Precatalytic composition for homo - and copolymerization- olefins and method of reception

 

(57) Abstract:

The invention relates to precatalytic compositions suitable for Homo - and copolymerization of olefins and to a method for producing such precatalytic composition. Precatalytic composition was prepared by treating an inorganic carrier component system consisting of a complex of mineraloid and tetraalkylated and gloriouse aluminum compounds. To increase the ratio of Mg:Ti system component further comprises magyarkanizsa connection. The technical result - the creation of the composition, upon receipt of which is not required titanium tetrachloride and electrondonor, resulting in shortcomings of their application. 2 C. and 10 C.p. f-crystals, 1 table.

The invention relates to precatalytic compositions suitable for Homo - and copolymerization of olefins and to a method for producing such precatalytic composition and to its use together with ORGANOMETALLIC socialisticheskom compound for the polymerization of olefins.

The catalytic system of the Ziegler-Natta, consisting of the so-called pronatalistic and socializaton, typically used for the polymerization of olefins. Precatalysts is ablity elements. The catalytic system usually also contains electron-donating compounds which improve and modify the catalytic properties.

Upon receipt of heterogeneous catalysts polymerization is traditional that as a component increasing polymerized activity pronatalistic, use the media, which caused a transition metal compound. Conventional carriers are silica, alumina, magnesium oxide, titanium oxide or of a mixture of various forms of carbon and different types of polymers. It turned out that an important connection carriers are magnesium compounds such as alkoxides, hydroxides, oxyhalide and halide compounds among the above, in particular magnesium dichloride has recently become the most important component pronatalistic compositions.

Because compounds of magnesium and magnesium halides in particular are not activated in their main crystalline form of their crystalline structure was very effective deformed by transition metal compounds. One way of ensuring deformed or amorphous crystal structure of the compounds of magnesium is the deposition of the magnesium connection, connect the e media. Such methods are well-known.

In U.S. patent 4 363 746 offered one option deposition of complex mineraloid-tetraallylsilane with dipterygium connection or alkylamidoamines and subsequent processing chetyrekhkhloristym titanium. Moreover, the catalyst may be diluted by mixing with, for example, silicon oxide. Thus, there is no question about the catalyst based on material media, but says the dilution of the catalyst is too active in certain conditions of polymerization, silicon oxide or equivalent inert material. There is no mention of the material of the carrier in the claims.

In European patent application 45969 described the dissolution of magnesium chloride, in tetraethoxide titanium in hexane and the precipitation mixture ethylaminoethanol. After decanting, the residue is suspended in hexane, prepolymerized ethylene and then treated with ethylaminoethanol and titanium tetrachloride. The disadvantage of the method described in the publication, is the uncontrolled deposition, as well as some processing compound of the transition metal.

In the above-mentioned publications activating laminated is removing excess titanium tetrachloride from the catalyst requires additional stages of leaching and leads to high costs and environmental problems when cleaning solvents used.

In the Finnish patent application 895703 describes a method for solid precatalytic composition in which the solid carrier is impregnated with a mixture of halide compounds of magnesium and transition metal compounds, the solvent is a halide compound of magnesium, and chlorine compound that does not contain titanium. The use of titanium tetrachloride shall be resolved in accordance with this method. The molar ratio of Mg : Ti, used in the way that is usually about 0.5 and cannot be higher than about 1. The obtained polymerization activity against titanium is usually about 100 kg PE/GT hour, and residual titanium in the polymer is about 10 ppm.

In the Finnish patent application 913020, which corresponds to Italian application 20740/90 P, describes how to obtain a solid catalytic component containing titanium, magnesium, chlorine and alkoxygroup on oxidechineese media. In the method first prepare a solution of magnesium chloride and electron-donating compound or ethanol and impregnate the carrier of this solution, after which the particles of the medium containing ethanol and magnesium chloride in a molar ratio of from 5:1 to 6:1. Followed by partial removal of the ethanol under load is of osites then treated with a compound of titanium, for example, a titanium alkoxide, and finally alkylamidoamines. Furthermore, the material of the medium containing the source material, can be activated in advance when heated, or alternatively, when the processing of ORGANOMETALLIC compound, for example, minialbum.

In the method of obtaining precatalytic compositions described in the Finnish patent application 901895, the solid carrier is impregnated with a mixture of halide compounds of magnesium, transition metal compounds, dissolved in halide compound of magnesium, and electron-donating compounds, dissolving/suspending the magnesium halide, and glorious connection, which does not contain titanium. The use of electrondonor allows to increase the molar ratio of Mg:Ti and at the same time provides a higher activity of the catalyst relative to the transition metal, typically above 200 kg/g Ti h, the residual titanium in the polymer then is less than 5 ppm.

