The catalyst on the carrier for the polymerization of olefins (options), its production method (variants), the method of polymerization of olefin

 

(57) Abstract:

Catalysts on the media for the polymerization of olefins, which include the following components: (A) a porous organic carrier having a functional group with active hydrogen atoms; (B) at least one ORGANOMETALLIC compound of aluminium containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom; and (C) at least one compound of a transition metal selected from the metals of group IVb, Vb or VIb. The periodic system of elements, which includes at least one ligand cyclopentadienyls type. These catalysts, which get in the form of spherical particles, can be used in the polymerization of olefins in the liquid and in the gas phase, and allow to obtain polymers with controlled morphology and high bulk density. 7 C. and 14 C. p. F.-ly, 3 tables.

The invention relates to a catalyst on the carrier for the polymerization of olefins, the method of its production and the use of such catalyst in the polymerization processes of olefins.

Known homogeneous catalytic systems for polymerization of olefins on the basis of the coordination is. In General, such catalysts include soluble socialization, such as methylalumoxane.

These homogeneous catalytic systems have several advantages compared to traditional heterogeneous catalysts of the type Ziegler-Natta. In particular, they allow reliable control over the degree and type of stereoregularity, molecular weight distribution and the distribution of co monomer, as well as facilitate the use as comonomers higher alpha-olefins, diolefins and dienes. Thus, there can be obtained new polymers or polymers having improved properties.

However, soluble in the reaction mixtures of the above catalyst system in the polymerization processes, which are not in solution, difficult to use. Moreover, the polymers obtained in the processes using the above catalysts, as a rule, do not have satisfactory morphological characteristics.

To address these shortcomings have been proposed system, in which at least one component of the above catalysts is applied to the insoluble solid support. In most cases the>The prior art provides for the use of media-based polymers.

In European patent applications 279863 and 295312 offers homogeneous catalysts on the media, including methylalumoxane dichloride and bis(cyclopentadienyl)zirconium. In addition to inorganic carriers on the basis of silicon oxide used media based on polyethylene and polystyrene. Upon receipt of the catalyst on the carrier using n-decane, which plays the role of the precipitator methylalumoxane. These catalysts on the media after terpolymerization treatment with ethylene in n-decane used in the polymerization reaction of ethylene from the gas phase. To obtain acceptable results apply a significant amount methylalumoxane for each gram of solid media.

In European patent application 518092 are catalysts of the type metallocene/alumoxane deposited on polypropylene. The catalysts used in the polymerization of propylene in the liquid monomer in the gas phase. Nothing is said about the bulk density of the obtained polymers.

Although these types of catalytic systems deposited on polymeric materials useful in the processes, which are held in WM is becausee good morphological characteristics.

Found that the catalytic system containing metallocene/alumoxane can be turned into a heterogeneous by applying them on a porous organic carriers containing functional group. In this way it becomes possible to obtain catalysts in the form of spherical particles having a satisfactory activity and capable of producing polymers whose shape follows the shape of the catalyst, and therefore possess a controlled morphology and high porosity.

Thus, the object of the invention is the catalyst on the carrier for the polymerization of olefins, which includes:

(A) a porous organic carrier having a functional group with active hydrogen atoms;

(B) at least one ORGANOMETALLIC compound of aluminium containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom;

(C) at least one compound of a transition metal selected from the metals of groups IVb, Vb or VIb of the Periodic system of elements, which includes at least one ligand cyclopentadienyls type.

The porosity (BET method) organic media is usually more than 0.2 with the media, suitable for use according to the invention have a porosity in the range from 1 to 3 cm3/,

Specific surface area (by BET method) of organic media is usually more than 30 m2/g, preferably more than 50 m2/g and even more preferably more than 100 m2/, In particular, the value of specific surface area can reach values of the order of 500 m2/g or more.

Organic media has mainly the form of particles with controlled morphology, in particular, microspheroidal morphology with particle diameters in the range from about 5 to 1000 μm, preferably 10 to 500 μm, more preferably 20 to 200 μm.

Carriers that can be used in the catalysts according to the invention are those polymers having the above parameters on porosity and specific surface area, which contain functional groups with active hydrogen atoms.

Examples of suitable functional groups are hydroxyl groups, primary and secondary amino groups, sulfopropyl, carboxyl group, aminopropyl, N-monosubstituted aminogroup, sulphhydryl group, aminogroup and gidrazidov.

The number of functions the grams of solid media, preferably more than 0.5 mEq per gram of the solid carrier, still more preferably 1 to 6 mEq per gram of the solid catalyst.

Class carriers, the most suitable for use in the catalyst according to the invention can be obtained, in particular from crosslinked porous polymer based on polystyrene. These carriers can be obtained by copolymerization of styrene monomers such as styrene, ethylvinylbenzene, vinyltoluene, methylsterol and mixtures thereof with comonomers, which can be crosslinked, such as divinylbenzene, dividercolor and mixtures thereof. The preferred polymers are, in particular, cross-linked copolymers of styrene/divinylbenzene. Methods of obtaining these copolymers are described, for example, in U.S. patent 4224415.

In the porous polymers of this type using known methods it is possible to introduce functional groups. The most common methods of functionalization of polystyrene resins are Comprehensive Pol. Sci., Pergamon Press, p. 82 - 85 (1989).

Methods of obtaining alpha-hydroxyalkylated resins are described in I. Fujita et al. , Separation Science and Technology, vol 1. 26, p. 1395 - 1402 (1991).

Porous styrene polymers with the introduced functional groups, Prigogine obtained by copolymerization of styrene monomers with comonomers, which contain functional groups with active hydrogen atoms, or their predecessors. Examples of such polymers are copolymers based on styrene, containing hydroxyl groups, which are described in European patent application 496405.

Transition metals of the IVb, Vb or VIb groups of the Periodic system of elements, preferably selected from titanium, zirconium, hafnium and vanadium, most preferably zirconium.

The transition metal compounds suitable as catalysts on a carrier according to the invention are, for example, cyclopentadienyls the compounds of formula (I):

(C5R15-mR2m(C5R15-m)nMQp-n,

where

M is titanium, zirconium, hafnium, or vanadium;

two groups of C5R15-mare pentadienyl rings containing identical or different substituents;

the substituents R1that may be the same or different from each other, are hydrogen atoms, alkyl, alkenylamine, aryl, alkalline or Uralkalij radicals containing from 1 to 20 carbon atoms, which may also include silicon atoms or the atom is tatianalulo rings can form one or two rings, containing from 4 to 6 carbon atoms;

R2is a bridging group which links the two cyclopentadienyls ring and which is chosen from the group of CR32C2R34, SiR33Si2R34, GeR32Ge2R34, R32SiCR32, NR1or PR1where the substituents R3the same or different from each other, have the same meanings as the substituents R1or two or four Deputy R3can form one or two rings containing 3 to 6 carbon atoms; the substituents Q are the same or different from each other are a halogen atom, a hydrogen atom, a group OH, SH, R1, OR1, SR1, NR12or PR12, m can be 0 or 1; n can be 0 or 1, it is 1 if m = 1; is 2 or 3 and preferably equal to 3.

In that case, if m = 0, the most suitable cyclopentadienyls compounds are those in which the group C5R15-mselected from cyclopentadienyls, pentamethylcyclopentadienyl, indenolol and 4,5,6,7-tetrahydroindole group, and the substituents Q are selected from a chlorine atom and a (C1-C7)- carbohydrate is pentadienyl compounds of formula (I), in which m = 0 are: (Cp)2MCl2; (MeCp)2MCl2; (BuCp)2MCl2; (Me3Cp)2MCl2; (Me5Cp)2MCl2; (Me5Cp)2MCl2; (Me5Cp)2MMe2; (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; (Me5Cp)MCl3; (Me5Cp)MBenz3; (Ind)MBenz3; (H4Ind)MBenz3; (Cp)MBu3; (Me5Cp)MCl; (Me5Cp)MH, where Me=methyl, Et= ethyl, Bu= butyl, Cp= cyclopentadienyl, Ind=indenyl, H4Ind= 4,5,6,7-tetrahydroindene, Benz= benzyl, M is Ti, Zr, Hf or V, mainly Zr.

In that case, if m = 1, the most suitable cyclopentadienyls compounds are those in which the group C5R5-mselected from cyclopentadienyls, tetramethylcyclopentadienyl, 2-methyl-4,5,6,7-tetrahydroindole, 4,7-dimethyl-4,5,6,7-tetrahydroindole, 2,4,7-trimethyl-4,5,6,7-tetrahydroindole or fluorenyl group, R2is a divalent group selected from groups (CH3)2Si, C2H4and C(CH3)2and the substituents Q are selected from a chlorine atom and a (C1-C7)-hydrocarbon group, mainly methyl group.

