Catalytic systems and their use in the polymerization process

 

The method of polymerization of olefin (olefin) in the presence of a catalytic system comprising garnisongasse catalytic connection with the element of group 15, where the method is carried out at a temperature in the range from 50°C to 200°C, and garnisongasse catalytic connection with the group element 15 corresponds to the formula:

Formula (I), in which

M denotes the hafnium;

X - the same anionic leaving group;

L denotes the atom of an element of group 15;

n denotes the oxidation state of M;

m is the formal charge Y, Z and L;

Y and Z denote the atom of an element of group 15;

R1and R2denote With2-C20hydrocarbon group;

R3denotes a hydrogen atom;

R4and R5denote aryl group, substituted aryl group.

Also stated method of polymerization of olefin (olefin) in the presence of a catalytic system comprising a bidentate or tridentate legirovannoi garnisongasse catalytic connection with the element of group 15, in which the hafnium atom is associated with at least one anionic leaving group and with cramento group 15 connected to the atom of an element of groups 15 through a bridging group, metallocene catalyst compound with a bulky ligand and activator. The catalytic system according to the present invention has a high activity, ensures acceptable for processing polyolefins preferably in the same reactor with the required combinations of processing AIDS, mechanical and optical properties. 4 N. and 14 C.p. f-crystals, 2 Il, 1 table.

The technical FIELD TO WHICH the INVENTION RELATES.

The present invention relates to a catalytic composition comprising garnisongasse catalytic compound of a transition metal element of group 15, to a mixed catalyst composition comprising garnisongasse catalytic compound of a transition metal element of group 15, and a metallocene catalyst compound with a bulky ligand, catalytic systems based on them and to their use in the polymerization of olefin (olefin).

BACKGROUND of INVENTION

Advances in the technique of polymerization and catalysis has led to the possibility of obtaining many having improved physical and chemical properties of the new polymers, which moralization helped greatly to expand the range of types of polymerization (solution, slurry, high pressure or gas phase) upon receipt of a specific polymer. Advances in polymerization technology has also allowed us to develop more effective, efficient and economically superior ways. Illustration of these achievements, in particular, is the development of technology with the use of metallocene catalyst systems of the type with the bulky ligand.

More modern developments led to the discovery of polydentate anionic heteroatomic ligands, which are discussed in the following articles: (1) Kempe and others "Aminopyridinato Ligands-New Directions and Limitations", 80thCanadian Society for Chemistry Meeting, Windsor, Ontario, Canada, 1-4 June 1997; (2) Kempe and others Jnorg. Chem. 1996, vol 35, 6742); (3) Jordan and others dedicated to catalysts based hydroxyquinoline (Bei, X.; Swenson, D. C.; Jordan, R. F. Organometallics 1997, 16, 3282); (4) Horton and others, "Cationic Alkylzirconium Complexes Based on a Tridentate Diamide Ligand: New Alkene Polimerization Catalysts", Organometallics 1996, 15, 2672-2674 dedicated tridentate zirconium complexes; (5) Baumann and others, "Synthesis of Titanium and Zirconium Complexes that Contain the Tridentate Diamide Ligand {[(tert-Bu-d6)N-O-C6H4)2O]2-[NON]2-} and the Living Polymerization of 1-Hexene by Activated [NON]ZrMe2", Journal of the American Chemical Society, volume 119, S. 3830-3831; (6) Cloke and other "Zirconium Complexes incorporating the New Tridentate Diamide Ligand {(Me3Si)N[CH]L}", J. Chem.Soc. Dalton Trans, cc. 25-30, 1995; (7) Clark and others, "Titanium (IV) complexes incorporating the aminodiamide ligand {(SiMe3)N[CH2CH2N(SiMe3)]2}2-(L); the X-ray crystal structure of[TiMe2(L)] and {TiCl[CH(SiMe3)2](L)}", Journal of Organometallics Chemistry, volume 50, cc. 333-340, 1995; (8) Scollard and other "Living Polimerization of alpha-olefins by Chelating Diamide Complexes of Titanium", J. Am.Chem.Soc., volume 118, No. 41, cc. 10008-10009, 1996, and (9) Guerin and others, "Conformationally Rigid Diamide Complexes: Synthesis and Structure of Titanium (IV) Alkyl Derivatives", Organometallics, vol 15, No. 24, S. 5085-5089, 1996.

In addition, in WO/98 37106 described polymerization system comprising a catalytic complex, representing a complex of a transition metal containing condensed heterocyclic cyclopentadienyls ligand with an element of group 13, 15, or 16. In EP-A1 0874005 described polymerization catalyst comprising phenoxide connection with iminobis Deputy.

Moreover, US No. 5576460 described getting arylamino ligands, and in US no 5889128 described method of making a living polymerization of olefins with the use of initiators, including metal atom and a ligand containing two atoms of the element of group 15 atom of an element of group 16, or three atoms of element of group 15. In EP-A1 893454 also described amide compounds of transition metals, preferably titanium. In addition, US No. 5318935 who described polypropylene. Polymerization catalysts containing bidentate and tridentate ligands, further discussed in US no 5506184.

Traditional metallocene catalytic systems with bulky ligands lead to the obtaining of polymers, processing of which, for example, in the film using the old extrusion equipment in some circumstances is associated with increased problems of a technological nature. One of the techniques to improve the properties of these polymers is mixed with other polymers in order to prepare a mixture having the target properties, which could have each component individually. Although mixtures of the two polymers have an inherent tendency to improved processing AIDS, their preparation a costly process and involves cumbersome stage of mixing.

Higher molecular weight leads to a target mechanical properties of the polymer and forming a stable sleeve in the manufacture of films. However, this property prevents extrusion processing due to the increase in the extruder back pressure, contributes to the occurrence of defects during the filling of the sleeve with the air due to the destruction of extince. Polydentate anionic heteroaromatics catalytic systems have an inherent tendency to cause the formation of very high molecular weight polymer. To eliminate such a disadvantage, in order to reduce the back pressure in the extruder and to suppress the destruction of the extrusion flow can be obtained as a minor component of the secondary polymer of lower molecular weight. According to this principle carry out a number of industrial processes using megaregional technologies for recyclable polyethylene high density (HDPE) with a bimodal molecular mass distribution (MMD). For a global standard to take the product HIZEXTM, HDPE firm Mitsui Chemicals. Product HIZEXTMget the need for costly process in two or more reactors. During megaregional process in each reactor receives one component of the finished product.

Other developers in the art attempt to simultaneously obtain in a single reactor of the two polymers using two different catalysts. In WO 99/03899 described application in the same reactor typical metallocene catalyst with heavy litecom the use of catalysts of two different types is a polymer, characteristics of which cannot be predicted by the properties of the polymers, which could be obtained with each catalyst at their separate application. This unpredictability is due to, for example, competition between the used catalysts or catalytic systems or other impact they are having.

Polyethylene is high density and with high molecular weight are of value in the manufacture of films to which the requirements of high stiffness, good impact strength and high performance. Such polymers are also appreciated in the manufacture of pipes, which have to meet the requirements of rigidity, impact strength and long-term durability, particularly resistance to cracking under the influence of the environment.

Thus, a need exists for an improved catalytic compounds and in combination catalysts able to provide acceptable for processing polyethylene polymers, preferably in the same reactor with the required combinations of processing AIDS, mechanical and optical properties.

A SUMMARY of IZOBRETENY the mixed catalyst system, and their use in polymerization processes.

One variant of execution of the invention it is a catalytic composition comprising garnisongasse catalytic connection with the element of group 15, a mixed catalyst composition comprising this compound and a metallocene catalyst compound with a bulky ligand, catalytic systems, including these catalytic compositions, and their use in the polymerization of olefin (olefin).

In another variant implementation of the invention it is a catalytic composition comprising a bidentate or tridentate legirovannoi garnisongasse catalytic compound of a transition metal element of group 15, a mixed catalyst composition comprising this compound, and a metallocene catalyst compound with the bulky ligand containing catalytic systems and their use in the polymerization of olefin (olefin).

According to another variant implementation of the invention it is the catalytic composition based catalytic compounds, including as the transition metal hafnium associated with at least one leaving group and also tie the element of group 15 or 16 through another group, a mixed catalyst composition comprising this compound and a metallocene catalyst compound with the bulky ligand containing catalytic systems and their use in the polymerization of olefin (olefin).

However, in another variant implementation of the invention, its object is a method of applying a polydentate catalytic compounds based on hafnium and metallocene catalyst compounds with bulky ligands on the same or different media; they themselves inflicted on the native catalytic systems and their use in the polymerization of olefin (olefin).

In another variant implementation of the invention, its object is a method of polymerization of olefin (olefin), in particular, when carrying out the process in the gas phase or slurry phase using any one of the catalyst systems or deposited on carriers catalytic systems discussed above, more specifically when conducting continuous gas-phase process of obtaining a multimodal polymer in a single reactor.

BRIEF DESCRIPTION of DRAWINGS

In Fig.1 shows a typical chromatogram resulting gel chromatography of polymers according to the invention of example 2.

In Fig.2 Eimer 4.

DETAILED description of the INVENTION

Introduction

It was found that the catalytic compounds on others base containing an element of group 15, exhibit much higher catalytic performance in comparison with their zirconium or titanium counterparts. Thanks to this discovery it is now possible to provide a highly efficient polymerization with acceptable industry levels of performance. Moreover, it was also found that these carriageway catalytic compounds containing elements of group 15, proposed according to the invention provide the ability to create an improved catalytic systems on the media, in particular, for use in the processes of polymerization in slurry phase or gas phase. In the art it is well known that the result of applying the catalytic compounds to the media, as a rule, is the reduction of the overall performance of the catalyst. This is in fact true for zirconium analogues carriageway compounds according to the invention with elements of group 15. Due to this undesirable effect such zirconium analogues are not well suited for application to the media. However, due to much b others the basis of these catalytic compounds may be deposited on carriers and retain technically acceptable performance. Polymers produced using these carriageway catalytic compounds containing elements of group 15, typically have a very high molecular weight.

In addition, carriageway catalytic compounds according to the invention with elements of group 15 can be used in mixed catalytic systems. In the preferred embodiment, these mixed systems also include metallocene catalysts with bulky ligands, which usually lead to the formation of polymers having low molecular weight. Thanks to this discovery it is now possible preparation of the mixed catalyst system using components, each of which is characterized by a technically acceptable level of performance, especially when they are used supported on a carrier in the process of suspension or gas-phase polymerization, in particular, in a continuous gas-phase process. Mixed catalysts according to the invention is particularly effective in obtaining a multimodal, mainly bimodal polymer, including high and low molecular weight components.

Garnisongasse catalytic connection with the element of group 15 and catalyt astavliaut a bidentate or tridentate legirovannye carriageway compounds of transition metals with elements of group 15, preferably the elements of group 15 are nitrogen and/or phosphorus and most preferably nitrogen.

Carriageway catalytic compounds according to the invention with elements of group 15 as the metal atom usually include a hafnium atom associated with at least one leaving group and also bound to at least two atoms of elements in group 15, at least one of which is through another group associated with the atom of an element of group 15 or 16.

In one preferred embodiment, at least one of the atoms of elements in group 15 is also connected with the atom of an element of group 15 or 16 through another group, which may be a hydrocarbon group, preferably a hydrocarbon group comprising from 1 to 20 carbon atoms, a group containing a heteroatom, preferably an atom of silicon, germanium, tin, lead, or phosphorus. In this embodiment, more preferably, when an atom of an element of group 15 or 16 is not associated with anything or with a hydrogen atom, a group containing an atom of an element of group 14, a halogen atom or heteroaromatics group. In addition, in this embodiment, preferably, when each of the two atoms of elements in group 15 is also connected with a cyclic group which may be (but is ostergade group.

