Components and catalysts for the polymerization of olefins

 

(57) Abstract:

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 300 it called the halide of magnesium contained in the above-mentioned prepolymer in amounts of between 50 and 50,000 hours per million. Also describes a catalyst for the polymerization of olefins on the basis of the above component and method for the polymerization of olefins. The technical result - obtaining polymers with controlled morphological properties. 4 C. and 20 C.p. f-crystals, 1 tab., 2 Il.

The present invention relates to components of catalysts for the polymerization of olefins, the catalysts derived from them, and above the, cloudily or aryl radical with 1-12 carbon atoms.

Another object of the present invention are polymers obtained by using the above-mentioned catalysts.

Complex catalysts obtained from compounds of the formula m lxin which M represents a transition metal valency, and in particular Ti, Zr and Hf, L is a ligand coordinating to the metal, x represents the valence of the metal, and at least one ligand L is cycloalkenyl the structure known from the literature. Catalysts of this type, which use connections Cp2TiCl2or Cp2ZrCl2(Cp - cyclopentadienyl) described in U.S. patent N 2827446 and 2924593. In the polymerization of ethylene compounds are used together with Al-alkyl compounds. The catalytic activity is very low. Catalysts with very high activity are obtained from compounds Cp2ZrCl2or Cp2TiCl2and their derivatives, substituted in cyclopentadienyls the ring, where the Cp-ring may be condensed with other rings, and polyaluminium compounds containing a repeating link - (R)AlO, in which R represents lower alkyl, preferably methyl (U.S. patent N 454 is indanilnykh or tetrahydroindole ring, linked by a bridge across the lower alkylene or other divalent radicals, are suitable for obtaining stereoregular polymers of propylene and other olefins (EP-A-185918).

Catalysts for stereoregular polymerization get from dicyclopentadienyl compounds in which two rings substituted in various ways groups with a spatial difficulty to prevent rotation of the rings about the axis coordinate to the metal.

Substitution indenyl or tetrahydroindene in the relevant provisions pentadienyl ring leads to the production of catalysts, which have a very high stereospecificity (EP-A-485823, EP-A-485820, EP-A-519237, U.S. patent N 5132262 and N 5162278).

Metallocene catalysts described above give polymers with very narrow molecular weight distribution (Mw/Mnabout 2).

Some of these catalysts also have the property to form copolymers of ethylene with a-olefins of the type of LDPE or ethylene/propylene elastomeric copolymers with a very uniform distribution comonomeric links. The resulting low density polyethylene is characterized, in addition, a low solubility in solvents, such as nuclear biological chemical (NBC polymerization, mentioned above, shows an increased crystallinity and a higher heat distortion temperature as compared with the polymer, which can be obtained with conventional catalysts of the Ziegler-Natta.

However, these metallocene catalysts are significant difficulties in relation to their potential use in industrial methods for obtaining polyolefins, which are not carried out in solution, since these catalysts are soluble in the reaction medium in which they are received, and in the liquid polymerization medium.

In order to be able to use them in ways polymerization which is conducted in solution, the catalyst must be on appropriate media, which give the polymer relevant morphological properties.

Use many types of media, including among other porous metal oxides, for example silica or porous polymeric substrate, such as polyethylene, polypropylene and polystyrene. As the carrier used as the magnesium halides. In some cases they are also used as counterions ion pairs for which the metallocene compound delivers cation, and the connection of Mg-g the activity of the catalysts. In the application Japan N 168408/88 (published 12.07.1988) described the use of magnesium chloride as a carrier metallocene compounds of the type Cp2TiCl2Cp2ZrCl2Cp2Ti(CH3)2for education with Al-trialkyl and/or polymethylsiloxane (MAO) catalysts for polymerization of ethylene. Component comprising magnesium chloride, is produced by grinding it together with the metallocene compound in the presence of electron-donating compounds or when the content of metallocene in the corresponding liquid adduct MgCl2with alcohol followed by reaction with AlEt2Cl. Catalysts do not possess a sufficiently high activity per MgCl2.

Catalysts, including metallocene compound type Cp2ZrCl2on the media MgCl2in spherical form and partially forming complex compounds with electron-donating compound described in U.S. patent N 5106804.

The properties of these catalysts are better than those described in the application Japan N 168408/88, but yet they are not such that can ensure the production of polymers containing a small amount of residual catalyst. The amount of Zr compounds on the carrier MgCl2is Dory require polymethylsiloxane (MAO) and are inactive with Al-alkilani Al-triaminnogo type. However, the outputs per MAO are low.

In the application EP-A-318048 presents catalysts, in which a solid component comprising a Ti compound supported on magnesium chloride which has a particular specific surface area and porosity and, if necessary, electron-donating compound is used with benzyl compounds of Ti or with metallocene compounds of the type Cp2Ti(CH3)2and bis-(indenyl)-Zr (CH3)2with the formation of catalysts for polymerization of ethylene and propylene. The weight ratio of metallocene to the magnesium chloride is very high (more than 1), so is necessary removal metallocene of the obtained polymer. The catalysts used in the processes carried out in the presence of a liquid polymerization medium.

In the application EP-A-439964 described bimetallic catalysts suitable for polymers of ethylene with a wide molecular weight distribution (Mw/Mnbetween 4 and 14), obtained by applying metallocene solid component containing Ti compound supported on magnesium chloride. MAO or its mixture with Al-alkyl use as socializaton. Al-trialkyl also used by themselves, but catalytique centers, obtained from Ti-compounds deposited on the MgCl2and from metallocene compounds are very high, when the catalysts used in hydrocarbon environment; on the other hand, they are low, when the polymerization is carried out in the gas phase.

In the application EP-A-522281 described catalysts obtained from Cp2ZrCl2supported on magnesium chloride, and mixtures of Al-trialkyl and connections supplying stable anions of compounds of the type of dimethylaniline-tetrakis-(pentafluorophenyl) borate. The catalysts obtained by grinding components and used for polymerization in the presence of a solvent (toluene), and the outputs of polyethylene per MgCl2be about 9000 g/,

In the application EP-A-509944 presents catalysts, using connection type of aniline-tetrakis-(pendaftar-phenyl) borate, or a Lewis acid such as MgCl2together with halides of metallocene, pre povzaimodeystvovat with Al-alkyl compounds.

Magnesium chloride before bringing into contact with a pre-proteinopathies metallocene compound is crushed. The outputs of the polymer in the calculation of the Mg halide is low.

BILETU, which give the opportunity to obtain polymers with controlled morphological properties, so that the catalysts can be used in gas-phase processes in the fluidized bed.