Not limiting the invention, examples of cyclopentadienyls compounds of formula (I) in which m = 1, are: Me2Si(Me4Cp)2MCl2; Me2Si(Me4Cp)2MMe2; Me2C(Me4Cp)(MeCp)MCl2; Me2Si(Ind)2MCl2; Me2Si(Ind)2MMe2;

Me2Si(Me4Cp)2MCl(OEt); C2H4(Ind)2MCl2; C2H4(Ind)2MMe2; C2H4(Ind)2M(NMe2)2;

C2H4(H4Ind)2MCl2; C2H4(H4Ind)2MMe2; C2H4(H4Ind)2M(NMe2)OMe;

Ph(Me)Si(Ind)2MCl2; Ph2Si(Ind)2MCl2; Me2C(Flu)(Cp)MCl2; C2H4(Me4Cp)2MCl2;

C2Me4(Ind)2MCl2; Me2SiCH2(Ind)2MCl2; C2H4(2-MeInd)H4(5,6-Me2Ind)2MCl2; C2H4(2,4,7-Me3Ind)2MCl2; C2H4(3,4,7-Me3Ind)2MCl2; C2H4(2-MeH4Ind)2MCl2; C2H4(4,7-Me2H4Ind)2MCl2; C2H4(2,4,7-Me3H4Ind)2MCl2; C2H4(Benz/e/Ind)2MCl2;

C2H4(2-Me-Benz/e/Ind)2MCl2; IU2Si(2-MeInd)2MCl2; MeSi(3-MeInd)2MCl2;

Me2Si(4,7-Me2Ind)2MCl4; Me2Si(5,6-Me2Ind)2MCl2; Me2Si(2,4,7-Me3Ind)2MCl2;

Me2Si(3,4,7-Me3Ind)2MCl2; Me2Si(2-MeH4Ind)2MCl2; Me2Si(4,7-Me2H4Ind)2MCl2;

Me2Si(2,4,7-Me3H4Ind)2MCl2; Me2Si(Flu)2MCl2; C2H4(Flu)2MCl2;

Me2Si(Benz/e/Ind)2MCl2, Me2Si(2-Me-Benz/e/Ind)2MCl2where Me = methyl, Ph = phenyl, H4Ind = 4,5,6,7-tetrahydroindene, M represents Ti, Zr, Hf or V, mainly Zr.

Another type of transition metal compounds suitable for use for preparation of catalysts according to the invention are monosyllabically sedimentate here for reference.

ORGANOMETALLIC compounds of aluminum, suitable for the production of catalysts on a carrier according to the invention are, for example, linear, branched or cyclic alumoxane containing at least one group of type

< / BR>
where the substituents R4the same or different from each other, have the same meaning as R1or represent a group-O-A1(R4)2while some R4if necessary, can indicate a halogen atom.

In particular, you can use alumoxane the following formula II

< / BR>
in the case of linear compounds, in which n denotes 0 or an integer from 1 to 40, or alumoxane formula III

< / BR>
in the case of cyclic compounds in which n denotes an integer from 2 to 40. The value of the radicals R1stated previously.

Examples of alumoxanes suitable for use in the catalysts on a carrier according to the invention are those in which the radicals R1selected from methyl, ethyl or isobutylene group, in particular, methylalumoxane (MAO) and isobutylamine (TIBAO).

A special class of ORGANOMETALLIC compounds of aluminum, suitable for use in catalysts for the media isabgol at a molar ratio of from 1:1 to 100:1, respectively. Compounds of this type are described in European patent application 575875.

Next ORGANOMETALLIC aluminum compounds, useful for use in the catalysts on a carrier according to the invention are those which have the formula IV

< / BR>
or formula V

< / BR>
where a value of R1stated previously. The molar ratio between the aluminum and the transition metal in the catalyst on the carrier is usually 10 to 500, preferably 20 to 200, more preferably 30 to 100.

The catalysts on a carrier according to the invention can be obtained by the interaction of the compounds (A), (B) and (C) in various sequences.

A convenient way to obtain a catalyst on the carrier according to the invention is the interaction in an inert solvent

(A) a porous organic carrier having a functional group with active hydrogen atoms;

(B) at least one ORGANOMETALLIC aluminum compounds containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom,

and the subsequent interaction of the obtained product with

(C) at least one compound of a transition metal selected from pentadienyl type,

and, finally, the selection of the catalyst on the carrier by removing the solvent.

Another way to obtain a catalyst on the carrier of the present invention involves reacting in an inert solvent

(B) at least one ORGANOMETALLIC aluminum compounds containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom,

(C) at least one compound of a transition metal selected from the metals of groups IVb, Vb or VIb of the Periodic system of elements, which includes at least one ligand cyclopentadiene type,

and the subsequent interaction of the obtained product with

(A) a porous organic carrier having a functional group with active hydrogen atoms,

and, finally, the selection of the catalyst on the carrier by removing the solvent.

Another way to obtain a catalyst on the carrier according to the invention involves reacting in an inert solvent

(A) a porous organic carrier having a functional group with active hydrogen atoms,

(B) at least one ORGANOMETALLIC aluminum compounds containing at least one R>
(B) at least one ORGANOMETALLIC aluminum compounds containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom, and

(C) at least one compound of a transition metal selected from the metals of groups IVb, Vb or VIb of the Periodic system of elements, which includes at least one ligand cyclopentadienyls type,

and the subsequent interaction of the product obtained by the reaction between (A) and (B) with the product obtained by the reaction of (B) and (C),

and, finally, the selection of the catalyst on the carrier by removing the solvent.

The above methods of preparation of the catalyst on the carrier according to the invention is carried out at a temperature which generally ranges from -80 to 100oC.

The organic carrier may preferably be pre-contacted with an alkyl compound of aluminum of the formula VI

R5qAlX3-q< / BR>
where

R5selected from alkyl, alkenyl, aryl, alkalline or Uralkalij radicals containing 1 to 10 carbon atoms, X is selected from a hydrogen atom or halogen atom, q represents an integer from 1 to 3.

Non-limiting invented trimethylaluminum, triethylaluminium, triisopropanolamine, and triisobutylaluminum, dialkylaminoalkyl, such as dimethylammoniumchloride, diethylaluminium, diisopropylaniline and diisobutylaluminium, dialkylaminoalkyl, such as diethylaluminium and diisobutylaluminium, isoprenaline. The preferred compound of aluminium is triisobutylaluminum.

The catalysts on a carrier according to the invention before use may be subjected terpolymerization processing by their prior contact with small quantities of olefin monomer.

Thus, the next object of the invention is the catalyst on the carrier subjected terpolymerization processing, for polymerization of olefins, which is obtained by exposing the catalyst on the carrier according to the invention terpolymerization processing at least one olefinic monomer.

Terpolymerization processing is usually carried out in an organic solvent. The amount of polymer that is formed at this stage, typically, ranges from 0.5 to 10 weight parts with respect to the weight of the used catalyst on the carrier.

The prepolymer is AlX3-q< / BR>
where the values of R5, X and q are indicated previously, or in the presence of ORGANOMETALLIC aluminium compound (B) described previously, in particular alumoxane. Preferred are alkyl aluminum compounds of the formula (VI).

The catalysts on a carrier according to the invention is useful for carrying out reactions of Homo - and copolymerization of olefins.

Thus, another object of the invention is a method for Homo - and copolymerization of olefins, consisting in the implementation of the polymerization reaction of one or more monomers in the presence of the above catalyst on the carrier.

Another object of the invention is a method for Homo - and copolymerization of olefins, consisting in the implementation of the polymerization reaction of one or more monomers in the presence of the above catalyst on the carrier subjected terpolymerization processing.

Before use the catalyst on the carrier according to the invention and, in particular, those which are subjected terpolymerization processing may preferably enter into preliminary engagement with alkyl aluminum compounds of the formula VI

R5qAlX3-q< / BR>
is anee, in particular, alumoxanes. Preferred are alkyl aluminum compounds of the formula (VI).

The catalysts on a carrier according to the invention is suitable for use in homopolymerization ethylene and, in particular, to obtain high-density polyethylene.

Moreover, the catalysts on a carrier according to the invention is suitable for use in copolymerization of ethylene with the olefinic comonomers, in particular, to obtain a linear low density polyethylene.

In the resulting linear low density polyethylene, the ethylene content of the fragments is from 80 to 90 mol.%. Its density is usually from of 0.87 to 0.95 cm3/g, and it differs uniform distribution comonomeric links in the polymer chain.

The olefins which are suitable for use as comonomers in the above copolymers based on ethylene, are alpha-olefins of the formula CH = CHR, where R denotes a linear or branched, or a cyclic radical containing 1 to 20 carbon atoms, and cycloolefin.

Not limiting the invention, examples of such olefins are propylene, 1-butene, 1-penten, 4-methyl-1-penten, 1-hexene, 1-octene, 1-mission 1-dodecamethyl-1-hepten.

The above copolymers based on ethylene may contain a small number of fragments of polyene, in particular, dienes, conjugated or non-paired, linear or cyclic, such as, for example, 1,4-hexadiene, isoprene, 1,3-butadiene, 1,5-hexadiene, 1,6-heptadiene.

Copolymers based on ethylene contain fragments derived from olefins of the formula CH2= CHR, cycloolefins and/or polyene in an amount of from 1 to 20 mol. %.

Other interest by the use of catalysts on a carrier according to the invention is the obtaining of elastomeric copolymers of ethylene with alpha-olefins of the formula CH2= CHR, where R denotes an alkyl radical having 1 to 10 carbon atoms, containing choice in a small proportion of the fragments derived from the polyene.

Saturated elastomeric copolymers obtained using catalysts on a carrier according to the invention usually contain from 15 to 85 mol.% ethylene fragments, and the rest are fragments of one or more alpha-olefins and/or one non-paired diolefin capable cyclopolymerization.

Unsaturated elastomeric copolymers contain in addition to the fragments obtained the s by copolymerization of one or more polymers. The content of unsaturated fragments is usually from 0.1 to 5 wt.% and is preferably from 0.2 to 2 wt.%.

