The spherical components of the catalyst for polymerization of olefins, polymerization catalysts, method of polymerization, copolymers of ethylene

 

(57) Abstract:

The invention relates to a spherical solid components of catalysts for the polymerization of olefins, comprising deposited on dihalogenide magnesium in an activated form of a compound of titanium, containing at least one link with a titanium halide and one OR group with the specified group OR is linked to an atom of titanium in such quantities that the molar ratio OR/Ti is greater than or equal to 0.5. It is also possible that the component includes an electron-donating compound. Spherical solid components of the catalyst are characterized by their porosity lies in the range between 0.35 and 0.7 cm3/g and such a pore distribution that at least 50% of the porosity is due to pores having an average radius of more than 800 Proposed catalysts of high activity and provide polymers with controlled morphology. 4 C. and 22 C.p. f-crystals.

The invention relates to components of catalysts for the polymerization of olefins, the catalysts obtained on their basis, and the use of catalysts for polymerization of ethylene and its mixtures with d-olefins of the formula CH2=CHR, where R is a hydrocarbon residue containing from 1 to 12 carbon atoms.

Heart and soul is trated form, which high level and provide polymers with controlled morphology, becomes more and more tangible.

Examples of catalysts having a controlled morphology, described in U.S. Pat. USA 3953414 and 4399054. In the latter patent, the components of the catalyst prepared from having a spherical form adducts MgCl2with about 3 moles of alcohol. To interact with TiCl4the alcohol content is reduced to a value of 2.5 to 2 moles: in this case, obtain the components, which have a porosity, measured by nitrogen, from 0.3 to 0.4 g/cm3and the average radius of the pores is between 15 and 20 .

Catalysts prepared from TiCl4or MgCl2in pellet form by spray drying an alcohol solution of magnesium chloride, followed by the application of the titanium compounds described in Heb. Pat. EP-B-65700 and EP-B-243327. However, the polymer obtained using these catalysts, does not have the necessary morphological characteristics. In particular, insufficient high bulk density. In addition, the activity of the catalyst is too small.

Method of increasing the activity of these catalysts is described in U.S. Pat. EP-A-281524. These catalysts are prepared by applying the alcoholate Titus is ylitalo drying its ethanol solution, with the subsequent chemical treatment of Et2AlCl or Et3Al2Cl3. Conditions of preparation of the media are critical and have an impact on the morphological stability of the resulting polymer. For example, polymers in the form of heterogeneous powder get when used in medium alcohol content lies outside the interval 18-20%, or use connections other than Et2AlCl or Et3Al2Cl3. In addition, to achieve high outputs of the Ti content in the solid component should be higher than 8% (wt.).

From Pat. application EP-A-395083 known catalysts suitable for polymers in a spherical form having a satisfactory morphological properties. These catalysts derived from adducts MgCl2-alcohol. Adduct, usually containing 3 mol of alcohol per 1 mol MgCl2is subjected to heat treatment to reduce the alcohol content is usually up to the level of 0.2-2 mole, and then it reacts with an excess of titanium tetrachloride, possibly containing dissolved therein electron-donating compound.

The solid components of these catalysts are characterized by high specific surface area and mikroporistogo (more than 50% of the pores have an average radius tilana low density leads to lack of uniformity in the distribution of co monomer.

Now unexpectedly been found that can be obtained catalysts having a spherical shape, which can lead to a homogeneous distribution of co monomer upon receipt of a linear low density polyethylene and, in General, upon receipt of the comonomers with the necessary morphological properties, in particular, polymers having a high bulk density, when carrying out the polymerization in the gas phase, despite the significant macroporosity solid components forming the catalyst.

The spherical components of the invention include applied on dihalogenide magnesium in an activated form titanium compound containing at least one chemical bond Ti - halogen and one OR group, where R represents alkyl, cycloalkyl or aryl group containing 1-18 carbon atoms or a COR group, and the above-mentioned OR-group is associated with a atom of titanium in such quantity that the resulting molar ratio OR/Ti was greater than or equal to 0.5; also may be present electron-donating compound.

The above components are characterized by a porosity value from 0.35 to 0.7 cm3/g and the distribution of pore pomade their surface generally lies in the range from 5 to 30 m2/,

The porosity values indicated above refer to measurements made on the pores having a radius of 10,000

The spherical components of the invention are additionally distinguished by the fact that at least 30% of the total porosity is due to pores having a radius greater than 10,000 Defined here total porosity refers to measurements carried out on the pores having a radius in the range from 0 to 300000

Porosity and specific surface area were determined using mercury porosimetry according to the method described below.

Dihalogenide magnesium in an activated form, included in the spherical component of the invention, different x-ray spectrum in which the most intense diffraction line appearing in the spectrum of active halide, has reduced the intensity and spectrum above line appears related to halogen, the maximum intensity of which is shifted towards smaller angles compared to the angles of the most intense line.

