 g and the run was terminated after 60 minutes including 3 minute induction. 49 g of polymer were recovered and the melt index of the polymer powder (ASTM D-1238-62 T) was 0.42 g / 10 min.

Example 6

The catalyst was prepared by the following steps: (1) Davison 952 MS-ID silica was dried in a pilot plant activator at 704 ° C for 5 hours as in Example 11.

(2) 45.0 g of this pre-dried silica was saturated with an organic solution containing 3.06 g of chromium acetylacetonate dissolved in 160 ml of toluene.

(3) About 20 g of this saturated and partially dried catalyst was activated in helium using the heating cycle of Example 5.

According to the general experimental procedure, 0.1666 g of catalyst was charged to the reactor. The running time was 60 minutes including a 2 minute induction. 100 g of polymer were recovered. The melt index of the polymer powder (ASTM D-1238-62 T) was 0.29 g / 10 min.

12,611 97

Example 7

The catalyst was prepared by the following steps: (1) 48.0 g of high pore volume silica prepared from. . . . 2 nut U.S. Industrial Chemical Co. and having a surface area of 350 m 2 / g, a pore volume of 2.5 cm 2 / g and an average particle size of 150 μm was saturated with an organic solution prepared by dissolving 3.0 g of chromium acetylacetonate in 140 ml of toluene.

(2) About 15 g of this saturated and partially dried catalyst was activated in a fluidized bed maintained with a mixture stream of 400 std cm 2 / min of nitrogen and 40 std cm 2 / min of carbon monoxide. The heating cycle for activation was the same as in Example 5. The catalyst thus prepared was tested according to the general procedure described previously. The net catalyst charge was 0.1988 g. The test run was terminated after 60 minutes including 7 minute induction. 95.1 g of polymer were recovered. The melt index of the polymer powder (ASTM D-1238-62 T) was 0.45 g / 10 min.

Example 8

The catalyst was prepared by the following steps: (1) Davison 952 MS-ID silica was dried in a pilot plant-wide activator at 704 ° C for 5 hours as in Example 11.

(2) 45.0 g of this pre-dried silica was saturated with an organic solution containing 3.06 g of chromium acetylacetonate dissolved in 160 ml of toluene.

(3) About 20 g of this saturated and partially dried catalyst was activated as in Example 7 except that the fluidized bed was maintained with a mixture stream of 400 std-cm 2 / min of nitrogen and 16 std-cm 2 / min of hydrogen.

For the activity test, 0.2482 g of catalyst was charged to the reactor. The test run was terminated after 60 minutes. Polymer recovered weight: 21.0 g.

Example 9

The catalyst was prepared by the following steps: 13,61197 (1) 10.25 g of Davison 952 MS-ID silica was saturated with an organic solution prepared by dissolving 0.647 g of chromium acetylacetonate in 50 ml of toluene.

(2) The saturated and partially dried catalyst (ca. 23 g) was activated under nitrogen as in Example 1 except that the heating cycle was as follows: (a) maintained at 93 ° C for 1 hour, (b) maintained at 121 ° C for 1/2 hours, (c) maintained at 149 ° C for 1 hour, (d) raised to 55 ° C every fifteen minutes up to 538 ° C, and (e) maintained at 538 ° C for 2 hours.

According to the general experimental procedure described previously, 0.3076 g of catalyst was charged to the reactor. The run was terminated after 160 minutes including a five minute induction. 190.0 g of polymer were recovered.

Example 10 The purpose of this example is to illustrate the use of this new catalyst in the polymerization of propylene. The catalyst was the same as used in Example 1.

The equipment used for the polymerization of propylene was essentially the same as that used for the polymerization of ethylene, except for the propylene charging process. A 300 cm 2 stainless steel cylinder containing 99 g of propylene was first connected to the reactor while the latter was purified with ethylene. After 0.1965 g of catalyst and 2500 ml of isobutane were sequentially charged to the reactor according to the general procedure previously described, the reaction medium was carefully degassed to remove substantially all of the ethylene entrapped therein. The valve of the propylene cylinder was then opened to allow a flow of propylene into the reactor. This transfer of propylene from the cylinder to the reactor was facilitated by heating the propylene cylinder with a heating tape wrapped around it throughout the run. The contents of the reactor, consisting of catalyst, propylene and isobutane, were heated to 107 ° C; and maintained there, with the stirrer running at 560 rpm as in the polymerization of ethylene. However, the reactor pressure was roughly 2.6 MP in this case. After 90 minutes, the run was terminated and the contents of the reactor were discharged into an outlet vessel to recover the polymer. 12.4 g of polypropylene were recovered.

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In the table above, column (1) shows the weight concentration of the catalyst as a percentage of chromium and also defines the support used in each case. Thus, in Example 4, the support is a mixture of silica and aluminum trioxide.

