Oxide-chromium catalyst (co)polymerization of ethylene and method thereof

 

(57) Abstract:

The invention relates to catalysts for (co)polymerization of ethylene containing chromium trioxide deposited on a solid inorganic oxide carrier of nature, i.e., an oxide-chromium catalysts, and methods for their preparation. Described oxide-chromium catalyst (co)polymerization of ethylene include chromium trioxide, aluminum oxide, silicon dioxide as a carrier and optionally zinc oxide in the following content of components in the catalyst, wt. %: chromium trioxide 0,4-4,0, aluminum oxide, 1,4-9,0, zinc oxide 0,7-3,5, silicon dioxide - the rest. According to the invention is a method of obtaining oxide-chromium catalyst (co)polymerization of ethylene comprises applying a mixture of nonahydrate nitrate chromium (III) and aluminium and addition of uranyl nitrate zinc from their solution in organic solvent media is silicon dioxide, evaporating the solvent, drying the resulting product and its oxidative activation in a stream of dry oxygen-containing gas. While the application of the nitrates of chromium, aluminum and additionally nitrate zinc exercise of their solution in a mixture of ethanol with acetone in a volume ratio of 1: (2-7), and thermal-oxidative temperature rise from the temperature drying before it is given a constant value carried out with the speed of 100-150oWith/including Technical result is an increase in the activity of the catalyst and the narrowing of the molecular mass distribution (MMD). 2 C. p. F.-ly, 3 tables.

The present invention relates to polymerization catalysts containing chromium trioxide deposited on a solid inorganic oxide carrier of nature, i.e., an oxide-chromium catalysts (UCC), and methods for their preparation. These catalysts are used for the polymerization of ethylene and copolymerization with-olefins (propylene, butene-1, hexene-1, 4-methylpentene-1 and other ) in suspension, solution or gas-phase processes by the method of low pressure.

Known [U.S. patent 3132125, NCI 260-88.2, publ. 1964] oxide-chromium catalyst (co)polymerization of ethylene, comprising trioxide chromium oxide and a carrier composition SiO2Al2ABOUT3(silica - alumina) with the following content of components in the catalyst, wt.%:

The chromium trioxide - 4,3 - 5,5

The aluminum oxide with 12.3 and 12.4

Silicon dioxide - Rest.

The specified catalyst is used in all three of the above processes, the polymerization of ethylene and copolymerization with-olefins at low pressure in suspension, solution and gas-phase.

oC and total pressure of 32 at the sample of this catalyst containing 4.3 wt.% SGAs3, 12.4 wt.% Al2ABOUT3and 83.3 wt.% SiO2the output of polyethylene (PE) is only 54 g PE/g catchat. Received PE when its average MM, equal to 120103g/mol, contains fractions with MM within 2,8103to 175103g/mol, i.e., has a very broad molecular mass distribution (MMD) (high polydispersity).

UCC for U.S. patent 3132125 are impregnated carrier composition SiO2Al2O3a solution of chromium trioxide or ammonium chromate (substance, decomposing when heated in an oxidizing atmosphere with the formation of SGAs3), drying, and subsequent activation of the obtained product in the stream of dry air at a temperature of 450-850oC for 5-10 hours (in the case of, for example, the above sample of the catalyst temperature and activation time were respectively 540oC and 10 h).

The disadvantage of this method of preparation of the catalyst is that it does not provide a sufficiently high activity catalysis is the deposition of chromium compounds on the carrier. In U.S. patent 3132125 specific type of solvent is not specified, however, it is known [U.S. patent 5543376, MKI C 08 F 4/24, publ. 1996], for example, that water can cause destruction of the pores of the support of the UCC and the reduction, as a consequence, the activity of the catalyst.

Also known [patent UK 1391772, MKI C 08 F 4/26, 4/24,publ. 1975] UCC (co)polymerization of ethylene, comprising trioxide chromium oxide and a carrier composition SiO2Al2O3having, in particular, the following content, wt.%:

The chromium trioxide - 2,0

Alumina - 0,2

Silicon dioxide - Rest

After processing modifier - fluorine-containing compound, the catalyst contains 1.1 wt.% fluorine.

This catalyst is used in the suspension polymerization of ethylene and copolymerization with-olefins.

The advantage of this catalyst is to ensure the synthesis of (co)polymers with a narrow MMD compared with the UCC, not containing fluorine. So, synthesized in the environment of isobutane at a temperature of 109oC and total pressure of 42 at this catalyst PE is characterized by the ratio of its melt flow index (MFR) at 190oWith defined with loads of 21.6 kg and 2.16 kg (MFR21, the sample of the same UCC, but not containing fluorine, the ratio of MFR21,6/VKT2,16is 130. The ratio of the TPP at various loads is an indirect characteristic width of the mold thermoplastics. In [Carrick W. L., R. J. Turbett, Karol F. J. et al., J. Polymer Sci., A-1, 1972, v. 10, N 9, p. 2609-2620], devoted to the study of the polymerization of ethylene deposited chromium catalysts, DFID produced PE with respect to the TPP21,6/VKT2,16= 80-100 characterized as "relatively wide" according to the direct study using high-temperature gel chromatography (GPC).