Elastomeric copolymers based on ethylene, obtained using catalysts on a carrier according to the invention possess valuable properties, such as low water content and a homogeneous distribution of the comonomers in the polymer chain.

Alpha-olefins suitable for use as comonomers to obtain the above elastomeric copolymers based on ethylene, are, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-penten.

Can be used unpaired olefins, capable of cyclopolymerization, in particular, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,5-hexadien.

The polyene, which can be used as comonomers are such polyene, which are included in the following classes:

- unpaired diolefine capable cyclopolymerization, such as, for example, 1.5-hexadiene, 1,6-heptadiene, 2-methyl-1,5-hexadien,

- diene able to give unsaturated Monomeric fragments, in particular, conjugate diene, such as butadiene and isoprene, linear unpaired diene, such as, for example, Tr is a mini-olefins, such as, for example, CIS-1, 5cyclooctadiene, and 5-methyl-1, 5cyclooctadiene, dziklicska diolefin, such as for example, 4,5,8,9-tetrahydroindene and 6 and/or 7-methyl-4,5,8,9-tetrahydroindene, alkenyl or alcaligenaceae, such as, for example, 5-ethylidene-2-norbornene, 5-ISO-propylidene-2-norbornene, Exo-5-ISO-propenyl-2-norbornene, polycyclic diolefin, such as, for example, Dicyclopentadiene, tricyclo /6.2.1.0.2.7./-4,9-undecadien and its 4-methyl derivative.

Another interest the use of catalysts on a carrier according to the invention is a Homo - and copolymerization of propylene and alpha-olefins, such as, for example, 1-butene. Depending on the catalytic system it is possible to obtain polymers with isotactic, syndiotactic or atactic structure.

Another interest the use of catalysts on a carrier according to the invention is to obtain polymers on the basis of cycloolefins. Monocyclic or polycyclic olefin monomers can be subjected to reaction as homopolymerization and copolymerization with an acyclic olefin monomers.

Not limiting the invention, examples of polymers on the basis of the cyclo is in European patent applications 501370 and 407870.

Polymerization process using the catalyst on the carrier according to the invention can be carried out in the liquid phase in the presence or absence of an inert hydrocarbon solvent. The solvent may be an aliphatic hydrocarbon, such as propane, hexane, heptane, isobutane, cyclohexane, or aromatic hydrocarbons, e.g. toluene.

The polymerization process that uses catalysts on a carrier according to the invention can be carried out in the gas phase.

The temperature during polymerization is usually maintained within the range of 0 to 250oC. for Example, upon receipt of high density polyethylene and linear low density polyethylene, the temperature of the polymerization process is typically 20 - 150oC, in particular 40 - 90oC. Upon receipt of elastomeric copolymers temperature in the polymerization process typically support in the range of 20 - 100oC, in particular 30 to 80oC.

The molecular weight of the resulting copolymers can be modified mainly by changing the polymerization temperature, the type or concentration of the catalyst components, or by using molecular weight regulators, t the Finance mixtures of different metallocene, and carrying out the polymerization in several stages, which differ in the temperature of polymerization and/or concentrations of the molecular weight regulator.

The outputs of the polymerization reaction depends on the purity of the metallocene component of the catalyst. Therefore, metallocene compounds can be used as catalysts on a carrier according to the invention or they may be treated.

The polymers produced by the catalyst on the carrier according to the invention have good morphological characteristics and can be manufactured in the form of particles whose diameter is 100 to 3000 μm, depending on the catalyst and conditions used when carrying out the polymerization reaction.

The following examples are provided to illustrate and not limit the invention.

The presence of functional groups in the media confirm IR spectroscopy. Quantitative determination of the content of functional groups containing active hydrogen atoms, conduct getobjectname analysis of the interaction of carriers with triethylaluminium.

Porosity and specific surface area determined by the absorption of nitrogen by the BET method on the device SORPTOMATIC 1900 firm Carlo Erba, and IU the t in tetrahydronaphtalene at 135oC.

Measurements by the method of differential scanning calorimetry is performed on the device DSC-7 company Perkin Elmer Co., Ltd in accordance with the following method. About 10 mg of sample was heated to 180oC at a scanning speed of 10oC/min, the Sample is maintained at a temperature of 180oC for 5 min, and then cooled at a scanning speed of 10oC/min then conduct a second scan in the same conditions as the first. Presents the results obtained during the second scan.

The content of groups of co monomer in the copolymer is determined by IR spectroscopy method.

The absolute density of the polymers is determined using columns with a density gradient according to the method of ASTM D-1505.

Bulk density with compaction and bulk volume density is determined according to the method of DIN-53194.

Obtaining catalyst components.

Dichloride, ethylene-bis(indenyl)zirconium

(A) Obtaining 1,2-bis(indenyl)ethane.

The method of obtaining the Annex to article J. Ewen, J. Am. Chem. Soc., vol. 109, R. 6544 (1987).

In a two-liter dvuhholos round bottom flask in an inert atmosphere dissolve 50 g (437 mmol) of indene in 500 ml of tetrahydrofuran and cooled to -78oC.

to warm to room temperature and kept under stirring for 4 hours Again cooled to -78oC and added dropwise a solution of 40, 42 g of dibromoethane (215 mmol) in 100 ml of tetrahydrofuran (within 20 min). Upon completion of addition, raise the temperature to 50oC and stirred the mixture at the specified temperature for 12 h, and then cooled to room temperature and add 20 ml of water. The organic layer is separated, evaporated, and the residue extracted with pentane. After removal of solvent in vacuo get 28,65 g of product (yield = 51.6 per cent).

(B) Obtaining dichloride ethylene-bis(indenyl)zirconium.

In dvuhgolosy round bottom flask with a capacity of 250 ml, equipped with a cooling system, placed 8 g (31 mmol) of 1,2-bis(indenyl)ethane and 100 ml of anhydrous tetrahydrofuran, thereby forming a yellow solution. After cooling to -78oC added dropwise 40 ml of a solution of utility (1.6 M in hexane), forming a precipitate, which when heated again dissolved, forming a solution of a reddish-yellow color. In chetyrehosnuju round bottom flask with a capacity of 250 ml, equipped with a cooling system, put 8,67 g (37,2 mmol) of zirconium tetrachloride; cool the mixture down to -196oC and condense in her 50 ml of tetrahydrofuran (the reaction is highly exothermic), give the mixture the th temperature with continuous stirring to the adduct ZrCl4/Add THF solution of lithium salt of bis(indenyl) and leave the mix in a dark place for 20 hours and Then at 0oC is blown through the mixture of gaseous hydrogen chloride, receiving a yellow solution and a precipitate of the same color. The solution is concentrated and pariva part of the solvent in vacuo, cooled to -20oC and the precipitate is filtered off. The residue is then distilled dichloromethane and obtain 2.3 g (14,7%) of product.

Dichloride, ethylene-bis(4,7-dimethyl-indenyl)zirconium

(A) Obtaining a 4.7-dimethylindole.

The synthesis is carried out in accordance with the methodology described in Organometallies, vol. 9, p. 3098 (1990) (yield 54% of p-xylene).

(B) Obtaining 1,2-bis(4,7-dimethyl-3-indenyl)ethane.

38,2 g (265 mmol) of 4,7-dimethylindole dissolved in 350 ml of tetrahydrofuran and bring the temperature of the solution to the 0oC. and Then added dropwise over 2.5 h add 165 ml of n-utility (1.6 M in hexane, 264 mmol). After the mixture for 1 h under stirring to warm to room temperature, forms a pink-red solution of 4,7-dimethylindole. The resulting solution was cooled to -70oC for 35 min add dropwise a solution of 25.3 g of 1,2-dibromethane (135 mmol) in 15 ml of tetrahydrofuran. After the Organic layer is separated and dried over sodium sulfate. The solvent is evaporated in vacuum and receive a 20 g (yield 48%) of product.

(C) Obtaining racemate and metatile-bis(4,7-dimethyl-indenyl)zirconiated.

To a solution 2,82 g KN (70,3 mmol) in 160 ml of tetrahydrofuran was added with stirring through a small tube suspension of 10 g (of 31.8 mmol) of 1,2-bis(4,7-dimethyl-3-indenyl)ethane in 80 ml of tetrahydrofuran. After the evolution of hydrogen ceases, the resulting brown solution is separated from the excess of the book. This solution and a solution of 12 g of the complex ZrCl42 (THF) (31,8 mmol) in 250 ml of tetrahydrofuran, using a small tube dropwise over 3 h with vigorous stirring in a round bottom flask containing 50 ml of tetrahydrofuran.

Formed yellow solution and precipitate. The solvent is evaporated in vacuum, the residue is orange-red color (a mixture racemate and mesosomal in the ratio of 2.33:1, according to PMR) is extracted with methylene chloride to dissolve the orange product. The obtained solid (1.7 g) yellow is the only stereoisomer, namely mesoforms (yield of 11.3%). After evaporation of methylene chloride from orange solution produce 4.9 g solid orange color, which predistribution from toluene at -20oC.

Dichloride, ethylene-bis(4,5,6,7-tetrahydroindene)zirconium. Receive in accordance with the method described in H. H. Brintzimger et al., J. Were Obtained. Che., vol. 288, p. 63 (1985).

Methylalumoxane.

Use a commercial product (firm Schering, molecular weight 1400) in the form of a 30% solution in toluene. After the removal of the vacuum volatile fractions obtained glassy substance grind, getting a white powder, which is then heated under vacuum (0.1 mm, RT.CT.) when 40oC. the resulting powder has good fluidity.