The components of the invention are obtained by the interaction of compounds of the transition metal valency selected from Ti, V, Zr and Hf containing at least one M--communication with the prepolymer, obtained by polymerization of one or more olefins of the formula CH2=CHR, in which R represents hydrogen or alkyl, cycloalkyl or aryl with 1 to 12 carbon atoms and/or one or more di - or polyene complex catalyst comprising the product obtained by contacting compounds of Ti, V, Zr, Hf, or a mixture thereof with a halide of magnesium in the form of particles with an average crystallite size below 300 Polymeric media get in an amount of from 0.5 to 2000 g/g of solid component, preferably in an amount of 5 to 500 g/g, and more preferably in the range from 10 to 100 g/g of solid component. The compound of the transition metal valency M includes, in particular, at least one ligand L coordinated relative to the metal M, having a mono - or polycyclic structure containing conjugated electrons.of structure

- Cp1MR1aR2bR3c(I)

- Cp1Cp11MR1aR2b(II)

- (Cp1-A-Cp11)M1R1aR2b(III)

in which M is Ti, V, Zr or Hf; Cp1and Cp11that may be the same or different from each other, cyclopentadienyls are groups which may be substituted; two or more substituents from cyclopentadienyls groups can form one or more rings having from 4 to 6 carbon atoms;

R1, R2and R3that may be the same or different, represent hydrogen atoms, halogen, alkyl or CNS group with 1-20 carbon atoms, aryl, alkaryl or aralkyl with 6-20 carbon atoms, alloctype with 1-20 carbon atoms, allyl group or Deputy containing a silicon atom; A is alkenyl bridge or has a structure selected from

< / BR>
< / BR>
-Ce, -Sn-, -O-, -S-, =SO, =SO2, =NR1, =PR1or =P(O)R1in which M1is silicon, germanium or tin; R1and R2that may be the same or different, represent alkyl groups with 1-4 carbon atoms or aryl groups who are radicals R1, R2and R3may form a ring. In the case when the Cp group is substituted, Deputy preferably is an alkyl group with 1-20 carbon atoms.

Typical compounds of formula (I) are:

(Me5Cp)MMe3, (Me5Cp)M(OMe)3, (Me5Cp)MCl3, (Cp)MMe3, (MeCp)MMe3, (Me3Cp)MMe3, (Me4Cp)MCl3, (Ind)MBenz3, (H4Ind)MBenz3, (Cp)MBu3.

Typical compounds of formula (II) are:

(Cp)2MMe2, (Cp)2Mph, (Cp)2Met, (Cp)2MCl2, (Cp)2M(OMe)2, (Cp)2M(OMe)Cl

(MeCp)2MCl2, (Me5Cp)2MCl2, (Me5Cp)2MMe2, (Me5Cp)2MMeCl, (Cp)(Me5Cp)MCl2, (1-MeFlu)2MCl2, (BuCp)2MCl2, (Me3Cp)2MCl2, (Me4Cp)2MCl2, (Me5Cp)2M(OMe2)

(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, (H4Ind2)MCl, (2, (Me4Cp) (Me5Cp)MCl2.

Typical compounds of formula (III) are:

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

Me2Si(Me4Cp)2MCl2, Me2Si(Me4Cp)2MMe2, Me2SiCp2MCl2, Me2SiCp2MMe2,

Me2Si(Me4Cp)2MMeOMe, Me2Si(Flu)2MCl2, Me2Si(2-Et-5-iPrCp)2MCl2, Me2Si(H4Ind)2MCl2, Me2Si(H4Flu)2MCl2, Me2SiCH2(Ind)2MCl2, Me2Si(2-Me-H4Ind)MCl2, Me2Si(2-MeInd)2MCl2, Me2Si(2-Et-5-iPr-Cp)2MCl2, Me2Si(2-Me-5-EtCp)2MCl2, Me2Si(2-Me-5-Me-Cp)2MCl2, Me2Si(2-Me-4,5-benzhydryl)2MCl2,

Me2Si(2-EtInd)2)2MCl2, Me2Si(4,5-benzhydryl)2MCl2, Me2Si(2-tert-butyl-Ind)MCl2, Me2Si(2-iPr-Ind)2MCl2, Me2Si(3-tert-butyl-5-MeCp)2MCl2, Me2Si(3 - tert-butyl-5-MeCp)2MMe2, Me2Si(2-MeInd)2MCl2C2H4(2-Me-4,5-benzhydryl)2MCl2, Me2C(Flu)CpMCl2<-tert-butyls)(Flu)MCl3, Me2C(Me4Cp)(MeCp)MCl2, MeSi(Ind)2MCl2, Me2Si(Ind)2MMe2, Me2Si(Me4Cp)MCl(OEt), C2H4(Ind)2M(NMe2)2C2H4(Me4Cp)2MCl2,

C2Me4(Ind)2MCl2, Me2Si(3-Me-Ind)2MCl2C2H4(2-Me-Ind)2MCl2C2H4(3-Me-Ind)2MCl2C2H4(4,7-Me-Ind)2MCl2C2H4(5,6-Me-Ind)2MCl2C2H4(2,4,7-Me3Ind)2MCl2C2H4(3,4,7-Me3Ind)2MCl2C2H4(2-Me-H4Ind)2MCl2C2H4(4,7-Me-H4Ind)2MCl2C2H4(2,4,7-Me3-H4Ind)2MCl2, Me2Si(4,7-Me-Ind)2MCl2,

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

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

Me is methyl, Et = ethyl, iPr = isopropyl, Bu = butyl, Ph = phenyl, Cp = cyclopentadienyl, Ind = indenyl, H4Ind=4,5,6,7-tetrahydroindene, Flu = fluorenyl, Be = benzyl, M=Ti, Zr or Hf, preferably Zr.

Join Me2Si(2-Me-Ind)2ZrCl2and Me2Si(2-Me-H4Ind)ZrCl2The P CLASS="ptx2">

Join Me2Si(3-tert-butyl/5-MeCp)2ZrCl2and type Me2Si(2-Me-4,5-benzhydryl)ZrCl2and their method of obtaining described respectively in U.S. patent N 5132262 and in the patent application EP-A-549900, herein by reference.

The catalysts used to obtain the prepolymer, preferably contain the product obtained by contacting the halide of Ti, V, Zr, Hf, or mixtures thereof, mainly chloride or halogenoalkane Ti or V, with magnesium chloride having an average crystallite size below 300 and preferably less than 150 and more preferably in the range from 30 to 120 . Chlorides and halogenoalkane Ti or V preferably include TiCl4, TiCl3chloralkali Ti, such as Ti(OBu)2Cl2and Ti(OB)Cl3, VCl3, VOCl3.