It is also known [J. H. Schut, Plast. World, 1996, v. 54, No. 9, p. 43-44, 46, 48] that PE too wide MMP contains a significant share of both low molecular weight and high molecular weight fractions. The first fraction affects the strength and organoleptic properties of the polymer, in particular gives it a smell and stickiness; significant content in the polymer macromolecules with very high MM, although it provides high strength characteristics, a negative effect on the technological properties of the material during its processing into products. According to [Baulin A. A., Black, A. I., L. Slavin, etc.. Reservoir, mass, 1985, 8, S. 7-9] for PE, obtained under the action of applied chromiferous taper pipes, optimal is the relationship PTR21,6/VKT2,16in the range of 80-90.

The disadvantage of the catalyst by the United Kingdom patent 1391772 is its low catalytic activity, characterized by the polymer yield, equal to 34 g PE/g catcat (polymerization conditions: isobutane, temperature 109oWith the pressure of 42 ut). Lower activity of this catalyst compared to the above UCC for U.S. patent 3132125 is probably connected not only with a lower content of chromium trioxide, but with a much lower content of aluminum oxide, i.e., suboptimal content component.

The catalyst according to the patent in the UK 1391772 receive treatment traditional UCC, for example, a commercial catalyst composition CrO3/SiO2Al2O3, hexaferrites ammonium (NH4)2TiF6(or in the dry mixture, or from a solution of the latter compound in "appropriate" (not specifically indicated) solvent) and subsequent heat treatment in the atmosphere of dry air at a temperature of 400-1000oC for 0.5 to 12 hours.

The disadvantages of this method of preparation of the catalyst are:

1. the inability to ensure a high yield of polymer research Institute of chromium compounds on the carrier, especially when getting commercial UCC, and the processing of the UCC hexaferrites ammonium);

2. the use (and education) in the preparation of the catalyst of toxic fluorine-containing substances. It is known [Harmful substances in industry. T. H. Inorganic and ORGANOMETALLIC compounds. /Ed. by N. In.Lazarev and I. D. Galassini. - L.: Chemistry, 1977, S. 28-41] that fluorides and hydrogen fluoride HF - in this case, it is formed by thermal decomposition of (NH4)2TiF6- have a high General toxicity.

Known [Patent EPO 0364635, MKI C 08 F 10/00, 4/24, publ. 1990] the catalyst for the (co)polymerization of ethylene, comprising trioxide chromium oxide carrier composition SiO2TiO2and oxide modifier selected from the oxides of metals of main group II group of the Periodic system of elements, such as beryllium, magnesium, calcium, strontium, barium or radium containing not less than 0.5. % of water, in particular, with the following content of components in the catalyst, wt.%:

The chromium trioxide - 0,3

Titanium dioxide - 5,9 - 6,4

Magnesium oxide - 9,0 - 15,0

Silicon dioxide - Rest

The specified catalyst used in the suspension polymerization of ethylene and copolymerization it is on the more narrow MMD, than in the case of unmodified UCC, and without the use of the preparation of the catalyst of toxic fluorine compounds.

So, synthesized in the environment of isobutane at a temperature of 97oC and total pressure of 33 at the sample of this catalyst containing 0.3 wt.% SGAs3, 5.9 wt.% TiO2, 15.0 wt.% MgO and 78.8 wt.% SiO2copolymer of ethylene with 1-hexene (SEG-1) is characterized by the ratio of MFR21,6/VKT2,16=92; in the absence of MgO in the catalyst of this attitude is 187.

The disadvantages of the catalyst according to the patent EPO 0364635 are low catalytic activity and the selectivity of its action (only in a narrow temperature range (co)polymerization). Thus, the output of a copolymer of ethylene (SEG-1) in the above conditions (at a temperature of 97o(C) in this catalyst (containing 15.0 wt.% MgO) is only 13 g SEG-1/y catchat. When carrying out copolymerization of ethylene with hexene-1 on the same sample of the catalyst, but not at a temperature of 97oAnd when 90oWith regard to the TPP21,6/VKT2,16synthesized SEG-1 is not only not reduced relative to the specified value 187 (in the case of unmodified UCC), and, conversely, increases and 395.

IDA chromium, but, in General, suboptimal ratio of all its components.