The aim of the present invention is to provide precatalytic composition, upon receipt of which is not required titanium tetrachloride and electrondonor, resulting in shortcomings of their application.

This goal is achieved predlozhenietaiwan socialization and which is obtained by forming component system, which consists of inorganic media, complex compounds of magnesium halide and tetraallylsilane, and chlorinated compounds not containing a transition metal, and for the specified component system additionally add magyarkanizsa compound in an amount such that the ratio of magnesium/titanium was at least equal to 1, preferably higher than 1, and the preceding stage is conducted without using any polar solvent.

The advantage of the invention in relation to Finnish application 895703 is that the molar ratio of Mg:Ti. usually above 1 mol/mol, and the activity is usually above 200 kgpe/g Ti h and achieve the residual quantity of titanium in the polymer is less than 5 ppm when using magyarkanizsa connection in addition to the halide to the compound of magnesium. Application magyarkanizsa connection can significantly accelerate the synthesis of the catalyst compared with the method described in Finnish patent application 901895. Not required evaporation and interaction with electron-donating compound and, consequently, upon receipt of the catalyst is sufficiently one stage of drying as the last stage of the synthesis.

Although the same source materin 913020, however, the claimed composition is distinguished by the fact that the same source material is added in a different order and, in addition, were used, such raw materials, which are not all used in the catalyst according to the present invention. The way you add and how to add the source materials is of great importance for the properties and composition of the catalyst, because the source material is added at each stage, reacts chemically with chemical compounds formed by the components added in the preceding steps, and not the components themselves. The complex of magnesium chloride and alkoxide of titanium, formed in advance, therefore, not used in the Finnish patent application 913020. Optional suggested use of manilkara to activate the material of the carrier causes minialbum reacts with surface hydroxyl on the silicon oxide. In accordance with the invention magyarkanizsa connection is added to the finished component system for end-stage catalytic system. In the Finnish patent application 913020 magnesium chloride is always in combination with ethanol, which is a polar solvent. Adding alkoxide ti is CI method, described in the Finnish patent application 913020, can be attributed to the number of magnesium, which is many times greater than titanium, high amounts of chlorine, which is optionally included in the product, the relatively low activity, counting on Titan, and the complexities and difficulties of preparation: high temperature, rising and falling temperatures, several separate stages of drying and washing stages, which lengthen the time of the synthesis catalyst.

The material of the carrier used in the invention may be any porous inorganic or organic substance. Among the organic materials carriers may be mentioned polymers. Inorganic material, which are particularly advantageous include media materials based on oxides of silicon, aluminum, titanium and/or magnesium, These substances include, for example, silicon oxide, aluminum oxide, magnesium oxide, magnesium silicate, titanium oxide, etc., Particularly preferred are silicon oxide, aluminum oxide and magnesium silicate and mixtures thereof. Most preferred is silicon oxide. Suitable particle size of the material of the carrier is 10-200 μm, and preferably 20-150 μm. The material of the carrier is preferably chosen so Yes and/or surface hydroxyl groups can be removed, if desired, the material of the carrier is thermally and/or chemically.

Heat treatment involves removal of water at temperatures below 200oC and the annealing of surface hydroxyl groups at higher temperatures. The heat treatment is conveniently carried out at temperatures from about 100 to 1000oC.

Materials suitable for chemical treatment of the material of the carrier include organic compounds of silicon, aluminum, zinc, phosphorus and/or fluorine. Among suitable organic silicon compounds that are beneficial, there may be mentioned compounds of the formula (R3Si)2NH or formula RnSi X4-nwhere R is hydrogen and/or alkyl, X is a halogen, a n =1, 2, or 3. Among the best alyuminiiorganicheskikh compounds can be mentioned the compounds of formula (RnAIX3-n)mwhere R is hydrogen and/or hydrocarbon group containing 1-20 carbon atoms, preferably lower alkyl. X is a halogen, n = 1, 2, or 3, m = 1 or 2. Best phosphorus compounds include triploidy phosphorus, exitreality phosphorus, dialkylphosphate, monoalkylphenol and diaminetetraacetate. Suitable fluorine compounds include tetraploid of creoda magnesium, preferably magnesium dichloride, titanium alkoxide, a solvent at a temperature of about 20oC. the titanium Alkoxide is used at least in an amount such that the magnesium chloride dissolved completely, which means at least two mole of titanium alkoxide per mole of magnesium halide. Can also be added to the hydrocarbon solvent to the solution, for example, pentane or hexane, to improve the viscosity or fluidity of the solution.