The particles have a spherical or spheroidal in shape with an average diameter of 10-150 μm. Under the particles have a spheroidal form, refers to particles for which the ratio of major axis to Starostina have the formula Ti(OR')nXy-nwhere n takes values greater than or equal to 0.5 and one less than the valence of titanium, y, and preferably lies between 1 and 2, if y = 4; X represents a halogen atom and R' represents an alkyl group containing 2-8 carbon atoms, in particular, ad-butyl, isobutyl, 2-ethylhexyl, N.-octyl and phenyl.

The connection of titanium, which must be applied to dihalogenide magnesium can be obtained in advance, or it is produced in situ by reaction of tetrachloride titanium, in particular, TiCl4with OH-groups of the residual alcohol present in bound form in the above dihalogenide magnesium, or by reaction of the above tetrachloride with alcohols ROH or titanium alcoholate having the formula Ti(OR)4.

Tetrachlorogallate titanium may also interact with halogenated compounds, such as, for example, SiCl4, AlCl3, CHLOROSILANES, Al-alkylhalogenide. In the latter case, the valence of titanium is reduced and formed galogenangidridy titanium, in which the valence of titanium is less than four.

Galogenangidridy titanium with a valence of titanium atom is less than four, can be also obtained by the reaction of therealchigoat Lesuuda in the preparation of catalyst component, can be in the form of complexes with halides of magnesium. Examples of receipt of the above complexes are given in U.S. Pat. USA 4218339, and their description is presented here.

Dihalogenide magnesium in an activated form, preferably magnesium dichloride, get in the form of adducts MgX2nROH, where R represents alkyl, cycloalkyl or aryl containing 1 to 12 carbon atoms, and n in the General case of more than two and, in particular, lies in the interval from 2.5 to 3.5.

Such adducts in a spherical form prepared from the molten adduct by emulsification in a liquid hydrocarbon, followed by curing at fast cooling. A typical method for the preparation of such adducts in spherical form are described in U.S. Pat. USA N 4469648. Thus obtained spherical adducts exposed to thermal destruction of the alcohol at a temperature of alcohol 50-150oC, as long as the alcohol content is reduced to values less than 2 and preferably 1.5 to 0.3 moles per 1 mole of dihalogenide magnesium. Then adducts are treated with chemicals that can interact with OH groups of the alcohol and optionally to remove the alcohol from the adduct, reducing its content to a value which mainly mensao the content of residual alcohol can be up to 0.5 moles; preferably it should be about 0.2 to 0.3 moles. Lower alcohol content is achieved when the initial adduct contains less alcohol.

Removing alcohol from the adducts can be carried out to a greater extent to values smaller than 0.05 m.

Processing spontainiously chemical reagents is carried out using such quantity of this reagent, which is more than sufficient for interaction with the OH-groups present in the alcohol contained in the adduct. Preferably this treatment is carried out using a small excess of the above reagent, which is then, to interaction thus obtained carrier with the compound of titanium is removed.

In the case when the chemical removal of alcohol from the adduct MgCl2d is carried out using a reagent having a restorative effect, for example, using such alkylaromatic compounds, as triethylaluminium obtained in this connection, to communicate with the connection of titanium can be processed deactivating reagent, for example, O2or alcohol, in order to inactivate possibly present triethylaluminum the mi is not carried out, if you wish to at least partially restore the connection titanium. If, on the other hand, it is necessary to reconnect the titanium to a much greater extent, the process of preparation of the components of the catalyst may include the successful use of reducing agents.

The reaction with the compound of titanium is performed using, as mentioned above, previously obtained halogenalkane or halogenocarboxylic, or by generating the above-mentioned compounds in situ by the interaction of tetrachloride titanium, in particular TiCl4with OH-groups present in the adduct or with alcohol ROH, or causing tetralogy titanium to react with a halogenation agent such as, for example, SiCl4halogenosilanes itself TiCl4, AlCl3alkylhalogenide aluminum.

In some cases, it is necessary that the connection of titanium was restored to a valence less than 4. This is achieved, for example, when using a halogenation agent, which also acts as a reducing agent, such as, for example, alkylhalogenide aluminum, or the use of such reducing agents as compounds of silicon, for example, polyhydroxybenzenes.

on the media, or use a slight excess; the excess is then removed.

In the General case, titanium is used in an amount such that the small ratio of Ti/Mg ranged from 0.05 to 3, and preferably in the range of 0.1-2.

The amount of titanium, which remains bound to the carrier, can be achieved, for example, up to 15% (wt.) based on elemental Ti, and is preferably 1-12%.

The connection of titanium deposited on dihalogenide magnesium, is recorded in a form that cannot be extracted by the solvent; in addition, partly it can be extracted in the form.

If you want to obtain a linear low density polyethylene (LLDPE), having a particularly narrow distribution of molecular weights, the catalyst in accordance with the present invention may optionally contain electron-donor compound (external donor), for example, the connection from among esters and ethers, amines and ketones.