The catalyst according to the patent EPO 0364635 obtained by processing the traditional UCC composition SGAs3/SiO2the hydrocarbon solution of the alcoholate of titanium, for example hexane solution of tetraisopropoxide, solvent removal (evaporation), drying of the product and its oxidative activation in a stream of dry air, for example at a temperature of 825oC for 16 hours, and further dried mixture cooled received UCC composition SGAs3/SiO2Tio2with the modifying oxide of a metal of main group II group of the Periodic system of elements.

The disadvantage of this method of preparation of the catalyst is that the method cannot provide a catalyst with high activity and stability of catalytic properties. This may be related to both duration (16 hours) high temperature (825o(C) stage oxidative activation that, in addition to significant energy costs can lead to the deterioration of the porous structure of the catalyst by sintering its pores), and with the introduction of the catalyst modifier oxide by dry mixing of powders that do not provide, varaaccurntom level.

Closest to the claimed catalyst essential features is the UCC according to the U.S. patent 4169925 [MKI C 08 F 004/26, 004/24, 010/00, 010/02, publ. 1979] (prototype). The specified oxide-chromium catalyst (co)polymerization of ethylene include chromium trioxide, aluminum in the form of aluminum oxide (Al2O3) and silicon dioxide as the carrier in the following, wt.h. on 100 wt.h. silicon dioxide:

The chromium trioxide - 0,3 - 10

The aluminum/aluminum oxide - 0,1/0,2 - 10/19

or in wt.%:

The chromium trioxide - 0,3 - 9,1

Aluminum oxide is 0.2 - 16,0

Silicon dioxide - Rest

The described catalyst is used in all three processes of polymerization of ethylene and copolymerization with-olefins at low pressure - suspension, solution and gas-phase.

The advantage of the catalyst according to U.S. patent 4169925 (the prototype) is higher catalytic activity than in the above equivalent yield of the polymer in the polymerization of ethylene in the environment pentane at a temperature of 102oC and total pressure of 35 at the sample catalyst containing 2.0 wt. including SGAs3and 1.5 wt. H. Al (2.8 wt. H. Al2O3to 100 wt. h SiO2or 2.0 wt.% SGAs3with 2.7 wt.% Al2

The disadvantage of this catalyst (the prototype) is getting this catalyst (co)polymers of ethylene with only broad MMD. The ratio of MFR21,6/VKT2,16for PE, synthesized on the catalyst in the above-mentioned polymerization conditions, is equal to 145. (Co)polymers with such a broad MMD recommended for the production of balagopalan films.

In addition, output (co)polymer using UCC prototype is not high enough.

UCC (co)polymerization according to the U.S. patent 4169925 (prototype) they are applied on the carrier - silicon dioxide mixture of compounds of chromium and aluminum from their solution in individual organic solvent, for example a mixture of nonahydrate nitrate chromium (III) CR(NO3)3N2O and nonahydrate of aluminium nitrate Al(NO3)3N2O from their solution in ethanol, evaporation of the solvent, drying the resulting product and its subsequent oxidative activation in a stream of dry oxygen-containing gas at a temperature of 600-1000oWith, preferably 700-950oWith over 0,17-to 6.67 hours, preferably 1-5 hours. E of nonahydrate nitrates of chromium and aluminum on silica gel (SiO2) is conducted in a stream of dry oxygen at a temperature of 850oC for 2 hours. The time-temperature conditions of the heat-dried product of the application of the compounds of chromium and aluminum to the media before the stated activation temperatures (600-1000oC) U.S. patent 4169925 not regulated.

As in U.S. patent 4169925 as the source of aluminum compounds in the preparation of the catalyst used, in particular, Al(NO3)3N2O, but in the "end" of the catalyst indicate the content of aluminum, it should be noted that in conditions similar to the above conditions thermal-oxidative activation, aluminum nitrate decomposes with the formation of aluminum oxide [Chemical encyclopedia/CH. Ed. I. L. Knunyants. -M.: Owls. day., 1988, T. 1, S. 118].

The method of obtaining the UCC (co)polymerization of ethylene according to the prototype allows to obtain a catalyst with a relatively high activity, but it does not provide the preparation of the catalyst, allowing to obtain (co)polymers of ethylene with a more narrow MMD than unmodified UCC. In addition, thermal-oxidative activation of the catalyst is carried out at high temperatures (preferably at 850oC).

Teachi ethylene, is getting on this catalyst (co)polymers of ethylene with a higher output and a more narrow molecular weight distribution.

This technical result is achieved due to the fact that oxide-chromium catalyst (co)polymerization of ethylene comprising chromium trioxide, aluminum oxide and silicon dioxide as the carrier additionally contains zinc oxide in the following content of components in the catalyst, wt.%:

The chromium trioxide - 0,4 - 4,0

Aluminum oxide - 1,4 - 9,0

Zinc oxide - 0,7 - 3,5

Silicon dioxide - Rest

The technical result, which provides the inventive method of obtaining UCC (co)polymerization of ethylene is increased activity of the prepared catalyst, the narrowing of the MMD of the synthesized (co)polymers, as well as to reduce the temperature of thermal-oxidative activation of the catalyst.

