The ball component of the catalyst for polymerization of olefins, process for its production, the catalyst for polymerization of olefins, a method of polymerization of olefin

 

(57) Abstract:

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 of Ti. Ball solid compounds are characterized by the fact that their specific surface area determined by the BET method, of less than 70 m2/1, pore volume, determined by the mercury method, above 0.5 cm3/g and at least 50% of the pores have a radius of more than 800 Describes a catalyst for the polymerization of olefins on the basis of the ball component and aluminiumgie. A method of obtaining a ball component of a catalyst for polymerization of olefins is in the interaction (a) MgCl2m ROH, where Om0,5, and R is alkyl, cycloalkyl or aryl containing C1-12and (b) titanium compounds of formula Ti (OR)nXy-nwhere n = 0 to 0.5, y is the valence of titanium, X is halogen, R is alkyl containing C2-8or COR, and the connection and receive chemical removal of alcohol from the adduct MgCl2p ROH, where 0,1p2. The method of polymerization of olefin CH2= CHR, where R is hydrogen or a hydrocarbon radical C1-12momosu to obtain polymers in the form of spherical particles with good morphological characteristics, in particular, a high bulk density. 4 C. and 28 C.PP. f-crystals.

The present invention relates to a component of a catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical containing 1 to 12 carbon atoms, the method of its production, the catalyst and method of polymerization of these Alifanov.

The catalysts deposited on diploidy/magnesium in the active form, well known from the literature. The first catalysts of this type are disclosed in U.S. patents 4298718 and 4495338.

Further development of the catalyst on the media has been taken when creating catalysts with controlled morphology, in particular, have a ball shape. These catalysts can be obtained polymers which result from the repetition of forms of catalysts and good morphological characteristics allow to simplify the retrieval and/or further processing of the polymers.

Examples of catalysts with controlled morphology is described in U.S. patent 3953414 and 4399054. In the latter patent components are given on the basis of ball adducts MgCl2with about 3 moles of alcohol. Obtaining a catalytic component can also be maintained in various ways, for example, reducing sederim interaction thus obtained carrier with TiCl4. In each case, the components have a porosity of nitrogen from 0.3 to 0.4 cm3/g, a specific surface area of from 300 to 500 m2/g, and the average radius of the pores is from about 15 to 30

The catalysts obtained from TiCl4and granulated MgCl2by spray drying an alcohol solution of minikleid and subsequent deposition of titanium, as described in patents EP-B-657000 and ER-IN-243327. However, the polymer obtained from such catalysts has no interest morphological characteristics. In particular, the bulk density is not high enough. In addition, the rather low activity of the catalyst.

Method of increasing the activity of such catalysts is described in the patent EP-A-281524. Katalizator prepared by depositing a titanium alcoholate on adduct MgCI2-ethanol, containing from 18 to 25 wt.% ethanol, which has a ball shape by spray drying an ethanol solution and subsequent chemical treatment Et2AlCl or Et3Al2Cl3. Conditions for obtaining media are substantial and determine the morphological stability of the obtained polymer. Receive polymers in the form of heterogeneous powders, for example, using media with alcohol content not exceeding the th, to achieve a sufficiently high output of the Ti content in the solid component is always higher than 8 wt.%.

From the application EP-A-395083 known catalysts derived from adducts MgCI2, is subjected to heat treatment to remove the alcohol until levels, usually constituting from 0.2 to 2 moles, and then subjected to interaction with an excess of tetrachloro titanium, optionally containing dissolved electron-donating compound.

Using these catalysts can be obtained polymers in the form of spherical particles with good morphological characteristics, in particular a high bulk density.

The solid components of catalysts described in EP-A-395083, and are characterized by a large specific surface and mikroporistogo (more than 50% of the pore radius is greater than 100 but less than

It has been unexpectedly discovered that ballpoint components of catalysts suitable for the polymerization of olefins, and they have low specific surface area (specific methods BET) and at the same time have a high porosity (measured by the mercury method, described below) and the distribution of pore radii above 800

Catalysts containing components of the present invention, described the native radical, containing 1 to 12 carbon atoms, and capable of obtaining polymers having valuable morphological characteristics, in particular having a high bulk density, regardless of the significant macro porosity of the solid components forming the catalyst. They are therefore particularly suitable for modern processes for the polymerization of olefins in the gas phase, where high productivity catalysts must be accompanied by their high morphological stability.