In particular, electron-donating compound may be selected from among alilovic, cycloalkyl and ariovich esters of polycarboxylic acids, such as esters of phthalic or maleic acid, in particular, from among ad-bucilla, disclosed in application EP-A-422755, for example, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-Diisobutyl-1,3-dimethoxypropane.

The molar ratio of present electron-donor compound to magnesium is 1:2.

Reacting with alkylamines compounds, in particular, with trialkylaluminium compounds of the claimed compounds form a catalytic system, which, as already mentioned, leads to a very narrow distribution of co monomer in the polymer chain and, in addition, allows you to get in the polymerization in the gas phase polymers that possess the necessary morphological characteristics, in particular, bulk density, the value of which can be very high.

Estimate of the distribution of co monomer was carried out by measuring the polymer fraction soluble in xylene at 25oC, the content of the associated co monomer and the true density of the polymer.

All the results obtained by polymerization in the gas phase, are unexpected results from the point of view of the bulk density of the polymer whose values are shifted into the region of more height is S="ptx2">

Examples alkylaromatic compounds that can be used to obtain the catalyst, are trialkylaluminium connection, in particular, triethylaluminium, three-BC-butylamine, triisobutylaluminum. The ratio of Al/Ti takes a value greater than 1 and, in General, lies in the range from 20 to 800.

The catalysts have been successfully used in the polymerization of atilano and its mixtures with d-olefins of the formula CH2=CHR, where R is an alkyl, cycloalkyl or aryl containing 1 to 12 carbon atoms. In particular, these catalysts were used to obtain:

- high density polyethylene (HD-PE, NDRE, having a density of more 0,940 g/cm3), including homopolymers of ethylene and copolymers of ethylene with d-olefins containing from 3 to 14 carbon atoms;

linear low density polyethylenes (LLDPE, ZZ, having a density of less 0,940 g/cm3) and linear polyethylenes, very low and ultra low density (LEONP, VZ and PSNP, UZ, having a density below 0,920 g/cm3and up to 800 g/cm3) consisting of copolymers of ethylene with one or more d-olefins containing from 3 to 12 carbon atoms, having an ethylene content of fragments of more than about 80% (wt.);

- e the maximum quantities of diene, in which the content of fragments of ethylene is 30 - 70% (wt.).

Polymerization of olefins in the presence of catalysts prepared on the basis of the catalytic components of the present invention may be carried out in accordance with known techniques both in liquid and gas phases, for example, by the method of the fluidized bed or in conditions of mechanical agitation.

An example of a process that can be used spherical components of the present invention is the process described in It. application N M1-91-A-002142. The above process includes a preliminary probe of catalytic components, stage prepolymerisation and stage vapor-phase polymerization in two or more apparatus of fluidized bed or in a cascade of reactors with mechanical mixed layer.

The following examples serve only to illustrate the invention and should not be construed as limiting.

The considered properties were determined using the following methods.

Porosity and specific surface area by nitrogen.

Determined in accordance with the C. E. I. methodology (used device - SORPTOMATIC 1800 firm Carlo Erba).

Pasta sample in a known amount of mercury in the dilatometer, followed by a gradual increase in pressure mercury by hydraulic pressure. The pressure of mercury penetrating into the pores is a function of the diameter of pores. The measurements were carried out using porosimetry company Carlo Erba "Porosimeter 200 Series". From the data on the reduction of mercury and magnitude of the applied pressure was calculated amount of porosity, pore distribution and specific surface area.

The size of the catalyst particles.

Determined in accordance with the method based on the principle of optical diffraction of monochromatic laser beam with the use of instruments Malvern Unstr, 2600".

MIE flow index ASTM-D 1238.

MIF flow index ASTM-D 1238.

Fluidity is the time required for 100 g of polymer to flow through a funnel, the diameter of the outlet which is 1.25 cm, and the side walls are angled 20ofrom the vertical.

Bulk density: DIN-53194.

The morphology and particle size distribution of particles: ASTM-D 1921-63.

Fraction soluble in xylene: determined at 25oC.

The content of the co monomer: wt.% determined according to the IR spectrum.

True density: ASTM-D 792.

Examples.

Preparation of spherical media (adduct MgCl2/EtOH).

Adduct containing about 3 mol of alcohol, had an average particle size of approximately 60 microns with a distribution of particle sizes in the range of about 30 to 90 μm.

Example 1. Obtaining a solid component.

Spherical carrier obtained in accordance with the General method, was subjected to heat treatment in a stream of nitrogen at a temperature of 50 to 150oC, up until the residual content of alcohol in the spherical particles is not reached approximately 35% (1,1 mol of alcohol per 1 mol MgCl2).