The components of the complex magnesium halide-alkoxide of titanium may also be added to the material of the carrier without a separate dissolution so that the magnesium halide, a hydrocarbon solvent, if present, and tetraallylsilane mixed with the material of the carrier in any order, after which the mixture is stirred at temperatures above 20oC for several hours.

Gloriouse agent not containing a transition metal, advantageously are HCl, CCl4or especially a compound of the formula (RnAlCl3-n)mwhere R is a hydrocarbon group containing 1-20 carbon atoms, preferably lower alkyl, n = 1 or 2, m = 1 or 2. Typical compounds of aluminum, suitable for chlorination are alkylaminocarbonyl, such as IER is m gloriouse reagent may be added to the material of the carrier either before or after addition of the complex of Mg/Ti. Preferred the first of the above ways. Gloriouse reagent may preferably be added in a hydrocarbon solvent, for example, in the form of a solution in pentane. Can be used in other hydrocarbon solvents usually employed for this purpose. The chlorination can be carried out by simple mixing glorieuses reagent or its hydrocarbon solution with the material of the carrier and by mixing preferably at an elevated temperature within the maximum period of time (several hours). Mixing time and temperature of mixing are not critical and may vary within a wide range. A suitable blending can be, therefore, the time from 10 minutes to 4 hours, and the temperature of the mixture is in the range from 15 to 50oC.

Magyarkanizsa compound can be any compound of the formula RMgR' or a mixture of compounds of the indicated formula, or a complex compound of a specified formula with an organic compound of aluminum, boron, beryllium or zinc. In the formula R is a hydrocarbon group containing 1-20 carbon atoms, and R' is a hydrocarbon group containing 1-20 carbon atoms, or halogen. Suitable magnesium is d, ethylaniline etc.

It is important to magyarkanizsa connection is always added after glorieuses connection. It was noted that when magyarkanizsa connection is added to the material carrier over the other components, is clearly visible effect as a very low value of the MFR of the product of polymerization, as shown in the comparative examples below. Therefore, magyarkanizsa the connection can be added or as the last component, or after glorieuses connection and before adding complex minikleid-alcasid titanium. However, it is preferable to add it as the last component, or after glorieuses connection and before adding complex mineraloid-titanium alkoxide. However, it is preferable to add it as the last component. Magyarkanizsa connection usually added dissolved in a suitable hydrocarbon solvent, for example, dissolved in pentane or heptane, after which the obtained product is mixed, preferably at an elevated temperature for some time, for example, from 10 minutes to 4 hours at 20-50oC.

The number of added magyarkanizsa compounds chosen so obrazovatelno specified ratio above 1.

Getting precatalytic compositions according to the invention is carried out quickly and easily and, therefore, it is economical. The catalytic composition also works well when using a material carrier, which has not been processed at all, in this case, the entire process of obtaining includes only one stage of drying as the last stage of the synthesis. It was also noted that not required stage of leaching at all at any stage of receipt. Don't get the wash effluent and a hydrocarbon solvent/solvents can be recicladora for reuse.

The catalyst according to the invention is particularly suitable for the polymerization of ethylene with good activity and sensitivity to hydrogen and co monomer. In addition to the above advantages, the polymer has a narrow molecular weight distribution /for measuring the molecular mass distribution typically use the ratio of FRR /the ratio of the flow rate/ flow velocity of the melt /MFR, the flow velocity of the melt/ when the above values are measured using 21,6 and 2.16 kg weight/ good morphology for different applications and low chlorine residual and titanium.

Trace the MgCl2*2Ti (OC4H9)4.

Mixing 3.0 g of anhydrous magnesium dichloride and 21.8 ml of tetrabutoxide titanium by heating in a bath of 90 - 110oC for 20 hours to dissolve the material completely. The number of the obtained solution of the complex is 24,75 g, its density is equal 1,058 g/ml.

Example 1. Added to 6.0 ml of n-pentane and 10.7 ml of 10% aqueous solution of ethylaminoethanol /EADS/ pantale to 2,222 g of silica dried at 100oC, and stirred for 1 hour at 45oC. To the mixture was added 0,77 ml MgCl22Ti /OBu/4complex and stirred for 3 hours at 45oC. then added to a mixture of 3.8 ml of a 20% aqueous solution butylaniline /BOMAG-A/ heptane, stirred for 1 hour at 45oC and dried in a stream of gaseous nitrogen for 30 minutes at the same temperature.