In one embodiment of the invention, garnisongasse connection according to the invention with an element of group 15 corresponds to the formula:

in which M denotes an atom of hafnium; each X independently denotes a leaving group, preferably anionic leaving group, more preferably a hydrogen atom, hydrocarbonous group, a heteroatom or a halogen atom, and most preferably alkyl;

y denotes 0 or 1 (where y denotes 0, group Lmissing);

n denotes the oxidation state of M, preferably +2, +3 or +4, preferably +4;

m is the formal charge of the ligand YZL or YZL, preferably 0, -1, -2 or -3, preferably -2;

L denotes the atom of an element of group 15 or 16, preferably nitrogen;

Ldenotes the atom of an element of group 15 or 16 or a group containing an atom of an element of group 14, preferably carbon, silicon or germanium;

Y represents an atom of an element of group 15, preferably nitrogen or phosphorus and most preferably nitrogen;

Z represents an atom of an element of group 15, preferably nitrogen denotes a hydrocarbon With1-C20group, heteroaromatics group containing up to twenty carbon atoms, silicon atom, germanium, tin, lead, or phosphorus, preferably alkyl, aryl or aracelio2-C20group, preferably a linear, branched or cyclic alkyl, C2-C20group, most preferably a hydrocarbon With2-C6group;

R3absent or denotes a hydrocarbon group, hydrogen atom, halogen, heteroaromatics group, preferably linear, cyclic or branched alkyl group containing from 1 to 20 carbon atoms, more preferred embodiment, R3absent or denotes a hydrogen atom or alkyl group, and most preferably a hydrogen atom;

R4and R5each independently from each other represents alkyl group, aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, cyclic arylalkyl group, a substituted cyclic arylalkyl group or polycyclic system, preferably comprising up to 20 carbon atoms, preferably in the range from 3 to 10 carbon atoms, and more p is1-C20group, or heteroaromatics group, such as PR3where R denotes an alkyl group;

R1and R2can be interconnected and/or R4and R5can also be interconnected;

R6and R7each independently from each other, is absent or represents a hydrogen atom, alkyl group, halogen atom, a heteroatom or hydrocarbonous group, preferably linear, cyclic or branched alkyl group containing from 1 to 20 carbon atoms, and more preferred variant is absent; and

Rabsent or denotes a hydrogen atom, a group containing an atom of an element of group 14, a halogen atom or heteroaromatics group.

The concept of "formal charge of the ligand YZL or YZL' represent the charge of the ligand without the metal and the leaving group X.

The expression "R1and R2can be interconnected" means that R1and R2can be directly connected to each other or may be connected by other groups.

The expression "R4and R5can be interconnected" means that R4and R5can be directly linked to Nanami and branched alkyl radicals, alkenylamine radicals, alkenylamine radicals, cycloalkenyl radicals, aryl radicals, acyl radicals, aroline radicals, alkoxyalkyl, aryloxyalkyl, alkilirovannami, dialkylaminoalkyl, alkoxycarbonyl radicals, aryloxypropanolamine radicals, carbamaepine radicals, alkyl - or dialkylammonium radicals, allometrically, acylaminoalkyl, kolmerattaline, remotemachine, branched or cyclic alkionovymi radicals or their combinations. Under arylalkyl group understand the substituted aryl group.

In the preferred embodiment, each of R4and R5independently of one another denotes a group corresponding to the following formula:

in which each R8for R12independently of one another denotes hydrogen atom, alkyl With1-C40group, a halide group, a heteroatom, heteroaromatics group containing up to 40 carbon atoms, preferably a linear or branched alkyl, C1-C20group, preferably methyl, ethyl, sawn or boutelou group, any two of the groups R may obrotowy Occitania embodiment, each of R9, R10and R12independently from each other represents methyl, ethyl, sawn or boutelou group (including all isomers), in a more preferred embodiment, R9, R10and R12denote a methyl group, and R8and R11denote hydrogen atoms.

In a particularly preferred embodiment, R4and R5together represent a group corresponding to the following formula:

In this embodiment, M denotes a hafnium atom; each of L, Y and Z denotes a nitrogen atom; each of R1and R2means hydrocarbonous group, preferably-CH2-CH2-; R represents a hydrogen atom; and R6and R7no.

In a preferred embodiment, at least one X represents a substituted hydrocarbon group, preferably a substituted alkyl group containing more than 6 carbon atoms, most preferably aryl-substituted alkyl group. The most preferred aryl-substituted alkyl group is benzyl.

In a particularly preferred variant of metallsoderjasimi connection with the group element 15 corresponds to the formula:

Ph denotes phenyl. finisterrae catalytic compounds according to the invention with elements of group 15 get ways which in this area is known in the art, such as described in application EP-A1 0893454, US patent No. 5889128 and in the references given in US patent No. 5889128, all of which are included in the present description as a reference. In the application U.S. serial number (09/312878, filed may 17, 1999) described a method of polymerization in the gas or slurry phase using supported on a carrier bisamides catalyst, and this application is also included in the present description by reference. A preferred direct synthesis of these compounds involves reacting the neutral ligand, (see for example YZL or YZLformula I or II) with HfXnwhere n denotes the oxidation state of Hf, each X represents an anionic group, such as halide, in coordinational or weakly coordinating solvent, such as diethyl ether, toluene, xylene, benzene, methylene chloride and/or hexane or other solvent having a boiling point exceeding 60° C, at a temperature of from about 20 to about 150° C (preferably from 20 to 100° C), preferably within 24 h or longer, and then processing the mixture by the excess (such four or more equivalents) of an alkylating agent, such as mutilatin methods.

One of the options garnisongasse catalytic connection with the element of group 15 of the get method, which involves reacting the neutral ligand, (see for example YZL or YZLformula 1 or 2) with a compound corresponding to the formula fn(where n denotes the oxidation state of Hf, and each X represents an anionic leaving group) in coordinational or weakly coordinating solvent, at a temperature of about 20° C or above, preferably at a temperature of from about 20 to about 100° C, and then processing the mixture with an excess of alkylating agent, followed by separation of the complex of the metal. In a preferred embodiment, the solvent is characterized by a boiling point above 60° C, such as toluene, xylene, benzene, and/or hexane. In another embodiment, the solvent comprises diethyl ether and/or methylene chloride, any of which is preferred.

Metallocene catalyst compounds with bulky ligand

One of the options carriageway catalytic compounds according to the invention with elements of group 15 can be combined with a metallocene catalyst compound with the bulky ligand with obtaining a mixed catalyst system. EDINENIE, contains one or more bulky ligands associated with at least one metal atom. Typical metallocene compounds with bulky ligand generally described as containing one or more bulky ligands and one or more leaving groups associated with at least one metal atom. In one preferred embodiment, at least one bulky ligandassociated with the metal atom, most preferably5associated with the metal atom.

Bulky ligands are typically in the form of one or more disclosed, acyclic or condensed rings or ring systems, or combinations thereof. These bulky ligands, preferably ring or ring system, typically composed of atoms selected from groups 13 to 16 of the Periodic table of elements, preferably the atoms are selected from a range, including carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and a combination thereof. The most preferred rings and ring systems consist of carbon atoms and are, in particular, although their list is not limited to, cyclopentadienyls lei, such as pentadienoic, cyclooctatetraene and kidny ligands. Preferred metal atom selected from groups 3 to 15 and of the series of lanthanides and actinides of the Periodic table of elements. Preferred metal atom is a transition metal atom of group 4 to 12, more preferably groups 4, 5 and 6, and most preferably group 4.

According to one variant of metallocene catalyst compounds according to the invention with the bulky ligand correspond to the formula:

LALBMQn(I)

where M denotes a metal atom, which may relate to the metals of groups 3 through 12 of the Periodic table of elements or a series of lanthanides or actinides of the Periodic table of elements, and the preferred value of M is a transition metal atom of group 4, 5 or 6, more preferred value of M is a transition metal atom of group 4, and even more preferred value of M is an atom of zirconium, hafnium or titanium. Bulky ligands LAndand LInare open, acyclic, or a condensed ring or ring system, which are ancillary ligand system consisting of unsubstituted or substituted cyclopentane ligands cyclopentadienyls type. Non-limiting examples of bulky ligands include cyclopentadienyls ligands, cyclopentanophenanthrene ligands, indanernas ligands, benzydamine ligands, fluorenyl ligands, octahydrophenanthrene ligands, cyclooctatetraene ligands, cyclopentadecanone ligands, asenalnoye ligands, Solenoye ligands, pentalene ligands, vospolenie ligands, postinitialize (see WO 99/40125), pyrrolidine ligands, pyrazolidine ligands, carbazolyl ligands, brabanconne ligands, etc., including their hydrogenated versions, for example tetrahydroindole ligands.

One of the options LAndand LIncan identify ligands of any other structures capable of forming with Mcommunication, preferably3communication with M, and most preferably5-communication. However, in another embodiment, the atomic molecular weight (Mw) LAndor LInmore than 60 at.ed.weight, preferably greater than 65 at.ed.mass. In yet another embodiment, LAndand LInmay include one or more heteroatoms, in particular nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination ring or ring system, for example heterocyclization auxiliary ligand. Other bulky ligands LAndand LIninclude, though not limited, bulky residues amides, phosphides, alkoxides, aryloxides, imides, carballido, ballidu, porphyrins, phthalocyanines, korinov and other polyazamacrocycles. Each of the LAndand LIncan independently from each other to define a bulky ligand of the same or another type that is associated with M. In one embodiment, in formula (I) contains only any one of the LAndand LIn.

Each of the LAndand LInmay be independently from each other unsubstituted or substituted by a combination of substitute groups R. non-limiting examples of substituting groups R include one or more groups selected from a hydrogen atom and linear and branched alkyl radicals and alkenyl radicals, etkinlik radicals, cycloalkyl radicals or aryl radicals, acyl radicals, rolnych radicals, alkoxyalkyl, aryloxyalkyl, alkylthiomethyl, dialkylaminoalkyl, alkoxycarbonyl radicals, aryloxyalkyl radicals, carbamoyl radicals, alkyl - or dialkylammonium radicals, allometrically or combinations thereof. In a preferred embodiment, the replacement group R contains up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon atoms, which can also be substituted by halogen atoms, heteroatoms, or similar non-limiting examples of alkyl substituents R cover of methyl, stylish, through boutelou, pentelow, hexeline, cyclopentyloxy, tsiklogeksilnogo, benzyl, phenyl group, etc., including all their isomers, for example tertiary butyl, isopropyl, etc., Other gidrolabilna radicals include vermeil, foradil, defloratin, improper, bromhexin, chlorbenzyl and gidrokarbonatnye metalloorganic radicals including trimethylsilyl, trimethylgermyl, methyldiethylamine etc.; glocalization metalloorganic radicals including Tris(trifluoromethyl)silyl, methylbis(deformity)silyl, bromomethylphenyl and so on; and disubstituted boron radicals including, for example, Dimethylol; disubstituted pnictogens radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphinic; chalcogenide radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfinyl and ethylsulfinyl. For the non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, and the n, alafinova-unsaturated substituents including ligands with terminal vinyl, for example but-3-enyl, prop-2-enyl, Gex-5-enyl, etc. in Addition, at least two groups R, preferably two adjacent groups R, associated with the formation of a ring structure containing from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron and combinations thereof. Substituted group R, such as 1-butanol, with the metal atom M may also form a Sigma bond.

With the metal atom M can be linked with other ligands, such as at least one leaving group Q. Bearing in mind the purposes of the present description and attached claims, the term "leaving group" is any ligand that can be split at the metallocene catalyst compounds with a bulky ligand, resulting in a metallocene catalyst cation with the bulky ligand capable of polymerization of one or more olefins. In one embodiment, Q represents monoanionic movable ligand that binds M a σ-bond. Depending on the oxidation state of the metal atom by the value of n is 0, 1 or 2, resulting in the above formula (I) displays a neutral Machaut remains weak bases, such as amines, phosphines, ethers, carboxylates, dieny, gidrolabilna radicals, each containing from 1 to 20 carbon atoms, hydrides, halogen atoms, etc., and combinations thereof. In another embodiment, two or more ligands Q form part of the condensed ring or ring system. Other examples of ligands Q include those substituents at R, which is shown above, including cyclobutenyl, tsiklogeksilnogo, Gately, colliny, triptorelin, tetramethylenebis, pentamethylenebis, metaliteracy, methoxy, ethoxy-, propoxy-, phenoxy-, bis(N-methylaniline), dimethylamine, dimethylphosphine radicals, etc.,

One of the options metallocene catalyst compounds with bulky ligand according to the invention include those compounds of formula (I) in which LAndand LIninterconnected by at least one bridging group And, consequently, this formula takes the following form:

LAALBMQn(II)

These are linked by the bridge compounds corresponding to the formula (II), known as the associated bridge metallocene catalyst compounds with bulky ligand. LALB, M, Q and n have the meanings specified above. Non-limiting examples of binding is called bivalent residues such as, though not limited to, at least one of the carbon atoms, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin, or a combination thereof. Preferred bridging group And includes a carbon atom, silicon or germanium, the most preferred group And includes at least one silicon atom or at least one carbon atom. Bridging group a may also include the replacement of the group R, which is shown above, including the atoms of halogen and iron. Non-limiting examples of bridging group a may be represented by the formula R2C, R2Si, R2SiR2Si, R2Ge, RP, where Rindependently of one another denotes a radical, which represents the balance of hydride, hydrocarbon, substituted hydrocarbon, Halocarbon, substituted Halocarbon, gidrokarbonatnyj metalloorganicheskie balance, allocability metalloorganicheskie balance, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen atom, or two grams of the resultant of the options associated bridges metallocene catalyst compounds of formula (II) with the bulky ligand containing two or more bridging groups a (see EP-B1 664301).