In the reactor 5000 cm3download 300 g of carrier, suspended in 3000 cm3anhydrous hexane. Under stirring, at room temperature and atmospheric pressure was slowly added a solution of 130 G. of AlEt3in hexane (107 g/l). The temperature was raised to 60oand maintained at this level for 60 minutes Stopped stirring, was allowed to form a precipitate and separating the clarified phase. Processing AlEt3repeated in the same conditions two or more times. Then thrice washed with anhydrous hexane and dried at 50oC.

Thus obtained carrier had the following'hara is the content of OEt - 5,5% (wt.)

Residual Al content of 3.6% (wt.)

Mg - 20,4% (wt.)

In the reactor at 1000 cm3downloaded 260 g of carrier and 3000 cm3anhydrous hexane. Within 30 minutes under stirring and at room temperature was added 242 g of Ti (OBu)4the stirring was continued for another 30 min and then at the same temperature for 30 min was added 350 g SiCl4diluted 250 cm3hexane. Within 40 minutes the temperature was raised to 65oC and maintained at this level for another 3 hours Then after settling of the reaction mass using a siphon selected liquid phase. Washed with hexane (73000 cm3), and three times with hexane, having a temperature of 60oC, and four times with hexane at room temperature. Get the component of the spherical shape was dried in vacuum at 50oC.

Characteristics of the component:

the total content of titanium and 3.4% (wt.)

Mg - 17,1% (wt.)

Si was 0.9% (wt.)

Cl - 57,4% (wt.)

The residual quantity of Al - 1,3% (wt.)

OEt is 2.9% (wt.)

OBu - 13,2% (wt.)

porosity (B. E. T.) - to 0.108 cm3/g and 50% is due to pores with a radius of > 350

specific surface area (B. E. T.) of 28.6 m2/g

porosity (mercury) - 0,536 cm3/g is due to pores with radius of the ptx2">

specific surface area (mercury) - 12.8 m2/,

The copolymerization of ethylene with butene-1 (LAND).

In the reactor 4 l stainless steel, purged with nitrogen for 2 h at 70oC, and then washed with anhydrous propane, download, 0.01 g of solid component and 0.96 g of triethylamine mixed with 25 cm3hexane and 800 g of anhydrous propane. The temperature was raised to 70oC, and then simultaneously filed H2(2 bars) and ethylene (7 bar) and 200 g of butene-1.

During the entire polymerization process the partial pressure of ethylene was maintained constant and for every 30 g of ethylene was added 3 g of butene-1. After 3 h the reaction was stopped by rapid ottomania reagents and propane. Received 280 g of polymer.

Characteristics of the obtained polymer:

MIE - 0,99 g/10 min

MIF/MIE - 25,8

true density - 0,922 g/cm3< / BR>
Fraction soluble in xylene - 7,5%

associated butene - 5,4%

bulk density, bulk - 0.35 g/cm3< / BR>
fluidity - 18

morphology spherical

the distribution of particle size (WBR)> 4000 μm - <a 0.5% (wt.)

2000 - 4000 mm 20 - 30% (wt.)

1000 - 2000 µm - 40 - 70% (wt.)

500 - 1000 µm - 1 to 3% (wt.)

< 500 μm - < 1% (wt.)

Polymerization, containing 0.45 g AlEt3and 0.01 g of a spherical component, suspended in 100 cm3the same mixture AlEt3/hexane. The mixture was stirred, raised the temperature to 75oC and then gave H2(3 bar) and ethylene (7 bar). The reaction time of the polymerization was 3 h, and the pressure of ethylene was maintained constant. After 3 h the reaction was stopped by rapid ottomania ethylene and hydrogen.

Received 270 g of polymer with the following characteristics:

MIE - 0,44 g/10 min

MIF/MIE - 28,8

true density - 0,961 g/cm3< / BR>
bulk density of 0.32 g/cm3< / BR>
fluidity - 18

morphology spherical

WBR > 4000 μm - < a 0.5% (wt.)

2000 - 4000 mm 20 - 30% (wt.)

1000 - 2000 µm - 40 - 70% (wt.)

500 - 1000 µm - 2 - 4% (wt.)

< 500 μm - < 2% (wt.)

Example 2. Spherical carrier was prepared in accordance with the General method and was subjected to heat treatment, followed by treatment AlEt3according to the method described in example 1. In the reactor of 5 liters was uploaded 260 g obtained as described carrier, suspended in 2.5 liters of anhydrous hexane. Under stirring and at room temperature was slowly added 568 g of Ti (OBu)4and in these conditions was stirred in techenego 300 cm3hexane. Raised the temperature to 65oC and after 60 min was reduced to 400oC and was added 320 g RMGS (polymethylhydrosiloxane). The temperature was again raised to 60oC and the reaction mixture was stirred at this temperature for 2 hours Solid catalytic component is then washed with hexane to remove free SiCl4and a small amount of very fine powder (1 to 2%) smaller than 5 μm, which are easily removed together with the washing liquid. The component was dried under vacuum at 50oC.