The catalyst has the composition: Ti 2,2%, Mg Of 2.3%, Cl 13,2%, Al of 3.9%.

Example 2. Work according to the method of example 1, except that use 1.3 ml of a 20% aqueous solution of BOMAG-A in heptane.

The composition of the catalyst: Ti. 2,7%, Mg Of 1.2%, Cl 13,3%, Al Of 5.1%.

Example 3. Work according to the method of example 2 with the exception that use of 8.6 ml of a 10% aqueous solution of EADS in pentane.

The composition of the catalyst : Ti 2,4%, Mg Of 1.1%, Cl 10.6 percent on silicon.

The composition of the catalyst: Ti at 2.0%, Mg Of 1.1%, Cl 11,7%, Al of 3.9%.

Example 5. Work according to the method of example 1, except that the use of silicon oxide, calcined at 300oC.

The composition of the catalyst: Ti at 2.0%, Mg Of 2.3%, Cl 11,3%, Al of 3.5%.

Example 6. Work according to the method of example 1, except that the use of silicon oxide, calcined at 600oC.

The composition of the catalyst: Ti 2,3%, Mg Of 2.4%, Cl 12,0%, Al of 3.6%.

Example 7. Added to 6.0 ml of n-pentane and 10.7 ml of 10% aqueous solution of EADS in pentane to 2,222 r of silicon oxide, dried at 100oC, and stirred for 1 hour at 45oC, is Added to the mixture 5,08 ml of 20% aqueous solution of BOMAG-A in heptane and stirred for 1 hour at 45oC. then added 0.77 ml solution of complex MgCl22Ti /OBu/4to the mixture, stirred for 3 hours at 45oC and dried at the same temperature in a stream of gaseous nitrogen for 30 minutes.

The composition of the catalyst: Ti 1.9 per cent, Mg, 2.2%, And Cl Of 11.3%, Al of 3.9%.

Example 8. Add 10.0 ml of n-pentane and 0.77 ml of a solution of the complex MgCl22Ti /OBu/4to 2,222 g of silicon oxide, calcined at 600oC, and stirred at 45oC for 1 hour. Added to a mixture of 8.6 ml of a 10% aqueous solution of EADS in pentane and stirred at 45oC for 3 hours at the same temperature in a stream of gaseous nitrogen for 30 minutes.

The composition of the catalyst: Ti 2,1%, Mg, 0.97%, And Cl Of 9.4%, Al of 3.4%.

Example 9. Suspended 10.0 g of silicon oxide, calcined at 600oC, 65 ml of n-pentane. Added to a suspension of 0.48 ml of triethylaluminum /TEA/, stirred for 30 minutes at room temperature and dried at 50oC in a stream of gaseous nitrogen for 90 minutes.

Added to 6.0 ml of n-pentane and 0.39 ml of a solution of the complex MgCl22Ti /OBu/4it is 1.11 g of silicon oxide, processed TEA, and stirred at 45oC for 1 hour. Add to the mixture of 4.3 ml of a 10% aqueous solution of EADS in pentane and stirred for 3 hours at 45oC. then added to a mixture of 0.64 ml of a 20% aqueous solution of BOMAG-A in heptane and stirred for 1 hour at 45oC, dried at the same temperature in a stream of gaseous nitrogen for 30 minutes.

The composition of the catalyst: Ti 2,6%, Mg Of 1.4%, Cl 12,2%, Al of 3.8%.

Example 10. Suspended 11 g of silicon oxide in 85 ml of n-heptane. Raise the bath temperature to 110oC and distilled off about half of heptane. Added to a mixture of 1.75 g hexamethyldisilazane /HMDS/, stirred at 110oC for 2 hours, after which the mixture is filtered and dried in a stream of gaseous nitrogen in a bath at 110oC.

Repeat the method of preparation of the catalyst of example 9 with isklucheniia: Ti - 2,9%, Mg Of 1.4%, Cl 12,2%, Al Of 2.8%.

Example 11. Add to 1,11 g of silicon oxide, calcined at 600oC, 53 mg MgCl2, 0,38 ml Ti/OBu/4and 4.0 ml of n-heptane. Stir the mixture at 110-120oC for 4 hours and left overnight at room temperature for 16 hours. Add to the mixture of 4.3 ml of a 10% aqueous solution of EADS in pentane, stirred for 3 hours at 45oC. Finally added to the mixture of 0.64 ml of a 20% aqueous solution BOMAG in heptane, stirred for 1 hour at 45oC and dried at the same temperature in a stream of gaseous nitrogen for 30 minutes.