Ball components of the present invention contain compounds of titanium deposited on a magnesium halide having more than one Ti-halogen communication, and optional content groups different from halogen, in the amount of less than 0.5 moles per mole of titanium, and are distinguished by the fact that the specific surface measured by the BET method, of less than 70 m2/g, and pore volume, determined by the mercury method, is more than 0.5 cm3/g and at least 50% of the pores have a radius above 800

Pore volume typically ranges from 0.6 to 1.2 cm3/g, and specific surface area is preferably from 30 to 70 m2/, Porosity, measured by the BET method, typically below 0.25 cm3/,

The most interesting ball components3/,

The particles of the solid component are almost spherical morphology and an average diameter of from 5 to 150 μm. The particles have spherical morphology, are those in which the ratio of maximum axis to the smallest axis is equal to or less than 1.5, preferably less than 1.3.

Dihalogenide magnesium included in the spherical component of the present invention are in the active form and are characterized by such x-ray spectra in which the most intense diffraction line appearing in the spectra of active halides, are reduced in intensity and is replaced by halo, the maximum intensity shifted to the corners corresponding to those that give a more intense line.

Preferably, dihalogenide magnesium was MgCI2.

The components of the present invention include electron-donor compound (internal donor), selected from, for example, simple or complex esters, amines, ketones. The specified connection is necessary if the component is used in the stereospecific polymerization of these olefins as propylene, 1-butene, 4-methyl-penten-1; internal donor can be used, if ognor> In particular, the internal electron-donor compound can be selected from alkyl, cycloalkyl and aryl simple ether and esters of polycarboxylic acids, such as esters of phthalic and maleic acids, in particular n-butylphthalate, diisobutylphthalate, di-n-octylphthalate.

Other electron-donating compounds who needs convenient to use, are 1,3-diesters of the formula;

< / BR>
where R1, R2- same or different and are alkyl, cycloalkyl, aryl radicals containing 1 to 18 carbon atoms;

RIII, RIV- same or different and are alkyl radicals containing 1 to 4 carbon atoms.

Electron-donating compound is typically present in a molar ratio with respect to magnesium 1 : 4 to 1 : 20.

The preferred titanium compounds have the formula Ti(OR)nXy-nwhere n = 0 to 0.5, y is the valence of titanium, R is alkyl, cycloalkyl or aryl radical containing 2 to 8 carbon atoms or a COR group, X represents a halogen. In particular, R can be n-bootrom, isobutyl, 2-ethylhexyl, n-actiom and phenyl; X is preferably chlorine.

If y= 4, n varies predpochtite brisout catalysts for the polymerization of alpha-olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical containing 1 to 12 carbon atoms by reaction with Al-alkyl compound. In particular, the compounds trialkylamine, for example, trimethyl Aluminium, triethyl Aluminium, tri-n-butyl Al, triisobutyl Al, are preferred. The ratio of Al/Ti>1 is usually from 20 to 800.

In the case of stereospecific polymerization of alpha-olefins, such as propylene and 1-butylene, electron-donor compound (external donor), which may be the same or different from the compounds which are used as internal donor, also tend to use upon receipt of the catalyst.

If the internal donor is a complex ester of polycarboxylic acid, in particular a phthalate, the external donor is preferably selected from silicon compounds containing at least one Si-OR bond having the formula, R14-nSi(ORIII)nwhere R1is alkyl, cycloalkyl, aryl radical containing 1 to 18 carbon atoms, RIIIis an alkyl radical containing 1 to 4 carbon atoms, and n=1,2,3. Examples of such silanes are methyl-cyclohexyl-dimethoxysilane, diphenylmethylsilane, tert-butyl In the case if the internal donor is one of these diesters can be avoided using an external donor, as stereospecificity catalyst is already quite high.

Method, suitable for receiving the spherical components of the present invention, includes providing interaction between:

(a) connection MgCI2mROH, where 0m0,5, and R represents alkyl, cycloalkyl or aryl radical containing 1 to 12 carbon atoms; and (b) the compound of titanium of the formula Ti(OR)nXy-nwhere n = 0 to 0.5, y is the valence of titanium, X is halogen, and R represents an alkyl radical containing 2 to 8 carbon atoms or the group COR.