Characteristics of the obtained product:

the total content of titanium and 4.5% (wt.)

TiWis 2.2% (wt.)

Mg - 15% (wt.)

Cl - 51% (wt.)

OEt is 1.2% (wt.)

OBu - 10,8% (wt.)

porosity (B. E. T.) - 0,114 cm3/g and 50% is due to pores with a radius of > 260

specific surface area (C. N. T - 33 m2/g

porosity (mercury) - 0,48 cm3/g due to pores with radius 0 - 10000 and 50% is due to pores with radius > 1200 . Among pores with a radius of 0 - 300000 55% had a radius of > 10000 .

The copolymerization of ethylene with butene-1 (LLDPE).

The copolymerization of ethylene with butene-1 was carried out in conditions similar to the conditions of example 1. When using 0,092 g of the solid component obtained 280 g of polymer clay is 3< / BR>
fraction soluble in xylene - 7,3%

associated butene - 5,8%

bulk density, bulk - 0.32 g/cm3< / BR>
fluidity - 18

morphology spherical

WBR: > 4000 mm < 1% (wt.)

2000 - 4000 mm 20 - 30% (wt.)

1000 - 2000 µm - 30 - 70% (wt.)

500 - 1000 µm - 1 to 3% (wt.)

< 500 μm - < 1% (wt.)

Polymerization of ethylene (HDPE).

The copolymerization of ethylene was conducted under the same conditions as in example 1. Received 300 g of polymer having the following characteristics:

MIE - 0,084 g/10 min

MIF/MIE - 27,9

bulk density, bulk - 0.33 g/cm3< / BR>
fluidity - 15

morphology spherical

WBR: > 4000 mm < 1% (wt.)

2000 - 4000 mm 20 - 30% (wt.)

1000 - 2000 µm - 30 - 70% (wt.)

500 - 1000 µm - 1 to 3% (wt.)

< 500 μm - < 2% (wt.)

Example 3. Spherical carrier was prepared in accordance with the General method and was subjected to heat treatment to obtain a residual alcohol content of 45% (molar ratio alcohol/ethanol = 1,7).

In the reactor of 30 l was downloaded 2360 g of the carrier, suspended in 18 liters of anhydrous hexane. Within 60 minutes under stirring and at room temperature was added a solution 1315 g AlEt3in hexane (concentration 100 g/l). Within 60 min under the project and filtering the separated liquid phase was added to 15 l of anhydrous hexanol. In such circumstances, the treatment was repeated two or more times. The spherical powder was washed with anhydrous hexane (5 x 10 l) and dried in vacuum.

Product feature:

the residual content of OEt - 8,4% (wt.)

Cl - 60,5% (wt.)

Mg - 13,8% (wt.)

morphology spherical

In the reactor of 25 l was loaded with 150 g of the obtained carrier, suspended in 17 liters of anhydrous hexane. Under stirring and at room temperature was added 2750 g of Ti (OBu)4. Stirring was continued at room temperature for 60 min, and then slowly added 2100 g SiCl4. The temperature was raised to 60oC and maintained for 2 hours Then conducted a series of washings with anhydrous hexane to remove any quantities of free SiCl4simultaneously from the settled solid component was removed very fine powder remaining in suspension (approximately 1% wt. with size < 5 μm). The obtained solid component was dried in vacuum at 50oC.

Product features:

the total titanium content is 6.7% (wt.)

TiIIIof 4.3% (wt.)

Mg - 11,5% (wt.)

Cl - 52,3% (wt.)

OEt is 1.0% (wt.)

OBu - 13,4% (wt.)

porosity (B. E. T.) - 0,083 cm3/g and 50% is due to pores with radius > 220
mustache 0 - 10000 and 50% is due to pores with radius > 1200 . Among the pore radius 0 - 3000000 60% of the pores have a radius of > 10000

The copolymerization of ethylene with butene-1 (LLDPE)

When copolymerization of ethylene with butene-1 according to the method described in example 1 was used 0,0114 g cooked spherical component.

Was 320 g of polymer with the following characteristics:

MIE - 1.5 g/10 min

MIF/MIE - 30

true density - 0,916 g/cm3< / BR>
fraction soluble in xylene - 14%

associated butene - 7,4%

bulk density, bulk - 0.33 g/cm3< / BR>
fluidity - 20 with

morphology spherical

WBR: > 4000 μm - < a 0.5% (wt.)

2000 - 4000 mm 20 - 30% (wt.)

1000 - 2000 µm - 40 - 60% (wt.)

500 - 1000 µm - 2 - 4% (wt.)

< 500 μm - < 1% (wt.)