The composition of the catalyst: Ti at 2.0%, Mg, 0,78%, Cl 10,2%, Al of 3.1%.

Example 12 (comparative). Added to 6.0 ml of n-pentane and 6.35 ml of 20% aqueous solution of BOMAG-A in heptane to 2,222 g of silicon oxide at 100oC and stirred at 45oC for 1 hour. Added to a mixture of 10.7 ml of a 10% aqueous solution of EADS in pentane and stirred for 1 hour at 45oC. then add of 0.77 ml solution of complex MgCl22Ti /OBu/4to the mixture, stirred for 3 hours at 45oC and dried for 60 minutes at the same temperature.

The composition of the catalyst: Ti at 2.0%, Mg Of 3.2%, Cl 11,3%, Al of 3.6%.

Example 13 (comparative). Placed 6.0 g of microspheres of silica /Crosfield ES70X/, dried at 200oC, in a flask with a capacity of 120 ml in anarthriaceae in the form of a 20% solution in heptane /6,039 mmole/. The mixture was stirred at 60oC for 30 minutes and dried by evaporation of solvent.

In a flask with a capacity of 120 ml injected 0.6 g /6,302 mmole/ anhydrous magnesium dichloride and 13,33 ml /228,38 mmole/ absolute atenolo with humidity 184 ppm. The mixture was stirred at 60oC for 30 minutes for complete dissolution of magnesium chloride. In solution suspended 2.0 g of silicon oxide, activated butylethylmagnesium. The suspension is stirred for 30 minutes at 60oC, then add of 0.43 ml /1,252 mmole/ tetrabutyrate titanium, stirred for 1 hour at 60oC and then dried at the same temperature for 60 minutes and at 120oC for another 60 minutes. The thus obtained solid substance is cooled to room temperature and then suspended in 7.0 ml of n-pentane. To the suspension was added to 8.3 ml /2,187 mmole/ 10%-aqueous solution of ethylaminoethanol in pentane and stirred the mixture for 1 hour at 25oC. filtered the solid, washed with anhydrous pentane up until the chloride is no longer detected in the washing liquid, and finally dried by evaporation of the solvent. The ratio of Mg:Ti:Cl obtained in the solid catalyst is 6:1:13.

The composition of the catalyst: Ti 2,5%, Mg Of 7.6% Cl Of 24.0%, Al of 1.7%.

Example 14 (absolutely ethanol, having a moisture content of 184 ppm. The mixture is stirred for 30 minutes at 60oC to dissolve magnesium chloride completely. In solution suspended 2.0 g of silicon oxide, activated butylethylmagnesium according to example 13. The suspension is stirred for 30 minutes at 60oC, then dried for 30 minutes at the same temperature and then a further 60 minutes at 120oC, after which the solid material is cooled to room temperature and suspended in 15 ml of n-pentane.

To the suspension was added 0.74 ml /2,17 mmole/ tetrabutyrate titanium, stirred at 60oC for one hour and dried, viparita solvent. Obtained thus the solid product is cooled to room temperature and then suspended in 13 ml of n-pentane. To the suspension was added 16,58 ml /of 4.38 mmole/ ethylaminoethanol in the form of a 10% solution in pentane and stirred the mixture for 15 minutes at 25oC. Then the solid product is filtered off and washed with n-pentane until, while in the wash water cannot be detected chloride. For washing is required 3 times 15 ml of pentane. Then the thus obtained dried substance, viparita solvent. The ratio of Mg:Ti:Cl in the resulting solid catalyst is 4.6:1:10,2.

The composition Catania and 174,6 ml tetrabutoxide titanium at 80oC for 16 hours for complete dissolution of the material. The mixture is cooled to approximately the 50oC, then added to the mixture under stirring 105 ml of n-pentane. Get solution of 263 g of the complex, its density is 0,919 g/ml.

2,0 r silicon oxide /Crosfield ES70X/; dried at 100oC, add 8.0 ml of n-pentane and 4,58 ml of EADS in the form of a 20% solution in pentane and stirred for 1 hour at 45oC. To the mixture was added 1.1 ml MgCl22Ti /OBu/4complex in the form of a 75% yoga solution and stirred for 3 hours at 45oC. Finally, the catalyst was dried at 45oC in a stream of gaseous nitrogen for 30 minutes. The ratio of Mg:Ti:Cl is the resulting solid catalyst is 0.5:1:5,4.