Example 1. Obtaining a polystyrene resin.

In a glass reactor with a capacity of 30 litres, equipped with a thermometer, reflux condenser, blade stirrer and temperature regulation system, placed in a nitrogen atmosphere aqueous solution containing 11 l of distilled water, 400 ml ROAGIT SVM (from the company Rohm) in the form of a 5% solution in water, of 55.5 g PROLIT C10 (from the firm Caffaro), 11 g of sodium chloride.

The resulting mixture was stirred at room temperature for 1 h with a speed of 350 rpm, then add organic solution containing 5,55 l n-octane, 1,85 l of toluene, 1.55 l of styrene, 2.55 l 64% of divinylbenzene in ethylvinylbenzene, 74 g of a 75% aqueous solution of peroxide of Dibenzoyl in water.

the tours. The resulting product is washed several times with distilled water, methanol at 50oC, and then dried at 100oC and a residual pressure of 1 mm RT. senior Get of 2.7 kg of product having microspheroidal morphology. The resulting product has the following characteristics: specific surface area: BET - 370 m2/g, Hg - 126 m2/g; porosity: BET - of 1.45 ml/g, Hg - 1,92 ml/g; average pore: BET - Hg -

The distribution of particle sizes:

0,8% - 300 µm

2,2% - 300 - 250 µm

7,0% - 250 - 180 µm

10,5% - 180 - 150 µm

73,2% - 150 - 106 μm

5,5% - 106 - 75 μm

0,8% - 75 μm

Receipt containing functional group of the carrier on the basis of polystyrene.

(A) Acylation.

In a glass reactor with a capacity of 750 ml, equipped with a thermometer, reflux condenser, blade stirrer and temperature regulation system in an atmosphere of nitrogen was placed 300 ml of carbon disulfide and 30 g of polystyrene resin. After the processing unit 12oC with 66 g (0.49 mol) pre-crunched trichloride aluminum for 1 h add 32 ml of fresh acetyl chloride. Then increase the temperature to 25oC and stirred at this temperature for 6 hours the mixture is transferred when peremeshennoi acid (37%) and stirred for 30 minutes Obtained after filtration of the resin washed sequentially with distilled water, acetone and finally with methanol. After drying obtain 34 g of the product having microspheroidal morphology. The IR spectrum of the observed broad band with center at 1685 cm-1that corresponds to a carbonyl group.

(B) Recovery.

In a glass reactor with a capacity of 500 ml equipped with a thermometer, reflux condenser, blade stirrer, placed 15.2 g acetylated resin obtained under paragraph (A), 100 ml of dioxane, 100 ml of distilled water and 15 g of sodium borohydride. Stir the mixture at 25oC for 50 h, add 4 g of sodium borohydride and stirred for 70 hours Obtained after filtration of the resin washed sequentially with distilled water, acetone and finally with methanol. After drying gain of 13.4 g of the product having microspheroidal morphology. The IR spectrum of the observed broad band with center at 3440 cm-1that corresponds to the hydroxyl group, while the band of the carbonyl group at 1685 cm-1significantly reduced compared to the same stripe in the resin under paragraph (A). The content of hydroxyl groups, defined the measures 2.

(A) obtaining a catalyst on the carrier.

In a glass reactor with a capacity of 350 ml, equipped with a thermometer, reflux condenser, blade stirrer with temperature regulation system, put 100 ml of anhydrous toluene and of 5.24 g of the resin obtained in example 1(B). The mixture is cooled to 0oC and with stirring for 40 min 30 ml of 1 M solution methylalumoxane in toluene. The reaction is carried out at 0oC for 1 h, and then for 4 h at 80oC. After cooling to 25oC for 55 min add 50 ml of toluene solution containing 221,2 mg dichloride ethylene-bis(indenyl)zirconium (EBI ZrCl2). Raise the temperature to 30oC and stirred for another 2 hours Getting the solution a reddish color, which allow to settle and receive sediment and colorless solution, which is removed by means of a siphon. The precipitate is washed several times with anhydrous toluene, and then dried in vacuum. Get 8 g of product with microspheroidal morphology, which has the following composition: Zr = 0,38%, Cl = 0,600, Al = 9,8%.

(B) Terpolymerization.

In a glass reactor with a capacity of 350 ml, equipped with a thermometer, reflux condenser, blade stirrer and temperature regulation system in Atmosfera solution, containing 5 mmol/triisobutylaluminum. The mixture is heated to 35oC and stirred for 15 minutes and Then for 90 min serves ethylene under a pressure of 30 mm RT. Art.

After evaporation of the solvent in vacuo obtain 5.8 g of a prepolymer having microspheroidal morphology.

Example 3. Copolymerization of ethylene/1-butene.

In a steel autoclave with a capacity of 1.35 l equipped with a stirrer, manometer, temperature indicator, system for conveying catalyst, lines for supplying monomers and heater, purified by washing with propane at 70oC, placed at room temperature 640 ml of propane and 1-butene, ethylene and hydrogen in amounts listed in table. 1. The slurry catalyst is prepared as follows. The solid catalyst according to example 2(A) and a solution of triisobutylaluminum (TIBAL) in 10 ml of hexane was placed in the addition funnel. After 5 min at 20oC, the suspension is injected into the autoclave, podavlivaya ethylene. Then, temperature for 5 min adjusted to the values required for polymerization and constant support during the entire polymerization process. The total pressure constant support, feeding a mixture of ethylene/1-butene. The reaction is stopped by rapid removal of the vapor of monomers, is redstavleny in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 4. Copolymerization of ethylene/1-butene in the gas phase.

In a steel autoclave with a capacity of 1.35 l equipped with a stirrer, manometer, temperature indicator, system for conveying catalyst, lines for supplying monomers and heater, purified by washing with ethylene at 70oC, placed at room temperature 60 g of pre-dried sodium chloride. Then add ethylene, 1-butene and hydrogen in amounts listed in table. 1. The slurry catalyst is prepared as follows. The solid catalyst according to example 2(A) and a solution of triisobutylaluminum (TIBAL) in 10 ml of hexane was placed in the addition funnel. After 5 min the suspension to a temperature of 20oC is introduced into the autoclave, heated to 45oC, slightly podavlivaya ethylene. Then, temperature for 5 min adjusted to the values required for polymerization and constant support during the entire polymerization process. The total pressure constant support, feeding a mixture of ethylene/1-butene. The reaction is stopped by rapid removal of the vapor of monomers and the resulting polymer at room temperature, washed with distilled water, then with acetone and with the data, concerning the characteristics of the obtained polymer are shown in table. 2.

Example 5. Copolymerization of ethylene/1-butene in the gas phase.

The process is carried out similarly to the method shown in example 4, except that use 2,019 g subjected terpolymerization solid catalyst according to example 2(B), without adding additional triisobutylaluminum.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 6. (A) obtaining a catalyst on the carrier.

The process is carried out similarly to the method shown in example 2(A), except that instead of ethylene dichloride bis(indenyl)zirconium use 224,2 g of the dichloride ethylene-bis(4,7-dimethylindole)zirconium. Obtain 7.9 g of product having microspheroidal morphology and the following composition: Al = 9,6%, Cl = 0,70%, Zr = 0.44 per cent.

Example 7. Homopolymerization ethylene.

In a steel autoclave with a capacity of 4.25 l equipped with a stirrer, manometer, temperature indicator, system for conveying catalyst, lines for supplying monomers and heater, purified by washing with propane at 70oC, placed 2,3 zoom. The solid catalyst according to example 6 and the solution triisobutylaluminum (TIBAL) in 10 ml of hexane was placed in the addition funnel. After 5 min the suspension to a temperature of 20oC is introduced into the autoclave, heated to 45oC, slightly podavlivaya ethylene. Then the temperature for approximately 5 min adjusted to the values required for polymerization, and maintain constant feeding ethylene. The reaction is stopped by rapid removal of the vapor of monomers and the resulting polymer is dried at 60oC in a stream of nitrogen.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 8. Copolymerization of ethylene/1-butene.

Carried out similarly to the method shown in example 3, except that they use an autoclave with a capacity of 4.25 l, which put a 2.3 liter propane and 1-butene, ethylene and hydrogen in amounts listed in table. 1. The suspension of catalyst, which is prepared as described in example 7, is introduced into the autoclave, heated to 45oC, slightly podavlivaya ethylene.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

is the W.

In a reactor with a capacity of 6 liters equipped with a stirrer and temperature regulation system, placed 4300 ml of methylene chloride and 225 g of polystyrene resin obtained in example 1. Cool the mixture to 10oC and quickly add 580 g pre-crushed trichloride aluminum. Within 1 h, maintaining the temperature at 10oC, is added dropwise 230 ml of acetyl chloride. Then stir the mixture at 25oC for 24 h the resulting mixture was carefully poured to a mixture of 2160 ml of distilled water, 2160 g of ice and 2160 ml of 37% hydrochloric acid. Upon completion of addition, the mixture is stirred for 15 min, then the solid residue is filtered off and washed several times with distilled water and then with acetone and finally with methanol. After drying at 60oC obtain 260 g of the product. The IR spectrum of the observed broad band with center at 1680 cm-1that corresponds to a carbonyl group.

(B) Recovery.