The compound (a) receive chemical removal of alcohol from the adducts MgCI2d, where 0.1p2, which in turn receive heat removing alcohol from adducts MgCI2gROH, where 2,5g3,5. In the reaction between compound (b) and compound (a) molar ratio of Ti/Mg is stoichiometric or higher, preferably above 3.

The method may also include the use of electron-donor compound (internal donor) previously described type on the reaction between the compound (a) and a compound of titanium (b). The molar ratio between the internal donor and the e from molten adducts, as a result of their emulsification in a liquid hydrocarbon, then utverjdayut by rapid cooling. Examples of methods for such ball of adducul are provided in U.S. patent 4469648. Other suitable means for receiving the ball of the particles is cooled by spraying, as described in U.S. patent 5100849 and 4829034.

Adducts ballpoint forms are subjected to thermal destruction of alcohol at 50 - 150oC as long as the alcohol content is not reduced to values below 2, preferably 1.5 to 0.3 mol per 1 mol of dihalide magnesium, and at the end of the process chemical reagents capable of reacting with Oh groups of the alcohol, and then again remove the alcohol from the adduct up until its content is not reduced to 0 to 0.5 mol per 1 mol of Mg, preferably less than 0.3 mol.

Handling chemical agents that remove the alcohol, exercise, using a sufficient amount of agent to interact with IT, present in the alcohol adduct. It is preferable to deal with some excess agent, which is then removed before the implementation of the interaction of compounds of titanium with the thus obtained carrier.

Chemical agents for removal of the alcohol include, for example, the compounds of alkylamine5)2, Al(iBu)3galoidirovaniya compounds of silicon and tin, such as SiCl4and SnCl4.

The preferred titanium compounds (b) are tetrachloride titanium, especially TiCl4. In this case, the connection obtained after chemical removal of the alcohol, suspend at low temperature in excess TiCl4. Then this suspension is heated to 80 - 135oC and kept at this temperature for 0.5 - 20 hours

Excess titanium emit at high temperature by filtration or sedimentation, which is also carried out at high temperatures. Processing TiCl4if you desire to repeat many times.

In that case, if the catalytic component must contain an internal electron donor previously described type, this can be successfully achieved during processing TiCl4using the above molar ratio relative to magnesium.

If the connection titanium is hard, for example, TiCl3it can be applied to the halide of magnesium, dissolving it in the source straightened adduct.

If the chemical removal of alcohol from the adduct MgCI2d carried out by the agents, with the ability to regenerate, for example,the unity of titanium can be processed decontamination agent, for example, O2or alcohol, for deaktivirovana triethyl Al, not necessarily still present, thereby avoiding reconnection titanium.

Processing decontamination agents avoid, if it is desirable to at least partially restore the connection titanium. On the contrary, if desired the highest degree of recovery of the titanium compounds, the method of producing a component can enable the use of a reducing agent.

Examples of reducing compounds are Al-alkali and Al-alkylhalogenide or silicone compounds such as polyhydroxyalkane.

As was earlier indicated, the ball component of the present invention and the receipt of these catalysts are used in the methods of obtaining certain types of olefinic polymers.

Received the following polymers: polymers of ethylene, high density (HDPE with a density above 0,940 g/cm3), including homopolymers of ethylene and copolymers of ethylene with alpha-olefins containing 3 to 12 carbon atoms; linear low density polyethylene (PENP with density below 0,940 g/cm3) and very low density and ultra low density and ultra low density (PAOP and PAOP, with pornstarsexy from 3 to 12 carbon atoms, with the molar content of fragments derived from ethylene, above 80%; elastomeric copolymers of ethylene and propylene and elastomeric terpolymer of ethylene and propylene with a low content of diene and a content by weight of the fragments obtained from ethylene, from about 30 to 70%, isotactic polypropylene and/or other polymers of alpha-olefins, containing fragments derived from propylene, more than 85 wt.%; impact-resistant polymers of propylene obtained by the sequential polymerization of propylene and mixtures of propylene with ethylene, containing up to 30 wt.% ethylene; copolymers of propylene and 1-butene containing the number of fragments obtained from 1-butylene, comprising from 10 to 40 wt.%.