Test for polymerization.

Carry out the polymerization of ethylene in each example as follows. In the autoclave with a capacity of 3 l load 1.8 l of isobutane, which was purified by trapping oxygen and moisture. Charged to the reactor 40-50 mg pronatalistic and socializaton /TEA, Al/Ti = 30-40/. Increase the temperature to 95oC. Pressure in the reactor with a capacity of 0.5 l is set equal to 5.5 bar using hydrogen, which is fed to the reactor together with ethylene as long as the total pressure is 28.5 bar. Provocati polymerization are presented in the table below.

As shown in comparative example 12, the procedure of adding the ORGANOMETALLIC compound is of considerable practical significance for the MFR value of the product of polymerization. In particular, when first added BOMAG directly to the silicon oxide, the MFR value of the product falls sharply.

Comparative examples 13 and 14 /mainly corresponding Finnish patent FI 914216 and FI 913020/ where BOMAG was added to the silicon oxide on the first stage of the synthesis and, in addition, a polar solvent, for example ethanol, was used for dissolving magnesium chloride, clearly show that the activity of the catalyst, calculated with respect to the titanium, significantly worse than kataliza tori according to the invention. Similarly, the amount of chlorine in the catalyst and, consequently, the amount of chlorine that have fallen into the product, and simultaneously the residual titanium content is significantly higher than similar values for the catalysts of the invention. Additionally, the synthesis of the catalyst is very difficult and slow compared to a very simple synthesis according to the invention.

Comparative example 15, which was not used magyarkanizsa connection, clearly the us in the table.

1. Precatalytic composition for Homo - and copolymerization of olefins, obtained using the impregnation of inorganic carrier solution MoCl2, connection Ti and gloriouse aluminum compounds in an organic solvent at a mass ratio Mg/Ti in the composition is at least 1, preferably above 1, wherein the inorganic carrier is additionally impregnated with magnetogenesis compound of the formula RMgR', where R, R' is alkyl WITH1-20.

2. The composition according to p. 1, characterized in that as magyarkanizsa compounds using n-butylethylamine or butylaniline.

3. The composition according to PP.1 to 2, characterized in that magyarkanizsa connection type as the last stage or at least after glorieuses connection.

4. The composition according to PP.1 to 3, characterized in that compounds of titanium use utiltity, propertythat or, more preferably, utiltity.

5. The composition according to PP.1 to 4, characterized in that as glorieuses connections use the connection formula (RnAlCl3-n)mwhere R is an alkyl with 1 to 20 carbon atoms, preferably lower alkyl, n = 1 or 2, m - 1 uninitialized.

7. The method of obtaining precatalytic compositions for Homo - or copolymerization of olefins, comprising the impregnation of inorganic carrier with a solution of MgCl2, connection Ti and gloriouse join Al in the medium of organic solvent when the mass ratio Mg/Ti in the composition is at least 1, preferably above 1, wherein the inorganic carrier is additionally impregnated with magnetogenesis compound of the formula RMgR', where R, R' is alkyl WITH1-20.

8. The method according to p. 7, characterized in that as magyarkanizsa compounds using n-butylethylamine or butylaniline.

9. The method according to PP.7 and 8, characterized in that magyarkanizsa connection type as the last stage or at least after glorieuses connection.

10. The method according to PP.7 to 9, characterized in that compounds of titanium use utiltity, propertythat or, more preferably, utiltity.

11. The method according to PP.7 to 10, characterized in that as glorieuses compound Al is used as a compound of the formula (RnAlCl3-n)mwhere R is an alkyl with 1 to 20 carbon atoms, preferably lower alkyl, n = 1 or 2, m is 1 or 2.

 

Same patents:

The invention relates to precatalytic component of the catalytic composition of the Ziegler-Natta, suitable for the production of polymers of ethylene

The invention relates to a ball of solid catalytic components for the polymerization of olefins containing compound of titanium deposited on a magnesium halide containing more than one relationship Ti-halogen and, optionally, containing groups other than halogen, in the amount of less than 0.5 mol per 1 mol Ti

The invention relates to a method for producing olefinic polymers (this is the name used to refer to both homopolymers and copolymers of olefins by polymerization (the term used to refer to as homopolymerization and copolymerization) of olefins

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely XkSiCl4-k, wherein X is OR' or R', in which R can be C1-C4-alkyl or phenyl, and k=1-2. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 13 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely phenyltrichloromethane PhCCl3. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 4 ex

FIELD: chemical technology, catalysts.

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EFFECT: improved and valuable properties of catalyst.