One of the options metallocene catalyst compounds with bulky ligand are those compounds in which the substituents R bulky ligands LAand LBin formulas (I) and (II) is substituted by the same or different number of substituents at each of the bulky ligands. In another embodiment, the bulky ligands LAand LBin formulas (I) and (II) different.

Other metallocene catalyst compounds and catalyst systems with the bulky ligand, which can be used according to the invention include those that are presented in US patents№№5064802, 5145819, 5149819, 5243001, 5239022, 5276208, 5296434, 5321106, 5329031, 5304614, 5677401, 5723398, 5753578, 5854363, 5856547, 5858903, 5859158, 5900517, 5939503 and 5962718, in PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221 and European publications EP-0578838, EP-A 0638595, EP-0513380, EP-A1 0816372, EP-A2 0839834, EP-B1 0632819, EP-B1 0739361, EP-B1 0748821 and EP-B1 0757996, all of which are in full included in this description as a reference.

In one embodiment, metallocene catalyst compounds with a bulky ligand, which can be used according to the invention include metallocene compounds containing one bulky ligand with St is blication PCT WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO 99/20637, in US patents№№5057475, 5096867, 5055438, 5198401, 5227440 and 5264405 and European publications EP-A 0420436, all of which are in full included in this description as a reference.

Under this scenario metallocene catalyst compounds with bulky ligands correspond to the formula:

LCAJMQn(III)

where M denotes a metal atom of groups 3 to 16 or metal atom selected from actinides or lanthanides of the Periodic table of elements, and the preferred value of M is a transition metal atom of group 4 to 12, more preferred value of M is a transition metal atom of group 4, 5 or 6, and the most preferred value of M is a transition metal atom of group 4 in any oxidation state, especially titanium atom; L represents a substituted or unsubstituted bulky ligand bound to M; J is associated with M; And is associated with M and J; J denotes heteroaromatics ancillary ligand; And means bridging group; Q represents a monovalent anionic ligand; and n denotes an integer of 0, 1 or 2. In the above formula (III) LC, A and J form a condensed ring system. In one embodiment, in formula (III) LChas come to rmula (I). In the formula (III) J denotes heteroaromatics ligand, in which J denotes an element of group 15 with the coordination number of three or an element of group 16 of the Periodic table of elements with a coordination number of two. In a preferred embodiment, J contains an atom of nitrogen, phosphorus, oxygen or sulfur, with the most preferred nitrogen atom.

According to another variant of the catalytic metallocene compound type with the bulky ligand is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted PI-bonded ligand, and one or more heteroallyl residues, such as those presented in US patents No. 5527752 and 5747406 and in EP-B1 0735057, which are fully included in the present description as a reference.

One of the options metallocene catalyst compound with the bulky ligand corresponds to the formula:

LDMQ2(YZ)Xn(IV)

where M denotes a metal atom of group 3 to 16, preferably a transition metal atom of group 4 to 12, and most preferably a transition metal atom of group 4, 5 or 6; LDdenotes a bulky ligand that is bound to M; each Q Nezavisimosty anionic ligand, also associated with M; X denotes a univalent anionic group when n represents 2, or X denotes a divalent anionic group when n represents 1; n represents 1 or 2.

In the formula (IV), L and M have the meanings indicated above for formula (I); Q has the values specified above for formula (I), the preferred value of Q is chosen from the series comprising-O-, -NR-, -CR2- and-S-; Y denotes either C or S; Z is selected from a range, including-OR, -NR2, -CR3, -SR, -SiR3, -PR2, -H, substituted and unsubstituted aryl groups, provided that when Q represents-NR-, Z is selected from a range, including-OR, -NR2, -SR, -SiR3, -PR2and-H; R is chosen from the group comprising atoms of carbon, silicon, nitrogen, oxygen and/or phosphorus, and the preferred value of R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably alkyl, cycloalkyl or aryl group; n denotes an integer from 1 to 4, preferably 1 or 2; X denotes a univalent anionic group when n represents 2, or X denotes a divalent anionic group when n denotes 1; the preferred value of X is urethane, carboxylate or the other gets the definition of the metallocene compounds of the type with the bulky ligand represent a heterocyclic ligand complexes, bulky ligands which ring or ring system that contains one or more heteroatoms or a combination thereof. Non-limiting examples of heteroatoms include atoms of elements of groups 13 to 16, preferably the atoms of nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus and tin. Examples of such metallocene catalyst compounds with bulky ligand represented in the applications WO 96/33202, WO 96/34021, WO 97/17379, WO 98/22486 and WO 99/40095 (decarbamoyl metal complexes), in EP-A1 0874005 and US patents№№5637660, 5539124, 5554775, 5756611, 5233049, 5744417 and 5856258, which are all included in the present description as a reference.

In another embodiment, a metallocene catalyst compounds with bulky ligand are those complexes, which are known as catalysts with transition metal based on bidentate ligands containing pyridine or quinoline residues, such as those presented in the application, USA (serial number 09/103620, filed June 23, 1998), which is incorporated into this description by reference. In another one embodiment, the metallocene catalyst compounds with bulky ligand are those that are presented in PCT publications WO 99/01481 and WO 98/42664, which are not fully included in the present description corresponds to the formula:

[(Z)XAt(YJ)]qMQn(V)

where M denotes a metal atom selected from group 3 to 13 or from a number of lanthanides or actinides of the Periodic table of elements; Q is associated to M and each Q denotes a monovalent, divalent or trivalent anion; X and Y are connected to M; one or more X and Y denote heteroatoms, preferably both X and Y denote heteroatoms; Y is contained in a heterocyclic ring J, where J contains from 2 to 50 non-hydrogen atoms, preferably from 2 to 30 carbon atoms; Z is associated with X, where Z contains from 1 to 50 non-hydrogen atoms, preferably from 1 to 50 carbon atoms, and in more preferred embodiment, Z represents a cyclic group containing 3 to 50 atoms, preferably from 3 to 30 carbon atoms; t represents 0 or 1; when t denotes 1, And indicates the bridge group associated with the at least one of X, Y or J, preferably X and J; q represents 1 or 2; n denotes an integer from 1 to 4 depending on the oxidation state M. In one embodiment, in which X denotes an oxygen atom or sulfur, fragment Z is optional. In another embodiment, in which X denotes a nitrogen atom or phosphorus, fragment Z is contained. One option preference is m variant it is also possible inclusion among the above-described metallocene catalysts according to the invention with the bulky ligand of their structural or optical, or enantiomeric isomers (meso and racemic isomers, for example, in US patent No. 5852143 included in the present description by reference) and mixtures thereof.

The invention further provides for the possibility of combining carriageway catalytic compounds containing elements of group 15 and metallocene catalyst compounds of the present invention with the bulky ligand with a catalytic compound of the usual type.

Activator and activation methods

The above carriageway catalytic compounds containing elements of group 15 and metallocene catalyst compounds with a bulky ligand, typically activated in various ways to obtain catalytic compounds with a free coordination site, which provides the coordination, implementation and polymerization of olefin (olefin).

Considering the purpose of the description of this application and the accompanying claims, the term "activator" is defined as referring to any compound, component, or method, the use of which allows to activate bidentate or tridentate legirovannye carriageway catalytic compounds containing elements of group 15 and/or metallic is relevant examples of activators include Lewis acid, recoordination ionic activators, ionizing activators and any other connections, including grounds Lewis, aluminiumgie, socializaton conventional type and combinations thereof that can convert a neutral garnisongasse catalytic connection with the element of group 15 in connection with the catalytically active carriageways cation with an element of group 15 and/or a neutral metallocene catalyst compound with the bulky ligand in connection with the catalytically active metallocene cation with the bulky ligand. The scope of the present invention covers the use of alumoxane or modified alumoxane as activator and/or also use ionizing activators, neutral or ionic, such as tri(n-butyl)ammoniates(pentafluorophenyl)boron, tripartitions metallosoderzhashhie predecessor and tripartitions metallosoderzhashhie predecessor, connection polyhalomethanes heteroborane anions (see WO 98/43983) and their combinations that are sure to ionize the neutral catalyst compound. Although most of the discussion in this publication relates to metallocene catalyst is the price of catalytic compounds with bulky ligands applicable to carriageways catalytic compounds of the present invention with the elements of group 15.

One of the options there is also an activation method using ionizing ionic compounds not containing an active proton but capable of education as a catalyst cation and coordinating anion, as described in applications EP-A 0426637 and EP-A 0573403 and in US patent No. 5387568, which are all included in the present description as a reference.

There are many ways to get alumoxane and modified alumoxanes, non-limiting examples of which are presented in US patents№№4665208, 4952540, 5091352, 5206199, 5204419, 4874734,4924018, 4908463, 4968827, 5308815, 5329032, 5248801, 5235081, 5157137, 5103031, 5391793, 5391529, 5693838, 5731253, 5731451, 5744656, 5847177, 5854166, 5856256 and 5939346 in European publications EP-A 0561476, EP-B1 0279586, EP-A 0594218 and EP-B1 0586665 and in PCT publication WO 94/10180, which are fully included in the present description as a reference.

Alyuminiiorganicheskikh compounds as activators include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylamine, tri-n-octylamine etc.

Ionizing compounds can include an active proton, or some other cation associated, but not coordinated or only loosely coordinated with the remaining ion of the ionizing compound. Such SOE, in the US patents№№5153157, 5198401, 5066741, 5206197, 5241025, 5384299 and 5502124 and in the patent application US serial number 08/285380, filed August 3, 1994), which are fully included in the present description as a reference.

Other activators include those compounds which are represented in PCT publication WO 98/07515, such as Tris(2,2,2"-nonaboriginal)peraluminous, and this publication in full included in the present description by reference. The invention also provides the use of combinations of activators, such as combinations of alumoxanes with ionizing activators (see, in particular, the publication EP-B1 0573120, PCT WO 94/07928 and WO 95/14044 and patents US 5153157 and 5453410, which are fully included in the present description as references). In the application WO 98/09996 included in the present description by reference, presents the activation of the catalytic compounds with perchlorates, periodate and Iodate, including their hydrates. In applications WO 98/30602 and WO 98/30603, which are included in the present description as reference, describes the use of lithium(2,2-biphenyldicarboxylic)· THF as activator for catalytic compounds. In the application WO 99/18135 included in this described the imposition of sicilieweg salt in combination with coordinationin compatible anion. For the conversion of the neutral catalyst compound or precursor in connection with the catalyst cation capable of polymerization of olefins, provided the application activation methods using radiation (see application EP-B1 0615981 included in the present description by reference), electrochemical oxidation, etc., Other activators and activation methods of catalytic compounds represented, for example, in US patents No. 5849852, 5859653 and 5869723 and applications WO 98/32775 and WO 99/42467 [{diastatochromogenes[Tris(pentafluorophenyl)borane]benzimidazole}], which is included in the present description as a reference.

One of the options activator is a Lewis acid, more preferably the Lewis acid-based aluminum, and most preferably a neutral Lewis acid-based aluminum, includes at least one, preferably two halogenated aryl ligand and one or two additional monoanionic ligand, excluding halogenated aryl ligands. In this embodiment, are compounds of the Lewis acid include those of a Lewis acid as activators of catalysts for the polymerization of olefins, which are based on aluminum and soda the data aryl ligands Tris(perftoralkil)borane or Tris(perforater)borane. The presence of such a bulky ancillary ligands enough to allow Lewis acids to perform the functions of electron-anti-roll compatible recoordination anions. The stability of ionic complexes reach, when the anions are not acceptable ligand donor containing transition metal cations with elements of group 15 as strong cationic Lewis acids used in the polymerization processes with the implementation, i.e., inhibit the transition of the ligand, which would neutralize the cations, and cause a lack of activity for polymerization. A Lewis acid corresponding to this description of such preferred activator, can answer the following formula:

RnAl(rl)3-n(VI)

where R denotes monoanionic ligand, a ArHal is a halogenated aromatic With6or higher carbon number polycyclic aromatic hydrocarbon or aromatic cyclic set, in which two or more rings (or condensed ring systems) are directly connected with each other or among themselves, and n denotes a number from 1 to 2, and the preferred value of n is 1.

In one or more high-molecular radical, preferably fluorinated naphthyl. Non-limiting examples of acceptable R-ligands include substituted and unsubstituted gidrolabilna aliphatic or aromatic With1-C30group, and the term "substituted" means that at least one hydrogen atom at the carbon atom substituted hydrocarbon, a halogen atom, Halocarbon, hydrocarbon or halocarbonyl metalloorganic radical, dialkylamino, alkoxy, siloxy, aryloxy, alkylsulfides, arylsulfatase, alkylphosphines, arylphosphine or other anionic Deputy; fluoride; bulky alkoxides, where the concept of "bulky" refers to hydrocarbonyl groups With4and with a large carbon number, for example, up to about20such as tert-piperonyl, 2,6-dimethylphenoxy and 2,6-di(tert-butyl)phenoxide; -SR, -NR2and-PR2where each R independently from each other represents a substituted or unsubstituted hydrocarbon, as presented above; and metalloorganicheskie radical, substituted C1-C30hydrocarbon, such as trimethylsilyl.

