Components and catalysts for the polymerization of olefins

 

(57) Abstract:

Describes a new catalyst component for polymerization of olefins, containing the compound of the transition metal M selected from Ti, Zr, Hf, which contains at least one M--communication, and the halide of magnesium, characterized in that it has a specific surface area (by BET method) exceeding 50 m2/g, the porosity by BET method above 0.15 cm3/g and porosity by mercury method above 0.3 cm3/g, when the specific surface area is less than 150 m2/g, the porosity by mercury method is less than 1.5 cm3/, Describes and catalysts for the polymerization of olefins. The technical result is an increase in the activity of the catalyst. 4 C. and 23 C.p. f-crystals.

The invention relates to components of catalysts for the polymerization of olefins, obtained from these catalysts and the use of these catalysts for the polymerization of olefins CH2=CHR, where R is hydrogen or alkyl, cycloalkyl or allrazolam with 1-10 carbon atoms. Another aspect of the present invention relates to polymers obtained by the use of these catalysts.

From literature is known catalysts that are obtained from the connection m lxwhere M is metal, and at least one ligand L is cycloalkenyl structure. Catalysts of this type, obtained by using the compounds Cp2TiCl2or Cp2ZrCl2(Cp - cyclopentadienyl) are described in U.S. patent N 2827446 and 2924593. Connections are used together with the alkyl-Al compounds for the polymerization of ethylene. The catalytic activity is very low. Catalysts with very high activity are obtained by using compounds Cp2ZrCl2or Cp2TiCl2or their derivatives, substituted in cyclopentadienyls the ring, where the Cp-ring may be condensed with other rings, and when using polyaluminium compounds containing a repeating element (R)AlO-, where R is lower alkyl, preferably methyl (U.S. patent N 4542199 and European patent EP-A-129368).

The catalysts of the above type, in which the metallocene compound contains two indanilnykh or tetrahydroindole rings linked by bridges over the lower alkylene or other divalent radicals, are suitable for the production of stereoregular polymers of propylene and other olefins (European patent EP-A-185918).

Stereospecific catalysts Tokushima spatial difficulty, for example, to prevent rotation of the rings about the axis of coordination with the metal.

Substitution indenyl or tetrahydroindene in the relevant provisions gives the catalysts, which have a very high stereospecificity (European patents EP-A-485823, EP-A-485820, EP-A-519237, U.S. patent N 5132262 and 5162278).

When using the above-described metallocene catalysts obtained polymers with very narrow molecular weight distribution (Mw/Mnabout 2).

Some of these catalysts also tend to form copolymers of ethylene with a-olefins type linear LDPE or elastomeric copolymers of ethylene with propylene, with a very homogeneous distribution comonomeric units. The linear LDPE additionally characterized by low solubility in solvents, such as xylene or N. Dean.

The polypropylene obtained with the above visokotehnologicheskie catalysts, has a higher crystallinity and a higher heat distortion temperature as compared with the polymer obtained with conventional catalysts of the Ziegler-Natta.

However, these metallocene catalysts have a great disadvantage in respect of vozmojnostey to they dissolve in the reaction medium in which they work, and in liquid medium polymerization.

In order to use the catalysts in the way of gas-phase polymerization, they must be applied to the corresponding carriers of the substrate that define the appropriate morphological properties of the polymer.

Use a variety of paper types, including, among others, porous metal oxides, such as silica or porous polymeric carriers, such as polyethylene, polypropylene and polystyrene. As carriers are also used magnesium halides. In some cases, the halides of magnesium are also used as counterion ion pairs, in which the metallocene compound gives the cation, and the connection, such as a magnesium halide, yields the anion.

When the donor anion is halide of magnesium, the catalytic system is formed by the halogen present in solid form, and metallocene compound dissolved in water. A system of this type cannot be used in the methods of gas-phase polymerization. The magnesium halide is preferably used in finely dispersed form, which can be obtained by grinding.

As nistory not have high performance characteristics. Quite a high output can be obtained only when the magnesium halide partially complexesa electron-donating compound, obtained by a special method of obtaining.

Japanese application N 168408/88 (published 12.07.88,) describes the use of magnesium chloride as a carrier metallocene compounds such as Cp2TiCl2Cp2ZrCl2Cp2Ti(CH3)2for education trialkylaluminium and/or polymethylsiloxane (PMO) catalysts for polymerization of ethylene. The component containing magnesium chloride, obtained by grinding MgCl2with the metallocene compound in the presence of electron-donor compounds. Alternative component is obtained by processing metallocene liquid adduct MgCl2-alcohol and subsequent interaction with AlEt2Cl. Catalytic activity towards MgCl2is very low.

In U.S. patent N 5106804 describes a catalyst containing a metallocene compound type Cp2ZrCl2printed on the ball MgCl2and partly from complexes with electron-donating compound. The characteristics of these catalysts are superior characteristics of the catalysts described in Japanese patent application N 168408/88, the second amount of catalyst. Used electron donor must not contain active hydrogen atoms and also should be uniformly distributed in the mass of the magnesium halide. Associated media cannot be obtained by simple mixing of the components. Homogeneous dispersion of the electron donor is obtained upon receipt of the halide of magnesium (halogenoalkanes Mg-dialkyl) in the presence of a solvent containing electron donor in solution. Specific surface area of the magnesium halide is not more than 100 m2/g and is preferably 30-60 m2/, there is No information about the porosity of the media. Electron-donating compound is used in an amount of from 0.5 to 15 mol.% with respect to the halide of magnesium; his presence is necessary. The resulting catalysts are much worse characteristics than the characteristics of the respective catalysts without the media, in which the metallocene compound used in the solution.

European patent EP-A-318048 describes the catalyst that uses a solid component containing compound of titanium deposited on magnesium chloride, which has certain characteristics of the specific surface and porosity, and possibly electron-donor compound with a benzyl 3)2for the formation of catalysts for polymerization of ethylene and polypropylene. The mass ratio of metallocene to the magnesium chloride is very high (more than 1), so you must remove metallocen of the obtained polymer. The catalysts used in the processes that are carried out in the presence of a liquid polymerization medium.