Polymerization olefinov in the presence of catalysts derived from Catholic components of the present invention can be conducted by known methods, either in liquid or in gas phase, using, for example, a known method, fluidized bed, or in conditions in which the polymer is stirred mechanically.

Examples of ways in which you can use ball components of the present invention, described in Italian patent application M1-91-A-000379 and M1-92-A-000589. This method uses the stage prior the tion in one or more of the reactors in series fluidized or mechanically peresylaemyh layers.

The following examples are given to illustrate the invention but are not restrictive.

These characteristics were determined in the following ways: porosity and specific surface area by nitrogen was determined by the BET; the porosity and specific surface of mercury is determined by immersing a known quantity of mercury in the dilatometer, and then hydraulic pressure increase mercury series up to 2000 kg/cm2. The pressure that enters the mercury into the pores depends on the dilatometer and the pores. Measurements are using the device for determining porosity "Porosimeter 2000". Porosity, pore distribution and specific surface area calculated from the data for the reduction of mercury and by the values of the pressure applied. The particle size of the catalyst is determined by the method based on the principle of optical diffraction of monochromatic laser light.

UPE melt index ASTM-D 1238

UPF melt index ASTM-D 1238

Fluidity: the time required for 100 g of polymer to flow through a funnel with the outlet 1.25 cm in diameter and with walls of inclination of the 20oto the vertical.

Bulk density: DN N 53194.

The morphology and particle size distribution"ptx2">

The content of the co monomer: the weight percent of the co monomer, defined according to the IR spectrum.

The effective density: ASTM-D 792.

Example. Getting the ball carrier (adduct MgCI2/EtOH).

Adduct of magnesium chloride and alcohol produced by the method described in example 2 of U.S. patent 4399054, but using speed 2000 rpm instead of 1000 rpm

The adduct contains about 3 mol of alcohol and has an average size of about 60 μm with a dispersion in the range of about 30 to 90 μm.

Example 1. Obtaining a solid component.

Ball carrier obtained by the General method, is subjected to heat treatment in a stream of nitrogen in the temperature range 50 - 150oC to obtain spherical particles with a residual alcohol content of 35% (1.1 mol of alcohol per every 1 mole MgCI2).

2700 g of this carrier is placed in an autoclave with a capacity of 60 l with 38 liters of anhydrous hexane. Under stirring at room temperature serves to 11.6 l of a hexane solution containing 100 g/l IEt3for 60 minutes the Temperature was raised to 50oC for 60 minutes, and maintain this temperature for a further 30 minutes, still stirring. The liquid phase is removed by decantation and siteniravam; processing IEt3repeat at 50oC in vacuum. Thus obtained carrier has the following characteristics:

Porosity (Hg), g/cm3- 1,144

Specific surface area (Hg), m2/g - 15,2

Residual OEt, wt.% - 5,5

Residual At, wt.% - 3,6

Mg,% wt. - 20,4

In a steel reactor with a stirrer, volume 72 l enter 40 l TiCl4at room temperature and with stirring, enter 1900 g of the above media. The mixture is heated to 100oC for 60 minutes, and these conditions remain within 60 minutes. The stirring is interrupted and after 30 minutes the liquid phase is separated from the sludge solid phase. Spend two additional processing in the same conditions, with the difference that the first of these treatments is carried out at 120oC, while the second 135oC. Then spend 7 washings with anhydrous hexane (about 19 liters), three of which are conducted at 60oC, and 4 at room temperature. Get 2400 g component with a spherical shape, which after drying in a vacuum at a temperature of about 50oC have the following characteristics:

Full titanium content, wt.% - 6

Ti(III), wt.% - 4,9

Al, wt.% - 3

Mg,% wt. - 12,2

Cl, wt.% - 68,2

OEt, wt.% - 0,3

Porosity (B. E. T.), cm3/year, of which 50% of the pores have a radius above 300 - 0,208

Specific powerdip up to 15000 - 0.674

Specific surface area (Hg), m2/g - 21

Polymerization of ethylene (HDPE).