Examples ArHal include phenyl, raftiline and antarctilyne radicals according to the US No. 5198401 and diphenylene radicals according to WO 97/29845 when they gorodilova. Ah, when at least one third of the hydrogen atoms at the carbon atoms of the aryl-substituted aromatic ligands substituted or substituted by halogen atoms, more preferred aromatic ligands perhalocarbon. The most preferred halogen is fluorine.

Alternatively the molar ratio between the metal of the activator component to the metal supported on a carrier garnisongasse catalytic connection with the group element 15 is in the range from 0.3:1 to 1000:1, preferably from 20:1 to 800:1, and most preferably from 50:1 to 500:1. When the activator is the ionizing activator such as activators based on anionic tetrakis(pentafluorophenyl)boron, the preferred molar ratio between the metal of the activator component and the metal component garnisongasse catalytic connection with the group element 15 is in the range from 0.3:1 to 3:1.

According to another variant implementation of the invention offers one or more carriageway catalytic compounds containing elements of group 15 and one or more metallocene catalyst compounds with bulky ligand in combination with one or more of the above, active catalysts with elements of group 15 and a mixed catalyst system, including carriageway catalyst with an element of group 15 and metallocene catalyst with a bulky ligand, can be combined with one or more substrate materials or carriers using one of the methods of application are well known in the art or as set forth below. For example, in the preferred embodiment, carriageway catalyst with an element of group 15 or a mixed catalyst system according to the invention is supported on a carrier form, for example deposited on a substrate or carrier, in contact with, vaporized with him, associated with him or embedded in it, adsorbed or absorbed in it. In addition, in the case of using the mixed system assumes the application of a metallocene catalyst system with the bulky ligand on separate media, non-media carriageway catalytic system with an element of group 15, in particular when used in the system from a variety of reactors, in which one of the catalytic system on the media used in the same reactor for the production of high-molecular component, and another catalytic system on the media used in the different reactor obtained for iminime to any substrate material, preferably to a porous substrate material, including inorganic and organic substrate materials. Non-limiting examples of inorganic materials of the substrate include inorganic oxides and inorganic chlorides. Other media include resinous materials of substrates, such as polystyrene, functionalized or crosslinked organic substrates, such as polystyrene, divinylbenzene, polyolefins and other polymeric compounds or any other organic or inorganic substrate material, etc., and mixtures thereof.

The preferred carriers are inorganic oxides that include the oxides of metals of groups 2, 3, 4, 5, 13 and 14. Preferred carriers include silica, alumina, kranidioti/aluminiumoxid and mixtures thereof. Other effective substrates include magnesium oxide, titanium dioxide, zirconium dioxide, magnesium chloride, montmorillonite (see EP-B1 0511665), phyllosilicate, zeolites, talc, clay, etc. May be used as combinations of these materials substrates, such as kranidioti/chrome, kranidioti/aluminiumoxid, kranidioti/titanpoker, etc., Additional wafers may include those porous acrylic polymer of the first carrier, most preferably an inorganic oxide, characterized by a specific surface area in the range of from about 10 to about 100 m2/g and a pore volume in the range of from about 0.1 to about 4.0 CC/g and an average particle size in the range of from about 5 to about 500 microns. In a more preferred embodiment, the specific surface area of the carrier is in the range from about 50 to about 500 m2/g, specific pore volume is from about 0.5 to about 3.5 CC/g and average particle size equal to from about 10 to about 200 microns. In the most preferred embodiment, the specific surface area of the carrier is in the range from about 100 to about 400 m2/g and the pore volume is from about 0.8 to about 5.0 to CC/g and average particle size equal to from about 5 to about 100 microns. The average pore size of the carrier according to the invention generally ranges from about 10 to about 1,000preferably from about 50 to about 500and most preferably from about 75 to about 450.

Examples of application to the carrier catalysts according to the invention presented is 625015, 5643847, 5665665, 5698487, 5714424, 5723400, 5723402, 5731261, 5759940, 5767032, 5770664, 5846895 and 5939348, in patent applications US serial number 271598, filed July 7, 1994, and 788736, filed January 23, 1997, and PCT publications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297 and in EP-B1 0685494, which are fully included in the present description as a reference.

In the art there are various other methods of applying the native catalytic polymerization of the compound or a mixed catalyst system according to the invention. For example, carriageway catalytic compounds containing elements of group 15 and/or a mixed catalyst system comprising a metallocene catalyst compounds with bulky ligands may include associated with the polymer ligand, as described in US patents No. 5473202 and 5770755, which are not fully included in the present description as references; carriageway catalytic compounds containing elements of group 15 and/or metallocene catalyst compounds with bulky ligands according to the invention can be dried by spraying, as described in US patent No. 5648310, which fully included in the present description by reference; the substrate used together with garnisongasse KATALITIChESKIE invention can be functionalitywith so, as described in European publication EP-A 0802203, which fully included in the present description by reference; or at least one Deputy or a leaving group chosen as described in US patent No. 5688880, which fully included in the present description by reference.

In a preferred embodiment, the invention features carriageway catalytic system with an element of group 15 and/or a mixed system comprising a metallocene catalyst compounds with bulky ligands, which includes the surface modifier used in the preparation of the catalytic system on the medium as set forth in PCT publication WO 96/11960, which fully included in the present description by reference. The catalytic system according to the invention can be prepared in the presence of olefins, such as hexene-1.

In a preferred embodiment, carriageway catalytic system with an element of group 15 and a mixed system comprising a metallocene catalyst compound with a bulky ligand, can be combined with a metal salt of carboxylic acid (ester), for example aluminum carboxylates such as aluminimun-, di - and tristearate, the 10 July 1998).

The preferred method of preparation carriageway catalytic system with an element of group 15 and/or metallocene catalytic system with the bulky ligand described below, it can be found in patent applications US serial number 265533 filed June 24, 1994, and 265532, filed June 24, 1994, and PCT applications WO 96/00245 and WO 96/00243, which were published on January 4, 1996, and which are fully included in the present description as a reference. This process is carried out either with garnisongasse catalytic compounds containing elements of group 15 together with the metallocene catalyst compounds with a bulky ligand, or separately from them. In this preferred embodiment, the catalytic compound or compounds are suspended in a liquid to obtain a solution and separately preparing a solution comprising an activator and a liquid. As a liquid, you can use any compatible solvent or other liquid capable of forming with a catalytic compound or compounds and/or the activator according to the invention, the solution or etc In the most preferred embodiment, as the liquid used cycloaliphatic or aromatic hydrocarbon, preferably truely thus, to the total amount of catalytic solution of the compound or compounds and the activator solution or the solution of the catalytic compound or compounds and the activator solution was less than four times the volume of pores of a porous support, more preferably less than three times the volume, and even more preferably less than double the volume, preferably the intervals range from 1.1 to 3.5 Krat, and most preferred is from 1.2 to 3 Krat.

Methods for the determination of the total pore volume of the porous media in the art are well known. The details of one of these methods are discussed in volume 1 of the works of Experimental Methods in Catalytic Research (Academic Press, 1968) (see specifically with. 67-96). This preferred method includes the use of a classical instrument BET to determine the absorption of nitrogen. Another method well known in the art, described in the work of Innes, Total Porosity and Particle Density of Fluid Catalysis by Liquid Titration, volume 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

Preferred application methods on the media carriageway compounds according to the invention with elements of group 15 described in the patent application US serial number 09/312878, filed may 17, 1999, which fully included in the present description by reference. Osenovo catalytic connection with the bulky ligand according to the invention is combined in molar ratios of from 1:1000 to 1000:1, preferably from 1:99 to 99:1, preferably from 10:90 to 90:10, more preferably from 20:80 to 80:20, more preferably from 30:70 to 70:30, more preferably from 40:60 to 60:40. In one embodiment, using a mixed system according to the invention, in particular, in the process of suspension polymerization, the total number garnisongasse connection with the element of group 15 and metallocene catalyst compounds with bulky ligand in mcmash per gram (g) in the finished catalyst on the carrier (includes material media, mixed catalyst and activator) is about 40 mcmole/g, preferably about 38 mcmole/year

In one embodiment, in particular in the process of gas-phase polymerization using a mixed system according to the invention, the total number garnisongasse connection with the element of group 15 and metallocene catalyst compounds with bulky ligand in mcmash per gram of finished catalyst on the carrier (includes material media, mixed catalyst and the activator is less than 30 mcmole/g, preferably less than 25 mcmole/g, more preferably less than 20 mcmole/year

In another embodiment the group R in the above formula (VI) (or ligand) may be the spoon. Including the Lewis base materials of the substrate or the substrate is usually interact with Lewis acids as activators with the formation of a Lewis acid bound to the substrate, activator on the substrate, where one group R at RnAl(ArHal)3-ncovalently linked to the substrate. For example, when the substrate material is silicon dioxide, it is a hydroxyl group Foundation Lewis, silicon dioxide are the place where this method of binding one of the coordination sites of aluminum. In this embodiment, the preferred substrate material is a metal or metalloid oxide, preferably showing the value of the PKandsurface hydroxyl groups, equal to or constituting less than observed for amorphous silicon dioxide, i.e., the value of the PKandconstituting less than or equal to about 11.

Not based on any particular theory, I believe that the covalently bound anionic activator, a Lewis acid, silanol group, such as silicon dioxide (which functions as the base Lewis), forms a first datiny complex, which formed as a result formally bipolar (zwitterion) structure of acid Bronsted, which seems to be group R a Lewis acid arseplay her, and at this point, the Lewis acid becomes covalently linked to an oxygen atom. Further substitution group R Lewis acid takes the form R-O-, where Rindicates an acceptable substrate material or substrate, such as silicon dioxide or a polymer substrate that includes a hydroxyl group. For use in this particular method of application to the substrate accept any substrate material that contains surface hydroxyl groups. Other materials of the substrate include glass beads.

In the version in which the substrate materials are metal oxide compositions, these compositions optionally may include oxides of other metals, such as A1, K, Mg, Na, Si, Ti and Zr, therefore, to remove water and free oxygen should (preferably) to handle thermal and/or chemical means. Such processing typically performed under vacuum in a hot oven, in a hot fluidized bed or dehydrating agents such as organosilanes, siloxanes, aluminiumallee connection, etc. the effectiveness of the treatment must be such as to ensure the destruction of the maximum possible is a strong functional groups. Thus, a valid calcination at temperatures up to 800° C or better up to a point above the decomposition temperature of the substrate material, within a few hours, and if necessary, to achieve a higher content caused anionic activator acceptable calcination at lower temperatures and for less time. When the metal oxide is silicon dioxide, acceptable target content typically ranges from less than 0.1 to 3.0 mmol activator/g SiO2that can be achieved, for example, by varying the temperature of calcination from 200 to 800° C and above (see Zhuralev, etc., Langmuir 1987, 3, 316, which describes the correlation between the temperature, the duration of calcination and the content of hydroxyl groups in the silica with varying specific surface area.

The need for accessible hydroxyl groups as sites of accession may be granted a preliminary treatment before adding the Lewis acid is less than the stoichiometric quantity of the chemical dehydrating agents. In the preferred embodiment, they are used in moderation and usually they are the Mat is, for example, (CH3)3Si1] or, in other words, can either hydrolyzed, allowing reduced to the minimum obstacle catalytic reaction of compounds of transition metals with an associated activator. If the calcination is carried out at temperatures below 400° C, you can use bifunctional agents [for example, (CH3)2Si12] for blocking the ends of hydrogen bonded pairs of silanol groups, which are contained in less harsh conditions of calcination (see, e.g., "Investigation of Quantitative SiOH Determination by the Silane Treatment of Disperse Silica", Gorski and others, Journ. of Colloid and Interface Science, volume 126, No. 2, December 1988, where it discusses the impact of Milanovich agent combinations for kremmidiotis polymer fillers, which are usually also effective for modification of silanol groups on the catalytic substrates according to the invention). Similarly, the use of Lewis acid in excess relative to the stoichiometric amount required for interaction with transition metal compounds, usually serves to neutralize excess silanol groups without significant negative effects on the preparation of the catalyst or subsequent polymerization.

In the preferred in the groups, but the functional groups can be any group of primary alkylamines followed, secondary alkylamines followed and other compounds, where these groups are structurally embedded in the polymer chain and are able to interact type of acid/base with a Lewis acid, resulting in ligand that fills one coordination site of aluminum, is protonated and replaced entered with the polymer functional group (for containing functional groups of polymers, see, for example, US patent No. 5288677, which is included in the present description by reference).