European patent EP-A-439964 describes bimetallic catalysts suitable for polymers of ethylene with a wide molecular weight distribution (Mw/Mnis 4-14) obtained by applying metallocene solid component containing compound of titanium deposited on the MgCl2. PMO or mixtures thereof with alkyl-Al are used as socializaton. Trialkyl-Al-compounds are also used as socialization, but the catalytic activity is low. The productivity of these mixed catalysts with the active centers, originating either from Ti-compounds deposited on the MgCl2or of metallocene compounds is very high, when the catalysts used in hydrocarbon environment; on the other hand, it is low when the polymerization is carried out in the gas phase. This is probably obyasnu media in a stable form, it is dissolved in the hydrocarbon polymerization solvent. In practice, the catalyst corresponds to the homogeneous catalyst, in which the metallocene compound used in the solution. When working in the gas-phase metallocene compound is present in solid form and obtained from him the catalyst has a lower activity than the activity of a corresponding catalyst used in the solution.

European patent EP-A-522281 describes catalysts obtained from Cp2ZrCl2with the carrier of the MgCl2and their mixtures trialkyl-Al and compounds, giving a stable anions type dimethylaniline-tetrakis-(pentafluorophenyl)-borate. The catalysts are obtained by grinding the components used for the polymerization of ethylene in the presence of a solvent (toluene) in good yield (relative to the MgCl2). In this case, the metallocene compound is mainly in solution and is not recorded on the MgCl2and the relatively high activity towards MgCl2mainly due to the catalyst dissolved in the polymerization medium.

European patent EP-A-509944 describes catalysts using aniline-tetrakis-(pentafluorobenzene with alkyl-Al compounds. Magnesium chloride prior to contacting with the pre-reacted metallocene compound is crushed. The polymer yield with respect to the halide of magnesium is low (less than about 100 g of polymer per 1 g MgCl2). Halogen magnesium has a specific surface area of from 1 to 300 m2/g, preferably from 30 to 300 m2/year of magnesium Chloride with a specific surface area of 30-300 m2/g is obtained mainly by industrial grinding chloride. In this case, it is difficult to obtain a surface above 100-150 m2/g and the porosity is relatively low (less than 0.1 cm3/g). In addition, in the case of the catalysts described in patent EP-A-509944, the catalyst is mainly attributed to the metallocene compound, dissolved in a polymerization solvent.

European patent EP-A-588404 describes catalysts obtained from metallocene compounds with the carrier of magnesium halides obtained by halogenoalkanes dialkyl-Mg - or alkyl-Mg-halides using SiCl4or SnCl4. The yield of polymer (polyethylene) per 1 g of solid component and 1 g of Zr is relatively high, especially when the catalyst is obtained from the MgCl2obtained using SnCl4. Again in the records of the metallocene compounds, which is dissolved in the polymerization medium, than the catalyst obtained from metallocene compounds actually applied to the halide of magnesium.

European patent EP-A-576213 describes the catalysts obtained from the solution of MgCl2in alcohol, from trialkyl-Al-compounds and metallocene compounds. The polymer yield is very low. The catalyst is practically inactive when a solution of MgCl2replaced with solid MgCl2activated by prolonged grinding.

Now unexpectedly been found solid components, which contain a metallocene compound and a magnesium halide which produces catalysts which exhibit very high activity in the polymerization of olefins, different specific surface area (by BET method) of more than about 50 m2/g and porosity (BET method) of more than about 0.15 cm3/g and porosity (mercury method) of more than 0.3 cm3/g, provided that, when the specific surface is less than approximately 150 m2/g, porosity (mercury method) is less than about 1.5 cm3/,

Porosity and specific surface area by BET method is defined using device "SORPTOMAT JC 1800" by Carlo is STI "Porosimeter" 2000 "series" by Carlo Erba in accordance with the following method.

The porosity (BET method) is preferably larger than 0.2 cm3/g and, in particular, is 0.3-1 cm3/g Specific surface area (by BET method) is preferably greater than 100 m2/g and more preferably 150 m2/, is Very suitable interval from 150 to 800 m2/year Components with a specific surface area less than 150 m2/g give catalysts with characteristics that are of interest, provided that the porosity (mercury method) is less than about 1.5 cm3/g, preferably 0.4 to 1.2 cm3/g and especially from 0.5 to 1.1 cm3/,

The components are preferably used in the form of balls of a size less than 150 microns.

Components with a specific surface area (by BET method) of less than about 150 m2/g more than 50% porosity (BET method) is defined by pores with a radius greater than 300 and preferably 600-1000

Components with a specific surface area (by BET method) of more than 150 m2/g, in particular more than 200 m2/g are simultaneously porosity (BET method) due to pores with radius 300-1000 the porosity (BET method) due to pores with a radius of about 10-100 Generally, more than 40% porosity (BET method) is defined by pores with a radius greater than 300 ang is 300 and more preferably below 100 scope of the invention also includes such components which under normal conditions do not have values of specific surface and porosity above, but reach them after processing a 10% solution of trialkyl-Al in N. hexane at 50oC for 1 hour.

Components according to the invention are obtained by applying the metallocene compound on a magnesium halide or a carrier containing a halide of magnesium, which has the characteristics of specific surface and porosity, which are within the limits specified for the catalytic component.

In General, the specific surface area (by BET method), porosity (BET method) and porosity (mercury method) of the source of halogen to magnesium is higher than the same characteristics of the component derived from it.

Preferably the halides of magnesium have a specific surface area (by BET method) of more than 200 m2/g, more preferably 300-800 m2/g and porosity (BET method) greater than 0.3 cm3/,

The magnesium halide may contain smaller amounts of other components, acting as conoidal or used to improve properties of the catalytic component. Examples of such components are AlCl3, SnCl4, Al(OEt)3, MnCl2, ZnCl2, VCl3Si(OEt)4.

The magnesium halide, in turn, may be deposited on an inert substrate, which has a specific surface area and porosity such that the product application has the above values. Appropriate inert substrate can be metal oxides, such as silica, Al2O3, SiO2-Al2O3with porosity (BET method) of more than 0.5 cm3/g and a specific surface area (by BET method) of more than 200 m2/g, for example, 300-600 m2/,

Other inert substrate can be porous polymers, such as polyethylene, polypropylene and polystyrene.