This technical result is achieved due to the fact that in a method of producing oxide-chromium catalyst (co)polymerization of ethylene, comprising applying a mixture of nonahydrate nitrate chromium (III) and aluminium from their solution in organic solvent media is silicon dioxide, evaporating the solvent, soo what about the gas, on the media - silicon dioxide simultaneously with the application of a mixture of nonahydrate nitrate chromium (III) and aluminium in addition put the uranyl nitrate zinc, as an organic solvent, a mixture of ethanol with acetone in a volume ratio of 1:(2-7), and thermal-oxidative activation of the obtained product is carried out in a stream of dry air at constant temperature lying in the range from 450 to 750oS, and the temperature rise from the temperature drying before it is given a constant value carried out with the speed of 100-150oC/hour. The uranyl nitrate zinc Zn(NO3)26H2O is a precursor of zinc oxide, as well as nonahydrate nitrate chromium (III) and aluminium are precursors SGAs3and Al2ABOUT3respectively.

When conducting research on modification of the UCC by the authors of the present invention was installed, the effect of the promotion of the catalytic properties of the catalyst with the introduction of its composition of zinc oxide in a specific narrow range of its quantities. The increase of catalytic activity of the UCC with the introduction of zinc oxide was an unexpected effect, since, as mentioned above, known modification is In 0364635), not only enhancing the catalytic activity of the catalyst, but even leads to the opposite result, namely to decrease. So, if the activity of the catalyst according to the patent EPO 0364635 - UCC, modified by the introduction into its composition MgO in an amount of 15 wt.%, is 13 g SEG-1/y catcat, in the same polymerization conditions of the original UCC, not containing MgO has a higher activity - 19 g SEG-1/y catchat.

The introduction of the oxide-chromium catalyst composition SGAs3/SiO2Al2O3zinc oxide is found according to the present invention the optimum quantitative content, along with identified and implemented optimal concentration of all other components, probably leads to an increase in the number of chromic active centers (AOC) in the catalyst and/or an increase in reactivity in the process of (co)polymerization, as well as to reduce "polycentricity" these AC (fewer types of AC with different reactivity). This may be due to specific electronic influence of zinc oxide on the neighboring chrome AOC as part of the UCC.

By reducing the content of zinc oxide in the catalyst below the bottom of the claimed PR is the actual content of ZnO is above the upper limit (more than 3.5 wt.%) does not lead to further improvement of the properties of the catalyst his activity and MMP (co)polymers are characteristic of the catalyst level (see our test examples 15 and 16).

Installed in accordance with the present invention the increased activity of the UCC and the narrowing of the MMD (co)polymers synthesized catalyst obtained by the present method, is probably associated with ensuring the application of this method of increasing concentrations of AC in the composition of the catalyst and reduce the number of types of AC with different reactivity in the process of (co)polymerization. Such unexpectedly discovered by the authors of the effective methods of preparation of the inventive catalyst, as applied to medium - silicon dioxide mixture of compounds, the precursors of chromium trioxide and oxides of aluminum and zinc it is from their solution in ethanol-acetone-specific composition, and conducting thermal-oxidative activation of the obtained product in the stream of dry air it is in the above temperature and time conditions, it was impossible to predict in advance as techniques that ensure the achievement of the technical result of the present invention.

At lower volume ratio ethanol: acetone below the lower limit (Myung-the ratio is above the upper limit (above 1: 7) significantly extends the MMD obtained (co)polymer (see our test examples 17 and 18). The decrease and increase of the constant temperature thermal-oxidative activation (tanrespectively above and below the stated its limits (below 450oAnd above 750oC), as the increase in the rate of temperature rise from the temperature of the drying up of tan(we denote this rate as Wt) is higher than (>150oWith/h), leads to a significant decrease of the catalytic activity of the UCC (see our test examples 19-22); in addition, the reduction of tanbelow the lower limit (below 450oWith, reference example 19), and the increase of Wtthe above stated values (>150oS/h, reference example 22) lead to a considerable increase in polydispersity MM on the synthesized catalyst (co)polymers. Reduction of Wtbelow the declared value (less than 100oWith/h) is impractical because although it does not impair the quality of the catalyst, but leads to a significant increase in the duration of thermal-oxidative activation in its preparation.

The choice of solvent in the coating hydrates nitrates of chromium, aluminum and zinc on silica gel (SiO2) mixture of ethanol-acetone find the optimal composition of the derivative substances in industry. So 1. Of organic matter./Ed. by N. In.Lazarev and E. N. Levina. - Leningrad: Khimiya, 1976, T. 1, S. 363-368], isopropanol mixed with acetone does not have sufficient dissolving power with respect to applied to the silica gel in the necessary quantities of salts, etc.