Other carriers include silica, alumina, kranidioti/aluminiumoxid, magnesium oxide, titanium dioxide, zirconium dioxide, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays, kranidioti/chrome, kranidioti/aluminiumoxid, kranidioti/titanpoker, porous acrylic polymers.

One variant of execution of the invention before the main polymerization process in the presence of garnisongasse of the catalyst element of group 15 and/or metallocene catalyst with the bulky ligand according to the invention will terpolymeric olefin (olefin), preferably2-C30olefin (-olefin can be periodic or continuous, it can be in gas, solution or slurry phase, including the creation of high blood pressure. Terpolymerization can be any olefin monomer or combination and/or in the presence of any of regulating the molecular weight of the agent, such as hydrogen. Examples of terpolymerization can be found in US patents№№4748221, 4789359, 4923833, 4921825, 5283278 and 5705578, in European publication EP-0279863 and PCT publication WO 97/44371, which are not fully included in the present description as a reference.

The polymerization process

The catalytic system, the catalytic system on the media or the composition according to the invention, described above, are acceptable for use in any process of terpolymerization and/or polymerization in a wide range of temperatures and pressures. The temperature may be in the range from -60 to about 280° C, preferably from 50 to about 200° C, and the generated pressure can be in the range from 1 to approximately 500 at or above.

Polymerization processes include processes in solution, gas phase, slurry phase, high pressure, and combinations thereof. Especially preferred is a polymerization in a gas phase or slurry phase one or nasalcease invention is suitable for carrying out the polymerization process in solution under high pressure, in suspension or in the gas phase of one or more olefin monomers containing from 2 to 30 carbon atoms each, preferably from 2 to 12 carbon atoms, and more preferably from 2 to 8 carbon atoms. The invention is particularly well suited for the polymerization of two or more of such olefinic monomers as ethylene, propylene, butene-1, penten-1, 4-methylpentene-1, hexene-1, octene-1 and the mission-1.

Other monomers which may be used in the method according to the invention include ethylene-unsaturated monomers, diolefin containing from 4 to 18 carbon atoms each, paired and unpaired diene, polyene, vinyl monomers and cyclic olefins. Non-limiting examples of monomers that are suitable for use according to the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzoate, styrene, alkyl substituted styrene, ethylidenenorbornene, Dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the method according to the invention receive a copolymer of ethylene, and in this case, during the gas-phase process will polimerizuet ethylene and comonomer representing at least one alpha-olefin containing orodnik atoms.

In another embodiment of the method according to the invention, the ethylene or propylene will polimerizuet with at least two other comonomers, one of which may (but not necessarily) be a diene, to obtain the ternary copolymer.

In one embodiment, the invention is applicable to the polymerization process, in particular for gas-phase or slurry process carried out in the polymerization of propylene, either individually or together with one or more other monomers, including ethylene and/or other olefins containing from 4 to 12 carbon atoms each.

In the process of gas-phase polymerization, as a rule, apply a continuous cycle, in one part of the reactor system in which the circulating gas stream, otherwise known as a recycle stream or pseudozyma environment, is heated in the reactor by the heat of polymerization. This heat away from the cycle of songs in another part of the cycle with a cooling system outside the reactor. Typically, in gas-phase process for obtaining polymers with fluidized bed through a fluidized bed in the presence of catalyst under reaction conditions continuously circulates the gaseous flow comprising one or more monomers. This gaseous at the same time, and instead of polymerized monomer add fresh monomer (see, for example, US patents№№4543399, 4588790, 5028670, 5317036, 5352749, 5405922, 5436304, 5453471, 5462999, 5616661 and 5668228, all of which are in full included in this description as a reference).

During the gas-phase process, the excess pressure in the reactor can vary from about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in the range of from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).

When carrying out gas-phase process temperature in the reactor can vary from about 30 to about 120° C, preferably from about 60 to about 115° C, more preferably in the range of from about 70 to about 110° C, and most preferably in the range of from about 70 to about 95° C.

Other gas-phase processes, for which it is intended the method according to the present invention include polymerization processes with step-by-step or multi-stage processes. The methods of gas-phase processes, for which is the present image is, The R-B1 0649992, EP-A 0802202 and EP-0634421, which are fully included in the present description as a reference.

In a preferred embodiment, the reactor used when performing the present invention and the method according to the invention provide the possibility of more than 500 lbs of polymer per hour (227 kg/HR) to about 200,000 lbs/HR (90900 kg/HR) or higher of polymer, preferably greater than 1000 lbs/HR (455 kg/HR), more preferably greater than 10,000 lbs/HR (4540 kg/HR), even more preferably more than 25000 lb/h (11300 kg/h), even more preferably 35000 lb/h (15900 kg/h), however, even more preferably greater than 50,000 lbs/HR (22700 kg/HR) and most preferably greater than 65,000 lbs/HR (29000 kg/HR) to over 100,000 lb/h (45500 kg/h).

During the process of suspension polymerization usually create a pressure in the range of from about 1 to about 50 at and even greater and temperatures in the interval from 0 to about 120° C. In the process of suspension polymerization, a suspension of solid powdered polymer is prepared in the liquid polymerization diluent, which is injected ethylene and comonomers and often together with the catalyst added hydrogen. The suspension comprising the diluent from the reactor periodically or nepot in the reactor. As the liquid diluent in the polymerization medium, as a rule, use alkane containing from 3 to 7 carbon atoms, preferably a branched alkane. The medium used in the polymerization conditions must be liquid and relatively inert. When using propane environment, the process should be carried out at a temperature and pressure above the critical parameters of the reaction diluent. The preferred media used is hexane or isobutane.

The preferred method of polymerization used in the implementation of the invention, referred to as polymerization in powdered form or by suspension polymerization, which support a lower temperature than that at which the polymer goes into solution. This method in the art are well known and described, for example, in US patent No. 3248179, which fully included in the present description by reference. Other methods of suspension polymerization include those carried out with the use of a reactor with circulation, and methods using multiple reactors mixing, placed in series, parallel or a combination of these configurations. Non-limiting examples of suspension spoe examples of the suspension means, presented in US patent No. 4613484, which fully included in the present description by reference.

In one embodiment, the reactor used in the suspension method according to the invention and the method according to the invention provide the possibility of obtaining more than 2000 lbs of polymer per hour (907 kg/HR), more preferably greater than 5000 lbs/HR (2268 kg/HR) and most preferably greater than 10,000 lbs/HR (4540 kg/HR). In another embodiment, in a suspension reactor used in the method according to the invention, receive more than 15000 pounds of polymer per hour (6804 kg/HR), preferably from more than 25,000 lbs/HR (11340 kg/h) to about 100,000 lbs/HR (45500 kg/h).

Examples of methods implemented in the solution presented in US patents No. 4271060, 5001205, 5236998 and 5589555 and PCT application WO 99/32525, which are not fully included in the present description as a reference.

In a preferred variant of the method according to the invention process, preferably a slurry or gas phase process is carried out in the presence of garnisongasse of the catalyst element of group 15 or a mixed catalyst system according to the invention and in the absence or near absence of any cleansing supplements, such as triethylaluminum, trimethylaluminum, triisobutylaluminum, Trikala PCT WO 96/08520 and US patents No. 5712352 and 5763543, which are not fully included in the present description as a reference.

In one embodiment, the invention features a method of injection is not supported on a carrier garnisongasse of the catalyst element of group 15 or a mixed catalyst system in a reactor, in particular in gas-phase reactor. One of the options polymerization catalysts according to the invention is used is not supported on a carrier form, preferably in the form of a liquid, such as described in US patents No. 5317036 and 5693727 and European publications EP-A 0593083, which are all included in the present description as a reference. The polymerization catalyst or catalyst (catalysts) in liquid form can be introduced into the reactor with activator jointly or separately using the methods of injection, presented in PCT publication WO 97/46599, which fully included in the present description by reference. When use is not supported on a carrier garnisongasse catalytic connection with elements of group 15, the molar ratio between the metal of the activator component to the metal garnisongasse catalytic connection with the group element 15 is in the range from 0.3:1 to 10,000:1, preferably from 1 100 to 5000 ppm million, preferably from 200 to 2000 ppm million, more preferably from 250 to 1900 frequent./million, even more preferably from 300 to 1800 ppm million, more preferably from 350 to 1700 ppm million, more preferably from 400 to 1600 ppm million, more preferably from 500 to 1500 ppm million, more preferably from 500 to 1400 ppm million, more preferably from 500 to 1200 ppm million, more preferably from 600 to 1200 ppm million, preferably from 700 to 1100 ppm million, and even more preferably from 800 to 1000 ppm million hydrogen Concentration in the reactor is inversely proportional to the average weight molecular weight of the polymer (Mw).

Polymer products

The polymers obtained according to the methods of the invention can be used in a wide variety of products and the ultimate goals of the application. The polymers produced according to the methods of the invention include linear low density polyethylene, elastomers, plastomer, high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene and polypropylene copolymers. Preferred new polymers include polyethylene, and more preferably, when using a mixed catalyst system, new polymers include the bimodal polyethylene is Naya system for obtaining a modal or multimodal polymer.

Polyolefins, in particular polyethylene is obtained according to the method according to the invention using garnisongasse catalytic metal link with an element of group 15, have a density in the range from 0.86 to 0.97 g/CC, preferably in the range from 0.88 to to 0,965 g/CC, more preferably in the range from 0.900 for up to 0.96 g/CC, even more preferably in the range from 0,905 to 0.95 g/CC, however, more preferable in the range of from 0.910 to 0,940 g/CC, most preferably more 0,915 g/CC, preferred more 0,920 g/CC, and still more preferably more 0,925 g/cubic cm Density determined according to ASTM D-1238.

Polyolefins, in particular polyethylene is obtained according to the method according to the invention using a mixed system garnisongasse catalytic metal link with an element of group 15 and metallocene catalyst compounds with a bulky ligand, have a density of from 0.89 to 0.97 g/cm3. In the preferred embodiment, can be obtained polyethylene having a density of from 0.910 to 0,965 g/cm3more preferably from 0,915 to 0,960 g/cm3even more preferably from 0,920 to 0,955 g/cm3. In some preferred embodiments,-VI/sup>. The density is determined by ASTM D-1238.

The polymers obtained according to the method according to the invention using garnisongasse catalytic metal link with an element of group 15, typically have a molecular weight distribution, a ratio between srednevekovoi molecular weight and srednekamennogo molecular weight (Mw/Mn) of greater than 1.5 to about 15, preferably from greater than 2 to about 10, more preferably from more than about 2.2 to less than about 8, and most preferably from 2.5 to 8.

The polymers obtained according to the method according to the invention using a mixed system garnisongasse catalytic metal link with an element of group 15 and metallocene catalyst compounds with a bulky ligand, generally have a molecular weight distribution, a ratio between srednevekovoi molecular weight and srednekamennogo molecular weight (Mw/Mn) greater than 5, more preferably greater than 10.

The polymers obtained according to the method according to the invention using garnisongasse catalytic metal link with an element of group 15, typically are characterized by a narrow compositional raspredeleniya PSCR copolymer specialists in this field known in the art (see, for example, PCT application WO 93/03093, published on 18 February 1993, which fully included in the present description by reference. In one embodiment, such polymers obtained according to the invention have PSCR, usually being in the range from greater than 50 to 100%, preferably 99%, preferably in the range from 55 to 85%, more preferably in the range from 60 to 80%, even more preferably greater than 60%, and yet more preferably more than 65%. In another embodiment, such polymers obtained using the catalytic system according to the invention have PSCR less than 50%, preferably less than 40%, and most preferably less than 30%.

The polymers obtained according to the method according to the invention using a mixed system garnisongasse catalytic metal link with an element of group 15 and metallocene catalyst compounds with a bulky ligand, as a rule, are characterized by a narrow compositional distribution as determined by the measure of the width of the compositional distribution (PSCR). The rest of the details determine PSCR copolymer specialists in this field known in the art (see, for example, PCT application WO 93/03093, published on 18 February 1993, in which Paul is using the catalytic system according to the invention, have PSCR less than 50%, preferably less than 40%, and most preferably less than 30%.