In a glass flask with a capacity of 3 l equipped with a mechanical stirrer and a thermal control system, placed 1060 ml of methanol and 260 g of acetylated resin obtained under paragraph (A). Maintaining the temperature of the mixture not exceeding 35oC add for 2 h in a solution containing 136 g is Uchenie 48 h, and then gently add 200 ml of acetone to destroy excess sodium borohydride. Then the resin is filtered off and successively washed with distilled water, acetone, methanol and again with acetone. Dried in vacuum at 60oC for 24 h and get 234 g of the product. The IR spectrum of the observed broad band with center at 3440 cm-1, while the band of the carbonyl group at 1680 cm-1disappears. The content of hydroxyl groups defined getobjectname titration using triethylaluminum, is 1.9 mEq per 1 g of resin. Particles of spherical shape have an average size of 150 μm with the following specific surface and porosity values: 327 m2/g and 0.7 ml/g with an average pore diameter of 43 (BET) and 144 m2/g and 1.53 ml/g with a size of pores 212 (Hg).

Example 10. (A) obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 350 ml, equipped with a thermometer, reflux condenser, blade stirrer and temperature regulation system is placed 100 ml of anhydrous toluene and 5.45 g of the carrier obtained in example 9(B). The suspension is cooled to -5oC and with stirring for 40 min 30 ml 1,04 M solution methylalumoxane (156 mg Al per 1 g of carrier). Mix in the 1 h and finally, heated to 80oC for 4 h Formed a whitish suspension is again cooled to -10oC for 40 min add it to the solution 246,1 mg EBY ZrCl2(9,2 mg Zr 1 g of carrier). The resulting orange solution then heated to 0oC and stirred at this temperature for 30 min, and then 2 h at 30oC. After desantirovaniya sludge liquid is filtered and the residue washed twice in 100 ml of toluene and once with 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. Allocate 9.0 g of spherical particles having the following composition: Zr = 0,55%, Cl = 1,38%, Al = 9,5%.

(B) Terpolymerization.

Carried out similarly to the method shown in example 2 (B), using of 1.33 g of the catalyst on the carrier obtained under paragraph (A) of this polymer, and the supply of ethylene is carried out for 5 hours Gain of 6.1 g of the prepolymer.

Example 11. Copolymerization of ethylene/1-butene.

Steel autoclave with a capacity of 2.5 liters, equipped with a blade magnetic stirrer, manometer, temperature indicator, system for conveying catalyst, lines for supplying monomers and thermostatic jacket, purified by washing with propane at 70oC. was charged To the reactor 5 mmol t is d in quantities listed in table. 1, and then the reactor is heated to 45oC. Suspension of the catalyst prepared in the tube Slinka with bottom discharge. Put it at 25oC solution of 5 mmol of triisobutylaluminum in 5 ml of hexane, and then add 108 mg of the catalyst on the carrier according to example 10(A). The reactants in contact for 5 min, after which the suspension is introduced into the autoclave, slightly podavlivaya ethylene. The temperature is brought to 50oC and constant support during the whole process, feeding a mixture of ethylene/1-butene in a molar ratio equal to 18. The reaction is stopped by the introduction of 0.6 l of carbon monoxide after rapid cooling to 30oC. the Reactor is slowly released from the gaseous products and the polymer is dried at 60oC in vacuum.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 12. Homopolymerization ethylene.

Steel autoclave with a capacity of 1.35 l, equipped with a blade magnetic stirrer, manometer, temperature indicator, system for conveying catalyst, a line for feeding monomer and thermostatic jacket, purified by washing with propane at 70oC. reachesthe, specified in the table. 1, and then the reactor is heated to 75oC. Suspension of the catalyst prepared in the tube Slinka with bottom discharge. Put it at 25oC solution of 5 mmol of triisobutylaluminum in 5 ml of hexane, and then add 390 mg of the catalyst on the carrier according to example 10(A). The reactants in contact for 5 min, after which the suspension is introduced into the autoclave, slightly other hand ethylene. The temperature is brought to 50oC and constant support during the whole process of feeding ethylene. The reaction is stopped by the introduction of 0.6 l of carbon monoxide after rapid cooling to 30oC. Suspension of the polymer is filtered off and the polymer is dried at 60oC in vacuum.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 13. Homopolymerization propylene.

Steel autoclave with a capacity of 4.25 l, equipped with a blade magnetic stirrer, manometer, temperature indicator, system for conveying catalyst, a line for feeding monomer and thermostatic jacket, purified by washing with propane at 70oC. When 40oC in a weak current of propylene placed in the reactor 10 mmol three is mperature increase to 50oC. maintain a constant Pressure when the supply of propylene. After 2 h the reactor Tegaserod and the selected polymer is dried at 60oC in vacuum. Get 18 grams of polypropylene in the form of granules having the following characteristics: bulk density with seal - 0.40 g/ml, the characteristic viscosity of 0.40 DL/g; differential scanning calorimetry: melting peak (second scan) - 134oC, heat of fusion (H) - 79 j/g, the content of insoluble in toluene components - 91,2%; gel permeation chromatography: Mw - 34900 g/mol, Mw/Mn of 2.2.

Example 14. Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method described in example 11, but instead of the catalyst on the carrier used 570 mg subjected terpolymerization catalyst according to example 10(B).

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 15. Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 350 ml, equipped with a blade magnetic stirrer, thermometer, reflux condenser and temperature regulation system, put 100 ml of toluene and 5.47 g of the carrier received by the sample is aged at room temperature for 30 min, containing 1.85 g methylaluminoxane (157 mg Al per 1 g of the carrier) and 243, 4 mg EBY ZrCl2(9.7 mg Zr 1 g of carrier) in 40 ml of toluene. The resulting orange suspension is then heated to 0oC for 1 h and stirred for 30 min, and then heated at 35oC within 2 hours After desantirovaniya sludge liquid is filtered and the residue washed twice in 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. Allocate 10.8 g of spheroidal particles, having the following composition: Zr=0,48%, Al=7.7%, solvent = 13.7 per cent.

Example 16. Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method described in example 11, but using 121 mg of the catalyst on the carrier according to example 11.

Conditions for the polymerization reaction are presented in table.1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 17. Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 350 ml, equipped with a blade magnetic stirrer, thermometer, reflux condenser and temperature regulation system, put 100 ml of toluene and 5.6 g of the carriers obtained in example 9(B). The suspension is cooled to -10oC and for 30 min dobavliaut 30oC and maintained at the specified temperature for 1 h Formed a whitish suspension is again cooled to 0oC for 40 min add pre-soaked solution containing 261,4 kg EBI ZrCl2(9,2 mg Zr 1 g of carrier) and 0.88 g methylalumoxane in 30 ml of toluene. The resulting orange solution then heated to 0oC and stirred at this temperature for 1 h Slowly (over 2 h) heat the suspension to 30oC and kept at this temperature for 1 h After desantirovaniya sludge liquid is filtered and the residue washed twice in 100 ml of toluene and once with 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. Allocate 5,6 spheroidal particles having the following composition: Zr = 0,64%, Cl = 1,25%, Al = 9,0%.

Example 18. Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method described in example 11, but using 165 mg of the catalyst on the carrier according to example 17.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 19. Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 35 who, put 100 ml of toluene and 10,15 g of the carrier obtained in example 9(B). The suspension is cooled to -10oC and under stirring for 40 min add 50 ml of 1.16 M solution methylalumoxane (154 mg Al per 1 g of carrier). The resulting mixture was stirred at -10oC for 1 h, then warmed to 0oC and maintained at the specified temperature for 1 h, then heated under 30oC for 1 h and finally heated at 80oC for 4 h to Give a whitish suspension to settle, the liquid decanted, and the solid support washed twice in 100 ml of toluene and once with 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. After drying allocate 13,8 spheroidal particles having the following composition: Al=8,95%, solvent = 7,6%.

In the same reactor was dispersed in 100 ml of anhydrous toluene and 5.6 g of resin-treated methylalumoxane and cooled to 0oC. for 1 h, add a solution containing 50 ml of toluene and 228 mg EBY ZrCl2(7.8 mg Zr 1 g of carrier). The resulting purple-red solution was stirred at 0oC for 1 h, and then heated to 30oC and stirred at this temperature for 2 hours After desantirovaniya sludge liquid is filtered and the residue is washed 2 times n the strong particles, having the composition: Zr = 0,44%, Cl = 1,09%, Al = 8,1%.

Example 20. Copolymerization of ethylene/1-hexene.

Steel autoclave with a capacity of 2.5 liters, equipped with a blade magnetic stirrer, manometer, temperature indicator, system for conveying catalyst, lines for supplying monomers and thermostatic jacket, purified by washing with propane at 70oC. was charged To the reactor at room temperature 5 mmol of triisobutylaluminum in 5 ml of hexane, 1260 ml of propane, 277 ml of 1-hexene and ethylene and hydrogen in amounts listed in table. 1, and then the reactor is heated to 55oC. Suspension of the catalyst prepared in the tube Slinka with bottom discharge. Put it at 25oC solution of 5 mmol of triisobutylaluminum in 5 ml of hexane, and then add 150 mg of the catalyst on the carrier obtained in example 19. The reactants in contact for 5 min, after which the suspension is introduced into the autoclave, slightly podavlivaya ethylene. The temperature is brought to 60oC and constant support during the entire polymerization process. The total pressure is maintained at the same level, feeding ethylene. The reaction is stopped by the introduction of 0.6 l of carbon monoxide after rapid cooling to 30oC. Allow the reactor to slowly break free from gas and polymerization are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 21. Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 750 ml, equipped with a paddle stirrer, thermometer, reflux condenser and temperature regulation system, placed 300 ml of toluene and 30.2 g of the carrier obtained in example 9 (B). The suspension is cooled to -10oC with stirring for 70 min add 200 ml of a 0.9 M solution methylalumoxane (160 mg Al per 1 g of carrier). The resulting mixture was stirred at -10oC for 1 h, then warmed to 0oC and maintained at the specified temperature for 1 h, then heated under 30oC for 1 h and finally heated at 80oC for 4 h to Give a whitish suspension to settle, the liquid decanted, and the solid support washed twice in 100 ml of toluene and once with 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. After drying allocate 66 g of spheroidal particles, having the following composition: Al=7,5%, solvent = 27%.