For preparation of the inventive catalyst as a carrier used silicon dioxide (silica gel) with the following structural characteristics: specific surface area (Sbeats) - 220-350 m2/g; pore volume (Vthen) is 1.3-1.9 cm3/g; average particle size is 70-100 microns.

Drawing on silica gel nonahydrate nitrate chromium (III) CR(NO3)3N2O, nonahydrate of aluminium nitrate Al(NO3)3N2O and uranyl nitrate zinc Zn(NO3)26N2O from their solution in a mixture of ethanol with acetone specified composition is carried out in one stage in the dispersion medium in a pre-prepared solution containing all three of these salts. To ensure that the claimed catalyst composition using the following quantities of these salts, wt.h. on 100 wt.h. silicon dioxide:

Nonahydrate nitrate chromium (III) - 1,8 - 19,1

Nonahydrate of aluminium nitrate - 10,6 - 79,4

The uranyl nitrate zinc - 2,8 - 15,3

In avodat in traitorously glass flask with a volume of 0.3 l, equipped with an electromagnetic stirrer drive and reverse water-fridge, and subsequent oxidative activation dried her product in a quartz column (the activator), equipped in the lower part of the porous plate to distribute the flow of gas and a pocket for thermocouple; this column was placed in a vertical muffle furnace. The duration of activation at a given constant temperature (in the range of 450-750oC) - 2-5 hours.

The inventive catalyst used in the polymerization of ethylene and copolymerization with-olefins (propylene, butene-1, hexene-1, 4-methylpentene-1 and others) at a temperature of 40-110oC and a pressure of 1-50 at in suspension or gas-phase modes (co)polymerization to obtain a linear polyethylene of high, medium and low density.

The molecular weight of synthesized on the claimed catalyst (co)polymers, indirectly characterized by the values of their TPP, regulate the temperature change of thermal-oxidative activation of the preparation of the catalyst, temperature change (co)polymerization and partial pressure of ethylene, and an introduction to the polymerization zone hydrogen and variation of its concentration; the density (with the use of the inventive catalyst (co)polymers, characterized by the ratio of MFR21,6/VKT2,16= 70-94, can be used for pipes and films by extrusion.

The melt flow index (co)polymers is determined at a temperature of 190oAnd loads of 2.16 kg and 21.6 kg according to GOST 11645-73; a density at a temperature of 20oWith GOST 15139-69. All of the following examples illustrating the present invention, the catalyst was tested in a reactor with a volume of 1.5 liters, equipped with a magnetic agitator and a jacket for heating, suspension and gas-phase (co)polymerization of ethylene.

Example 1.

1. The preparation of the catalyst.

To 10 g of silica gel - SiO2(Sbeats=305 m2/g, Vthen=1,80 cm3/g), dried at 200oWith a stream of nitrogen, poured 100 ml of the solution prepared by dissolving in a mixture of 20 ml ethanol and 80 ml of acetone (volume ratio 1:4) 0,81 g SG(NO3)3N2O, 4,16 g of Al(NO3)3N2O and 0.84 g of Zn(NO3)26N2O, and stirred at 20oWith four hours. Then the solvent is removed by evaporation at elevated temperature to 100oWith continued stirring and dried the product at this temperature in a stream of nitrogen for 4 hours.

Conditions of preparation and the composition of the catalyst obtained in example 1 and all the following examples in table 1.

2. The suspension polymerization of ethylene.

The received UCC experience in the suspension polymerization of ethylene in the environment, clean and dry isopentane (0.75 l) at a temperature of 100oC and total pressure of 35 ATA, supported by a constant supply of ethylene. The addition of catalyst equal 0,046 g, the polymerization of 2 hours. The polymer yield (PE) is 314, the Average activity of the catalyst is equal to 98 g of PE/g catchat. The resulting polymer is characterized PTR21,6=14,7 g/10 min, MFR21,6/VKT2,16= 77, density 0,961 g/cm3.

Conditions and results of the polymerization tests catalysis is found in tables 2 and 3.

Example 2.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but feel it when the suspension copolymerization of ethylene with hexene-1.

2. Suspension copolymerization of ethylene with hexene-1.

The copolymerization of ethylene with hexene-1 is carried out in the conditions of example 1, but before the process is injected into the reactor of 6.73 g (10 ml) of 1-hexene, and the addition of catalyst equal 0,039, the Output of the copolymer (SEG-1) is 371 the Average activity of the catalyst is equal to 136 g SEG-1/y catchat. The resulting copolymer is characterized PTR21,6= 16.0 g/10 min, MFR21,6/VKT2,16=76, density 0,944 g/cm3.

Example 3.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but feel it when the suspension copolymerization of ethylene with 4-methylpentene-1.