In a stainless steel autoclave with a volume of 2.4 l, degassed by a stream of nitrogen 70oC, load 2000 cm3anhydrous hexane, 0,0095 g ball component and 0.5 g of triisobutylaluminum. All this stirred, heated to 75oC, and then served H2/4 bar/ and the ethylene /7 bar/. The polymerization are 3 hours, all the while feeding ethylene to maintain the pressure constant. Get 350 g of polymer with the following characteristics:

UPE g/10 min - 0.12 g/10

UPF/UPE - 120

The effective density, g/cm3- 0,960

Bulk density, g/cm3- 0,32

Fluidity, C - 11

Morphology Spherical

The distribution of particle size (microns) wt.%

>4000 - 0.6

2000 - 4000 - 87,8

1000 - 2000 - 11

500 - 1000 - 0,3

<500 - 0,3

Example 2. In the same autoclave as in example 1, after loading 0,0122 g ball component and 0.5 g of triisobutylaluminum at 30oC enter ethylene (7 bar) and H2(4 bar). All this support when 30oC as long as the system will not absorb about 5 g of ethylene. Then it is heated to 75oC and polymerized for 3 hours, feeding ethylene to maintain postoyannaya density, g/cm3- 0,36

Fluidity, C - 11

Morphology Spherical

The distribution of particle size (microns) wt.%:

>4000 - 0.1

2000 - 4000 - 69,7

1000 - 2000 - 29,3

500 - 1000 - 0,4

<500 - 0,5

Example 3. 80 g of the carrier obtained in example 1 after treatment AIEt3handle dry air in the fluidized bed for about 4 hours at 40oC. After this treatment the media fed into the reactor containing 800 cm3TiCl4at room temperature. With careful stirring the resulting mixture was slowly heated to 100oC, and then maintained under these conditions for 60 minutes. Stirring is stopped and after desantirovaniya solid phase liquid phase allocate using a siphon. Spend two additional processing in the same conditions, but with the difference that the first of these treatments is carried out at 120oC, and the second with 135oC. Then spend 7 leaching of anhydrous hexane, three of which at 60oC, and four at room temperature.

The components of the spherical shape is dried in vacuum at 50oC and get the following features:

Full titanium content, wt.% - 3,1

Ti(III), wt.% - <0,1
Cl, wt.% - 67,9

OEt, estate (B. E. T.), m2/g - 5,8

Full porosity (Hg) cm350% of the pores have a radius above 1600 90% of the pores have a radius of up to 15000 - 0,751

Specific surface area (Hg), m2/g - 26

Polymerization of ethylene (HDPE).

0,0106 g ball component used in the polymerization of ethylene under the same conditions as in example 1. Obtain 380 g of a polymer with the following characteristics:

UPE g/10 min of 0.565

UPF/UPE - 90

Bulk density, g/cm3- 0,34

Morphology Spherical

Fluidity, C - 12

The distribution of particle size (microns) wt.%:

>4000 - 0,3

2000 - 4000 - 5,3

1000 - 2000 - 13,7

500 - 1000 - 0,5

<500 - 0,1

Example 4. 100 g of the carrier obtained by the method of example 1, after processing AIEt3enter in one litre glass reactor equipped with a mixer. After that consistently sell 500 cm3anhydrous heptane and after about 10 minutes 70 grams of TiCl4. The resulting mixture was stirred for 30 minutes at room temperature. Slowly serves a mixture containing 100 cm3AI2Et3Cl3and 100 cm3anhydrous hexane. After mixing, the mixture is slowly heated to 98oC, and then maintained under these conditions for 2 hours. Mixing stop the room temperature, using 800 cm3anhydrous hexane for each wash. At the end of the solid portion is dried at 50oC in vacuum. Get 117 g sartogo component with the following characteristics:

Full titanium content, wt.% - 9,75

Ti(III), wt.% - 9,25

Al, wt.% - 2,5

Mg,% wt. - 13,9

Cl, wt.% - 67,6

OEt, wt.% - 0,6

Porosity (B. E. T.), cm3/g 50% of the pores have a radius greater than 150 cm3/g - of 0.182

Specific surface area (B. E. T.), m2/g - 59

Full porosity (Hg) cm350% of the pores have a radius above 3000 - 1,099

Specific surface area(Hg), m2/g - 30

Polymerization of ethylene (HSE).