The polymers obtained according to the method according to the invention using garnisongasse catalytic metal link with an element of group 15, have a melt index (IL) or (I2) (as determined by ASTM D-1238 (condition E, at 190° C), in the interval from the lack of a definable expiration up to 1000 DG/min, more preferably from about 0.01 to about 100 DG/min, even more preferably from about 0.1 to about 50 DG/min, and most preferably from about 0.1 to about 10 DG/min

One of the options polymers obtained according to the method according to the invention using a mixed system garnisongasse catalytic metal link with an element of group 15 and metallocene catalyst compounds with a bulky ligand, generally have a melt index (IR) from about 0.01 to 1000 DG/min or less. In a preferred embodiment, the polyolefin is an ethylene Homo-polymer or copolymer. In a preferred embodiment for some applications such as the manufacture of films, tubes, molded parts, etc., the preferred melt index of 10 g/m is. The preferred polyethylene is IL which is in the range from 0.01 to 10 DG/min

In one embodiment, the polymers obtained according to the method according to the invention using garnisongasse catalytic metal link with an element of group 15, characterized by the values of the ratio of the melt index (RD21/IL2) (RD21determined according to ASTM D-1238-F) of from 10 to less than 25, more preferably from about 15 to less than 25. In the preferred embodiment, these polymers are characterized by values of the ratio of the melt index is preferably greater than 25, more preferably greater than 30, even more preferably greater than 40, yet more preferably greater than 50, and most preferably more than 65. In another embodiment, such polymers according to the invention may have a narrow molecular weight distribution and compositional distribution, or Vice versa. Such polymers can be those presented in US patent No. 5798427 included in the present description by reference.

One of the options polymers obtained according to the method according to the invention using a mixed system garnisongasse catalytic metal joining element sub>2from 0.1 to 100 DG/min, preferably from 0.5 to 50 DG/min, more preferably from 2 to 20 DG/min (primarily for use as pipe materials), and most preferably for use in the form of films) from 5 to 10 DG/min In the preferred embodiment, these polymers according to the invention are characterized by the values of the ratio of the melt index (RD21/IL2) more preferably 80, more preferably greater than 90, more preferably greater than 100, yet more preferably more than 110, and most preferably greater than 120.

When garnisongasse connection metal element of group 15 is used alone, it produces a polymer with a high srednevekovoi molecular weight Mw, such as, for example, exceeding 100,000, preferably greater than 150000, preferably greater than 200000, preferably greater than 250000, more preferably greater than 300000.

When the metallocene catalyst compound with the bulky ligand used alone, it produces a polymer with a low srednevekovoi molecular weight, such as, for example, less than 100,000, preferably less than about 80,000, more preferably less than 60000, even bol and over 5000.

Alternatively, the polymers obtained according to the method according to the invention using a mixed system garnisongasse catalytic metal link with an element of group 15 and metallocene catalyst compounds with a bulky ligand, in addition to the above properties for this system are characterized by one or more of the following properties:

(a) the value of Mw/Mn in the range from 15 to 80, preferably from 20 to 60, preferably from 20 to 40; molecular weight (Mw and mn) determined as set forth below in the examples section;

(b) density (as it is determined under ASTM 2839) from 0.94 to 0,970 g/cm3preferably from 0,945 to 0,965 g/cm3preferably from 0,945 to 0,960 g/cm3;

(C) a residual metal content of 5.0 ppm million transition metal or less, preferably 2.0 to frequent./million transition metal or less, preferably 1.8 to frequent./million transition metal or less, preferably 1.6 to frequent./million transition metal or less, preferably 1.5 to frequent./million transition metal or less, preferably 2.0 to frequent./million or less of a metal of group 4, preferably 1.8 to frequent./million or less of a metal of group 4, predpochtitelney compared to the technically available standards experimental analysis inductively coupled plasma emission spectroscopy (ICPES), in which the sample is heated so that there is a complete decomposition of all organic substances, and the solvent is nitric acid, and in the case of any substrate other acid in order to dissolve any substrate (such as hydrofluoric acid, to dissolve kremmidiotis media)]; and/or

(g) 35 wt.% or more of the component with high srednevekovoi molecular weight, as determined gel chromatography, preferably 40% or more; in a particularly preferred embodiment, the content of the high molecular weight fraction is in the range from 35 to 70 wt.%, more preferably in the range from 40 to 60 wt.%.

According to one preferred variant of the above mixed catalytic composition is used to produce polyethylene having a density in the range from 0.94 to 0,970 g/cm (as it is determined under ASTM D-2839) and value IL20.5 g/10 min or less. In another embodiment, the above-described mixed catalytic composition used for obtaining polyethylene having a value IL21less than 10 and a density in the range from 0,940 to 0,950 g/cm3or is IR21less than 20 and a density of less 0,945 g/cm3or less.

For others who isomerase catalytic metal link with an element of group 15 and metallocene catalyst compounds with a bulky ligand, characterized by an ash content less than 100 ppm million, more preferably less than 75 ppm million, preferably less than 50 ppm million In yet another variant ash includes negligibly small, trace amounts of titanium, which, as is well known in the art, determined using inductively coupled plasma-atomic emission spectroscopy (ICPAES).

According to another variant according to the method according to the invention have the propylene polymers on the basis of. These polymers include atactic polypropylene, isotactic polypropylene, polisomaticheskoi and syndiotactic polypropylene. Other propylene polymers include propylene block or impact copolymers. Propylene polymers of these types in the art are well known (see, for example, US patents No. 4794096, 3248455, 4376851, 5036034 and 5459117, which are all included in the present description as a reference).

The polymers according to the invention can be combined and/or ekstradiroval together with any other polymer. Non-limiting examples of other polymers include linear low density polyethylene, elastomers, plastomer, polyethylene, high pressure low density polyethylene is high density, full of such forming processes, as extrusion and co-extrusion films and sheets and spinning fiber, as well as blow molding, injection molding and rotary molding. Film materials include films made of blow-molding and casting, film, produced by joint extrusion layer and the molding, which can be used as shrink film, cling film, stretch film, sealing films, oriented films, packaging for snacks, bags for harsh environments, bags for groceries, packaging for baked and frozen food packaging for medical purposes, sealing materials for industrial use, membranes, etc. used in contact and without contact with food products. The manufacture of fibers includes spinning from melt spinning from solution and the processes of spinning from the melt of the hollow fiber for use in woven and non-woven forms in the manufacture of filter fabrics for towels, clothing, health care workers, geotextile materials, etc. Extruded products include tubes for medical purposes, the coating of wires and cables, pipes, geomembranes and facing materials for swimming pools. To formula itie hollow articles, rigid containers for food, toys, etc.

EXAMPLES

For a better understanding of the present invention, including describing the advantages, the following examples.

Example 1: a catalytic system comprising carriageway catalyst with an element of group 15

Getting [(2,4,6-Me3With6H2)N2CH2]2NH (ligand)

A 2-liter odnogolosy the flask Slanka injected with a magnetic stirrer shaft and downloaded 23,450 g (0,227 mole) of Diethylenetriamine, 90,51 g (0,455 mole) of mediterranid, 1,041 g (1,14 mmole) of Tris(dibenzylideneacetone)diplodia, 2,123 g (3,41 mmole) of racemic 2,2bis(diphenylphosphino)-1,1-dinaphthyl, 65,535 g (0,682 mole) of tert-butoxide sodium and 800 ml of toluene. The reaction mixture was heated to 95° C and stirred. After 4 days the reaction was completed, what was judged according to proton NMR spectroscopy. All solvent was removed under vacuum and the residues were dissolved in 1 l of diethyl ether. Solution in diethyl ether three times washed with 1 l of water and 500 ml saturated aqueous NaCl and dried over magnesium sulfate. After removal of diethyl ether under vacuum in the form of a red oil was obtained prophetic Messiah. src="https://img.russianpatents.com/chr/948.gif" border="0">: 6,83 (s, 4), 3,39 (broad s, 2), 2,86 (t, 4), 2,49 (t, 4), and 2.27 (s, 12), of 2.21 (s, 6), 0,68 (broad s, 1).13C-NMR,: 143,74, 131,35, 129,83, 129,55, 50,17, 48,56, 20,70, 18,51.

Receive { [(2,4,6-Me3C6H2)NCH2CH2]2NH} Zr(CH2Ph)2or (Zr-HN3) IN 500-ml round bottom flask in a dry nitrogen atmosphere not containing oxygen, is injected with a magnetic stirrer shaft, 41,729 g (91,56 mmole) tetramethylsilane and 300 ml of toluene. Under stirring for 1 min was added 32,773 g (96,52 mmole) of the above-mentioned solid criminologia ligand (target compound to precipitate). The volume of the suspension was reduced to 100 ml and with stirring was added 300 ml of pentane. Solid yellow-orange product was collected by filtration and dried under vacuum (44,811 g, 80% yield).1H-NMR (C6D6,): 7,22-for 6.81 (m, 12), 5,90 (d, 2), to 3.38 (m, 2), 3,11 (m, 2), a 3.01 (m, 1), 2,49 (m, 4), 2,43 (s, 6), is 2.41 (s, 6), to 2.18 (s, 6), 1,89 (s, 2), is 0.96 (s, 2).

Receive {[(2,4,6-Me3With6H2)NC2CH2]2NN} HF(CH2Ph)2or (Hf-HN3)

In a 250 ml round bottom flask in a dry nitrogen atmosphere not containing oxygen, is injected with a magnetic stirrer shaft, 4,063 g (7,482 mmole) tetrabenzoate and 150 ml of toluene. When mixing in the new connection). The volume of the suspension was reduced to 30 ml and with stirring was added 120 ml of pentane. Solid pale yellow product was collected by filtration and dried under vacuum (4,562 g, 87% yield).1H-NMR (C6About6,): 7,21-6,79 (m, 12), 6,16 (d, 2), 3,39 (m, 2), 3,14 (m, 2), 2,65 (s, 6), is 2.40 (s, 6), to 2.35 (m, 2), of 2.23 (m, 2), are 2.19 (s, 6), 1,60 (s, 2), of 1.26 (s, 2), NH was invisible.

Obtaining catalyst 1A

To 1,335 g of MAO (methylalumoxane) (4,450 g of a solution in toluene concentration of 30 wt.%, the firm Albemarle) and 4,691 g of toluene in a 100-ml round-bottom flask were added 0,117 g obtained by the above Zr-HN3. The solution was stirred for 15 minutes was Added 3,550 g of silica (Crosfield ES-70, calcinated at 600° C, available on the company Crosfield Limited, Warrington, England), followed by stirring. The mixture was dried overnight under vacuum. With stirring was added 0,300 g (6 wt.%) the dry product of Witco Aluminum Stearate # 22 (AlSt #22), [CH3(CH2)16Soo]2A1-IT is available on the company Witco Corporation, Memphis, PCs Tennessee, receiving 5,160 g of finished catalyst contained to 0.35 wt.% zirconium in a ratio of Al/Zr 120:1.

Obtaining catalyst 1B

To of 1.321 g of MAO (4,405 g of a solution in toluene concentration of 30 wt.%, the firm Albemarle) and 4,717 g of toluene in a 100-ml Crawley 3,546 g of silica (Crosfield ES-70, calcinated at 600° C, available on the company Crosfield Limited, Warrington, England), followed by stirring. The mixture was dried overnight under vacuum. With stirring was added 0,300 g (6 wt.%) the dry product of Witco Aluminum Stearate # 22 (AlSt #22), [CH3(CH2)16Soo]2A1-IT is available on the company Witco Corporation, Memphis, PCs Tennessee, receiving 5,040 g of finished catalyst contained 0.67 wt.% hafnium with a ratio of Al/Hf 120:1.

Comparative example 1A: polymerization with catalyst 1A

Polymerization in slurry phase was performed in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. Downloaded 400 ml of isobutane as a diluent and using a gastight syringe as a cleaning agent was added 0.7 ml of a solution trioctylamine in hexane concentration of 25 wt.%. The reactor was heated to 90° C. Under the pressure of ethylene was introduced 0,100 g prepared above catalyst 1A (Zr-HN3) and the reactor was created pressure ethylene 137 pounds per square inch (945 kPa). The polymerization product is of 137 pounds per square inch (945 kPa). The reaction was stopped by rapid cooling and pressure relief. Got to 21.0 g of polyethylene [PT (flow index): no expiry activity: 1198 g polyethylene/mmol catalyst· al· h].

Example 1B: polymerization catalyst 1B

Polymerization in slurry phase was performed in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. Downloaded 400 ml of isobutane as a diluent and using a gastight syringe as a cleaning agent was added 0.7 ml of a solution trioctylamine in hexane concentration of 25 wt.%. The reactor was heated to 90° C. Under the pressure of ethylene was introduced 0,100 g prepared above catalyst 1B (Hf-HN3) and the reactor was created pressure ethylene 146 pounds per square inch (1007 kPa). The polymerization was continued for 30 minutes while maintaining the reactor temperature 90° C and DC ethylene pressure 146 pounds per square inch (1007 kPa). The reaction was stopped by rapid cooling and pressure relief. Got to 36.7 g of polyethylene (FR: listed above, in the same conditions garnisongasse catalytic connection with the group element 15 according to the invention in comparison with its zirconium analogue was characterized by almost double performance.

Example 2: a mixed catalyst system comprising the catalyst as the metal containing hafnium, with an element of group 15 and metallocene catalyst with the bulky ligand

In the following examples used the metallocene catalyst compound with the bulky ligand [(n-propylcyclopentanol)2Zr12], which were obtained on the firm Boulder Scientific, Mead, PCs Colorado. [(2,4,6-Me3C6H2)NHCH2CH2]2NH (ligand) and {[(2,4,6-Me3C6H2)NCH2CH2]2NH}Hf(CH2Ph)2(Hf-HN3) received for the above.