Partially cross-linked polystyrene, which has high values of specific surface and porosity, is particularly suitable.

Polystyrenes of this type are described in U.S. patent 5139985, method of production and application of magnesium halide which is reproduced here for comparison. These polystyrenes usually have a specific surface area (by BET method) 100-600 m2/g and porosity (BET method) higher than 0.5 cm3/,

ü. The preferred magnesium halide is magnesium chloride. The magnesium halide may be applied in accordance with known methods of solutions in solvents such as tetrahydrofuran, or by impregnation of the inert substrate solutions of halogen in alcohol; the alcohol is then removed by interaction with the connection, such as trialkyl-Al or dialkyl-Al-halide or halides of silicon. Used alcohols are typically alkanols with 1 to 8 carbon atoms.

By the way, which is very suitable for the production of magnesium halide having the above characteristics, the porosity and specific surface, interact spherolitic adducts MgCl2with alcohols, and these adducts contain from 0.1 to 3 moles of alcohol with alkyl-Al compounds, in particular triethyl-Al, triisobutyl-Al, AlEt2Cl.

Obtaining this type is described in U.S. patent N 4399054, which is given here as a reference.

In order to obtain media with morphological characteristics that are particularly suitable for processes of gas polymerization in the fluidized bed, the adduct MgCl2with about 3 moles of alcohol must be subjected before reaction with alkyl-Al controls titsa as a reference. Thus obtained magnesium halides have a spheroidal form, the average size of less than 150 μm, the specific surface area (by BET method) of more than 60-70 m2/g and usually 60-500 m2/,

Other ways to get magnesium halides, suitable for receiving the components according to the invention, are the methods described in the European patent EP-A-553805, which is given here as a reference.

Drawing on media metallocene compounds is performed by known methods when the contacting of the magnesium halides, for example, with a solution of metallocene compounds at temperatures from room temperature up to 120oC. the Metallocene compound, which is not fixed on the carrier is removed by filtration or similar methods, or by evaporation of solvent.

The number printed on the media metallocene compound is usually 0.1 to 5 wt.%, expressed as the metal.

The atomic ratio of magnesium to transition metal is typically 10-200; however, it may be smaller and can reach values of 1 or even less, when the magnesium halide is applied to an inert substrate.

Metallocene compounds are sparingly soluble in hydrocarbons (most often the COI is acetelyne increases, if the solvent contains dissolved alkyl-Al compound, such as triethyl-Al, triisobutyl-Al or polyalkyloxy, in particular PMA (polymethylsiloxane), in a molar ratio for metallocene compounds more than 2 and preferably 5-100.

The carrier impregnated with the above solution makes it possible to obtain particularly active catalysts (activity higher than the activity of catalysts which can be obtained from solutions of metallocene compounds that do not contain alkyl-Al compound or PMA).

Used metallocene compounds are compounds of the transition metal M selected from Ti, V, Zr and Hf containing at least one metal--communication and preferably containing at least one ligand L, coordinating associated with the metal M, having a mono - or polycyclic structure containing paired electrons.

These compounds of Ti, V, Zr or Hf, preferably selected from components having the structure:

CpIM(R1)a(R2)(R3)c(I)

CpI1CpIIM(R1)a(R2) (II)

(CpI-Ae-CpII)M1(R1)a(R2) (III)

where M is Ti, V, Zr or Hf;

the group; moreover, two or more substituents associated with the specified cyclopentadienyls groups can form one or more rings having from 4 to 6 carbon atoms;

R1, R2and R3identical or different, are atoms of hydrogen, halogen, alkyl - or alkoxygroup with 1-20 carbon atoms, aryl, alkaryl or aralkyl with 6-20 carbon atoms, alloctype with 1-20 carbon atoms, allgroups, Deputy containing a silicon atom;

A - alkanniny bridge or a bridge structure selected from

=BR1, =AlR1, -Ge-, -Sn-, -O-, -S-, = SO, =SO2, = NR1, =PR1, =P(O)R1,

where M1- Si, Ge or Sn;

R1and R2identical or different, accelgroup with 1-4 carbon atoms or aryl groups with 6-10 carbon atoms;

independently of one another, integers from 0 to 4;

an integer from 1 to 6; and 2 or more of the radicals R1, R2and R3may form a ring. When the Cp-group is substituted, the Deputy is preferably altergroup with 1-20 carbon atoms.

Representatives of the compounds which have the General formula (I) include:

(Me5Cp)MMe3, (Me5Cp)M(OMe)3, (Me5Cp)MCl3, (Cp)MCl33. Representatives of the compounds which have the General formula (II) include:

(Cp)2MMe2, (Cp)2MPh2, (Cp)2MEt2, (Cp)2MCl2, (CP)2M(OMe)2, (Cp)2M(OMe)Cl, (MeCp)2MCl2, (Me5Cp)2MCl2, (Me5Cp)2MMe2, (Me5Cp)2MMeCl, (Cp)(Me5Cp)MCl2,

(1-MeFIu)2MCl2, (BuCp)2MCl2, (Me3Cp)2MCl2, (Me4Cp)2MCl2, (Me5Cp)2M(OMe)2, (Me5Cp)2M(OH)Cl, (Me5Cp)2M(OH)2, (Me5Cp)2M(C6H5)2, (Me5Cp)2M(CH3)Cl, (EtMe4Cp)2MCl2, [(C6H5)Me4Cp]2MCl2, (Et5Cp)2MCl2, (Me5Cp)2M(C6H5)Cl, (Ind)2MCl2, (Ind)2MMe2, (H4Ind)2MCl2, (H4Ind)2MMe2, {[Si(CH3)3] Cp}2MCl2, {[Si(CH3)3]2Cp}2MCl2, (Me4Cp)(Me5Cp)MCl2.