0,075 ball component used for the polymerization of ethylene under the conditions described in example 1. Get 90 g of polymer with the following characteristics:

UPE g/min 0,15

UPF/UPE - 66,6

Bulk density, g/cm3- 0,30

Morphology Spherical

Fluidity, C - 14

The distribution of particle size (microns) wt.%:

>4000 - 2,5

2000 - 4000 - 86,2

1000 - 2000 - 11,5

500 - 1000 - 0,3

<500 - 0,2

Example 5. Gas polymerization of a mixture of ethylene and butene. A solid component obtained according to the procedure of example 1, and the solution triisobutylaluminum (L) in n-hexane served in a disabled reacto propane.

Suspension of propane containing prepolymer, which is continuously discharged from terpolymerization in the first gas-phase reactor. In terpolymerization also served hydrogen to control the molecular weight of the prepolymer. For better control of the reactivity of the system in the first and second gas-phase reactor type propane.

Basic working conditions

Preliminary interaction:

TemperatureoC - 20

L/Ti mol - 30

Stage terpolymerization:

TemperatureoC - 25

The first gas-phase reactor

TemperatureoC - 85

Pressure, bar - 24

The hydrogen/ethylene mol - 0,14

Butylene/(butylene+ethylene), mol - 0,15

Propane mol% - 50,0

The characteristics of the target product:

The final yield, kg/g cat. - 10,4

Real density, g/1 - 0,918

Index melting point "E", g/10 min - 1

Associated butene, wt.% - 8

Example 6. Gas-phase polymerization of ethylene and octene. The process is repeated similarly to the process of example 1 under the following reaction conditions:

Preliminary interaction:

Temperature oC - 20

L/Ti mol - 30

Stage terpolymerization

Temperature oC - 25

First guzofsky+ethylene), mol - 0,22

Propane mol% - 70,0

The second gas-phase reactor

Temperature oC - 90

Pressure, bar - 22

The hydrogen/ethylene mol - 0,2

Octene/(octene+ethylene), mol - 0,22

Propane mol% - 60.0 sec

The characteristics of the target product:

Real density, g/1 - 0,912

Index melting point "E", g/10 min - 0,7

Associated octene, wt.% - 6

1. The ball component of the catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical C1-C12containing compound of titanium deposited on a magnesium halide and having 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 of Ti, characterized in that it has a specific surface area, a certain way BET, below 70 m2/g, pore volume, determined by the mercury method, above 0.5 cm3/g and at least 50% of the pores have a radius above 800

2. Component under item 1, characterized in that the pore volume is 0.6-1.2 cm3/g, and specific surface 30-70 m2/,

3. Component under item 1 or 2, characterized in that at least 80% of the pores have a radius of up to 15000 and a porosity of 0.6-0.9 cm3/,

4. Component under item 1 or 2, otlichayushiesya 1:2 - 1:20.

5. Component under item 1 or 2, characterized in that the magnesium halide is MgCl2.

6. Component under item 1 or 2, characterized in that the compound of titanium is of the form Ti(OR)nXy-nwhere n= 0-0,5, y is the valence of titanium, X is halogen and R is alkyl, cycloalkyl or aryl radical containing 2 to 8 carbon atoms or a COR group.

7. Component under item 6, characterized in that y=4, a n=0-0,02.

8. Component under item 6, characterized in that y=3, a n=0-0,015.

9. Component under item 4, characterized in that the electron-donating compound selected from ethers and alkyl-, cycloalkyl-killarny esters, polycarboxylic acids.

10. Component under item 4, characterized in that the electron-donating compound selected from 1,3-diesters of the formula

< / BR>
where RIand RIIthe same or different and are alkyl, cycloalkyl, aryl radicals containing 1-18 carbon atoms;

RIIIand RIVthe same or different and are alkyl radicals containing 1-4 carbon atoms.

11. The catalyst for polymerization of olefins, which is a product of the interaction of the component containing deposited on a magnesium halide Svetlichnyi from halogen, with aluminiuim, characterized in that, as specified component of the catalyst, it contains a ball component having a specific surface according to BET below 70 m2/g, pore volume, determined by the mercury method, above 0.5 cm3/g, in which at least 50% of the pores have a radius above 800

12. The catalyst according to p. 11, characterized in that the connection alkylamine is trialkylaluminium.

13. The catalyst according to p. 11, characterized in that it contains the product of the reaction between the component under item 4 and the connection alkylamine.