Examples of catalysts of this type are described in U.S. patent N 4495338, 4298718 and 4542198, which is included here for reference. Other examples of catalysts containing product produced by contacting one or more compounds of Ti, V, Zr or Hf with a magnesium halide having the above characteristics, is presented in the patent applications Italy M1-94-A-001065 and M1-94-A-001421. The solid components of catalysts are used preferably in 2/g and porosity (nitrogen method) is more than 0.3 cm3/g or when the specific surface area (BET) of less than 200 m2/g and porosity (mercury method) of between about 0.5 and 2 cm3/,

Examples of catalysts comprising the components of this type, and method for producing components described in U.S. patent N 4399054, EP-A-395083, EP-A-553805 and EP-A-553806, which is included here for reference. The content of titanium or vanadium in the catalyst components is preferably more than 1% by weight and preferably between 2 and 10% by weight.

The catalysts preferably used Al-alkyl compound, Al-trialkyl, for example AlEt3, Al-triisobutyl, Al-tri-n-butyl, and mixtures thereof with Al-dialkylamide. Can also be used alumoxane connection. The olefins used to obtain the prepolymer include ethylene, propylene, 1-butene, 4-methyl-1-penten, 1-hexene, 1-octene and mixtures thereof.

The prepolymer preferably is produced from polyethylene, copolymers of ethylene content is less than 20 mol.% the olefin selected from propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, cyclopentene, cyclohexene; polypropylene with a measure of stereoregularity above 80%; crystalline copolymers of propylene with nathnac used the prepolymers of dienes or conjugated of polyene.

Terpolymerization preferably carried out in a liquid phase consisting of an inert hydrocarbon solvent such as propane, hexane, heptane, isobutane, or of the monomer, or in the gas phase, typically at temperatures below 100oC and preferably between 20 and 70oC.

The prepolymer get more than about 0.5 g/g component and up to about 2000 g/, Preferably the amount is between 5 and 500 g/g of solid component, and more preferably between 10 and 100 g/g of solid component.

The porosity of the prepolymer, measured by the mercury method, described below, is preferably higher than 0.3 cm3/g, more preferably above 0.4 cm3/g and mostly above 0.5 cm3/g the Above values of porosity refers to pores with radius up to 50000

The amount of the halide of magnesium present in the prepolymer, in terms of M is usually between 50 and 50000 ppm (per million hours), preferably between 100 and 20000 ppm (per million hours), and more preferably between 300 and 10000 ppm (per million hours).

The atomic ratio of the transition metal valency M, containing at least one link, to the halide of magnesium, in particular the ratio of Zr/Mg (relative to Zr of niemyski at a concentration of 100 g/l at 20oC) is more than 0.1, in particular more than 0.2 and preferably between 0.3 and 3.

Atomic relations of the transition metal valency to magnesium above 0.1 has never been achieved in the components comprising a magnesium halide and metalocene connection Zr, Ti, V, or Hf. Catalytic components comprising a prepolymer containing dispersed fine particles of magnesium halide and comprising at least partially associated with a magnesium halide compound of a transition metal of valency M, chosen from Ti, V, Zr or Hf containing at least one M--link under the atomic ratio M/Mg is more than 0.1, were not previously described in the literature.

The reaction of the prepolymer containing a solid component of catalyst terpolymerization, with the compound of the transition metal valency carried out preferably in an inert hydrocarbon medium in which soluble metallocene compound (toluene, benzene and other hydrocarbons) at temperatures between -40oC and melting point of the prepolymer, preferably between 0 and 100oC, and more preferably between 10 and 70oC.

The reaction between the prepolymer and the compound of the transition metal valency, stevedevane thus, to set the number of electron-donor compounds between 0.1 and 15 wt.% relative to total consumption.

The solubility of the metallocene compounds containing at least one M--communication, increases when the above compound is dissolved in toluene and other hydrocarbons, also containing dissolved therein the Al-alkyl compound, such as Al-triethyl, Al-triisobutyl or polyalkyloxy, and in particular MAO or its mixture with Al-alkyl compound, using molar relationship And-alkyl compound to the metallocene compound is more than 2, preferably between 5 and 100.

The obtained solutions are particularly suitable as catalyst components having very high activity. This activity is more active, which can be obtained by using solutions of metallocene compounds that were obtained in the absence of Al-compounds mentioned above.

The components of the invention form with Al-alkyl compounds or polyallylamine compounds or mixtures thereof catalysts, which have a very high activity relative to the halide of Mg, which is much more active catalysts containing R3in which R represents alkyl with 1-12 carbon atoms, and alumoxane compounds containing a repeating link -(R4)AlO-, in which R4represents an alkyl radical containing from 1 to 6 carbon atoms, with alumoxane compounds contain from 2 to 50 repeating units having the formula presented above. Typical examples of compounds of the formula AlR3are Al-trimethyl, Al-triethyl, Al-triisobutyl, Al-tri-n-butyl, Al-trihexy and Al-trioctyl. Among alumoxane compounds preferred is the use of MAO. Advantageously, the use of mixtures of Al-alkyl compounds, preferably Al-triisobutyl, and alumoxane compounds, preferably MAO.

When the compound of the transition metal valency, containing at least one M-7 communications, is a compound of the type described in formulas (II) and (III), can be advantageously used compounds obtained by reactions AlR3and H2O when the molar relationship between 0.01 and 0.5. Activity equal to at least 100 kg/g MgCl2and even above 1000 kg/g MgCl2can usually be obtained even in the processes of gas-phase polymerization.

When using prepolymers obtained from katalinmiloiu component of the catalyst, and, therefore, to carry out the processes in the gas phase in the fluidized bed is easily adjustable way to avoid such difficulties, as local overheating layer, heat transfer, etc. that make it difficult to conduct processes in the gas phase.

In Fig. 1 shows a photograph of the catalyst, played at a 12-fold increase; Fig. 2 presents a photograph of a polymer obtained by polymerization in the gas phase, played at a 3.5-fold increase.

When using prepolymers obtained with catalysts, components which are in the form of spherical particles which have a high macroporosity (for example, the porosity by mercury more than 1 cm3/g) can also be obtained in the gas phase polymers or copolymers koukopoulos nature, which usually have a tendency to agglomerate and create problems when carrying out gas-phase process.

The catalysts of the invention can be used for (co)polymerization of olefins of the formula CH2=CHR, where R is hydrogen or an alkyl radical with 1-10 carbon atoms or aryl.