Representatives of the compounds of the formula (III) include:

C2H4(Ind)2MCl2C2H4(Ind)2MMe2C2H4(H4Ind)2MCl2C2H4(H4Ind)2MMe2,
< Me2SiCp2MMe2,

Me2Si(Me4Cp)2MMeOMe, Me2Si(FIn)2MCl2, Me2Si(2-Et-5-iPrCp)2MCl2, Me2Si(H4Ind)2MCl2, Me2Si(H4FIu)2MCl2, Me2SiCH2(Ind)2MCl2, Me2Si(2-Me-H4Ind)2MCl2, Me2Si(2-MeInd)2MCl2, Me2Si(2-Et-5-iPr-Cp)2MCl2, Me2Si(2-Me-5-Et-Cp)2MCl2, Me2Si(2-Me-5-Me-Cp)2MCl2, Me2Si(2-Me-4,5-benzhydryl)2MCl2,

Me2Si(4,5-benzhydryl)2MCl2, Me2Si(2-Et-Ind)2MCl2, Me2Si(2-iPr-Ind)2MCl2,

Me2Si(2-t-butyl-Ind)MCl2, Me2Si(3-t-butyl-5-MeCp)2MCl2, Me2Si(3-t-butyl-5-MeCp)2MMe2, Me2Si(2-MeInd)2MCl2C2H4(2-Me-4,5-benzhydryl)2MCl2,

Me2C(FIu)CpMCl2Ph2Si(Ind)2MCl2Ph(Me)Si(Ind)2MCl2C2H4(H4Ind)M(NMe2)OMe, isopropylidene-(3-t-butyl-Cp)(FIu)MCl2, Me2C(Me4Cp)(MCp)MCl2, MeSi(Ind)2MCl2, Me2Si(Ind)2MMe2, Me2Si(Me4Cp)MCl(OEt),

C2H4(Ind)2M(NMe2)2C2H4(Me4Cp)2MCl2C2Me4(Ind)2MClCl2,

C2H4(4,7-Me2-Ind)2MCl2C2H4(5,6-Me2-Ind)2MCl2C2H4(2,4,7-Me3Ind)2MCl2,

C2H4(3,4,7-Me3Ind)2MCl2C2H4(2-Me-H4Ind)2MCl2C2H4(4,7-Me2-H4Ind)2MCl2,

C2H4(2,4,7-Me3-H4Ind)2MCl2, Me2Si(4,7-Me2-Ind)2MCl2, Me2Si(5,6-Me2-Ind)2MCl2, Me2Si(2,4,7-Me3-H4Ind)2MCl2.

In the above simplified formula the symbols have the following meanings:

Me is methyl, E is ethyl, iPr is isopropyl, Bn - butyl, Ph is phenyl, Cp is cyclopentadienyl, Ind - indenyl, H4Ind - 4,5,6,7-tetrahydroindene, FIn - fluorenyl, Benz - benzyl, M is Ti, Zr or Hf, preferably Zr.

Join Me2Si(2-Me-Ind)2ZrCl2and Me2Si(2-Me-H4Ind)ZrCl2and methods for their preparation are described, respectively, in European patents EP-A-485822 and 485820, which are listed here as references.

Join Me2Si(3-t-butyl-5-MeCp)2ZrCl2and type Me2Si(2-Me-4,5-benzhydryl)ZrCl and method of production thereof are described respectively in U.S. patent N 5132262 and European-Al connections or polyallylamine compounds (or mixtures thereof) catalysts, which have a very high activity relative to the halide of magnesium.

The alkyl-Al compound is typically selected from compounds of the formula AlR3in which R3- alkyl which has 1 to 12 carbon atoms, and alumoxane compounds containing the repeating unit -(R4)AlO-, where R4- alkylaryl containing from 1 to 6 carbon atoms, and these alumoxane compounds contain from 2 to 50 repeating units, which have the above formula. Typical examples of compounds of the General formula AlR3are trimethyl-Al, triethyl-Al, triisobutyl-Al, tri-n-butyl-Al, trihexy-Al, trioxin-Al. Among alumoxanes connections using PMO is preferred. Mainly also used a mixture of alkyl-Al compounds, preferably triisobutyl-Al, and alumoxane compounds, preferably PMO.

When the transition metal compound containing at least one M-link is a connection of the type described General formula (II) and (III), mainly can be used compounds obtained by the reaction between AlR3and H2O in a molar ratio of 0.01 to 0.5.

In General, the alkyl-Al compound used in a molar ratio with the PE the Deposit can be used for copolymerization of olefins CH2= CHR, where R is hydrogen or alkylation with 1-10 carbon atoms, or aryl.

They are used in particular for the polymerization of ethylene and its mixtures with olefins of the type specified above, where R is alkylaryl.

Catalysts, in particular, obtained from compounds of the type C2H4(Ind)2ZrCl2C2H4(H4Ind)ZrCl2and Me2Si(Me4Cp)2ZrCl2are suitable for the production of LLDPE (copolymers of ethylene having a low content, usually below 20 mol.%, C3-12--olefins) characterized by relatively low density values in relation to the content of the olefin, with low solubility in xylene at room temperature (below about 10 wt. %) and molecular weight distribution Mw/Mnapproximately 2.5-5.

Polypropylene that can be obtained with the catalysts using a chiral metallocene compounds are characterized by a high stereoregularity, high molecular weight, which is easily adjustable, and a high degree of crystallinity.

Used chiral metallocene compounds are, for example, compounds of the type described in the European patellectomy, but do not limit the scope of the invention. Characteristics are determined in accordance with the following methods:

The porosity and specific surface area (by BET method): determined in accordance with the methods of the BET (used device: SORPTOMATIC 1800 firm Carlo Erba). The porosity is calculated on the cumulative distribution curve of the pore as a function of the size of the pores.

The porosity and specific surface area by the mercury method: determine when immersing a known quantity of sample in a known amount of mercury inside the dilatometer and then with a gradual increase in hydraulic pressure of mercury. The pressure pushing the mercury into the pores is a function of their diameter. The measurement is performed using a device for measuring the pore size "Porosimeter 2000 series" by Carlo Erba. Porosity, pore distribution and specific surface area are calculated according to the reduction of mercury and the values of the applied pressure.