14. The catalyst according to p. 11, characterized in that it contains the reaction product between the components under item 4, the connection alkylamine and electron-donor compound (external donor).

15. The catalyst according to p. 14, characterized in that the connection of the external electron donor is chosen from 1,3-diesters of the formula

< / BR>
where RIand RIIthe same or different and are alkyl, cycloalkyl, aryl radicals containing 1-18 carbon atoms;

RIII, RIVthe same or different and are alkyl radicals containing 1-4 carbon atoms.

16. The catalyst according to p. 11, characterized in that it contains the product of the reaction between the components is in the formula, RIy-nSi (ORIII)nwhere RI- alkyl, cycloalkyl, aryl radical containing 1-18 carbon atoms, RIIIis an alkyl radical containing 1-4 carbon atoms, n=1-3.

17. A method of obtaining a ball component of a catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or hydrocarbon radical containing 1-12 carbon atoms, by the interaction between (a) the connection MgCl2mROH, where 0 m to 0.5 and R is alkyl, cycloalkyl or aryl radical containing 1-12 carbon atoms and (b) the compound of titanium of the formula Ti(or SIG)nXy-nwhere n=0-0,5, y is the valence of titanium, X is halogen and R is an alkyl radical containing 2 to 8 carbon atoms, or COR-group, wherein compound (a) receive chemical removal of alcohol from the adduct MgCl2d, 0,1p2, obtained by thermal removal of alcohol from the adduct MgCl2q ROH, where 2,5q3,5.

18. The method according to p. 17, characterized in that the reaction between compound (b) and compound (a), the ratio of Ti/Mg varies from 0.05 to 3.0.

19. The method according to p. 17, characterized in that the reaction between compound (b) and compound (a), the ratio of Ti/Mg > 3.

20. The method according to p. 17, characterized in that the reaction:2 - 1:20.

21. The method according to p. 17, characterized in that a compound of titanium is TiCl4.

22. The method according to p. 21, characterized in that the reaction of lead in liquid TiCl4or in hydrocarbon solution.

23. The method according to p. 17, wherein removing the alcohol from the adduct MgCl2p ROH connection alkylamine.

24. The method according to p. 23, characterized in that the compound (a) is treated with the agent, decontamination connection alkylamine, before it is subjected to interaction with the compound (b).

25. The method according to p. 24, wherein the deactivating agent is oxygen.

26. The method according to p. 17, characterized in that it includes the use of a reducing compound.

27. The method according to p. 26, characterized in that the regenerating connection is trialkylaluminium or aluminiumalloy.

28. The method according to p. 27, characterized in that the regenerating compound is Al2Et3Cl3.

29. The method of polymerization of olefin CH2=CHR, where R is hydrogen or hydrocarbon radical C1-C12in the presence of a catalyst, wherein the catalyst used cammesa with olefins CH2=CHRVwhere RVis alkyl, cycloalkyl or aryl radical containing 1-12 carbon atoms, optionally in the presence of small amounts of a diene, and use the catalyst PP.11-13.

31. The method according to p. 30, characterized in that the olefin CH2=CHRVchoose from 1-butene, 1-pentene, 1-hexene, 4-methylpentene-1,1-octene.

32. The method according to p. 29, characterized in that carry out the polymerization of propylene and its mixtures with olefins CH2=CHR, optionally in the presence of small amounts of a diene, using catalysts for PP.14-16.

 

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The invention relates to the components of the catalyst, the way they are received and catalysts for polymerization of olefins of General formula CH2= CHR

The invention relates to a method for producing polymers and copolymers of olefins CH2=CHR, where R is a hydrogen atom or an alkyl radical having from 1 to 10 carbon atoms that includes at least one phase (co)polymerization in the gas phase in the presence of a highly active catalyst, obtained from compounds of titanium with a magnesium halide in active form as a carrier and alkyl aluminum compounds

The invention relates to a method for producing alpha-olefins of high molecular weight polymers in solution by polymerization of ethylene or mixtures of ethylene and at least one higher olefin C3-C12in the presence of a coordination catalyst, consisting of two components: the first contains Ti, Mg, Al, and the second mixture alkylamine and alkoxyalkane, when heated to 180-320oC, and the formation of the first and second catalyst components and their mixing is carried out in the stream at a temperature lower than the 30oC
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