Example 4. In the reactor at 1000 cm3download 40 g of the carrier of example 1, after processing AlEt3suspended in 500 cm3anhydrous hexane. Under stirring and at room temperature was added 40 g of Ti (OC4H9)Cl3diluted 100 cm3hexane. Raised the temperature to 55oC and maintained the reaction mixture at this temperature for 1 h the Liquid phase was separated, then repeated the treatment with an additional 40 g of Ti (OCoC (3 300 cm3) and room temperature (4 300 cm3).

After vacuum drying at 40oC solid powder of spherical shape has the following features:

the total titanium content of 5.4% (wt.)

porosity (B. E. T.) - 0,116 cm3/g and 50% is due to pores with a radius of > 300

specific surface area (B. E. T.) - 2,75 m2/g

porosity (mercury) - 0,520 cm3/g due to pores with a radius of 0 - 10000 and 50% is due to pores with radius > 1320 . Among the pore radius 0 - 300000 , 52% of the pores have a radius of > 10000

Polymerization of ethylene (HDPE)

Polymerization of ethylene was conducted under the same conditions as in example 1, using 0,0093 g of solid catalytic component. The polymerization time of 3 hours was 320 g of polymer with the following characteristics:

MIE - 0,413 g/10 min

MIF/MIE - 30,2

bulk density, bulk - 0.33 g/cm3< / BR>
fluidity - 17

morphology spherical

WBR: > 4000 mm < 1% (wt.)

2000 - 4000 μm - 30 - 50% (wt.)

1000 - 2000 ám 20 - 40% (wt.)

500 - 1000 µm - 3 - 5% (wt.)

< 500 μm - < 2% (wt.)

Example 5. In the reactor of 1 l was loaded with 50 g of the carrier of example 1, after processing AlEt3in suspension in 500 cm3hexane. Under stirring and at comnational 1 h and then for 15 min was added 20 g SiCl4. The temperature was raised to 50oC and kept constant for 2 h were Washed with hexane to remove free SiCl4, and then was dried in vacuum at 50oC.

The catalyst of the spherical shape has the following features:

the total titanium content of 2.7% (wt.)

Cl - 57,4% (wt.)

OEt - 5,6% (wt.)

OBu to 10.5% (wt.)

porosity (B. E. T.) - 0,22 cm3/g and 50% is due to pores with a radius of > 300

porosity (mercury) is 0.58 cm3/g due to pores with a radius of 0 - 10000 and 50% is due to pores with radius > 1250 . Among pores with a radius of 0 - 300000 51,6% of the pores have a radius of > 10000

Polymerization of ethylene (HDPE)

Polymerization was performed in the same conditions as in example 1, using 0,013 g of the solid catalyst. Received 215 g of polymer with the following characteristics:

MIE - 0,153 g/10 min

MIF/MIE - 30

bulk density, bulk - 0.33 g/cm3< / BR>
fluidity - 18

morphology spherical

WBR: > 4000 mm < 1% (wt.)

2000 - 4000 mm 20-30% (wt.)

1000 - 2000 µm - 50-60% (wt.)

500 - 1000 µm - 2-4% (wt.)

< 500 μm - < 2% (wt.)

Example 6. Continuous polymerization of ethylene in the gas phase with obtaining high density polyethylene

1,14 g/h SUP>C, and gave 10.0 g/h TE Al.

Received prepolymer continuously fed into the gas-phase reactor with fluidized bed" at 80oC and a pressure of 20 bar, with the molar composition of the gas phase was as follows:

Propane for 77.2%

Ethylene - 12,3%

Hydrogen is 7.7%

Inert gas up to 100%

The average yield was 6.23 kg/g catalyst, and the obtained polymer had the following characteristics:

MIE - 1,75 g/10 min

MIF/MIE - 28

true density - 0,960 g/cm3< / BR>
bulk density, bulk - 0.400 g/cm3< / BR>
bulk density, compaction - 0,438 g/cm3< / BR>
fluidity - 9

morphology spherical

WBR > 4000 μm - < 0,0% (wt.)

2000 - 40000 μm - 51,8% (wt.)

1000 - 2000 µm - 43,9% (wt.)

500 - 1000 µm and 3.7% (wt.)

< 500 μm - < 0,6% (wt.)

Example 7. Continuous polymerization of ethylene and butene-1 with obtaining linear low density polyethylene

1,25 g/h of the catalyst obtained in example 2 was prepolymerisation ethylene continuously into the reactor at 30oC, and served 10 4 g/h TE Al.

Get prepolymer continuously fed into the gas-phase fluidized bed reactor at a temperature of 80oC and a pressure of 20 bar, while the gas phase had the following average yield was 10.4 kg/g catalyst, and the obtained product had the following characteristics:

MIE - 1.01 g/10 min

MIF/MIE - 28,0

the content of butene-1 - 7,0%

fraction soluble in xylene - 12,5%

true density - 0,919 g/cm3< / BR>
bulk density, bulk - 0.40 g/cm3< / BR>
bulk density, compaction 0,423 g/cm3< / BR>
melting point - 123,9oC

fluidity 12

WBR: > 4000 μm - 0,0% (wt.)