In particular, their use for the polymerization of ethylene and its mixtures with-olefin obtained from compounds of the type C2H4(Ind)2ZrCl2C2H4(H4Ind)ZrCl2and Me2Si(Me4Cp)2ZrCl2are appropriate to obtain LDPE (of ethylene copolymers having a low content, usually less than 20 mol.% (C3-C12--olefin), characterized by relatively low density values with respect to the content of the olefin, low solubility in xylene at room temperature (below about 10 wt.%) and the molecular weight distribution Mw/Mnbetween 2.5 and 5.

When the density of 0.912 content-olefin equal to about 5 mol.%. When the density of 0.906 content-olefin is equal to about 7 mol.%.

The values of Mw/Mnusually higher than the values achieved with the known metallocene catalysts used in the solution or on the media, and they determine the ability of the polymers to the processing, which exceeds the ability of the polymer having a narrower molecular weight distribution.

Polypropylene, which can be obtained on the catalysts containing chiral metallocene compound, characterized by high stereoregularity, high molecular masses, which are legalregulatory, are, for example, compounds of the type described in European applications EP-A-485823, EP-A-485820, EP-A - 519237 and U.S. patent N 5132262 and 5162278.

Below are examples to illustrate the invention and are non-limiting. These properties were determined in accordance with the following methods.

The porosity and specific surface area by nitrogen:

determined in accordance with the BET method (method of brunauer, Emmett and teller) (used equipment: SORPTOMA-TIC 1800 from Carlo Erba).

The porosity and specific surface of mercury:

was determined by immersing a known amount of sample in a known amount of mercury inside the dilatometer, and then a gradual increase in pressure mercury by hydraulic pressure. The pressure of penetration of mercury into the pores is a function of their diameter. The measurements were carried out using a Porosimeter 2000 series" from Carlo Erba. Porosity, pore distribution and specific surface area was calculated from the data reduce the amount of mercury and of the values of the applied pressure.

The degree of dispersion of the catalyst:

was determined using a method based on the principle of optical diffraction of monochromatic laser light and equipment "Malvern Instr. 260>- Flow index MIF:

ASTM-D 1238, condition F.

- Turnover:

represents the time required for the flow to 100 g of the polymer through the funnel, the outlet of which has a diameter of 1.25 cm and walls of which are inclined from the vertical at 20o.

- Apparent density:

DIN-53194.

The morphology and particle size distribution of polymer particles:

ASTM-D-1921-63.

The fraction soluble in xylene:

determined at 25oC.

- The content of the co monomer:

the percentage of co monomer by weight, determined from the spectrum of infrared radiation.

Actual weight:

ASTM-D792.

- The average crystallite size of (110):

was determined by measuring the width at half height (110) diffraction line in the x-ray spectrum of the halide of magnesium using the sherrer equation:

(110) = (K1542573)/(B-b) cos,

where K = constant (1.83 in the case of magnesium chloride);

B = width at half height (in degrees) (110) diffraction line;

= instrumental broadening;

= angle according to Bragg.

In the case of magnesium chloride (110) diffraction line appears at an angle of 28 equal to 50.2o.

Examples.

Example 1.

Getting media.

10 g of hexane was loaded in a glass autoclave with a capacity of 25 liters, equipped with anchor stirrer and baffles and treated with nitrogen at 90oC for 3 hours was Added 290 g of catalyst, in the form of particles with an average diameter of 30 microns, with stirring and at a temperature of 20oC, obtained in the following way. 28.4 g of anhydrous MgCl2and 49.5 g of anhydrous ethanol, 100 ml of paraffin oil ROL OB/30 and 100 ml of silicone oil (viscosity 350 cSt) is placed in an inert atmosphere in the flask was lowered into a bath with stabilized by heating at 120oC under stirring until then, until completely dissolved MgCl2. Thus, the formed adduct MgCl2with ethanol in the mixture with oils. The hot mixture is then transferred still in an inert atmosphere in a 1500-ml vessel equipped with a thermal shirt and containing 150 ml of vaseline oil and 150 ml of silicone oil. This mixture is support @ 120oC and under stirring using a stirrer-type Ultra Turrax T-45 N, manufactured by Janke & K. G. Kunkel Ika Werke. The mixture is stirred for 3 min at 10000 and is cooled thereby, what is the final temperature does not exceed 0oC.

Thus obtained microspheres after filtration, dried under vacuum at room temperature and then sieved, and then get a fraction L of 50 μm, corresponding to 78 wt.%. Once activated, these microspheres are solid catalytic component containing 1,95% wt. Ti and 7.5 wt.% ethylbenzoic, with the following characteristics:

Porosity - 0,322 cm2/g

Specific surface - 397 m2/g

The average radius of the pore - 16

The obtained spherical substrate is subjected to heat treatment up to 45% residual alcohol (molar ratio alcohol/ethanol = 1,7).

2360 g of the media in suspension 18 liters of anhydrous hexane download a 30-liter reactor. 1315 g AlEt3in hexane solution (concentration 100 g/l) are introduced with stirring and at room temperature for 60 minutes the Temperature was raised to 60oC after 60 min and constant support for a further 60 minutes the Liquid phase is removed by settling and filtration, and load 15 l of anhydrous hexanol. The process is repeated two more times under the same conditions. Spherical powder is washed 5 times with 10 liters of anhydrous hexane and dried under vacuum. Define the following characteristic is 1500 g of the thus obtained carrier in suspension with 17 liters of anhydrous hexane loaded into a 25 liter reactor. Under stirring and at room temperature load 2750 g of Ti(OBu)4. Stirring is continued at room temperature for 60 min and then slowly add 2100 g SCl4.

The temperature was raised to 60oC and maintained for 2 hours Spend several washings with anhydrous hexane to exclude any SiCl4and remaining in suspension of very fine powder (about 1 wt.% with size < 5 μm) simultaneously removed from the solid component, which precipitates.

The solid component is then dried under vacuum at 50oC.

The following characteristics (see table).

Then for 15 min at 20oC introduced a 2 l solution of Al-triisobutyl (CHIBA) in hexane (100 g/l) and stirring continued for 15 minutes At a partial pressure of 100 mm Hg and a temperature of 35oC filed ethylene, and polymerization was carried out up until the received output equal to 40 g of polymer per 1 g of solid component of catalyst. Conducted three washing in hexane with a concentration of 100 g/l at 20oC. After drying, got 11.6 kg spherical prepolymer with the following characteristics:

- Specific surface area = 1.6 m2/g (Hg);

- Porosity = 0,702 cm3/g (Hg; acne Lozen/polymethylsiloxanes solution.

1000 cm3a reactor equipped with anchor stirrer and treated with N2downloaded 600 cm3toluene, 47,7 g polymethylsiloxane (MAO) and 8.46 g of ethylene-bis-(indenyl)zirconiated (EBI). The system was continuously stirred in a nitrogen atmosphere at 20oC for 3 h In the end of this period received a clear solution.