Porosity and specific surface area referred to in the description and examples, refer to the pore size of 10,000

- The size of the catalyst particles

is determined by a method based on the principle of optical diffraction of monochromatic laser light, with the help of the device "Malvern Instr, 2600". The average size usecs melt (F)

determined according to ASTM-D1238, method F.

The ratio C (F/E)

the ratio between the melt index F and melt index E.

- Turnover

this is the time in which 100 g of the polymer passes through the hopper, the discharge hole which has a diameter of 1.25 cm and the walls of which have an inclination of 20oto the vertical.

- Apparent density

DIN 53194.

- Structure and the particle size distribution of polymer particles

ASTM-D 1921-63.

The fraction soluble in xylene,

is determined by dissolving the polymer in hot xylene and the determination of insoluble residue after cooling, 25oC.

- The content of the co monomer -

the percentage by weight of the co monomer is determined by IR spectrum.

- Density

ASTM-D 792.

The average size of the crystals MgCl2[D(110)]

is determined by measuring the width of the half height of the diffraction (110) line, which appears in the x-ray spectrum of the magnesium halide, using the Scherer equation of:

D(110) = (K1,54257,3)/(B-b)Cos ,

where K is a constant (1.83 in the case of magnesium chloride),

B - half the width (in degrees) of the line diraction processes (110),

b - broadening of the device,

.

Example 1.

Getting media.

Ball adduct MgCl23EtOH receive in accordance with the procedure described in example 2 of U.S. patent N 4399054, at 3000 rpm instead of 10000 rpm Of the adduct partially remove the alcohol by heating in a stream of nitrogen at temperatures increasing from 30oC to 180oC to the content in the adduct 10 wt. % EtOH.

Obtaining solution metallocene/triisobutylaluminum.

In a reactor with a capacity of 1000 cm3equipped with anchor stirrer and treated with N2serves 382,5 cm3triisobutylaluminum (TIB Al) in hexane solution (100 g/l) and 14.25 g of ethylene-bis-interchangealbe (EBI). The system is stirred in nitrogen atmosphere at 20oC for 1 hour. At the end of this period is obtained a clear solution.

Obtaining a catalyst.

In a reactor with a capacity of 1000 cm3equipped with anchor stirrer and treated with N2when 90oC for 3 hours, loaded at 20oC in nitrogen atmosphere of 600 cm3heptane and 60 g of the carrier obtained in advance. Under stirring at 20oC enter for 30 minutes 238 cm3hexane solution TIB Al (100 g/l). The mixture is heated to 80oC for 1 hour and incubated for p is Ino the resulting solution TIB Al/EBI. The system is heated to 60oC within 30 minutes and maintained at that temperature for 2 hours. At the end of this period spend three washing with hexane at 60oC with removal of the solvent by evaporation under vacuum at a maximum temperature of about 60oC. Receive approximately 62 g ball of the catalyst with the following characteristics: Mg - 21,33%, Cl - 66,59%, Al - 0.96%, and Zr - 0,41%, EtO - 0,3%.

Specific surface area (Hg), m2/g - 70,9

Porosity (Hg), cm3/g - 1,041

Specific surface area (BET), m2/g - 61,9

The porosity (BET), cm3/g - 0,687

Polymerization (LLDPE).

0.05 g of the above catalyst and 0.42 g PMA 100 cm3toluene pre-mix for 5 minutes at 20oC in a glass flask, which is pre-treated in nitrogen at 90oC for 3 hours. All placed in a 4-liter steel autoclave equipped with an anchor stirrer and treated with nitrogen at 90oC for 3 hours, containing 800 g of propane at 30oC. the Autoclave is heated to 75oC, enter 0.1 bar H2and then at the same time 7 bar of ethylene and 100 g of 1-butene. The polymerization is carried out in the course of 1 hour, maintaining a constant temperature and pressure of ethylene. Get the a new by: JIREH = 0,84; /E = 49,16; = 1,35; density - 0,914; butene - 10,1%; insoluble in xylene - 97,42%.

Polymerization (HDPE).

0,42 g PMO and 0.05 g of the above catalyst in 100 cm3toluene mixed for 5 minutes at 30oC in a glass flask, which is treated with nitrogen at 90oC for 3 hours. All is then placed in 4-liter steel autoclave equipped with an anchor stirrer and treated with nitrogen at 90oC for 3 hours, containing 1.6 l of hexane at 20oC. the Autoclave is heated to 75oC and serves 7 bar of ethylene and 0.25 bar H2. The polymerization is carried out for 1 hour with maintaining constant temperature and pressure of ethylene. The polymerization is stopped instantaneous venting of the autoclave, and after cooling to 20oC unload the suspension of the polymer and dried at 80oC in nitrogen atmosphere. Get 100 g of polyethylene (2000 g of polyethylene /g of catalyst; 492 kg of polyethylene/g Zr) with the following characteristics: IRA = 12,9; F/E = 22,5; = 0,7.

Example 2.

Obtaining solution metallocene/alumoxane.

In the reactor, with a capacity of 1000 cm3equipped with anchor stirrer and treated with nitrogen load 600 cm3toluene, 18,87 g PMO and 8,46 g EBI. System paramashiva is S="ptx2">

Obtaining a catalyst.

In the reactor, with a capacity of 1000 cm3equipped with anchor stirrer and treated with nitrogen at 90oC for 3 hours, served in an atmosphere of N2at 20oC 600 cm3heptane and 60 g of the carrier obtained according to the method of example 1. Under stirring at 20oC enter 86,4 cm3solution of trimethylaluminum (TM Al) in hexane (100 g/l) for 30 minutes. Within 1 hour the system is heated to 80oC and maintained at this temperature for 2 hours. The mixture was then cooled to 20oC and enter 62,5 cm3pre-obtained solution of PMAO/EBI. The system is heated to 60oC within 30 minutes and maintained at that temperature for 2 hours. At the end of this period is given by 3 washing with hexane at 60oC with removal of the solvent by evaporation under vacuum at a maximum temperature of about 60oC. Obtain 65 g of the pelletized catalyst with the following characteristics: Mg - 19,3%; Cl - 61,5%; Al - a 3.87%; Zr - 0,33%; OEt - 4,3%.