18 cl, 8 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to the catalyst component used in polymerization of olefins comprising Mg, Ti, halogen and at least two electron-donor compounds wherein indicated catalyst component and at least one of electron-donor compounds repenting in the amount in the range from 20 to 50 mole% with respect to the complete amount of donors are chosen from succinic acid esters that are not extractable by above 25 mole% and at least one additional electron-donor compound that is extractable by above 35 mole%. Indicated components of catalyst provides preparing polymers possessing good insolubility level in xylene, high content level of stereoblocks and broad MWD value that is suitable for preparing polymers used in the region using bi-oriented polypropylene films. Also, invention relates to catalyst used in polymerization of olefins, methods for preparing propylene polymers and propylene polymer.

EFFECT: improved preparing method, valuable properties of catalyst.

24 cl, 3 tbl, 17 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic systems used in polymerization of alpha-olefins, methods for preparing catalytic systems for polymerization of alpha-olefins and methods for polymerization (and copolymerization) of alpha-olefins. Invention describes the catalytic system for polymerization of olefins comprising solid titanium component of catalyst, organoaluminum compound comprising at least one bond aluminum-carbon and organosilicon compound comprising at least one (cycloalkyl)-methyl group used as an external donor of electrons. Also, invention describes the catalytic system for polymerization of olefins comprising solid titanium component of the catalyst prepared by contacting titanium compound with magnesium compound and comprising from about 0.01 to about 500 moles of titanium compound per one mole of magnesium compound, organoaluminum compound comprising at least one bond aluminum-carbon wherein the mole ratio of aluminum to titanium in the catalytic system is in the range from about 5 to about 1000, and organosilicon compound comprising at least one (cycloalkyl)-methyl group and used a external donor of electrons wherein the mole ratio of organoaluminum compound and organosilicon compound in the catalytic system is in the range from about 2 to about 90. Also, invention describes methods for preparing catalyst used in polymerization of olefins and comprising interaction of Grignard reactive comprising (cycloalkyl)-methyl group with ortho-silicate to form organosilicon compound comprising a (cycloalkyl)-methyl link, mixing organosilicon compound with organoaluminum compound comprising at least one bond aluminum-carbon and solid titanium component of the catalyst to form the catalyst, and a method for polymerization of olefins. Invention provides preparing propylene block-copolymer showing good fluidity in the melt, capacity for molding, hardness, impact viscosity and impact strength in combination with high effectiveness of the catalyst and good technological effectiveness of the preparing process.

EFFECT: improved and valuable properties of catalysts.

17 cl, 10 ex

FIELD: chemical industry; petrochemical industry; methods of production of the composition of the solid procatalytic agent for utilization in the catalytic compositions for polymerization.

SUBSTANCE: the invention is pertaining to the method of production of: the composition of the solid procatalytic agent for usage in the Ziegler-Natta type catalytic composition for polymerization; to the procatalytic agents for usage in the formation of the similar catalytic compositions; to the methods of their production and to the methods of their application for production of the olefinic polymer. The invention presents the method of production of the composition of the solid procatalytic agent for usage in the composition of the Ziegler-Natta procatalytic agent for polymerization of the olefins providing for: contacting the predecessor composition containing the magnesium compound with the compound being the titanium halogenide and the internal donor of electrons; separation of the solid procatalytic agent from the reactionary medium; the extraction of the composition of the solid procatalytic agent by its contacting one or several times with the liquid dilutant. The invention also presents the method (a version)providing for the phase of the solid procatalytic agent drying before the extraction of the composition. The invention also presents the description of the composition of the solid procatalytic agent for the usage in the Ziegler-Natta type catalytic composition for polymerization of olefins. The technical result of the invention is production of the catalytic compositions used in the production of the polymeric compounds of α-olefins, having the reduced contents of the xylene-soluble fractions and the heightened rigidity. The catalytic agents have the higher productivity and produce the polymers of α-olefins having the higher volumetric possibility to use the reduced levels of hydrogen for achievement of the equivalent molecular mass of the polymer, need the reduced quantities of the agents of regulation of selectivity and produce the polymers having the reduced contents of oligomers.

EFFECT: the invention ensures production of the catalytic compositions for production of the polymeric compounds of α-olefins with the reduced share of the xylene-soluble fractions, heightened rigidity, higher productivity, producing the polymers of α-olefins with the reduced share of oligomers.

9 cl, 11 tbl, 90 ex

FIELD: polymer production.