2. Suspension copolymerization of ethylene with 4-methylpentene-1.

The copolymerization of ethylene with 4-methylpentene-1 (obtained copolymer - SA-MP-1) is carried out in the conditions of example 1, but before the beginning of the process in the reactor is injected 6,66 g (10 ml) 4-methylpentene-1, and the addition of catalyst equal 0,043, the Output of the copolymer is 338, Sredna min, PTR21,6/VKT2,16=74, density 0,943 g/cm3.

Example 4.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but feel it when gas-phase copolymerization of ethylene with propylene.

2. Gas-phase copolymerization of ethylene with propylene.

The copolymerization of ethylene with propylene (obtained copolymer - BOT) is carried out in the same reactor as in example 1, but in the absence of isopentane, i.e., in-phase mode. The catalyst was tested at a molar ratio of the comonomers in their gas mixture WITH3H6/S2H4=0,08, temperature 90oWith constant total pressure of 11 at. The addition of catalyst equal to 0.036 g, the copolymerization time is 1 hour. The yield of copolymer is 69.3, the Average activity of the catalyst is equal to 175 g EPA/d catchat. The resulting copolymer is characterized PTR21,6= 12,1 g/10 min, MFR21,6/VKT2,16=81, density 0,938 g/cm3.

Example 5.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but feel it when gas-phase copolymerization of ethylene with butene-1.

2. Gas-phase copolymerization of ethylene with butene, what about as co monomer instead use propylene butene-1. The molar ratio of C4H8/C2H4=0,08, the addition of catalyst equal 0,045, the Output of the copolymer is 83,8 the Average activity of the catalyst is equal to 169 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6= 8.5 g/10 min, MFR21,6/VKT2,16=85, density 0,923 g/cm3.

Example 6.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but feel it when gas-phase copolymerization of ethylene with butene-1.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but in the reactor before the beginning of the process impose additional hydrogen. The partial pressure of hydrogen to 1.0 at a constant total pressure of 12 ATA, issued by the catalyst 0,040, the Output of the copolymer is 93.7 the Average activity of the catalyst is equal to 195 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6= 10.2 g/10 min, MFR21,6/VKT2,16=85, density 0,924 g/cm3.

Example 7.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, n of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 6, but at a temperature of 105oC. Suspension of the catalyst is equal to or 0.035, the Output of the copolymer is 90.9 the Average activity of the catalyst is equal to 216 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6= 21,7 g/10 min, MFR21,6/VKT2,16=70, density 0,926 g/cm3.

Example 8.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but thermal-oxidative activation of conduct, raising the temperature of the activator from the 100oWith speeds of 150oS/h to 550oS, i.e. within 3 hours, and 4 hours to activate the product at a constant temperature of 550oC. the Composition of the obtained catalyst similar to the catalyst composition of example 1.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 7, but with the addition of the catalyst obtained in this example, equal 0,034, the Output of the copolymer is 83,8 the Average activity of the catalyst is equal to 205 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=8.6 g/10 min, MFR21,6/VKT2,16=86, density 0,923 g/cm3.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 6, but at a molar ratio of butene-1 to ethylene WITH4H8/S2H4=0,03, the partial pressure of hydrogen of 0.5 and at a temperature of 110oC. Suspension of the catalyst obtained in this example, equal 0,037, the Output of the copolymer 84.4, the Average activity of the catalyst is equal to 190 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6= 13.5 g/10 min, MFR21,6/VKT2,16=79, density 0,940 g/cm3.

Example 10.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but thermal-oxidative activation of conduct, raising the temperature of the activator from the 100oWith speeds of up to 100oS/h to 450oS, i.e. for 3.5 hours, and 5 hours to activate the product at a constant temperature of 450oC. the Composition of the obtained catalyst similar to the catalyst composition of example 1.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this example, equal 0.048, measures characterized PTR21,6=11.2 g/10 min, MFR21,6/VKT2,16=86, density 0,940 g/cm3.

Example 11.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 8, but drawing on silica gel salts of chromium, aluminum and zinc are produced from their solution in a mixture of 33 ml of ethanol and 66 ml of acetone (volume ratio 1:2). The composition of the obtained catalyst similar to the catalyst composition of example 1.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this example, equal 0,041, the Output of the copolymer is 86.6, the Average activity of the catalyst is equal to 176 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=14.0 g/10 min, MFR21,6/VKT2,16=82, density 0,941 g/cm3.

Example 12.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 8, but drawing on silica gel salts of chromium, aluminum and zinc are produced from their solution in a mixture of 13 ml of ethanol and 91 ml of acetone (volume ratio 1:7). The composition of the obtained catalyst similar to the catalyst composition according primer-1 is carried out in the conditions of example 9, but when hanging the catalyst obtained according to this example, equal 0,034, the Output of the copolymer is 75,5 the Average activity of the catalyst is equal to 185 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=12.7 g/10 min, MFR21,6/VKT2,16=91, density 0,939 g/cm3.