In the same reactor was dispersed in 300 ml of anhydrous toluene 10.6 g of resin-treated methylalumoxane and cooled to 0oC. for 1 h, add a solution containing 50 ml of toluene and 176,8 mg e the 30oC and stirred at this temperature for 2 hours After desantirovaniya sludge liquid is filtered and the residue washed with 2 times 100 ml of toluene and once with 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. Obtain 8.7 g of spheroidal particles having the composition: Zr = 0,40%, Cl - 0,92%, Al = 7,8%.

Example 22. Copolymerization of ethylene/propylene.

Steel autoclave with a capacity of 4.25 l equipped with a stirrer, manometer, temperature indicator, system for conveying catalyst, lines for supplying monomers and thermostatic jacket, purified by washing with propylene at 70oC and load it at room temperature for 2 liters of propylene and ethylene in amounts listed in table. 3. The suspension of catalyst prepared as described in example 4, except that use 220 mg of the catalyst on the carrier obtained in example 21, which is introduced into the autoclave from a steel vial, slightly podavlivaya ethylene. Then the temperature for approximately 5 min adjusted to the values required for polymerization and constant support during the whole time of the polymerization. Pressure support constant feeding ethylene. The reaction is stopped by rapid removal of vapors MES is urbanized and data concerning the characteristics of the obtained polymer are shown in table. 3.

Example 23. Copolymerization of ethylene/propylene.

The process is carried out similarly to the method described in example 22, but using 20 mg of the catalyst on the carrier according to example 21.

Conditions for the polymerization reaction and the data concerning the characteristics of the obtained polymer are shown in table.3.

Example 24. Receipt containing functional group of the carrier on the basis of polystyrene.

(A) Chlorotoluene.

In a three-neck flask with a capacity of 500 ml, equipped with a mechanical stirrer and water cooling, placed 30 g of crosslinked polystyrene, having the following characteristics: an average particle size - 248 μm; specific surface area: BET - 891 m2/g; Hg - 112 m2/g; porosity: BET - of 2.21 ml/g; Hg - 1,32 ml/g, 17,25 g trioxane, 8.6 g of zinc chloride, 250 ml of 37% hydrochloric acid and 50 ml of dioxane. Pass a strong current of gaseous hydrogen chloride, the mixture is heated to 80oC for 4 h, and then 3 h at 100oC. the Suspension is cooled to room temperature and washed several times with water and an aqueous solution of sodium carbonate. Part of the obtained solid is dried in vacuum at 60oC under a pressure of 7.5 - 8 bar. After 5 h, the polymer is filtered off at room temperature and washed repeatedly with water, then with a mixture of water:acetone (1:1), then with acetone and finally with methanol. After drying in vacuum at a temperature of 60oC obtain 32 g of the polymer. For him the following features: chlorine content of 1.6 wt.%, the content of functional groups to 1.22 mEq/g, the average particle size is 240 μm; specific surface area: BET - 621 m2/g, Hg - 118 m2/g; porosity: BET is 1.34 ml/g, Hg - 1,18 ml/g; IR spectroscopy is a broad band with center at 2400 cm-1(OH).

Example 25. Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 350 ml, equipped with a blade magnetic stirrer, thermometer, reflux condenser and temperature regulation system, put 100 ml of toluene and 5.5 g of the carrier obtained in example 24(C). The suspension is cooled to -10oC for 60 min add 50 ml of 0.61 M solution methylalumoxane (151 mg per 1 g of carrier). The resulting mixture was stirred at -10oC for 1 h, and then heated to 30ooC for 1 h, add to it a solution containing 230 mg EBY ZrCl2(9.1 mg Zr 1 g of carrier) in 50 ml of toluene. The resulting orange solution is left for 1 h to warm to 0oC, then heated to 30oC and kept at this temperature for 1 h After desantirovaniya with sludge liquid is filtered, and the residue washed twice in 100 ml of toluene and once with 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. Allocate 6.4g spheroidal particles having the following composition: Zr=0,54%, Cl=1,48%, Al=5,8%.

Example 26. Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method described in example 11, but using 538 mg of the catalyst on the carrier according to example 25.

Conditions for the polymerization reaction are presented in table. 1. The data relating to the characteristics of the obtained polymer are shown in table. 2.

Example 27. Receipt containing functional group of the carrier on the basis of polystyrene.

(A) Polystyrene, containing tert-butylene group.

In the glass the regulation, placed in a nitrogen atmosphere aqueous solution containing 400 ml of distilled water, and 36.2 ml ROAGIT SVM (company Rohm) in the form of a 5% solution in water, 2.25 g PROLIT C10 (firm Caffaro), 0.45 g of sodium chloride.

The resulting mixture was stirred at room temperature for 1 h with a speed of 400 rpm, then add organic solution containing 225 ml of n-octane, 75 ml of toluene, 120 ml of 55% divinylbenzene in ethylvinylbenzene, 45 ml of p-tert-butylstyrene (firm Hokko Chemical Industry), 3.13 g of a 75% aqueous solution of peroxide of Dibenzoyl in water.

Within 1 h to increase the temperature of the reaction mixture up to 80oC, incubated for 8 h, then cooled to 50oC and poured 700 ml of distilled water. The solid product is separated, washed several times with distilled water, methanol at 50oC, and then dried at 100oC and a residual pressure of 1 mm RT. Art. Obtain 108 g of the product having microspheroidal morphology. The resulting product has the following characteristics: specific surface area: BET - 441 m2/g, Hg - 86 m2/g; porosity: BET - of 0.85 ml/g, Hg - 0,66 ml/g; average pore - average particle size of 170 microns; the IR spectrum of the peak at 1240 cm-1(aryl-o-tert-butyl).

(B) Hydrolysis.

In a glass reacti, put 200 ml of hydrochloric acid (37% solution) and 36.5 g of the carrier prepared according to paragraph (A) of this example. The mixture is heated to 90oC and stirred at the same temperature for 8 hours, the Solid is separated, poured thereto 200 ml of fresh hydrochloric acid and stirred at 90oC for 4 h After filtering the selected solid is washed with water until until the pH of wash water reaches 7, then with acetone and dried in vacuum at 60oC. Gain of 34.7 g of spherical particles with a content of functional groups of 1.5 mEq/g In the IR spectrum is observed sharp peak at 3450 cm-1and the peak at 1240 cm-1disappears.

Example 28. Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 350 ml, equipped with a paddle stirrer, thermometer, reflux condenser and temperature regulation system, put 100 ml of toluene and 5.3 g of the carrier obtained in example 27(B). The suspension is cooled to 0oC and add 3 ml of toluene solution containing 5 g of triethylaluminum. After adding the reagent solution is heated to 25oC and stirred for 1 h, the Solid is filtered off, washed with toluene and re-dispersed in 100 ml of toluene. Received the l Al per 1 g of carrier). Heat the resulting mixture to 0oC and stirred at this temperature for 1 h, then 1 h at 30oC and then heated to 80oC and stirred at the same temperature for 4 hours Cooled to -10oC for 1 h, add 50 ml of toluene and 218 mg EBY ZrCl2(9.0 mg Zr 1 g of carrier). The resulting orange solution is left for 1 h to warm to 0oC, then heated to 30oC and kept at this temperature for 2 hours After desantirovaniya with sludge liquid is filtered and the residue washed twice in 100 ml of toluene and once with 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. Allocate 6.0 g of spheroidal particles, having the following composition: Zr = 0,42%, Cl = 1,1%, Al = 11.9 per cent.

Example 29. Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method described in example 11, but using 185 mg of the catalyst on the carrier according to example 28.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 30. Receipt containing functional group of the carrier on the basis of polystyrene.

In jacketed reactors eat amemait in nitrogen atmosphere with 100 ml of cyclohexane, 13.8 g of polystyrene resin obtained in example 1, to 17.8 ml of N, N, N', N'-tetramethylethylenediamine (TMEDA). Maintaining the temperature of the suspension 20-22oC add to her for 1.5 h, 100 ml of a 1.6 M solution of n-utillity. The color of the suspension changed from yellow to orange and finally red. The mixture is heated to 65oC and stirred at this temperature for 4.5 hours, the Solid is filtered in an inert atmosphere and washed twice in 100 ml of cyclohexane, and then add 150 ml of tetrahydrofuran saturated with carbon dioxide. Then directly under stirring to a suspension add approximately 300 g of solid carbon dioxide. The color of the suspension changed to whitish, Leave the suspension to react overnight, filtered and the obtained solid is washed several times with a solution of hydrogen chloride in tetrahydrofuran, a solution of hydrogen chloride in methanol, methanol and finally dried in vacuum at 40oC. Obtain 14 g of the resin with a spherical particle that has the following characteristics: the content of functional groups - 1.2 mEq/g, average pore - average particle size of 150 μm; specific surface area: BET - 303 m2/g, Hg - 109 m2/g; porosity: BET - of 1.12 ml/g, Hg - 1.69 Aligator on the media.