Obtaining a catalyst.

1000 cm3a reactor equipped with anchor stirrer and treated with nitrogen at 90oC for 3 h, loaded in nitrogen atmosphere at 20oC 300 cm3toluene and 100 g of pre-prepared media. 200 cm3pre-obtained solution metallocene/MAO introduced for 10 min at 20oC and stirring. The system was brought to the 40oC and maintained at this temperature for 4 h and then the solvent was removed by vacuum evaporation at a maximum temperature of about 40oC for 3 hours Got 118.62 g of spherical catalyst with the following characteristics: Zr = 0.5%; Mg = 0.26%; Cl = 1.28%; Al = 5.2%.

Polymerization (HDPE).

In a glass flask, treated with nitrogen at 90oC for 3 h, pre-mixed 100 cm3toluene for 5 min at 30oC 0.42 g of MAO and 0.0 stirrer, processed N2when 90oC for 3 h and containing 1.6 l of hexane at a temperature of approximately 20oC.

The temperature and pressure in the autoclave respectively increased to 75oC and 7 bar of ethylene and filed 0.1 bar of hydrogen.

Within 1 h carried out the polymerization, by maintaining the temperature and pressure of ethylene permanent.

The polymerization was interrupted by instantaneous degassing of the autoclave, and after cooling to 20oC, the suspension polymer was unloaded and dried in an oven at 80oC in nitrogen. Received 325 g of polyethylene in the form of spherical particles (yield 6500 g of polyethylene/g of catalyst: 1300 kg/g Zr; 640 kg/g MgCl2) with the following characteristics:

MIE = 0.8; F/E = 62; = 1.1; Mw/Mn,=3.4.

Example 2.

Polymerization (LDPE).

In a glass flask, treated with nitrogen at 90oC for 3 h, pre-mixed 100 cm3toluene for 5 min at 20oC 0.42 g of MAO and 0.05 g of catalyst from example 1.

Then it was loaded into a 4-liter steel autoclave equipped with an anchor stirrer, treated with nitrogen at 90oC for 3 h and containing 800 g of propane at 30oC. the Autoclave was heated to 75oC and filed 0.1 bar afilename. Got 125 g of a copolymer of ethylene and butene in the form of spherical particles (yield 2500 g copolymer/g catalyst; 500 kg/g Zr; 245 kg/g MgCl2) with the following characteristics:

MIE = 8.4; F/E = 19; = 1; actual density = 0,912; associated butene = 11%; insoluble in xylene 94%; Mw/Mn=2.8.

Example 3.

Polymerization (LDPE).

0.05 g of the catalyst of example 1 was pre-treated under the same conditions as in example 2, using instead of 0.42 g of MAO 1.4 g TIBAS. Then under the same conditions as in example 2, was copolymerizable ethylene and butene. Received 75 g of a copolymer of ethylene and butene (yield 1500 g of copolymer/g catalyst) with the following characteristics;

MIE = 3; F/E =35.3; = 11, the actual density = 0.912; insoluble in xylene at 90%.

Example 4.

Getting media.

The same procedure as in example 1.

Obtaining solution metallocene/MAO.

The conditions were the same as in example 1, but with the following amounts of reagents: 300 cm3toluene, 43.26 g MAO; 19.58 g of EBI.

Obtaining a catalyst.

Conditions were the same as in example 1, but using 100 cm3solution metallocene/l = 1.35; Al = 3.95%.

The polymerization.

The polymerization conditions were identical to the conditions of the polymerization of example 2, but instead of 0.1 bar H2and 100 g of butene used 0.5 bar H2and 150 g of butene. Got 350 g of ethylene-butenova copolymer in the form of spherical particles (yield 7000 g of copolymer/g catalyst; 1000 kg/g Zr; 1050 kg/g MgCl2) with the following characteristics: MIE = 5.9; F/E = 41; = 0,8; actual density = 0.906; associated butene = 15%; insoluble in xylene 88%.

Example 5

In this example, upon receipt of the catalyst solution was used to metallocene TIBAS.

Getting media.

The same procedure as in example 1.

Obtaining solution metallocene TIBAS.

500 cm3a reactor equipped with anchor stirrer and treated with N2when 90oC for 3 h gave 382.5 cm3hexane solution of TIBAS (100 g/l) and 14.25 g of EBI in the atmosphere N2at 20oC for 60 minutes At the end of this period received a clear solution.

Obtaining a catalyst.

Used the same reactor at the same temperature as that in example 1, but took 110 cm3solution metallocene TIBAS, when this reaction was carried out in the course 1.54%; Al =1.4%.

The polymerization.

The procedure was the same as in example 1, but instead of 0.1 bar H2used 0.5 bar H2. Got 175 g of polyethylene spherical shape (yield 3500 g of polyethylene/g of catalyst; 470 kg/g Zr; 640 kg/g MgCl2) with the following characteristics: MIE =17; F/E=31; = 0.9.

Example 6.

The polymerization.

When using the catalyst of example 5 was carried out the polymerization in accordance with the method of example 2, but with the following changes: the catalyst obtained according to the method of example 5, the pre-processed 1.45 g TIBAS instead of 0.42 g of MAO; in the autoclave, the hydrogen pressure was 1 bar instead of 0.1 and downloaded 200 g of butene instead of 100 was Obtained 35 g of a copolymer of ethylene and butene spherical shape (yield 700 g of copolymer/g catalyst; 127 kg/g MgCl2) with the following characteristics:

MIE = 14; F/E = 33; actual density =0.909; associated butene = 13%; insoluble in xylene 74%.

Example 7.

Getting media.

Media received in accordance with the method and conditions of example 1.

Obtaining solution metallocene TIBAS.

Followed the method of example 5.

Obtaining a catalyst.

cm3solution metallocene/TIBAS instead of 110 cm3and the reaction was conducted for 4 hours instead of 3 hours Got 117.5 g of spherical catalyst with the following characteristics: Zr = 1.02%; Mg =0.16%; Al = 1.61%.

The polymerization.

Conditions were the same as in example 1, but used the catalyst obtained by the method described previously. Got 280 g of polyethylene spherical shape (exit 5600 g of polyethylene/g catalyst) with the following characteristics:

= 1.3; MIE=0.5; F/E =70; Mw/Mn=3.4.

Example 8.

Obtaining a catalyst.

The catalyst obtained in accordance with the method and conditions of example 7.

The polymerization.

Carried out the procedure in accordance with example 2, but using 50 g of butene instead of 100 g was applied to the catalyst obtained in accordance with the methodology described above. Got 220 g of a copolymer of ethylene and butene spherical shape (exit copolymer/catalyst = 4400) with the following characteristics:

MIE = 5; F/E = 31.8; = 1.17; insoluble in xylene=97.4; actual density = 0.920; associated C4=3.9%.