Getting mixed catalyst 2A

To 1.85 g of MAO (6,18 g of a solution in toluene concentration of 30 wt.%, the company Albemarle Corporation, Baton Rouge, PCs Louisiana) and 6,63 g of toluene in a 100-ml round-bottom flask were added 0,139 g Hf-HN3 and 0.025 g (n-propylcyclopentanol)2ZrCl2. The solution was stirred for 10 minutes was Added to 4.98 g of silica (Crosfield ES-70, calcinated at 600° C, available on the company Crosfield Limited, Warrington, England) is.%) the dry product of Witco Aluminum Stearate # 22 (AlSt #22), [CH3(CH2)]16Soo]2A1-IT is available on the company Witco Corporation, Memphis, PCs Tennessee, with getting to 7.15 g of finished catalyst, containing a total of 38 mcmole/g catalyst with a ratio between the total metal and aluminum 120:1 and the ratio of Hf-HN3 and (n-propylcyclopentanol)2Zr123:1.

Getting mixed catalyst 2B

To of 7.95 g of MAO (26,50 g of a solution in toluene concentration of 30 wt.%, the company Albemarle Corporation, Baton Rouge, PCs Louisiana) and 94,41 g of toluene in a 1000 ml round bottom flask was added 0,596 g Hf-HN3 and to 0.108 g (n-propylcyclopentanol)2Zr12. The solution was stirred for 10 minutes was Added 51,35 g of silica (Crosfield ES-70, calcinated at 600° C, available on the company Crosfield Limited, Warrington, England), followed by stirring. The mixture was dried overnight under vacuum. With stirring was added to 2.40 g (6 wt.%) the dry product of Witco Aluminum Stearate # 22 (AlSt #22), [CH3(CH2)16Soo]2A1-IT is available on the company Witco Corporation, Memphis, PCs Tennessee, receiving 62,33 g of finished catalyst, containing a total of 19 mcmole/g catalyst with a ratio between the total metal and A1 120:1.

Example 2A: the polymerization of ethylene in suspension facesay stirrer, external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. Downloaded 400 ml of isobutane as a diluent and using a gastight syringe as a cleaning agent was added 0.7 ml of a solution trioctylamine in hexane concentration of 25 wt%. The reactor was heated to 90° C. Under the pressure of ethylene was introduced 0,100 g of a mixed catalyst 2A and the reactor was created pressure ethylene 136 pounds per square inch (938 kPa). The polymerization was continued for 30 minutes while maintaining the reactor temperature 90° C and DC ethylene pressure 136 pounds per square inch (938 kPa). The reaction was stopped by rapid cooling and pressure relief. Allocated 83,0 g ethylene homopolymer (RD21:3,5, activity: 4770 g PE/mmol cat.· al· h).

Example 2B: gas-phase polymerization of ethylene/hexene

The above mixed catalyst 2B was used for the study described below copolymerization of ethylene/hexene. To determine the effectiveness of the catalyst, the ability to implement comonomeric links (1-hexene) and the ability to regulate the molecular weight is of 300 psig (2069 kPa) and at a speed of circulating gas 1.60 ft/s (49 cm/s). The polymer had the following properties: IR21:10.1, IL10:0,95, IL2:0,008, Mw: 185143, Mn: 12861, Mw/Mn: 14.4V, density: 0,9487 g/cm3. The total process data are summarized in table 1. In Fig.1 shows gel chromatography of polymers of example 2.

Example 3: a catalytic system comprising associated with silicon dioxide aluminum and Hf-HN3

Obtaining associated with the silicon dioxide aluminum [Si-0-A1(C6F5)2]

Sample (40,686 g) of silica (Davison 948, calcined at 600° C, available on the company W. R. Grace, Davison Division, Baltimore, PCs Maryland) in 500-ml round-bottom flask suspended in 300 ml of toluene. Added 15,470 g (of 24.90 mmole) of solid Al(C6F5)3·toluene and the mixture was stirred for 30 minutes and the Mixture was left to stand for 18 hours Associated with silicon dioxide aluminum was isolated by filtration and dried under vacuum for 6 h to obtain 49,211 g of substance. Synthesis of (l6F5)3·toluene was carried out according to the method described in the application EP-A1 0694548, which fully included in the present description by reference.

Preparation of catalyst 3A

Example 3A: polymerization of ethylene with catalyst 3A in the suspension phase

Polymerization in slurry phase was performed in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. Downloaded 400 ml of isobutane as a diluent and using a gastight syringe as a cleaning agent was added 0.7 ml of a solution trioctylamine in hexane concentration of 25 wt.%. The reactor was heated to 90° C. Under the pressure of ethylene was introduced 0,200 g of finished catalyst 3A and the reactor was created pressure ethylene 134 pounds per square inch (924 kPa). The polymerization was continued for 30 minutes while maintaining the reactor temperature 90° C and DC ethylene pressure 134 lbs/to the no expiration activity: 364 g polyethylene/mmol catalyst· al· h).

Example 3B: polymerization of ethylene/hexene with catalyst 3A in the suspension phase

Polymerization in slurry phase was performed in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. Downloaded 400 ml of isobutane as a diluent, 35 ml of 1-hexene and using a gastight syringe as a cleaning agent was added 0.7 ml of a solution trioctylamine in hexane concentration of 25 wt.%. The reactor was heated to 90° C. Under the pressure of ethylene was introduced 0,100 g of finished catalyst 3A and the reactor was created pressure ethylene 113 pounds per square inch (889 kPa). The polymerization was continued for 25 min, while maintaining in the reactor a temperature of 90° C and DC ethylene pressure of 113 pounds per square inch (889 kPa). The reaction was stopped by rapid cooling and pressure relief. Allocated to 68.0 g of polyethylene (FR: no expiry activity: 1650 g polyethylene/mmol catalyst· al· h).

Example 4: mixed katsouli catalytic metallocene compound type with the bulky ligand {[dimethylsilane(3-n-propylcyclopentanol)zirconiated (GIFP-CL2)]}, which was received at the company Boulder Scientific, Mead, PCs Colorado. Synthesis of (A1C6F5)3toluene was carried out according to the method described in the application EP-A1 0694548, which fully included in the present description by reference.

Getting ligand [(2,4,6-Me3C6H2)NHCH2CH2]2NH

A 2-liter odnogolosy the flask Slanka in dry nitrogen atmosphere not containing oxygen, is injected with a magnetic stirrer shaft and downloaded 23,450 g (0,227 mole) of Diethylenetriamine, 90,51 g (0,455 mole) 2-bromoethylene, 1,041 g (1,14 mmole) of Tris(dibenzylideneacetone)diplodia, 2,123 g (3,41 mmole) of racemic 2,2bis(diphenylphosphino)-1,1-dinaphthyl (racemic DINAF), 65,535 g (0,682 mole) of tert-butoxide sodium and 800 ml of toluene. The reaction mixture was stirred and heated to 100° C. after 18 h the reaction was completed, what was judged according to proton NMR spectroscopy. All other operations can be performed in the air. All solvent was removed under vacuum and the residues were dissolved in 1 l of diethyl ether. Solution in diethyl ether, washed with 3 portions of 250 ml of water, and then saturated aqueous NaCl (180 g in 500 mesto, which was dried under vacuum at 70° C for 12 h to obtain 71,10 g (yield: 92%) of product.1H-NMR (C6D6,): 6,83 (s, 4), 3,39 (broad s, 2), 2,86 (t, 4), 2,49 (t, 4), and 2.27 (s, 12), of 2.21 (s, 6), 0,68 (broad s, 1).

Receive {[(2,4,6-Me3C6H2)NCH2CH2]2NH}Hf(CH2Ph)2(Hf-HN3)

In a 250 ml round bottom flask in a dry nitrogen atmosphere not containing oxygen, is injected with a magnetic stirrer shaft, 4,063 g (7,482 mmole) tetrabenzoate and 150 ml of toluene. Under stirring for 1 min was added 2,545 g (7,495 mmole) of the above-mentioned solid criminologia ligand (precipitate fell out of the target compound). The volume of the suspension was reduced to 30 ml and with stirring was added 120 ml of pentane. Solid pale yellow product was collected by filtration and dried under vacuum (4,562 g, 87% yield).1H-NMR (C6D6,): 7,21-6,79 (m, 12), 6,16 (d, 2), 3,39 (m, 2), 3,14 (m, 2), 2,65 (s, 6), is 2.40 (s, 6), to 2.35 (m, 2), of 2.23 (m, 2), are 2.19 (s, 6), 1,60 (s, 2), of 1.26 (s, 2), NH was invisible.

Preparation of dimethylsilane(3-n-replicacartier)zeronicotine (GIFP-Me2)

In a 250 ml round bottom flask was introduced a magnetic stirrer shaft, 5,990 g (at 13.84 mmole) GIFP-CL2and 125 ml of diethyl ether. RA is re, 28,42 mmole). The mixture was heated to room temperature and was stirred for 2 hours Under vacuum was removed diethyl ether and the residues were extracted with 50 ml of toluene. To remove LiCl toluene and the mixture was filtered through brownmillerite and under vacuum, toluene was removed. Oily residues was dissolved in pentane, filtered through brownmillerite and solvent was removed to obtain the product as a clear yellow oil. This product is in the form of oil was a mixture of rat and mesosomal in the ratio of 1:1.1H-NMR (C6D6,): of 6.49 (m, 4), of 5.48 (m, 2), of 5.39 (m, 2), a 5.25 (m, 2), 5,20 (m, 2), 2,59 (m, CH2, 8), of 1.62 (m, CH2,8), is 0.96 (m, CH3, 12), 0,20 (s, SiMe, 3), 0,18 (s, SiMe, 6), 0,16 (s, SiMe, 3), -0,08 (s, ZrMe, 3), -0,17 (s, ZrMe, 6), -0,23 (s, ZrMe, 3).

Obtaining associated with the silicon dioxide aluminum [-Si-O-Al(C6F5)2]

11,50 g of silica (Davison 948, calcined at 600° C, available on the company W. R. Grace, Davison Division, Baltimore, PCs Maryland) in 500-ml round-bottom flask suspended in 300 ml of toluene and added 5,706 g (of 24.90 mmole) of solid Al(C6F5)3·of toluene. The mixture was stirred at 85° C for 1 h and then left to cool overnight (20 h). Associated with the silicon dioxide of aluminosilicate 4A

To 1,000 g associated with silicon dioxide aluminum in 20 ml of toluene was added 0,056 g (0,080 mmole) Hf-HN3 in 5 ml of toluene. The mixture was stirred for 30 minutes Colorless silicon dioxide was orange-red. Silica was isolated by filtration and dried under vacuum for 6 h to obtain 1,041 g of substance. The final content of the transition metal was 76 mcmole/year

The preparation of the catalyst 4B

To 1,000 g associated with silicon dioxide aluminum in 20 ml of toluene was added 0,031 g (0,079 mmole) GIFP-Me2in 5 ml of toluene. The mixture was stirred for 30 minutes Colorless silicon dioxide was orange-red. Silica was isolated by filtration and dried under vacuum for 6 h to obtain 1,059 g of substance. The final content of the transition metal was 76 mcmole/year

The preparation of the catalyst 4B (mixture)

To 2,000 g associated with silicon dioxide aluminum in 40 ml of toluene was added 0,098 g (0,140 mmole) Hf-HN3 and 0.008 g (0,20 mmole) GIFP-Me2. The mixture was stirred for 30 minutes Colorless silicon dioxide was orange-red. Silica was isolated by filtration and dried under vacuum for 6 h to obtain 2,065 g of substance. The final content of the transition metal costable in the suspension phase was performed in a 1-liter autoclave reactor, equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. via gastight syringe as a cleaning agent was injected 100 μl of triisobutylaluminum, and then added 400 ml of isobutane diluent. The reactor was heated to 85° C. Under the pressure of ethylene was introduced 0.025 g of finished catalyst 4A and the reactor was created pressure ethylene 124 pounds per square inch (975 kPa). The polymerization was continued for 40 min while maintaining a reactor temperature of 85° C and DC ethylene pressure of 124 pounds/square inch (975 kPa). The reaction was stopped by rapid cooling and pressure relief. Allocated 9.2 grams of polyethylene (FR:no expiry activity: 879 g polyethylene/mmol catalyst· al· h).