In jacketed reactors with a capacity of 350 ml, equipped with a paddle stirrer, thermometer, reflux condenser and temperature regulation system, put 100 ml of toluene and 5.7 g of the carrier obtained in example 30. The suspension is cooled to 0oC and add 10 ml of toluene solution containing 1.5 g of triethylaluminum. After adding the reagent solution is heated to 80oC and stirred for 1 h, the Solid is filtered off, washed with toluene and re-dispersed in 100 ml of toluene. The resulting suspension is cooled to 0oC and add to it for 40 minutes, 50 ml of 0.64 M solution methylalumoxane (153 mg Al per 1 g of carrier). Heat the resulting mixture to 0oC and stirred at this temperature for 1 h, then 1 h at 30oC and then heated to 80oC and stirred at this temperature for 1 h, After cooling to room temperature the suspension is filtered and again add 100 ml of anhydrous toluene. Cool the suspension to 0oC and add 40 ml of toluene and 212 mg EBY ZrCl2(8,1 mg Zr 1 g of carrier). The resulting orange solution is heated to 30oC and kept at this temperature for 2 hours After desantirovaniya with sediment fluid ochiltree at a temperature of 25oC. Allocate 5.9 g of spheroidal particles, having the following composition: Zr = 0,2% Cl = 0,46%, Al = 7,2%.

Example 32. Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method shown in example 3, however, use 370 mg of the catalyst on the carrier according to example 31.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 33. Receipt containing functional group of the carrier on the basis of polystyrene.

(A) Polystyrene, containing a methyl group.

In a glass reactor with a capacity of 2 l, equipped with a thermometer, reflux condenser, blade stirrer and temperature regulation system, placed in a nitrogen atmosphere aqueous solution containing 400 ml of distilled water, 30 ml ROAGIT SVM (company Rohm) in the form of a 5% solution in water, 2.25 g PROLIT C10 (firm Caffaro), 0.45 g of chlorine sodium.

The resulting mixture was stirred at room temperature for 1 h with a speed of 400 rpm, then add organic solution containing 225 ml of n-octane, 75 ml of toluene, 120 ml of 55% divinylbenzene in ethylvinylbenzene, to 31.5 ml of m - and p-methylstyrene, 3.13 g of a 75% aqueous solution of peroxide of Dibenzoyl in votem cooled to 50oC and poured 700 ml of distilled water. The solid product is separated, washed several times with distilled water, 5% hydrochloric acid, distilled water and methanol at 50oC, and then dried at 100oC and a residual pressure of 1 mm RT. Art. Obtain 117 g of the product having microspheroidal morphology. The resulting product has the following characteristics: the average radius of the pores is , the average particle size of 150 μm; specific surface area: BET - 495 m2/g, Hg - 137 m2/g; porosity: BET - 1,72 ml/g, Hg - 1,87 ml/year

(B) Acetylation.

In a glass reactor with a capacity of 1500 ml equipped with a thermometer, reflux condenser, blade stirrer and temperature regulation system, placed 1000 ml of acetic acid and 20 g of the carrier obtained under paragraph (A) of this example. Slowly add 56 g Mn(SLA)33H2O. Maintaining the temperature not exceeding 40oC, is added to the suspension dropwise and with stirring, 100 ml of sulfuric acid (96%). The mixture is heated to 45oC and stirred at the same temperature for 4 hours After filtration of the obtained solid is washed with sodium bicarbonate solution, water, methyl alcohol, and finally with acetone and dried in vacuum at 80and 1220 cm-1(-OAc).

(C) Hydrolysis.

In a glass reactor with a capacity of 1 l equipped with a thermometer, reflux condenser, blade stirrer and temperature regulation system, placed 500 ml of toluene, 200 ml of 40% KOH solution, the product prepared according to paragraph (B) of this example and 10 ml of 40% aqueous solution Bu4NOH. The mixture is heated to 85oC and stirred at the same temperature for 21 hours, the Solid is separated, washed with 300 ml of a mixture of hydrochloric acid/water, distilled water, methanol, acetone and dried in vacuum at 80oC. Obtain 19 g of spherical particles.

The IR spectrum of the observed broad peak at 3400 cm-1and peaks at 1740 and 1220 cm-1completely disappear. Titration of triethylaluminium indicates the content of hydroxyl groups in the amount of 1.5 mEq/g

Example 34. Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 350 ml, equipped with a blade magnetic stirrer, thermometer, reflux condenser and temperature regulation system, put 100 ml of toluene and 3.9 g of the carrier obtained in example 33(C). The suspension is cooled to -10oC for 20 min add 50 ml of 0.51 M solution methylalumoxane (178 mg Al per 1 g of carrier). Recip isoC for 4 h, the Suspension is filtered, washed with 100 ml of toluene and again add in 100 ml of anhydrous toluene. Cool the suspension to 0oC for 1 h, add to it a solution containing 194 mg EBY ZrCl2in 50 ml of toluene. The resulting orange solution is left for 1 h to warm to 0oC, then heated to 30oC and kept at this temperature for 2 hours After desantirovaniya with sludge liquid is filtered and the residue washed twice in 100 ml of toluene and once with 100 ml of anhydrous hexane and finally dried in vacuum at 25oC. Allocate 6.5 g of spheroidal particles, having the following composition: Zr = 0,55%, Cl = 1,1%, Al = 10,2%.

Example 35. Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method described in example 11, but using 1085 mg of the catalyst on the carrier according to example 34.

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 36 (comparative). Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 350 ml, equipped with a paddle stirrer, thermometer, reflux condenser and system armor and stirring, 40 ml of 0.74 M toluene solution methylalumoxane. The resulting mixture was stirred at 0oC for 1 h, and then heated to 30oC and maintained at the specified temperature for 1 h and finally heated at 80oC for 4 h Cooled to 25oC and for 30 min add it solution containing 196.7 mg dichloride ethylene-bis(indenyl)zirconium in 50 ml of toluene. Increase the temperature to 30oC and stirred for 2 h the Resulting orange solution is left to settle. The liquid from the sediment removed by means of a siphon. The residue is washed several times with toluene and dried in vacuum. Allocate 6 g of the product with spheroidal morphology, having the following composition: Zr = 0,26%, Cl = 0,2%, Al = 6,2%.

Example 37 (comparative). Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method shown in example 8, but using 478 mg of the catalyst on the carrier according to example 36 (comparative).

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

Example 38 (comparative). Receipt containing functional group of the carrier on the basis of polystyrene.

In a reactor with a capacity of 750 ml, equipped with a stirrer, and the system is a neigh 4% divinylbenzene). Cool the mixture to 10oC and quickly added 41 g of pre-crushed trichloride aluminum. Within 20 min, keeping the temperature at 10oC, is added dropwise to 15.5 ml of acetyl chloride. Then stir the mixture at 25oC for 24 h the resulting mixture was carefully poured to a mixture of 150 ml of 37% hydrochloric acid and 200 g of crushed ice. Upon completion of addition, the mixture is stirred for 30 min, then the solid residue is filtered off and washed several times with distilled water, methanol and acetone. The product is dried in vacuum at 60oC.

In a reactor with a capacity of 750 ml, equipped with a mechanical stirrer and temperature regulation system, put the resulting product. Heated to 30oC and add a solution containing 9.2 grams sodium borohydride, 11.5 ml of 20% NaOH solution and 70 ml of distilled water. Stir the mixture at 35oC for 72 h, and then carefully add 100 ml of acetone for the destruction of sodium borohydride. Then the resin is filtered off and successively washed with distilled water, acetone, methanol and again with acetone. Dried in vacuum at 40oC for 4 h Obtain 19 g of the product with a spherical particle that has the following shall 0,14 m2/g; porosity: BET - not specified, Hg - 0.01 ml/g; average particle size is 110 μm; IR spectroscopy peak at 1701 cm-1(-C=O), a broad peak at 3400 cm-1(-OH).

Example 39 (comparative). Obtaining a catalyst on the carrier.

In jacketed reactors with a capacity of 350 ml, equipped with a blade magnetic stirrer, thermometer, reflux condenser, temperature regulation system, put 100 ml of toluene and 3.6 g of polystyrene carrier obtained in example 38 (comparative). The suspension is cooled to -10oC for 60 min add 50 ml of 0.68 M toluene solution methylalumoxane (166 mg Al per 1 g of carrier). The resulting mixture was stirred at -10oC for 1 h, then 1 h at 0oC, heated to 30oC and maintained at the specified temperature for 1 h and finally heated at 80oC for 3 hours, the Suspension is filtered, washed twice in 100 ml of toluene and again add in 100 ml of anhydrous toluene. Cool the suspension to 0oC for 1 h, add to it a solution containing 221 mg EBY ZrCl2in 50 ml of toluene. The resulting orange solution is left for 1 h to warm to 0oC, then heated to 30oC and kept at this temperature for 2 hours After dozvolennogo hexane and finally, dried in vacuum at 25oC. Distinguish 5.0 g of spheroidal particles, having the following composition: Zr = 0,09%, Cl = 0,08%, Al = 1,69%.

Example 40 (comparative). Copolymerization of ethylene/1-butene.

The process is carried out similarly to the method described in example 11, but using 1460 mg of the catalyst on the carrier according to example 39 (comparative).