Example 9.

Getting media.

Followed the procedure of example 1.

S="ptx2">

The catalyst was obtained as in example 1, washed 3 times with toluene (100 g/l) at a temperature of approximately 20oC. the Solvent was removed under vacuum at a maximum temperature of 40oC.

The obtained spherical catalyst had the following characteristics:

Zr=0.45%; Mg =0.26; Cl = 1.22%; Al = 2.9%.

The polymerization.

The polymerization was carried out in the same conditions as in example 1. Got 112.5 g of polyethylene spherical shape (output 2250 g of polyethylene/g catalyst) with the following characteristics:

MIE =0.9; F/E=58; = 1.43.

Example 10.

Getting media.

Media received in accordance with the method described in example 1.

Obtaining a catalyst.

In a reactor with a capacity of 100 cm3equipped with anchor stirrer and treated with N2when 90oC for 3 h, downloaded 500 cm3toluene, 6 g of MAO and 50 g of the medium in an atmosphere of N2at 20oC and stirring.

Then the system was heated to 80oC for 2 h, followed by evaporation at 20 mm H, solvent removed. The obtained solid mass suspended in 500 cm3toluene and 20oC and stirring gave 1.2 g of EBI. The system was maintained in an atmosphere of NTorical, receiving 57.2 g of the catalyst with the following characteristics: Zr= 0.4%; Mg =0.26%; Cl = 1.37%; Al= 5.2%.

The polymerization.

When using the catalyst obtained in accordance with the methodology described above, carried out the polymerization in the same conditions as in example 1.

Received 100 g of polyethylene in the form of spherical particles (yield 2000 g PE/g catalyst) with the following characteristics: MIE=0.5; F/E=78; = 1.6.

Example 11.

Getting media.

Media received in accordance with the method described in example 1.

Obtaining a catalyst.

3000-cm3a reactor equipped with anchor stirrer and baffles, treated beforehand with nitrogen at 90oC for 3 h, was supplied at 20oC under stirring in an atmosphere of N220 g of the carrier, 2000 cm3toluene and 0.914 g EBI. Implemented the interaction of the mixture at 40oC for 20 h In the end of this period by evaporation at a pressure of 20 mm Hg removed the solvent, receiving 21 g of spherical catalyst with the following characteristics:

Zr=0.98%; Mg = 0.27%.

The polymerization.

When using the catalyst obtained in accordance with the method and army (output 3200 g of polyethylene/g catalyst) with the following characteristics:

MIE=2.96; F/E=40.5; = 1.12.

Example 12.

Getting media.

Obtaining carried out as in example 1, but instead of feeding ethylene to until got out of 40 g of polymer/g of catalyst, the reaction was carried out in such a way as to obtain an output of 10 g of polymer/g of catalyst. Received 2.9 kg spherical prepolymer with the following characteristics:

Specific surface area = 2.6 m2/,

- Porosity = 1.215 cm3/g;

- P50 = 79.49 microns;

- Ti = 0.8%; Cl = 4.45%; Mg =1.05%; Al = 0.18%.

Obtaining solution metallocene/MAO.

Repeated the method and conditions of example 1.

Obtaining a catalyst.

Following the procedure of example 1 and using the media described previously received 118.2 g of spherical catalyst with the following characteristics:

Zr =0.44%; Cl = 4.16%; Mg=0,95%; Al = 5.09%; Ti =0.78%.

The polymerization.

The polymerization was carried out as in example 1 using the catalyst described above. Received 105 g of polyethylene spherical shape (exit 2100 g of polyethylene/g catalyst) with the following characteristics:

MIE = 0.48; F/E = 70.

Example 13.

Getting media.

Followed the procedure as in example 1, but instead of downloading 290 g Catalina/catalyst =100 by weight. Unloaded 9.6 kg spherical prepolymer with the following characteristics:

- Specific surface area = 0.9 m2/g (Hg)

- Porosity = 0.618 cm3/g (Hg)

- P50 = 192.68 microns.

Obtaining solution metallocene/MAO.

Repeating the procedure of example 1.

Obtaining a catalyst.

Following the procedure of example and using the media described previously received 118.2 g of spherical catalyst with the following characteristics: Zr=0.41%; Cl = 0.66%; Mg =0.072%; Al = 4.95%.

The polymerization.

The polymerization was carried out as in example 1 using the catalyst described above. Got 35 g of polyethylene spherical shape at the output of 700 g of polyethylene/g of catalyst and a = 1.15.

Example 14.

Getting media.

The method was the same as in example 1, but instead of downloading 290 g of catalyst was loaded 48 g, and ethylene was served up until he received the degree of conversion of polyethylene/catalyst = 300 by weight. Unloaded 14.4 kg spherical prepolymer with the following characteristics:

- Specific surface area = 7 m2/g;

- Porosity = 0,499 cm3/g;

- P50 = 392.29 microns.

Obtaining solution metallocene/MAO.

The solution OI same, as in example 1 was used above the media. Received 18.2 g of spherical catalyst with the following characteristics: Zr =0.55%; Cl=0.54%; Mg=0.02%; Al=6.40%.

The polymerization.

The polymerization was carried out as in example 1 and obtained 35 g of polyethylene spherical shape with output equal to 700 g of polyethylene/g of catalyst. The polymer had the following characteristics: MIE=12.6; F/E=23.9; = 0.95.

Example 15.

The polymerization.

In a glass flask, treated with nitrogen at 90oC for 3 h, pre-mixed 50 cm3hexane for 5 min at 20oC 0,216 g of the catalyst obtained in accordance with the method of example 1 and 6 g TIBAS. At the end of this period, all downloaded in the gas-phase reactor with a fluidized bed with a volume of 35 liters, which was attended by 7 bar of ethylene and 8 bar of propane at a temperature of 75oC. the Reaction was carried out in the gas phase for 3 h, keeping the temperature and pressure of ethylene permanent. Made degassing and unloaded 520 g of spherical polyethylene at the output of 2400 g of polyethylene/g of catalyst. The volumetric weight of the polymer was 0.36 g/cm3and fluidity 18 C.

Example 16.

210 g of the catalyst will polimerizuet when those same at the UJC size 35-5 mesh washed with 250 ml of n-hexane at 68oC for 1 h in a 1000 ml flask and then dried in a dry nitrogen. of 104.5 g tetraethylorthosilicate then load in communicating the suspension to 65oC and 0.2 ml of a solution of 2 g of iodine in 10 ml of methyliodide enters as a promoter, and a solution consisting of of 50.9 g of n-butyl chloride in 100 ml of n-hexane is then introduced dropwise in 45 minutes the temperature of the support at 70oC by heat associated in the reaction. The reaction is then continued at 70oC for 6 hours Washing with n-hexane at 50oC is carried out by decantation, using 200 ml of n-hexane each time for 6 consecutive times. The obtained solid product is dried at 50oC under vacuum.