SUBSTANCE: invention relates to supported catalytic compositions, methods for preparing such compositions, and polymer preparation processes using these compositions. In particular, invention provides supported catalytic composition including interaction product of: (i) catalyst precursor composition comprising product of reaction of magnesium halide, an ether, electronodonor compound, in particular linear or branched aliphatic C1-C25-alcohol, and transition metal compound, in particular compound of group IV element; (ii) porous inert carrier; and (iii) cocatalytic composition; wherein supported catalytic composition contains less than 1% electronodonor compounds other than those including linear or branched aliphatic or aromatic alcohol having from 1 to 25 carbon atoms and wherein molar ratio of electronodonor compound to magnesium is less than or equal to 1.9. Described are also method of preparing supported catalytic composition, method of preparing polymer comprising reaction of at least one olefin monomer in presence of above-mentioned supported catalytic composition. Described are also supported catalyst precursor composition, supported catalytic composition, method of preparing supported catalytic composition, and method of preparing polymer comprising reaction of at least one olefin monomer in presence of supported catalytic composition, and supported catalyst precursor composition.

EFFECT: increased catalytic activity and enabled preparation of polymer for films at lower partial pressure of ethylene.

15 cl, 5 dwg, 3 tbl, 7 ex

FIELD: polymer production.

SUBSTANCE: invention relates to magnesium halide-based compositions, processes for preparation thereof and catalysts as well as to polymerization processes. Invention provides a component of magnesium halide-based olefin polymerization catalyst prepared from magnesium halide, solvent appropriate as electron donor, and electron-donor compound represented by linear or branched, substituted or unsubstituted aliphatic or aromatic alcohol having 1 to 25 carbon atoms, wherein magnesium halide is characterized by solubility in the solvent exceeds 0.7 mole/L and does fall under effect of increase in temperature up to boiling temperature. Catalyst precursor includes reaction product of the above-defined catalyst component and a second component including transition metal selected from group consisting of titanium, zirconium, hafnium, vanadium, and a combination thereof. Olefin polymerization catalyst disclosed includes reaction product of catalyst precursor with co-catalyst, namely alkylaluminum compound.

EFFECT: increased contend of magnesium in catalyst, increased solubility of catalyst, and reduced expenses on catalyst preparation in case of small amount of charge.

14 cl, 4 dg, 1 tbl

FIELD: polymerization catalysts.

SUBSTANCE: catalytic component according to invention contains magnesium, titanium, halogen, and electron donor, wherein the latter contains at least one compound, notably polyol ester I having general formula R1CO-O-CR3R4-A-CR5R6-O-CO-R2 (I), wherein groups R1 and R2, the same or different, represent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; groups R3-R5, the same or different, are selected from group consisting of hydrogen, halogen, and above-defined hydrocarbon residue, said groups R3-R6 optionally containing one or several heteroatoms substituting carbon and/or hydrogen atom, wherein said heteroatoms are selected from group consisting of oxygen and halogen atoms, or two or more groups R3-R6 being connected with each other to form saturated or unsaturated monocyclic ring; and A represents bivalent linking group between two hydrocarbon radicals having from 1 to 10 atoms, said linking group being selected from group consisting of aliphatic, alicyclic, and aromatic bivalent radicals and can bear linear or branched C1-C20-substituents, provided that two or more substituents of said linking group and above-defined R3-R6 groups can be interconnected to form saturated or unsaturated monocyclic ring. Invention further discloses catalyst containing above-defined solid catalytic component and its employment in polymerization of CH2=CHR hydrocarbons, wherein R represents hydrogen or C1-C6-alkyl group.

EFFECT: enabled preparation of polymers characterized by high stereoregularity and increased polymerization yield.

34 cl, 6 tbl, 110 ex

FIELD: polymer production.

SUBSTANCE: superhigh-molecular weight polyethylene is obtained in suspension conditions at temperature between 40 and less than 70°C in hydrocarbon solvent medium using supported catalyst. The latter is prepared through interaction of compound Mg(C6H5)2n*MgCl2*mR2O (R2O is ether, R = i-Am, n-Bu) with silicon compound, which is a product prepared by reaction of compound R1kSiCl4-k with silicon tetraethoxide Si(OR)4 (R1 represents methyl or phenyl and k=0.1) at molar ratio R1kSiCl4-k/Si(OR)4 = 2-4 at 15-45°C and Si/Mg = 1-2.5. Loose weight of obtained polymer is higher than 0.35 g/cc.

EFFECT: increased yield of superhigh-molecular weight polyethylene with improved morphology.

1 tbl, 13 ex

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