Example 13.

1. The preparation of the catalyst.

UCC get in conditions analogous to example 8, but use for drawing on silica gel following salts: SG(BUT3)3N2About - 0.18 g, Al(NO3)3N2O - 1.06 g, Zn(NO3)26N2O - 0,28, the resulting catalyst contains 0.4 wt.% SGAs3, 1.4 wt.% Al2ABOUT3, 0.7 wt.% ZnO and 97.5 wt.% SiO2.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this example, equal 0,047, the Output of the copolymer is 96,0 the Average activity of the catalyst is equal to 170 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=13,2 g/10 min, MFR21,6/VKT2,16=94, density 0,939 g/cm3.

Example 14.

1. The preparation of the catalyst.

UCC is the amount of salts: SG(BUT3)3N2O is 1.91 g, Al(NO3)3N2O - 7,94 g, Zn(NO3)26N2O - 1,53, the catalyst containing 4.0 wt.% SGAs3, to 9.0 wt.% Al2ABOUT3and 3.5 wt.% ZnO 83.5 wt.% SiO2.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this example, equal to or 0.035, the Output of the copolymer is 85,4 the Average activity of the catalyst is equal to 203 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=14.3 g/10 min, MFR21,6/VKT2,16=75, density 0,942 g/cm3.

Example 15 (control).

1. The preparation of the catalyst.

UCC get in conditions analogous to example 8, but use for drawing on silica gel following salts: SG(NO3)3N2O - 0,79 g, Al(NO3)3N2O - of 4.05 g, Zn(NO3)26N2O - 0,16, the catalyst containing 1.8 wt.% SGAs3, 5.1 wt.% Al2ABOUT3, 0.4 wt.% ZnO and of 92.7 wt.% SiO2.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but when the catalyst is equal to 181 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=12.8 g/10 min, MFR21,6/VKT2,16=128, density 0,941 g/cm3.

Example 16 (control).

1. The preparation of the catalyst.

UCC get in conditions analogous to example 8, but use for drawing on silica gel following salts: SG(NO3)3N2O - 0,83 g, Al(NO3)3N2O - to 4.23 g, Zn(NO3)26H2O - 1,65, the catalyst containing 1.8 wt.% SGAs3, 5.1 wt.% Al2ABOUT3, 4.0 wt.% ZnO and 89.1 wt.% SiO2.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this example, equal 0,033, the Output of the copolymer is 80,8 the Average activity of the catalyst is equal to 204 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=14.5 g/10 min, MFR21,6/VKT2,16=76, density 0,942 g/cm3.

Example 17 (control).

1. The preparation of the catalyst.

UCC get in conditions analogous to example 8, but drawing on silica gel salts of chromium, aluminum and zinc are produced from their solution in the catalyst according to example 8.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this this example, equal 0,049, the Output of the copolymer is 81,9 the Average activity of the catalyst is equal to 139 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=14.5 g/10 min, MFR21,6/VKT2,16=104, density 0,942 g/cm3.

Example 18 (control).

1. The preparation of the catalyst.

UCC get in conditions analogous to example 8, but drawing on silica gel salts of chromium, aluminum and zinc are produced from their solution in a mixture of 10 ml of ethanol and 90 ml of acetone (volume ratio 1:9). The composition of the obtained catalyst similar to the catalyst composition in example 8.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this example, equal 0,038, the Output of the copolymer is 85.2, the Average activity of the catalyst is equal to 187 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=12.2 g/10 min, MFR21,6/VKT2,16=111, density 0,940 g/is up in the conditions, the same conditions of example 1, but thermal-oxidative activation of conduct, raising the temperature of the activator from the 100oWith speeds of up to 100oS/h to 400oS, i.e. within 3 hours, and 5 hours to activate the product at a constant temperature of 400oC. the Composition of the obtained catalyst similar to the catalyst composition of example 1.

2. Gas-phase copolymerization of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this example, equal 0,052, the Output of the copolymer is 83,3 the Average activity of the catalyst is equal to 133 g of SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=9.3 g/10 min, MFR21,6/VKT2,16=103, density 0,940 g/cm3.

Example 20 (control).

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but thermal-oxidative activation of conduct, raising the temperature of the activator from the 100oWith speeds of 150oS/h to 850oS, i.e. for 5 hours, and another 2 hours to activate the product at a constant temperature of 850oC. the Composition of the obtained catalyst similar to the catalyst composition according to application 1 is carried out in the conditions of example 9, but when hanging the catalyst obtained according to this example, equal 0,047, the Output of the copolymer is 71.2, the Average activity of the catalyst is equal to 126 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=26,6 g/10 min, MFR21,6/VKT2,16=72, density 0,943 g/cm3.

Example 21 (control).

1. The preparation of the catalyst.

UCC get in conditions analogous to example 20.