Polymerization (HDPE).

0.05 g of the above catalyst is first mixed with PMA (0,42 g) under the conditions specified in example 2. Then ethylene is polymerized under the conditions specified in example 2, with the output of the 12,68; = 0,66.

Example 3.

Obtaining solution metallocene/alumoxane.

Receiving is carried out under the conditions specified in example 2, but using 47,18 g PMO instead 18,87,

Obtaining a catalyst.

The catalyst was prepared according to the procedure described in example 2, using 166,6 cm3the above solution metallocen/alumoxane. Immediately after the removal by evaporation of the solvent receive approximately 6.5 g of spherical catalyst with the following characteristics: Mg - 18,41%; Cl - 57,5%; Al - 5,56%; Zr - 0,42%.

Polymerization (HDPE).

0.05 g of the above catalyst are mixed in advance and carry out the polymerization under the conditions specified in example 1, using 0.1 bar H2instead of 0.25 bar. Get 80 g of polyethylene (1600 g of polyethylene/g of catalyst; 381 kg of polyethylene/g Zr) with the following characteristics: IRA = 5,9; F/E = 17,9; = 0,77.

Example 4.

Getting media.

Spherical adduct MgCl23EtOH receive in accordance with the procedure described in example 2 of U.S. patent N 4399054, work at 3000 rpm instead of 10000 rpm Of the adduct partially remove the alcohol by heating in a stream of nitrogen at temperatures from 30oC to 180o

In a reactor with a capacity of 1000 cm3equipped with anchor stirrer and treated with nitrogen, download 382,5 cm3triisobutylaluminum (TIB Al) in hexane solution (100 g/l) and 14.25 g of ethylene-bis-interchangealbe (EBI). The system is stirred in nitrogen atmosphere at 20oC for 1 hour. At the end of this period is obtained a clear solution.

Obtaining a catalyst.

In a reactor with a capacity of 3000 cm3equipped with anchor stirrer and treated with nitrogen at 90oC for 3 hours, loaded at 20oC in nitrogen atmosphere of 600 cm3heptane and 60 g of a previously received media. 900 cm3hexane solution TIB Al (100 g/l) was injected over 30 minutes under stirring at 20oC. the Mixture is heated to 80oC for 1 hour and maintained at this temperature for 2 hours. The mixture is then cooled to 20oC and enter 62,5 cm3the previously obtained solution TIB Al/EBI. The system is heated to 65oC within 30 minutes and maintained at that temperature for 2 hours. At the end of this period is given by 3 washing with hexane at 60oC with removal of the solvent by evaporation under vacuum at a maximum temperature of about 60oC. After drying receive about 65 Gretna method), m2/g - 21,4

Porosity (mercury method), cm3/g - 0,359

Specific surface area (by BET method), m2/g - 129, 2mm

The porosity (BET method), cm3/g - 0,837

Polymerization (HDPE).

Perform preliminary engagement 0.05 g of the above catalyst and conducting the polymerization in accordance with the procedure described in example 1, using 0.25 bar H2instead of 0,1 bar. End up with 170 g of a copolymer of ethylene and butylene (3400 g of copolymer/g catalyst; 564 g of copolymer/g Zr) with the following characteristics: IRA = 4,76; F/E = 32,2; = 1,1; density = 0,9135; butene - 10,5%; insoluble in xylene - 95%.

Example 5.

Obtaining a catalyst.

In a reactor with a capacity of 1000 cm3equipped with anchor stirrer and treated with nitrogen at 90oC for 3 hours, loaded in a nitrogen atmosphere at 20oC 500 cm3toluene and 100 g of the carrier obtained according to the method of example 4. Under stirring at 20oC enter 55 g of trimethylaluminum (heptane solution of 100 g/l), then the mixture is heated at 105oC for 3 hours. In the end, reduce the temperature to 20oC and enter 102 cm3solution TIB Al/EBI obtained in accordance with methods which are anxious about 120 g of the pelletized catalyst with the following characteristics: Zr 0,6%; Mg - 16,5%; Cl And 49.2%; Al - 6,7%.

Specific surface area (mercury method), m2/g - 33,8

Porosity (mercury method), cm3/g - 0,495

Specific surface area (by BET method), m2/g - is 171.3

The porosity (BET method), cm3/g - 0,291

Polymerization (HDPE).

Perform preliminary engagement 0.05 g of the above catalyst and conducting the polymerization conditions described in example 1, using 0.1 bar H2instead of 0.25 bar. Obtain 115 g of polyethylene (2300 g of polyethylene/g catalyst) with the following characteristics: IRA = 0,78; F/E = 66,8.

Example 6.

Getting media.

In accordance with the procedure described in example 2 of U.S. patent N 4399054, get the ball adduct MgCl23EtOH, operating at 3000 rpm instead of 10000 rpm Of the adduct partially remove the alcohol by heating in a stream of nitrogen at temperatures increasing from 30oC to 180oC, to obtain the content in the adduct 45 wt.% EtOH. 2360 g of thus obtained ball adduct download a 30-liter reactor containing 18 l of hexane. Under stirring at room temperature is injected 1315 g AlEt3in hexane solution (100 g/l). The mixture is heated to 60oC for 60 minutes is the target AlEt3repeated twice under the same conditions. In the end received the ball carrier is washed 5 times with hexane and dried under vacuum.

Obtaining a catalyst.

In a reactor with a capacity of 1000 cm3equipped with anchor stirrer and treated with nitrogen at 90oC for 3 hours, loaded in a nitrogen atmosphere at 20oC 500 cm3toluene and 60 g of the carrier. Then enter 53,68 cm3solution metallocen/TIB Al obtained in accordance with the method of example 4, with continuous stirring for 2 hours at 20oC. At the end of a 4 washing with hexane at 20oC with removal of the solvent by evaporation under vacuum. Obtain 62 g of spherical catalyst with the following characteristics: Zr - 1,1%; Mg - 16,6%; Cl - 55,3%; Al - 3,6%; OEt - 3,2%.