Column (2) defines the pretreatment of the carrier or base material when used using temperature, time and the nature of the surrounding atmosphere.

Column (3) is similar to column (2), but indicates the activation conditions used to activate the catalyst.

Column (4) gives the reactivity of the catalyst in grams of polymer produced per gram of catalyst and per hour.

Column (5) shows the total number of grams of polymer produced per gram of catalyst.

Column (6) lists the melt index for the polymer obtained, which in all cases is in powder form.

The following examples illustrate procedures and preparations at the pilot plant scale.

Example 11 2

A silica base having a surface area of approximately 350 m 2 / g and a pore volume of approximately 1.7 cm 2 / g was used as a catalyst support in this example.

This type of material is commercially available from Davison Chemical Company and is designated 952 MS-ID silica gel for this type of material. The catalyst of this example was prepared by taking up the silica base and first drying it at 704 ° C in a fluidized bed using nitrogen as the fluidizing gas. The equipment used for this drying step consisted of a tube with an inner diameter of 10 cm and a length of about 120 cm made of Inconel metal. The pipes were equipped with electric heaters around the outside of the pipe. The heaters were able to heat the tube and its contents up to temperatures of 1093 ° C.

The bottom of the pipe was equipped with a diffuser plate designed to give an even distribution of the gas that came in from the bottom of the pipe and flowed upwards through the pipe. The layer of regenerated molecular sieves was used to dry the nitrogen to a total moisture content of less than 2 ppm (v / v) before entering the tube. A flow meter device was connected to the device to control the gas flow rate through the activator. Likewise, it was connected to a controller for heating elements capable of raising the temperature of the fluidization tube to elevated temperatures according to a predetermined cycle.

After drying at 70H ° C, the stock was cooled to near ambient temperature while still fluidized with nitrogen. The dried silica was then removed from the tube with care to prevent moisture from escaping from the atmosphere. The dried silica was then saturated with a sufficient solution of chromium acetylacetonate in dried toluene to give a chromium concentration of 1 wt% of the total dried catalyst. The catalyst was then placed in an oven and the toluene was removed by heating at about 66-93 ° C in the presence of a dry nitrogen atmosphere. After most of the toluene was removed, the dried catalyst was transferred to the fluidizing tube described above.

In this tube, the catalyst was fluidized with nitrogen and heated to 177 ° C for 3 hours, then raised to 288 ° C and held for 3 hours, and then raised to 899 ° C and held for 6 hours. The heating rate between the maintenance temperatures was about 83 ° C per hour. The flow of nitrogen was kept constant throughout to provide fluidization of the catalyst in the heated tube. The catalyst was then cooled to approximately ambient temperature while still fluidized and then discharged from the tube into a pre-dried flask that had been thoroughly rinsed to remove all traces of oxygen and moisture from inside the flask. This flask was then sealed and stored in a tank with a dry nitrogen medium until the catalyst was to be used in the polymerization system. The activated catalyst in this example was black in color. At the appropriate time, the catalyst was charged to a continuous polymerization reactor and used to polymerize ethylene at about 108 ° C in the presence of dry isobutane and at an ethylene concentration of about 5% by weight in the reactor.

The reactor used for the continuous polymer experiments consisted of a vessel equipped with a jacket and a device to achieve good mixing inside the vessel. The volume of the vessel was about 3 ^ 0 liters. Water was circulated through the reactor jacket to remove the heat released during the polymerization reaction. A device was used to control the coolant temperature and coolant flow to monitor the reactor temperature. The system was equipped with a device for feeding the catalyst slurry to the reactor at a controlled rate. The system was also equipped with a device for feeding ethylene to the reactor at a controlled rate. The system was equipped with devices for feeding the second monomer or comonomer as well as modifiers to the reactor to control the molecular weight of the polymer formed in the reactor, although these were not used in this example. The system was equipped with a device for feeding the diluent separately to the reactor at a controlled rate. The system was equipped with a device for removing the polymer mixture, unreacted monomer and / or comonomer and diluent formed in the reactor from the reactor. The polymer mixture removed from the reactor flowed into a heated removal vessel where the diluent and unreacted ethylene were removed as steam and the polymer was recovered with only very small amounts of hydrocarbons. The recovered polymer was flushed in batches with an inert gas to remove traces of hydrocarbons and analyzed for its melt index, density and ash content. These factors are determined by standard tests well known in the art. The test used to determine the melt index is ASTM-1238-62 T and the density measurement method is given in ASTM D-1505 · The ash was determined by the pyrolysis method. In all cases, the polymer yields have been calculated from the ash values.