Allocate 60 g of the solid product, the elementary analysis gives the following results.

(Percent by weight): Mg = 18,65%; Cl = 27.05 per cent.

The surface area (determined in accordance with method C. E. T. SORPTOMATIC 1860 device - C. ERBA) is equal to 550 m2/g, porosity 0,156 ml/year

of 13.1 g of the obtained dry product is suspended in a solution containing of 4.67 g of benzoyl chloride (33.3 mmol) in 200 ml of anhydrous n-hexane and provide interaction for 2 h at 60oC. the Solid obtained after filtration at room temperature promyvayut 110 ml of TiCl4if 120oC for 2 hours, After this period of time TiCl4removed by filtration at 120oC and the solid is then washed with n-hexane at 65oC until, until there is no chlorine ion.

Analysis: Ti=1,85%; Mg = 20,7%; Cl = 70 wt.%.

Get 8.4 kg of prepolymer in pellet form, having the following characteristics:

Specific surface area (Hg)=1 m2/g; porosity (Hg attributed to pores with radius up to 50000 = strength of 0.159 cm3/,

Obtaining a catalyst.

Obtaining carried out under the same conditions as in example 1, but using 70,9 cm3solution metallocene/MAO instead of 200 cm3. Got about 106 g of granulated catalyst with the following characteristics: Zr=0,1%; Ti-0,05%; Cl=1,28%; Mg=0,38%; Al=1,85%.

Polymerization (HDPE)

The above catalyst was polymerizable as described in example 1 was obtained 1.25 g of polyethylene spherical shape (exit 484 g of polyethylene/g of catalyst; 484 kg/g Zr) with the following characteristics: = 4.2.

Example 17.

Getting media.

The same method as in example 1.

Obtaining solution metallocene/TIBAS.

Obtaining carried out as in example 5, but when ="ptx2">

Obtaining a catalyst.

Using the above carrier and the solution metallocene/TIBAS, has been receiving as in example 1, with the difference that used 176.7 cm3solution metallocene/TIBAS. Got about 110 g of the catalyst of the spherical shape with the following characteristics:

Cl=1.26%; Mg=0.24%; Ti=0.16%; Al=0.62%; Zr=0.35%.

The polymerization.

The above catalyst was polymerizable as in example 2, using 50 g of 1-butene instead of 100, Received 185 g of a copolymer of ethylene and butene (exit 3700 g of copolymer/g catalyst; 1060 kg/g Zr), with the following characteristics: MIE= 0.45; F/E =24; = 2.18; associated butene =4.2%; actual density = 0.9258; insoluble in xylene 99.3%.

Example 18.

Getting media.

The same method as in example 1.

Obtaining solution metallocene TIBAS

Obtaining carried out as in example 5, but using 15 g of ethylene-bis(4,7-dimethylindole)zirconiated (BDMI) and 332 cm3hexane solution of TIBAS (100 g/l).

Obtaining a catalyst.

Using the above carrier and the solution metallocene/TIBAS, has been receiving as in example 1, with the difference that using the features:

Cl =1.55%; Mg=0.75%; Ti =0.2%; Al=4.05%; Zr =0.75%.

The polymerization.

The above catalyst was polymerizable as in example 1. Got 225.9 g of polyethylene spherical shape (exit 4518 g polyethylene/g catalyst; 602 g/g Zr) with the following characteristics: MIE =2.55; F/E=39.21.

Example 19.

0.05 g of the catalyst of example 18 was pre-contacted with 0.5 g TIBAS at 20oC for 5 min and then filed in a 4-liter autoclave of stainless steel, which contained 800 g of propane at 20oC.

Ethylene was applied at 40oC up until absorbed 5 g of monomer. Gave 0.5 g of the modified MAO (20% solution in Isopar C) and the temperature was raised to 75oC. Carried out the polymerization under a partial pressure of 7 bar of ethylene for 1 h Received 395 g of polyethylene spherical shape (exit 7452 g polyethylene/g catalyst; 1552 kg/g Zr), which had a bulk weight of 0.3 g/cm3.

Example 20.

Getting media.

The same method as in example 1.

Obtaining solution metallocene/MAO.

Obtaining carried out as in example 1, but using 9 g of ethylene-bis(4,5,6,7-tetrahydroindene)zirconiated (BTGI) and 49.24 g MAO.

Poluchenie as in example 1, with the difference that used 170 cm3solution metallocene/MAO. Got about 115 g of the catalyst of the spherical shape with the following characteristics:

Cl=1.26%; Al = 4.2%; Mg=0.28%; Ti=0.16%; Zr=0.33%.

The polymerization.

The above catalyst was polymerizable as in example 1. Got 125 g of polyethylene spherical shape (exit 2520 g of polyethylene/g of catalyst; 763 kg/g Zr) with the following characteristics: MIE=68.6; = 0.79.

Example 21.

The polymerization.

0.05 g of the catalyst of example 19 was previously precontractual with 0.42 g of MAO 100 cm3toluene for 5 min at 30oC. the Catalyst was filed in purged with propylene, the autoclave (3 treatments, 5 bar of propylene). Filed 1000 cm3H2and 2300 cm3propylene and set the temperature to 70oC. the Polymerization was carried out for 2 hours Got about 330 g of propylene spherical shape (exit 6521 g of polypropylene/g of catalyst; 1976 kg/g Zr) with the following characteristics: insoluble in xylene 74.1%.

Example 22.

Getting media.

The same method as in example 1.

Obtaining solution metallocene/MAO.

The same method as in example 4.

SUP>3of toluene. At 20oC filed 10 cm3diisobutylphthalate; the mixture is then heated at 40oC for 2 h Gave 70.5 cm3the above solution metallocene/MAO, and the mixture was maintained for 4 h at 40oC and stirring. After removal of the solvent under vacuum received 115 g of spherical catalyst with the following characteristics:

Zr=0.7%; Al = 3,44%; Ti =0.17%; Cl = 1,41%; Mg =0,22%.

The polymerization.

The above catalyst was polymerizable as in example 8. Received 290 g of copolymer spherical shape (exit 5300 g copolymer/g catalyst; 732 kg/g Zr) with the following characteristics: MIE=0.088; F/E=151.3; = 1,48; actual density = 0.910; insoluble in xylene 90.4%; Mw/Mn=4,4.

Example 23.