Conditions for the polymerization reaction are presented in table. 1. Data regarding the characteristics of the obtained polymer are shown in table. 2.

1. The catalyst on the carrier for the polymerization of olefins, characterized in that it contains (A) a porous organic carrier having a functional group with active hydrogen atoms; (C) at least one ORGANOMETALLIC compound of aluminium containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom; and (C) at least one compound of a transition metal selected from the metals of groups IVb, Vb or VIb of the Periodic system of elements, which includes at least one ligand cyclopentadienyls type.

2. The catalyst on the carrier under item 1, characterized in that the organic medium has a porosity greater than 0.2 cm3/g and pay, what organic carrier has the form of spheroidal particles with morphology, the diameter of which is 5 to 1000 microns.

4. The catalyst on the carrier according to any one of paragraphs.1 to 3, characterized in that the functional group of the organic carrier selected from a hydroxyl group, primary amino group, secondary amino group, sulfopropyl, carboxyl group, aminopropyl, N-monosubstituted aminogroup, sulfhydryl group, aminogroup and gidrazidov.

5. The catalyst on the carrier according to any one of paragraphs.1 to 4, characterized in that the content of functional groups is more than 0.2 milliequivalents for every gram of carrier.

6. The catalyst on the carrier according to any one of paragraphs.1 to 5, characterized in that the organic carrier is a partially cross-linked polymer based on styrene.

7. The catalyst on the carrier according to any one of paragraphs.1 - 6, characterized in that the compound of the transition metal is selected from cyclopentadienyls compounds of the formula I

(C5R15-mR2m(C5R15-m)nMQp-n< / BR>
where M is titanium, zirconium, hafnium, or vanadium;

two groups of C5R15-mis pentadienyl ring is e differ from each other, are hydrogen atoms, alkyl, alkenylamine, aryl, alkalline or Uralkalij radicals containing from 1 to 20 carbon atoms, which may also include atoms of silicon atoms or germanium or group Si (CH3)3or two or four Deputy R1the same cyclopentadienyls rings can form one or two rings containing 4 to 6 carbon atoms;

R2is a bridging group which links the two cyclopentadienyls ring and which is chosen from the group of CR32C2R34, SiR33Si2R34, GeR32Ge2R34, R32SiCR32, NR1or PR1where the substituents R3the same or different from each other, have the same meanings as the substituents R1or two or four Deputy R3can form one or two rings containing 3 to 6 carbon atoms, the substituents Q are the same or different from each other, are halogen atoms, a hydrogen atom, a group OH, SH, R1, OR1, SR1, NR12or PR12, m can be 0 or 1, n can be 0 or 1, while it is equal to 1, islamicism compound of aluminum is alumoxane.

9. The catalyst on the carrier according to any one of paragraphs.1 to 8, characterized in that the molar ratio between the content of the ORGANOMETALLIC aluminum compounds and compounds of the transition metal is 10 to 500.

10. The method of preparation of the catalyst on the media for the polymerization of olefins, characterized in that communicate in an inert solvent (A) a porous organic carrier having a functional group with active hydrogen atoms, (C) at least one ORGANOMETALLIC aluminum compounds containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom, and then communicate the resulting product with (C) at least one compound of a transition metal selected from the metals of groups IVb, VIb or VIb of the Periodic system of elements, which includes at least one ligand cyclopentadienyls type, finally, allocate the catalyst on the carrier by removing the solvent.

11. The method of preparation of the catalyst on the media for the polymerization of olefins, characterized in that communicate in an inert solvent (C) at least one ORGANOMETALLIC compound of aluminum is at least one compound of the transition metal, selected from metals of groups IVb, Vb or VIb of the Periodic system of elements, which includes at least one ligand cyclopentadienyls type, then communicate the resulting product with (A) a porous organic carrier having a functional group with active hydrogen atoms, finally, allocate the catalyst on the carrier by removing the solvent.

12. The method of preparation of the catalyst on the media for the polymerization of olefins, characterized in that communicate in an inert solvent (A) a porous organic carrier having a functional group with active hydrogen atoms, and (C) at least one ORGANOMETALLIC aluminum compounds containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom, then the interaction in an inert solvent (C) at least one ORGANOMETALLIC aluminum compounds containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur, and (C) at least one compound of a transition metal selected from the metals of groups IVb, Vb or VIb of the Periodic system of elements, which includes at least one lyamide (a) and (b), with the product obtained by the reaction of (b) and (C) finally, allocate the catalyst on the carrier by removing the solvent.

13. The method according to any of paragraphs.10 to 12, characterized in that the organic carrier pre-contact with an alkyl compound of aluminum of the formula VI

R5qAlX3-q< / BR>
where R5selected from alkyl, alkenyl, aryl, alkalline or Uralkalij radicals containing 1 to 10 carbon atoms; X is chosen from a hydrogen atom or halogen atom; q is an integer from 1 to 3.

14. The method according to p. 13, characterized in that the alkyl compound of aluminum is triisobutylaluminum.

15. The catalyst on the carrier for the polymerization of olefins, characterized in that it is the product of the method by which the catalyst on the carrier contains (A) a porous organic carrier having a functional group with active hydrogen atoms, (C) at least one ORGANOMETALLIC compound of aluminium containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom, (C) at least one compound of a transition metal selected from the metals of groups IVb, Vb or VIb of the Periodic system of elements, Katowice at least one olefinic monomer.

16. The catalyst according to p. 15, wherein the amount of polymer is 0.5 to 10 weight parts with respect to the weight of the catalyst on the carrier.

17. The catalyst according to any one of paragraphs. 15 and 16, characterized in that it includes an alkyl compound of aluminum of the formula VI

R5qAlX3-q< / BR>
where the values of R5, X and q are indicated previously.

18. The way Homo - and copolymerization of olefins comprising the polymerization reaction of one or more olefinic monomers in the presence of a catalyst on a carrier, characterized in that the use of the catalyst according to any one of paragraphs.1 to 9.

19. The way Homo - and copolymerization of olefins comprising the polymerization reaction of one or more olefinic monomers in the presence of a catalyst on a carrier, characterized in that the used catalyst, previously subjected terpolymerization processing according to any one of paragraphs. 15 - 17.

20. The way Homo - and copolymerization of olefins according to any one of paragraphs.18 and 19, characterized in that the pre-catalyst is in contact with at least one alkyl compound of aluminium of the formula VI

R5qAlX3-q< / BR>
where the values of R5, X and q are specified RA is p from oxygen atom, nitrogen atom, sulfur atom.

21. The method according to p. 20, characterized in that the ORGANOMETALLIC compound of aluminum is alumoxane.

 

Same patents:

The invention relates to a method of gas-phase polymerization of olefins of the formula CH2= СНR, where R is hydrogen, alkyl or aryl with 1 to 8 carbon atoms
The invention relates to methods of producing stabilized polypropylene and can be used in the plastics industry

The invention relates to catalysts for (co)polymerization of olefins and method () polymerizatio olefins

The invention relates to a catalyst intended for use in polymerization by Ziegler and containing ORGANOMETALLIC compound and complex (transition metalloidal)

The invention relates to a catalyst for polymerization of olefins, comprising a transition metal selected from the metals of groups IIIA, including the family of lanthanides, IVA, VA, VIA, VIIA and VIII of the Periodic table of elements, and ligands L1and L2associated with it , where the combination of L1and L2is: (1) a combination of ligand L1that is a group containing at least one phosphorus-containing group, and a ligand L2that is a ligand havingconnection, or a ligand having-communication and selected from at least oneconnection and at least one electron-electron bond formed free electron pair; (2) a combination of ligand L1that is a 5-membered heterocyclic pentadentate ligand having one or more heteroatoms, and ligand L2that is a ligand havingconnection, or a ligand having-communication and selected from at least oneconnection and at least one electron-donor communication, education is the roath, L2is a ligand havingconnection, or a ligand havingconnection and at least one electron-donor relationship, formed a free electron pair; (3) a combination of ligand L1that is tripersonal-tridentate ligand, and the ligand L2that is ulkopoliittinen ligand, each L1contains an element of group VB or group VIB

The invention relates to a polyethylene having a characteristic viscosity at least 4 DL/g, and the method of its production

The invention relates to a method of gas-phase polymerization of olefins of the formula CH2= СНR, where R is hydrogen, alkyl or aryl with 1 to 8 carbon atoms

The invention relates to a method for producing polyolefins by polymerization or copolymerization of an olefin of the formula Ra- CH=CH - Rbwhere Raand Rbthe same or different and represent a hydrogen atom or a hydrocarbon residue with 1 to 14 carbon atoms, or Raand Rbrelated atoms may form a ring, at a temperature of from -60 to 200oC, a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gaseous state in the presence of a catalyst containing metallocene as the compound of the transition metal and socialization

The invention relates to techniques for polymerization of isobutylene, and the obtained product is used as a thickening additive for lubricating oils for the manufacture of sealants, adhesives and many other purposes

The invention relates to a method of polymerization of ethylene, which allows to obtain polyethylene having a density of about 0,93 and less

The invention relates to a component of the catalyst or catalyst, which is suitable for use in the reaction stereoregular polymerization or copolymerization of alpha-olefins and particularly relates to a magnesium-containing, titanium containing catalyst component on the substrate or catalyst suitable for receiving homopolymer or copolymer of alpha-olefin

The invention relates to the synthesis of catalysts that can be used in a variety of chemical-technological processes in the chemical, oil and gas industry and for wastewater treatment and. etc
Up!