2000 - 4000 mm - 55% (wt.)

1000 - 2000 µm - 41,5% (wt.)

500 - 1000 µm and 2.8% (wt.)

< 500 μm to 0.5% (wt.)

Example 8. Stage (a). In a reactor of 10 l equipped with a stirrer, the reaction 3662 g tetraethoxysilane with 2840 g of silicon tetrachloride. To tetramethoxysilane added silicon tetrachloride for 60 min at room temperature. Then the temperature was raised to 30oC and kept constant for a further 60 minutes

Stage (b). In the second reactor at 25 l equipped with a stirrer, was loaded 2000 media of example 1 after treatment AlEt3and 10 liters of anhydrous hexane. At room temperature for 60 min product from step a) was introduced into the reactor of stage b), containing mixed slurry of the carrier in hexane. Then the temperature was raised to 60oC for 60 min, and kept constant even in number of very fine powder TiCl3.

Then the solid product was washed with anhydrous hexane (7 10 l) at room temperature and dried in vacuum at approximately 40oC.

The obtained dry powder of spherical shape with good fluidity had the following characteristics:

the total content of titanium and 5.3% (wt.)

TiIIIjust 3.2% (wt.)

Mg - 15,9% (wt.)

Cl - 53,5% (wt.)

OEt is 2.6% (wt.)

OBu - 13% (wt.)

porosity (B. E. T.) - 0,122 cm3/g and 50% is due to pores with a radius of > 100

porosity (mercury) - total porosity = 0,79 cm3/g - porosity due to pores with radius 0-10000 0,453 cm3/g and 50% due to pores with a radius of > 1000

Polymerization of ethylene (HDPE)

The polymerization was carried out according to the method of example 1, with the only difference that the ethylene and hydrogen was applied at 40oC as long, until he reached the yield of the reaction of polymerization of approximately 50-100 g of polymer per 1 g of catalyst (stage prepolymerisation), and then the reaction temperature was raised to 75oC and kept constant for 3 hours

Using 0,0101 g of the solid catalyst, received 230 g of polymer with the following characteristics:

MIE - of 4.38 g/10 min

MIF/MIE - 34,93

the true density is I - spherical

The copolymerization of ethylene with butene-1 (LLDPE)

The copolymerization was carried out according to the method described in example 1, using the amount of 0.118 g of spherical catalyst, the receipt of which is described above, with the only difference that was held a short stage of prepolymerisation at 40oC to achieve yield of about 50-100 g of polymer per 1 g of catalyst, followed by raising the temperature to 75oC.

Received 385 g of polymer with the following characteristics:

MIE - 0.8 g/10 min

MIF/MIE - 29

fraction soluble in xylene - 12%

true density - 0,9212 g/cm3< / BR>
bulk density, bulk - 0,330 g/cm3< / BR>
fluidity - 18

WBR: > 4000 μm - < 2% (wt.)

2000 - 4000 mcm - 49% (wt.)

1000 - 2000 µm - 45,5 (wt.)

500 - 1000 µm and 2.8% (wt.)

< 500 μm to 0.7% (wt.)

Example 9. Stage a). In the reactor at 50 cm3in the conditions of example 8, step a) was prepared with 12.5 g of Ti (OBu)4+ SiCl4.

Stage b). 50 g of the carrier of example 1 after treatment AlEt3was treated with dry air to remove residual C2H5groups.

In the reactor at 500 cm3download 150 cm3anhydrous hexane and 50 g of the carrier prepared according to the method of staza 30 minutes The temperature was raised to 60oC, maintained at this level for 2 hours Gave a reaction mass to settle, the liquid phase was removed with a siphon. The residue was washed with anhydrous hexane (7 x 200 cm3), consistently defending the mixture and removing the liquid phase by using a siphon, and then dried in vacuum at 40oC.

Received 60 g of dry powder with spherical particles, with good fluidity, with the following characteristics:

the total content of titanium is 1.25% (wt.)

TiIIIto 0.15% (wt.)

Mg - 15,95% (wt.)

Cl - won with 51.75% (wt.)

OEt - 9,8% (wt.)

OBu is 6.7% (wt.)

Polymerization of ethylene (HDPE).

Polymerization was performed in the same conditions as in example 8, using 0,098 g of solid catalyst component. Received 215 g of polymer having the following characteristics:

MIE - 2,88 g/10 min

MIF/MIE - 32,29

true density - 0,961 g/cm3< / BR>
bulk density, bulk - 0.34 g/cm3< / BR>
fluidity - 18

morphology spherical

WBR: > 4000 μm - < 0,2% (wt.)

2000 - 4000 mm 38,8% (wt.)

1000 - 2000 µm - 57,5% (wt.)

500 - 1000 ám and 2.9% (wt.)

< 500 μm - < 0,6% (wt.)