Specific surface area (mercury method), m2/g - 38,3

Porosity (mercury method), cm3/g - 0,604

Specific surface area (by BET method), m2/g - 298,8

The porosity (BET method), cm3/g - 0,327

Polymerization (LLDPE).

Using 0.05 g of the above catalyst to carry out the polymerization in accordance with the method of example 1 to obtain 160 g of a copolymer of ethylene with butene (3200 g/copolymer/g catalyst; 290 ; latest - 0,9122.

Repeat the experience using 1,45 TIB Al instead of 0.42 g PMA and 1 bar H2instead of 0,1 bar. Get 10 g of the copolymer (200 g copolymer/g catalyst; 17,3 kg of copolymer/g Zr) = 0,3.

Example 7.

Obtaining a catalyst.

The catalyst was prepared according to the method of example 6, except that the four washing with hexane at the receiving end are not held. Get about 63 g of the pelletized catalyst with the following characteristics: Zr - 1,11%; Mg - 13%; Cl - 44,8%; Al - 3,9%; OEt - 6,4%.

Specific surface area (mercury method), m2/g - 19,7

Porosity (mercury method), cm3/g - 0,476

Specific surface area (by BET method), m2/g - 230,2

The porosity (BET method), cm3/g - 0,197

Polymerization (LLDPE).

Using 0.05 g of the above catalyst to carry out the polymerization in accordance with the procedure described in example 1, using 1 bar of H2instead of 0.1 bar and 150 g of butene instead of 100, Obtain 330 g of a copolymer of ethylene with butene (660 g of copolymer/g catalyst; 597 kg of copolymer/g Zr) with the following characteristics: IRA = 16,3; F/E = 34,6; = 0,76; density = 0,9097; Mw/Mn= 3,7.

Example 8.

Getting kata 90oC for 3 hours, loaded in a nitrogen atmosphere at 20oC 600 cm3heptane and 60 g of the carrier obtained according to the method of example 6. Under stirring at 20oC enter 86,4 cm3solution of trimethylaluminum (TM Al) in hexane (100 g/l) for 30 minutes. The system is heated to 80oC for 1 hour and maintained at this temperature for 2 hours. The solution is then cooled to 20oC and enter 272 cm3solution EBI/PMA obtained according to the method of example 3. The mixture is heated within 30 minutes and kept at this temperature for 2 hours. At the end of this period remove the solvent by evaporation under vacuum at a maximum temperature of about 60oC for about 3 hours. Get about 63 g of spherical catalyst with the following characteristics: Zr - 0,8%; Mg - 12,6%; Cl - 40%; Al - 9,3%.

Polymerization (LLDPE).

0.05 g of the above catalyst is used to produce a copolymer of ethylene with butene in accordance with the method of example 1, and take 1.45 g TIB Al instead of 0.42 g PMO. End up with 45 g of the copolymer (900 g copolymer/g catalyst, 110 kg of copolymer/g Zr) with the following characteristics: IRA = 8.34 PER; F/E = 28,91; insoluble in xylene - 8 is accordance with the methodology described in example 1.

Obtaining a catalyst.

In a reactor with a capacity of 1000 cm3equipped with a mechanical stirrer and previously treated with nitrogen at 90oC for 3 hours, serves 600 cm3hexane and 120 g of the above-described carrier at 20oC in nitrogen atmosphere, then within 30 minutes added 16.2 g of isoamyl ether, and the system is heated to 50oC and maintained at this temperature for 1 hour. At the end of this period the system is cooled to 20oC, add 5 g of ethylene-bis-interchangealbe, and everything is stirred for 15 minutes. Then add 15.7 g of diethylaminocoumarin (100 g/l solution in hexane), the mixture is heated to 40oC and kept at this temperature for 1 hour. After that, the mixture is cooled to 20oC, allow to settle solid precipitate and the liquid phase removed. Serves 600 cm3hexane and 15.7 G. of AlEt2Cl and repeat the above processing. Finally washed three times with 200 cm3hexane at 20oC to obtain 102 g ball catalytic component with the following characteristics: Mg - 21,4%; Cl - 65,79%; Al - 0,3%; Zr - 0,67%; isoamyl ether and 2.0%; EtO - 3,8%.

Polymerization (PAWN).

Obtained in this Abrash polymer (4813 g PE/g catalyst; 780 kg PE/g Zr), with the following characteristics: IRA = 1,02; F/E = 62; = 1,08; Mw/Mn= 2,9.

Example 10.

Getting media.

The carrier is obtained in accordance with the procedure described in example 6.

Obtaining solution metallocen/triisobutylaluminum.

In a reactor with a capacity of 1000 cm3equipped with a mechanical stirrer and purged with nitrogen, serves 620 cm3triisobutylaluminum in hexane solution (100 g/l) and 42 g of ethylene-bis-4,7-dimethylammoniumchloride (BDMI). The reaction is carried out as described in example 1.

Obtaining a catalyst.

In pre-purged 2-liter reactor serves 250 cm3heptane and 35 g of the above media. The mixture is cooled to 0oC and add 505 cm3TIB Al (100 g/l solution in hexane), all heated to 60oC for 1 hour and then cooled to 20oC. Serves 31 cm3the above solution ERIMI/TIB Al and heat the mixture to 70oC for 2 hours, after which it is cooled to 20oC, allow to settle solid precipitate, and the liquid is drained by the siphon. After drying under vacuum at 50oC get about 30 grams of the pelletized catalyst having the following characteristics: Mg - for used for LPMP analogously to example 1, and take 1.45 g TIB Al instead of 0.42 g PMO. Get 100 g of the copolymer (200 g copolymer/g catalyst; 200 kg of copolymer/g Zr), with the following characteristics: IRA = 0,48; F/E = 45,83; density = 0,919; insoluble in xylene - 98,51%.

Example 11.

Getting media.

Media receive in accordance with the procedure described in example 8.

Obtaining solution metallocen/methylalumoxane.

In pre-purged 1-liter reactor serves 600 cm3toluene, a 76.5 g methylalumoxane and 15.6 g BDMI. The system is kept under stirring at 20oC within 2 hours.