2. The suspension polymerization of ethylene.

The polymerization of ethylene is carried out in the conditions of example 1, but with the addition of the catalyst obtained in this example, equal 0,052, the polymer Yield is 298, the Average activity of the catalyst is equal to 82 g PE/g catchat. The resulting polymer is characterized PTR21,6=17,7 g/10 min, MFR21,6/VKT2,16= 74, density 0,961 g/cm3.

Example 22 (control).

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but thermal-oxidative activation of conduct, raising the temperature of the activator from the 100oWith speeds of 200oS/h to 750oS, i.e. for 3.25 hours, and another 2 hours to activate the product at a constant temperature of 750oC. the Composition of Poia of ethylene with butene-1.

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 9, but with the addition of the catalyst obtained in this example, equal 0,044, the Output of the copolymer is 63,0 the Average activity of the catalyst is equal to 119 g SEB-1/y catchat. The resulting copolymer is characterized PTR21,6=19,4 g/10 min, MFR21,6/VKT2,16=108, density 0,943 g/cm3.

Example 23 (control, prototype).

1. The preparation of the catalyst.

UCC get in conditions analogous to example 1, but on silica gel cause 0,81 g SG(NO3)3N2O and of 2.08 g of Al(NO3)3N2O from their solution in ethanol (100 ml), evaporation of solvent and drying of the product is carried out at a temperature of 80oWith the vacuum 8-10 MND, and thermal-oxidative activation of the obtained dried product is carried out in a flow of dry oxygen at a constant temperature of 850oC for 2 hours. Because this temperature is reached in the prototype are not regulated, the heated activator with loaded product from room temperature to 850oTo operate with an arbitrary velocity, namely 250oC/h, i.e., approximately 3.33 per hour. The catalyst containing 2.0 wt.h. SGAs2">

2. The suspension polymerization of ethylene.

The polymerization of ethylene is carried out in the conditions of example 1, but with the addition of the catalyst obtained in this example, equal 0,049, the polymer Yield is 263, the Average activity of the catalyst is equal to 77 g of PE/g catchat. The resulting copolymer is characterized PTR21,6=15.5 g/10 min, MFR21,6/VKT2,16= 141, density 0,961 g/cm3.

Thus, implemented in our test case the prototype out of the polymer and its relation PTR21,6/VKT2,16are similar to those specified in the patent-prototype (respectively 80 g PE/g catcat and 145), which allows to correctly match the performance characteristics of the inventive catalyst, identified in our polymerization conditions and catalyst of the prototype.

As can be seen from the data above, the description text and in tables 1-3, the inventive catalyst, such as chromium trioxide, aluminum oxide and silicon dioxide as the carrier of the oxide of zinc for optimal content of all these components has a higher activity, characterized by output (co)polymers of ethylene within 98-216 g/g catcat than the catalyst about the polymers are characterized by a narrow MMD (PTR21,6/VKT2,16=70-94) than the (co)polymers produced by the catalyst of the prototype (PTR21,6/VKT2,16=145).

Realized the advantages of the proposed catalyst in comparison with the catalyst of the prototype are provided not only additional inclusion in the composition of oxide of zinc for optimal content of all components in the catalyst, but also by the claimed method thereof. These features of the proposed method, as the use during the simultaneous application to the media - silicon dioxide mixture of salts of chromium, aluminum and zinc are not individual organic solvent, and a pair of selected organic solvents in their optimal volume ratio, and more "soft" temperature thermal-oxidative activation of the obtained product (lower permanent activation temperature (not more than 750oC) and regulated low speed achieve constant temperature) provide a good distribution of components in the composition of the catalyst and its optimal structure due to, for example, exceptions sintering time.

1. Oxide-chromium catalyst (co)polymerization of ethylene comprising chromium trioxide, aluminum oxide and silicon dioxide in which onenow in the catalyst, wt. %:

The chromium trioxide - 0,4 - 4,0

Aluminum oxide - 1,4 - 9,0

Zinc oxide - 0,7 - 3,5

Silicon dioxide - Rest

2. The method of obtaining oxide-chromium catalyst (co)polymerization of ethylene, comprising applying a mixture of nonahydrate nitrate chromium (III) and aluminium from their solution in organic solvent media is silicon dioxide, evaporating the solvent, drying the resulting product and its subsequent oxidative activation in a stream of dry oxygen-containing gas, characterized in that the carrier is silicon dioxide simultaneously with the application of nonahydrate nitrate chromium (III) and aluminium in addition put the uranyl nitrate zinc, as an organic solvent, a mixture of ethanol with acetone in a volume ratio of 1: (2-7), and thermal-oxidative activation is carried out in a stream of dry air at constant temperature in the range from 450 to 750oS, and the temperature rise from the temperature drying before it is given a constant value carried out with the speed of 100-150oS/h

 

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