1 1. The spherical components of the catalyst for polymerization of olefins, CH23/g and at least 50% of the porosity is due to pores having a radius greater than 800 2 2. Components under item 1, characterized in that at least 30% of the total porosity is due to pores having a radius greater than 10000 2 3. Components under item 1, characterized in that their specific surface area lies in the interval from 5 to 30 m2/, 2 4. Components under item 1, characterized in that dihalogenide magnesium in an activated form represents MgCl2. 2 5. Components under item 1, characterized in that they contain electron-donating compound. 2 6. Components under item 1, characterized in that the compound titanium has the formula 6 Ti(OR')nXy - n, 1 where 0.5 n (y - 1); 4 y is the valence of titanium atom; 4 X is a halogen atom, R' is an alkyl group containing 2 to 8 carbon atoms. 2 7. Components under item 6, characterized in that y = 4, and the value of n varies from 1 to 2. 2 8. Components p is moved from the group including n-butyl, isobutyl, 2-ethylhexyl, n-octyl. 2 10. Components under item 1, characterized in that they are obtained by reaction of: (a) adduct MgCl2d, where p 0.5 and R represents alkyl containing 1 to 8 carbon atoms, with (b) a compound of titanium formulas 6 Ti(OR)nXy - n, 1 where 0.5 n (y - 1); 4 y is the valence of titanium atom; 4, X is halogen atom; 4 R is alkyl containing 1 to 8 carbon atoms, or COR - group, 1 and the adduct (a) receive chemical removal of alcohol from the adduct MgCl2mROH when m 2, which, in turn, is produced by thermal removal of alcohol from MgCl2qROH, where 2,5 q of 3.5. 2 11. Components under item 10, characterized in that in the interaction of the compound (b) with the adduct (a) the molar ratio of Ti/Mg is in the range from 0.05 to 3. 2 12. Components under item 10, characterized in that the compound (b) is trichloranisole tetravalent titanium. 2 13. Components under item 1, characterized in that they are obtained by reaction of (a) adduct MgCl2d, where p 0.5 and R represents alkyl containing 1 to 8 carbon atoms, with (b) a compound of titanium formulas 6 Ti(OR)nXy - n, 1 0 n 2; 4, X is halogen atom; 4 R is alkyl containing 1 to 8 carbon atoms or a COR group, and the adduct (a) receive a chemical the spirit of the MgCl2qROH, where 2,5 q of 3.5. 2 14. Components on p. 13, characterized in that the reaction is carried out in the presence of the compound ROH, where R is alkyl containing 1 to 8 carbon atoms. 2 15. Components on p. 13, characterized in that the reaction is carried out in the presence of a reducing agent. 2 16. Components on p. 13, characterized in that during the reaction the molar ratio of titanium in the compound (b), for magnesium, which is part of the adduct (a), varies in the range from 0.05 to 3. 2 17. Components on p. 13, characterized in that the compound (b) is a TiCl4or Ti(OR)Cl3. 2 18. Components under item 1, characterized in that they are obtained by reaction of (a) adduct MgCl2d, where p 0.5 and R is alkyl containing 1 to 8 carbon atoms, with (b) a compound of titanium formulas 6 Ti(OR)nXy - n, 1 where 2 n 4; 4, X is halogen atom; 4 R is alkyl containing 1 to 8 carbon atoms or a COR group, and (b) halogenation of the compound, possibly in combination with a reducing agent, or a compound which has as halogenation, and restoring action, and the above-mentioned adduct (a) receive chemical removal of alcohol from the adduct MgCl2mROH when m 2, which, in turn, is produced by thermal removal of alcohol from the adduct MgCl2qROH, where 2,5 q of 3.5. 2 is unity (b), to magnesium, which is part of the adduct (a), varies in the range from 0.05 to 3. 2 20. Components under item 16, characterized in that the compound (b) is a Ti(OR)4. 2 21. Catalysts for polymerization of olefins CH2= CHR, where R is hydrogen or alkyl containing 1 to 8 carbon atoms, characterized in that they comprise the reaction product of spherical components under item 1 and alkylamino connection. 2 22. The catalysts according to p. 21, characterized in that alkylamino connection is trialkylaluminium connection. 2 23. The method of polymerization of ethylene and its mixtures with olefins of the formula CH2= CHR, where R is alkyl containing 1 to 8 carbon atoms, characterized in that it includes the use of catalysts under item 21. 2 24. The method according to p. 23, characterized in that the olefin CH2= CHR is selected from butene-1, pentene-1, hexene-1, 4-methyl-pentene-1 and octene-1. 2 25. Copolymers of ethylene, obtained by the method of p. 23, wherein the weight percent of units of ethylene is more than 80%. 2 26. Elastomeric copolymers of ethylene and propylene, characterized in that they are obtained by the method of p. 23, and the weight percent of units of ethylene in said copolymer is changed in the range from 30 to 70%.

 

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