Obtaining a catalyst.

In pre-purged 1-liter reactor load 200 cm3toluene and 100 g of the above-described carrier; then add 200 cm3the above solution metallocen/PMO, and the system is heated to 40oC and stirred at this temperature for 2 hours. Finally, allow to settle solid precipitate and the liquid is removed using a siphon. The obtained solid is washed 4 times with 200 cm3hexane at 20oC and then dried. Get a 125g ball of catalyst having the following characteristics: Cl - 45,35%; Mg - 16,25%; Al - 7,1% Zr - 0,45%.

pursuant to the method of example 10. Gain of 37.7 g of the polymer (754 g of copolymer/g catalyst; 167 kg of copolymer/g Zr) with the following characteristics: IRA = 0,4; F/E = 46,25; insoluble in xylene - 97%; = 1,77; density = 0,913.

1. Component of the catalyst for polymerization of olefins, containing the compound of the transition metal M selected from Ti, Zr, Hf, which contains at least one M--communication, and the halide of magnesium, characterized in that it has a specific surface area by BET method above 50 m2/g, the porosity by BET method above 0.15 cm3/g and porosity by mercury method above 0.3 cm3/g, when the specific surface area is less than 150 m2/g, the porosity by mercury method is less than 1.5 cm3/,

2. Component under item 1, characterized in that it has a specific surface area greater than 150 m2/g, the porosity by BET method above 0.2 cm3/,

3. Component under item 1, characterized in that it has a specific surface of more than about 50 m2/g and below 1502/g, the porosity by mercury method is 0.5 - 1.2 cm3/,

4. Component PP.1 to 3, characterized in that more than 40% porosity by BET method is determined by the pore radius of more than 300

5. Component PP.1 to 3, characterized in that more than 50% of pariston is in the form of a ball of particles less than 150 microns.

7. Component PP.1 - 6, characterized in that it is obtained by applying the compound of the transition metal M selected from Ti, Zr, Hf, having at least one M--communication, magnesium halide or carrier material containing a halide of magnesium, which has a specific surface of 200 - 800 m2/g and porosity by BET method above 0.3 cm3/g and porosity by mercury method above 0.3 cm3/,

8. Component under item 7, wherein the magnesium halide is in the form of a ball of particles less than 150 microns.

9. Component under item 7, characterized in that the halide of magnesium deposited on inert support selected from SiO2, Al2O3, SiO2- Al2O3possessing a specific surface area of 300 - 600 m2/g and porosity by BET method above 0.5 cm3/,

10. Component under item 8, characterized in that the magnesium halide obtained from steroidogenic adducts MgX2alcohol, proteinopathy with alkyl-Al compound to remove the alcohol.

11. Component under item 10, wherein the magnesium halide is magnesium chloride derived from adducts MgCl23ROH, where R is an alkyl radical with 1 to 8 carbon atoms, which is partially removed alcohol, and then browseimages metal contains, at least one ligand L, coordinating associated with the metal M, which is mono - or polycyclic structure containing conjugated electrons.

13. Component under item 12, characterized in that the compound of the transition metal is selected from compounds having the structure:

(CpI-A-CpIIMR1R2,

where M is Ti, Zr, Hf;

CpIand CpII- identical cyclopentadienyls group, including substituted groups, and two or more Deputy associated with these cyclopentadienyls groups can form one or more rings having 4 to 6 carbon atoms;

R1and R2- identical atoms of halogen;

A - C2H4.

14. Component under item 12, characterized in that the compound of the transition metal is selected from the compounds: C2H4(Ind)2MCl2C2H4(4,7-Me2-Ind)2MCl2. 15. Component under item 12, characterized in that the compound of the transition metal is contained in an amount of 0.1 - 5 wt.% in terms of not metal.

16. Component PP.1 - 15, characterized in that it further comprises at least one electron-donor compound not containing an active hydrogen, in the amount of up to 30 my connection is contained in an amount of 5 - 15 mol.%, based on the number of halide Mg.

18. Component under item 16, characterized in that electron-donor compound is selected from porous ethers, esters and ketones.

19. Component under item 16, characterized in that electron-donor compound is a simple isoamyl ether.

20. The catalyst for polymerization of olefins, containing the reaction product component of the PP.1 - 19 with alkyl-Al compound selected from trialkyl-Al, whose altergroup have 1 to 12 carbon atoms, and linear or cyclic alumoxane compounds containing the repeating unit -(R4)AlO-, where R4-altergroup with 1 to 6 carbon atoms and containing 2 to 50 repeating units.

21. The catalyst according to p. 20, characterized in that the alkyl-Al compound is a mixture of trialkyl-Al and alumoxane.

22. The catalyst p. 20 and 21, characterized in that alumoxane is polymethylsiloxane.

23. The catalyst p. 20 or 21, characterized in that it is the product of the reaction of trialkyl-Al connection from 0.5 to 0.01 mole of water per mole trialkyl-Al and a transition metal compound selected from

C2H4(Ind)2MCl2C2H4(4,7-Me2-Ind)and alkylation 1 10 carbon atoms, characterized in that it uses the catalyst PP.20 - 23.

25. The method of polymerization of olefins p. 24, characterized in that the catalyst is obtained from a component under item 14.

26. The method of polymerization of ethylene and its mixtures with olefins of General formula CH2= CHR, in which R is hydrogen or alkylaryl with 1 to 10 carbon atoms, characterized in that the catalyst is obtained from a component under item 14.

27. The polyolefins obtained by the method according to PP.24 - 26.

 

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The invention relates to the components of the catalyst for polymerization of olefins comprising the product obtained by the reaction of compounds of the transition metal M selected from Ti, Zr, HF containing at least one M--communication with the porous polymer carrier, representing a prepolymer obtained by polymerization of one or more olefins of the General formula CH2=CHR, in which R is hydrogen or alkyl with 1-12 carbon atoms, with a complex catalyst comprising the product obtained by contacting connection Ti with a halide of magnesium in the form of particles with an average crystallite size below 300it called the halide of magnesium contained in the above-mentioned prepolymer in amounts of between 50 and 50000 h

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