The polymer of this example had a melt index of 0.2 and a density of 0.960. The polymer yield obtained with the catalyst increased to 1 * 150 kg of recovered polymer per kg of catalyst fed to the reactor. These results, together with the results obtained from the following examples, are summarized in Table II. In all examples, isobutane was used as a diluent in the reactor system.

A sample of the catalyst used in this example was analyzed for Cr + 2 by extracting the catalyst with hot water and determining the chromium dissolved in water by adding potassium chloride and then titrating with sodium thiosulfate. The water used to extract the catalyst was clear and colorless and no Cr + 2 was found by titration.

61197 ϊ8

Example 12 The catalyst of this example was prepared in the same manner as in Example 11 except that chromium acetylacetonate was added to the pre-dried base as a dry powder and the base and Cr (AcAc) 2 were dry blended before being charged to the fluidization tube. The activated catalyst was black in color. This catalyst was tested in the continuous polymerization reactor of Example 11. The catalyst was active as shown by the results in Table II. This example demonstrates that active catalysts can be prepared by dry blending chromium acetylacetonate and silica base in a manner comparable to solution impregnation of a dry base.

Example 13 This example illustrates the effect of not exemplifying a catalyst support during catalyst preparation. The catalyst used in this example was prepared in the same manner as the catalyst in Example 12 except that the silica base was not pre-dried before mixing the base and dry chromium acetylacetonate. The results obtained when testing this catalyst, for example in a continuous polymerization reactor, are shown in Table II. Analysis of the catalyst of this example for Cr + 2 by the method of Example 11 shows that this catalyst contains less than 0.01% by weight of? Cr +6.

*

Example IA

The catalyst of this example was prepared in an identical manner to the catalyst of Example 11 except that the silica base used to prepare the catalyst was a Davison 951 MS silica gel having a pore volume of approximately 1 cm -1 / g and a surface area of about 600 m / g. The results obtained with this catalyst in a continuous polymerization reactor are shown in Table II. This example demonstrates that supports with a wide variety of surface areas and pore volumes can be used to prepare the catalysts of this invention. A sample of this catalyst was analyzed for Cr + 2 by the method of Example 11. Analysis did not show any Cr + 2 by titration.

Example 15 This example illustrates the use of a catalyst of the present invention in the preparation of a copolymer of ethylene and hexene-1. The catalyst of this example was prepared in the same manner as in Example 12. The catalyst was fed to a continuous polymerization unit together with hexene-1 and ethylene. The weight ratio of hexene-1 to ethylene in the reactor feed was 0.48 / 100. The results of the run are shown in Table II.

Example 16 This example illustrates the use of a catalyst in the preparation of a copolymer of ethylene and butene-1. The catalyst of this invention was prepared in the same manner as in Example 12. The catalyst was fed to the polymerization reactor together with ethylene and butene-1. The weight ratio of butene-1 to ethylene in the reactor feed was 0.42 / 100. The results of this run are shown in Table II.

Example 17 This example shows the effect of using hydrogen during a polymerization reaction to increase the melt index of a polymer. The catalyst was prepared in the same manner as in Example 11. This catalyst was used in a continuous polymerization reactor. In addition to ethylene, solvent and catalyst, deoxygenated and dried hydrogen was continuously fed to the reactor. The rate of hydrogen addition was 0.007 mol / mol of ethylene fed to the reactor. As shown in Table II, the addition of hydrogen resulted in a higher melt index compared to that obtained in Example 11.

Example 18 This example compares a catalyst used in the process of this invention to a catalyst prepared using Davison 952 MS silica impregnated with CrO 4 and activated on dry nitrogen according to the process of this invention. The catalyst consisting of 952 silica impregnated with CrO 2 is a Phillips-type catalyst, although according to U.S. Patents 2,825,721 and 2,951,866, the recommended procedure for activating this type of catalyst is to use an oxidizing atmosphere.

The catalyst used in this example was Davison's 969 MS catalyst, which is a catalyst containing about 2% by weight of CrO 2 with a 952 silica base. This catalyst was activated in the activator described in Example 11 using nitrogen as the fluidizing gas and a maximum activation temperature of 899 ° C. This catalyst was then used in a continuous polymerization unit as described in Example 11. This catalyst had essentially no activity at all. The catalyst was found to contain 0.06 wt%? Cr + ^ by the analytical method described in Example 11.

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ω 21 61197 This Example 18 demonstrates that the technique of activating the catalyst in an inert gas such as nitrogen results in a catalyst containing little or no Cr + ^ even when the catalyst contains all chromium in the form of Cr + ^ prior to activation. This Example 18 further demonstrates that the catalysts of this invention have superior activity over CrO 2 / SiO 2 type catalysts when activated according to the process of this invention.