2.5-liter reactor made of stainless steel with 30oC gave the following reagents: propane = 10 kg/h; TIBAS=33,6 g/h; MAO=5.6 g/h; the catalyst of example 1 = 3 g/H. the Average time of stay of 7 minutes the mixture is Then filed in a reactor with a fluidized bed having a volume of 350 liters Polymerization was carried out at 80oC and a pressure of 24 bar by feeding propane (23 kg/h), ethylene (15 kg/h), butene (5 kg/h). The polymer obtained spherical shape (yield 6000 g polymer/g catalyst) with the following'hara is th butene =6%; insoluble in xylene 95.6%; the content of CC<5 ppm (per million hours).

1. Component 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 a porous polymer carrier, characterized in that as the carrier component contains 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 to 12 carbon atoms, with a complex catalyst comprising the product obtained by contacting compounds of Ti, Zr or Hf with a halide of magnesium in the form of particles with an average crystallite size below PI this called the halide of magnesium contained in the above-mentioned prepolymer in amounts of between 50 and 50000 hours in a million.

2. Component of the catalyst under item 1, characterized in that the compound of the transition metal M contains at least one ligand L coordinated relative to the metal M, the ligand L has a mono - or polycyclic structure containing conjugated electrons.

3. Component of catalyst according to PP.1 and 2, characterized in that the atomic ratio M/Mg tsya between 0.3 and 3.

5. Component of catalyst according to PP.1 to 4, characterized in that the crystallites of magnesium halide have a size of less than 150

6. Component of catalyst according to PP.1 to 5, characterized in that the magnesium halide is MgCl2.

7. Component of catalyst according to PP.1 - 6, characterized in that the compound of the transition metal is selected from compounds having the structure

CpICpIIMR1R2(I)

(CpI-A-CpIIMR1R2(II)

where M is Ti, Zr, Hf;

CpIand CpIIthe same cyclopentadienyls group which may be substituted, two or more of the substituents at cyclopentadienyls groups can form one or more rings having 4 to 6 carbon atoms;

R1and R2the same and represent halogen atoms;

A - C2H4.

8. Component of catalyst according to p. 7, characterized in that the compound of the transition metal is selected from the following compounds

(4,7-Me2-Ind)2MCl2,(Ind)2MCl2(H4Ind)2MCl2,

where M is Ti, Zr, Hf.

9. Component of catalyst according to p. 7, characterized in that the compound of the transition metal is selected from the following compounds:

C2H4(Ind)2

10. Component of catalyst according to PP.1 to 10, characterized in that the prepolymer obtained with the catalyst solid component which is in the form of spherical particles with a size below 100 microns, a specific surface area of less than 200 m2/g and porosity by mercury between 0.5 and 2 cm3/,

11. Component of catalyst according to PP.1 - 11, characterized in that the prepolymer has a porosity by mercury attributed to pores with radius up to 50000 more than 0.3 cm3/,

12. Component of catalyst according to PP.1 - 12, characterized in that the prepolymer has a porosity by mercury attributed to pores with radius up to 50000 more than 0.4 cm3/,

13. Component of catalyst according to PP.1 - 13, characterized in that the prepolymer has a porosity by mercury attributed to pores with radius up to 50000 more than 0.5 cm3/,

14. Component of catalyst according to p. 10, characterized in that the content of titanium in the solid component is more than 1 wt.%.

15. Component of catalyst according to PP.1 to 14, characterized in that it is the product of the processing of olefin prepolymer solution in hydrocarbon solvent of the compound of the transition metal M and Al - alkyl compounds selected from Al-trialkyls and polyalkylene="ptx2">

16. Component of the catalyst for polymerization of olefins, comprising the olefin prepolymer containing a dispersion of a halide of magnesium in the form of particles with an average crystallite size less than 300 and the connection of the transition metal M selected from Ti, Zr, Hf containing at least one M--communication, in which the compound of the transition metal valency M is in the form of at least partially related to the halide of magnesium, while the atomic ratio M/Mg is more than 0.1.

17. The catalyst for polymerization of olefins comprising the reaction product component of the PP.1 - 16 with Al-alkyl compound selected from Al-trialkyl, in which the alkyl groups have 1 to 12 carbon atoms, and linear or cyclic alumoxane compounds containing a repeating link -(R4)AlO-, in which R4is an alkyl group with 1 to 6 carbon atoms and containing 2 to 50 repeating units.

18. The catalyst p. 17, characterized in that the Al-alkyl compound is a mixture of Al-trialkyl and alumoxane.

19. Catalyst under item 17 or 18, characterized in that alumoxane is polymethylsiloxane.

20. The catalyst p. 18 or 19, characterized in that it is selling is from

C2H4(Ind)2MCl2C2H4(4,7-Me2-Ind)2MCl2C2H4(H4Ind)2MCl2. 21. The method of polymerization of olefins of the formula CH2=CHR, where R is hydrogen or alkyl with 1 to 10 carbon atoms, characterized in that it uses the catalyst PP.18 - 21.

22. The method according to p. 21, characterized in that the polymerization of ethylene and its mixtures with olefins of the formula CH2=CHR, where R is hydrogen or alkyl with 1 to 10 carbon atoms, using a catalyst obtained from a component under item 9.

23. The method according to p. 21, characterized in that the polymerization of ethylene and its mixtures with olefins of the formula CH2=CHR, where R is an alkyl radical with 1 to 10 carbon atoms, using a catalyst obtained from a component under item 9.

24. The polyolefins obtained by the methods in paragraphs.21-23.

 

Same patents:

The invention relates to the field of catalytic systems for the polymerization or copolymerization of cycloolefins norbornene-type

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The invention relates to new multi-core metallocene compounds of the formula I, in which M1denotes a metal of group IVб of the Periodic system of the elements; X is a halogen atom; L and L1are the same or different and represent a substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl; denotes a group of formula (a), in which R1denotes a divalent hydrocarbon bridging group, the residues R2are the same and denote WITH1-C4is an alkyl group; M2denotes the silicon, as well as the way they are received, containing the catalytic system, a method for producing a polyolefin and a polymer molded product

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The invention relates to the chemistry of polymers, and to methods of producing stereoregular polypropylene, and can be used in the chemical industry in the manufacture of plastics

The invention relates to a solid catalyst component obtained by a process comprising a stage of bringing (a) a liquid magnesium compounds into contact with (b) a liquid compound of titanium in the presence of (C) organosilicon compounds having inactive hydrogen in an amount of from 0.25 to 0.35 mol per 1 mol of compound of magnesium (a) increasing the temperature of the obtained contact product (i) to a temperature of from 105 to 115oWith and holding the contact product at this temperature
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