Example 19

The catalyst was prepared as follows: 1) Davison 952 MS-ID silica was pre-dried in an experimental scale activator at 700 ° C for 5 hours as described in Example 11.

2) 20.0 g of this pre-dried silica was dry blended with 1.824 g of chromium-5,5'-dimethyl-1,3-cyclohexanedione (methionium chromium III derivative).

3) The resulting mixture was activated under a nitrogen atmosphere according to Example 5.

According to the general experimental procedure, 0.1731 g of catalyst was charged to the reactor. About 16 g of ethylene was introduced into the polymerized tuft during the first hour.

Example 20

The catalyst was prepared as follows: 1) Davison 952 MS-ID silica was first dried in an experimental plant scale activator at 700 ° C for 5 hours as in Example 11.

2) 30.0 g of this pre-dried silica were impregnated with 3-0 g of chromium-2-acetylcyclohexanonate dissolved in 85 cm -1 of methyl ethyl ketone.

3) About 15 g of this impregnated and partially dried catalyst was activated under a nitrogen atmosphere according to Example 5.

22,611 97 This activated catalyst was used for the polymerization of ethylene according to a general experimental procedure. After 1 hour, about 30 g of polymer was obtained using a 0.146 g catalyst charge. The melt index of the resin was 0.71 g / 10 min.

Example 21

The catalyst was prepared as follows: 1) Davison 952 MS-ID silica was pre-dried in a pilot plant scale activator at 700 ° C as described in Example 11.

2) 20 g of gaseous pre-dried silica was impregnated with 60 moles of a toluene solution containing 1.51 g of chromium-2,1-hexanedioneate.

3) This impregnated and partially dried catalyst was activated under a nitrogen atmosphere using the method of Example 5.

To test the activity according to the general test procedure, 0.1701 g of catalyst was charged to the reactor. The experiment was already stopped after 60 minutes and 18 g of polyethylene were recovered. The melt index of the resin was 0.7 g / 10 min.

Claims (9)

A process for the preparation of polymers from 1-olefins containing 2-8 carbon atoms and for the production of copolymers from said olefins and from 1-olefins containing 2-20 carbon atoms, characterized in that said olefins are polymerized in polymerization conditions with a catalyst prepared by dispersing on a finely divided, highly reducible inorganic carrier of such a chromium chelate of a beta-dicarbonyl compound of formula (R - C - CH - C - R) CrX, to nmn * 0 0 (1 C - CH - C - R 1) CrX + or O (R - C - C - C - R'1) CrX with OO where each and every R is independently a hydrogen atom, an alkyl-alkenyl, aryl, cycloalkyl or cycloalkenyl radical or a combination of these radicals, each of which contains 0-10 carbon atoms and a corresponding valence saturating amount of hydrogen atoms, R * is an alkylene, alkenylene, arylene, cycloalkylene or cycloalkenylene radical or a combination of these transverse radicals, meda n groups R 'contain from 1 to 10 carbon atoms and a corresponding valence-saturating amount of hydrogen atoms, m is a whole tai 1-3, n is a whole tai 0-2, while the sum m + n is a whole tai 2-3 X is a valence-fulfilling negative group, and by activating the mixture thus obtained at an elevated temperature in a non-oxidizing atmosphere. 26 61 1 97 Process according to claim 1, characterized in that dispersion of the chromium chelates has been realized by dry mixing with the finely divided carrier and activation by heating in a fluidized bed which has been maintained in a suspension with a non-oxidizing gas flowing through the carrier. during heating. Process according to claims 1-2, characterized in that the activation takes place in a fluidized bed, in which a non-oxidizing gas is used to maintain the mixture of the support and the chromium chelate in a fluidizing form, while being heated to the final activation temperature of about 48 to 1093. ° C. Process according to the preceding claim, characterized in that the chromium chelate is chromium 2,4-hexanedione, which is a chromium derivative of 2,4-hexanedione. Process according to any one of the preceding claims, characterized in that the chromium chelate is chromium acetylacetonate, which is a chromium derivative of 2,4-pentadione. Process according to any one of the preceding claims, characterized in that the chromium chelate is chromobenzoylacetonate, which is a chromium derivative of 1-phenyl-1,3 'butanedione. Process according to any of the preceding claims, characterized in that the chromium chelate is chromium-5β-dimethyl-1,3-cyclohexanedione which is a chromium derivative of 5,5-dimethyl-1,3-cyclohexanedione. Process according to any one of the preceding claims, characterized in that the chromium chelate is chromium-2-acetylcyclohexanonate, which is a chromium derivative of 2-acetylcyclohexanone. A process according to any preceding claim, characterized in that, in a finely divided, highly reducible, inorganic carrier, a chromium chelate of a beta-dicarbonyl compound of the formula is first mixed