Example 4B: polymerization of ethylene with catalyst 4B in the suspension phase

Polymerization in slurry phase was performed in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and cf is permeable syringe as a cleaning agent was injected 100 μl of triisobutylaluminum, and then added 400 ml of isobutane diluent. The reactor was heated to 85° C. Under the pressure of ethylene was introduced 0.025 g of finished catalyst 4B and the reactor was created pressure ethylene 122 pounds per square inch (959 kPa). The polymerization was continued for 40 min while maintaining a reactor temperature of 85° C and DC ethylene pressure of 122 pounds per square inch (959 kPa). The reaction was stopped by rapid cooling and pressure relief. Allocated to 74.7 g of polyethylene (IL: 193, activity: 7250 g polyethylene/mmol catalyst· al· h).

Example 4B: polymerization of ethylene with catalyst 4B in the suspension phase

Polymerization in slurry phase was performed in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. via gastight syringe as a cleaning agent was injected 100 μl of triisobutylaluminum, and then added 400 ml of isobutane diluent. The reactor was heated to 85° C. Under the pressure of ethylene was introduced 0.025 g of finished catalyst 4B and the reactor was created pressure is re temperature 85° And DC ethylene pressure of 123 pounds/square inch (967 kPa). The reaction was stopped by rapid cooling and pressure relief. Allocated to 17.2 g of polyethylene (FR: 10,9, activity: 1656 g polyethylene/mmol catalyst· al· h). In Fig.2 shows gel chromatography of the polymer obtained in example 4.

Example 5: a catalytic system comprising benzyl leaving group

Getting [(2,4,6-Me3C6H2)NHCH2CH2]2(ligand NH)

A 2-liter odnogolosy the flask Slanka in dry nitrogen atmosphere not containing oxygen, is injected with a magnetic stirrer shaft and downloaded 23,450 g (0,227 mole) of Diethylenetriamine, 90,51 g (0,455 mole) 2-bromoethylene, 1,041 g (1,14 mmole) of Tris(dibenzylideneacetone)diplodia, 2,123 g (3,41 mmole) of racemic 2,2bis(diphenylphosphino)-l,l-dinaphthyl (racemic DINAF), 65,535 g (0,682 mole) of tert-butoxide sodium and 800 ml of toluene. The reaction mixture was stirred and heated to 100° C. after 18 h the reaction was completed, what was judged according to proton NMR spectroscopy. All other operations can be performed in the air. All solvent was removed under vacuum and the residues were dissolved in 1 l of diethyl EF is sewed over 30 g of magnesium sulfate. After removal of diethyl ether in the form of a red oil was obtained substance was dried under vacuum at 70° C for 12 h to obtain 71,10 g (yield: 92%) of product. H-NMR (C6D6,): 6,83 (s, 4), 3,39 (broad s, 2), 2,86 (t, 4), 2,49 (t, 4), and 2.27 (s, 12), of 2.21 (s, 6), 0,68 (broad s, 1).

Receive { [(2,4,6-Me3C6H2)NCH2CH2)2NH}HfCl2(HfCl2-HN3)

In a 250-ml round-bottom flask 3,075 g NG(Miu2)4(8,66 mmole) was dissolved in 100 ml of pentane. In the form of a solid substance was added 2,942 g [(2,4,6-Me3C6H2)NHCH2CH2]2NH (8,66 mmole) and the solution was stirred for 2 hours Mixed amide {[(2,4,6 - Me3C6H2)NCH2CH2]2NH}Hf(NMe2)2identified proton NMR, but was not allocated.1H-NMR (C6D6,): to 6.95 (s, 4), 3,40 (m, 2), is 3.08 (s, 6), totaling 3.04 (m, 2), 2,52 (m, 4), 2,49 (s, 6), 2,47 (s, 6), 2,32 (s, 6), of 2.20 (s, 6), 1,72 (m, 1). The solvent was removed under vacuum. The residues were dissolved in toluene and one portion was added 2,825 g ClSiMe3(26,0 mmole). The solution was stirred for 24 h Under vacuum solvent was removed and the solid particles suspended in pentane. The solid is collected by filtration and about the 2 identified proton NMR.1H-NMR (C6D6,): 6,89 (s, 2), at 6.84 (s, 2), 3,40 (m, 2), 2,95 (m, 2), of 2.51 (s, 6), a 2.45 (s, 6), is 2.40 (m, 4), and 2.14 (s, 6), NH was invisible.

Receive { [(2,4,6-Me3C6H2)NCH2CH2]2NH} Hf(CH2Ph)2(Hf-HN3)

In a 250 ml round bottom flask in a dry nitrogen atmosphere not containing oxygen, is injected with a magnetic stirrer shaft, 4,063 g (7,482 mmole) tetrabenzoate and 150 ml of toluene. Under stirring for 1 min was added 2,545 g (7,495 mmole) of the above-mentioned solid criminologia ligand (precipitate fell out of the target compound). The volume of the suspension was reduced to 30 ml and with stirring was added 120 ml of pentane. Solid pale yellow product was collected by filtration and dried under vacuum (4,562 g, 87% yield).1H-NMR (C6D6,): 7,21-6,79 (m, 12), 6,16 (d, 2), 3,39 (m, 2), 3,14 (m, 2), 2,65 (s, 6), is 2.40 (s, 6), to 2.35 (m, 2), of 2.23 (m, 2), are 2.19 (s, 6), 1,60 (s, 2), of 1.26 (s, 2), NH was invisible.

Obtaining catalyst 5A

To 0,858 g of MAO (2,640 g of a solution in toluene concentration of 30 wt.%, available on the company Albemarle Corporation, Baton Rouge, PCs Louisiana) and 2,860 g of toluene in a 100-ml round-bottom flask were added 0,067 g HfCl2-HN3. The solution was stirred for 15 minutes was Added to 2.1 the end), followed by stirring. The mixture was dried overnight under vacuum to obtain 2,901 g of finished catalyst contained 0.68 wt.% hafnium with a ratio of Al/Hf 129:1.

Obtaining catalyst 5B

To 0,792 g of MAO (2,640 g of a solution in toluene concentration of 30 wt.%, available on the company Albemarle Corporation, Baton Rouge, PCs Louisiana) and 2,830 g of toluene in a 100-ml round-bottom flask were added 0,080 g HF-HN3. The solution was stirred for 15 minutes was Added 2,130 g of silica (Davison 948, calcined at 600° C, available on the company W. R. Grace, Davison Division, Baltimore, PCs Maryland), followed by stirring. The mixture was dried overnight under vacuum to obtain 2,908 g of finished catalyst contained 0.68 wt.% hafnium with a ratio of Al/Hf 119:1.

Comparative example 5A: polymerization of ethylene with catalyst 5A in the suspension phase

Polymerization in slurry phase was performed in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. Downloaded 400 ml of isobutane as a diluent and using a gas-tight syringe was kajastavale up to 90° C. Under pressure of ethylene was introduced 0,200 g of finished catalyst 5A and the reactor was created pressure ethylene 113 pounds per square inch (779 kPa). The polymerization was continued for 40 min, while maintaining in the reactor a temperature of 90° C and DC ethylene pressure of 113 pounds per square inch (779 kPa). The reaction was stopped by rapid cooling and pressure relief. Received 11.9 g of polyethylene [PT: no expiry activity: 311 g polyethylene/mmol catalyst· al· h].

Example 5B: polymerization of ethylene with catalyst 5B in the suspension phase

Polymerization in slurry phase was performed in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, membrane line to the suction line for ventilation and means a regulated supply of dry nitrogen and ethylene. The reactor was dried and was degirolami at 160° C. Downloaded 400 ml of isobutane as a diluent and using a gastight syringe as a cleaning agent was added 0.7 ml of a solution trioctylamine in hexane concentration of 25 wt.%. The reactor was heated to 90° C. Under the pressure of ethylene was introduced 0,200 g of finished catalyst and 5B in the reactor was created pressure ethylene 130 Punto° And DC ethylene pressure 130 psi (896 kPa). The reaction was stopped by rapid cooling and pressure relief. Received of 29.1 g of polyethylene (FR: no expiry activity: 881 g polyethylene/mmol catalyst· al· h).

As evidenced by the above data, in the same conditions metallsoderjasimi catalytic compound according to the invention with an element of group 15, which has substituted hydrocarbon leaving group, preferably alkyl, substituted aryl group, characterized by much higher performance than the same connection involving halogen atom.

Although the present invention is presented and illustrated with reference to specific embodiments of the for the usual experts in the field of technology is apparent that the invention leads to variants, which in the present description it is not necessary to illustrate. For example, you can use two or more supported on a carrier of the catalytic compositions according to the invention, containing elements of group 15, alone or together with nenalezena media metallocene catalyst compound with a bulky Tom group 15 together with the titanium - or zirconium bearing catalytic compound of element of group 15 and/or metallocene catalyst compound with the bulky ligand. In addition, it is assumed the use of catalytic systems according to the invention in configurations with one or more polymerization reactors, including those used for carrying out processes of different types. For these reasons, in order to determine the actual scope of the present invention should be handled only by the attached claims.

Claims

1. The method of polymerization of olefin (olefin) in the presence of a catalytic system comprising garnisongasse catalytic connection with the element of group 15, where the method is carried out at a temperature in the range of 50-200°C, and garnisongasse catalytic connection with the group element 15 corresponds to the formula:

in which M is hafnium;

X - the same anionic leaving group;

L - atom of an element of group 15;

n is the oxidation state of M;

m is the formal charge Y, Z and L;

Y and Z is an atom of an element of group 15;

R1and R2- C2-C20hydrocarbon group;

R3is a hydrogen atom;

R4and R5- aryl group, substituted aryl group.

2. The method according to p. 1, where each of L, Y and Z independently of one another denotes a nitrogen atom, persons under item 1, in which the catalytic system can be supported on a carrier.

4. The method according to p. 1, in which the polymerization process is selected from a range that includes a continuous gas-phase process and a continuous process in the suspension phase.

5. The method according to p. 4, wherein the catalyst system further comprises an activator, representing the aluminium-containing Lewis acid corresponding to the formula

RnAl(rl)3-n,

where R denotes monoanionic ligand;

ArHal is a halogenated aromatic With6or higher carbon number polycyclic aromatic hydrocarbon or aromatic cyclic set, in which two or more rings (or condensed ring systems) are directly connected with each other or among themselves;

n denotes a number from 1 to 2, preferably n is 1.

6. The method according to p. 1 in which the olefin (olefin) is an ethylene, propylene or ethylene and at least one other monomer containing 3-20 carbon atoms.

7. The method according to p. 1, in which the polymerization process is a gas-phase process is conducted at a temperature in the range 30-120°C.

8. The method of polymerization of the e garnisongasse catalytic connection with the element of group 15, in which the hafnium atom is associated with at least one anionic leaving group and at least two atoms of elements in group 15 and in which at least one of at least two atoms of elements in group 15 is associated with the atom of an element of groups 15 through a bridging group, a metallocene catalyst compound with a bulky ligand and activator.

9. The method according to p. 8, in which the catalytic system can be supported on a carrier.

10. The method according to p. 8, in which the polymerization process is selected from a range that includes a continuous gas-phase process and a continuous process in the suspension phase.

11. The method according to p. 8, in which the activator is an aluminium-containing the Lewis acid corresponding to the formula

RnAl(rl)3-n,

where R denotes monoanionic ligand;

ArHal is a halogenated aromatic With6or higher carbon number polycyclic aromatic hydrocarbon or aromatic cyclic set, in which two or more rings (or condensed ring systems) are directly connected with each other or among themselves;

n denotes a number from 1 to 2, preferably n is 1.

12. The method according to p. 8, codename 3-20 carbon atoms.

13. The catalytic system on the media, including garnisongasse catalytic connection with the element of group 15, corresponding to the formula:

in which M is hafnium;

X is an anionic leaving group;

L - atom of an element of group 15;

n is the oxidation state of M;

m is the formal charge Y, Z and L;

Y and Z is an atom of an element of group 15;

R1and R2- C2-C20hydrocarbon group;

R3is a hydrogen atom;

R4and R5- aryl group, substituted aryl group.

14. The catalytic system on the media under item 13, in which garnisongasse catalytic connection with the element of group 15 and a metallocene catalyst compound with a bulky ligand, if it is contained, are in contact with the activator with the formation of a reaction product, which is then put in contact with the media.

15. The catalytic system on the media under item 13, which further comprises an activator, representing the aluminium-containing Lewis acid corresponding to the formula

RnAl(rl)3-n,

where R denotes monoanionic ligand;

ArHal is a halogenated aromatic With6or higher carbon number is not more rings (or condensed ring systems) are directly connected with each other or among themselves;

n denotes a number from 1 to 2, preferably n is 1.

16. The catalytic system on the media, including bidentate or tridentate legirovannoi garnisongasse catalytic connection with the element of group 15, in which the hafnium atom is associated with at least one anionic leaving group and at least two atoms of elements in group 15 and in which at least one of at least two atoms of elements in group 15 is associated with the atom of an element of groups 15 through a bridging group, a metallocene catalyst compound with a bulky ligand and activator.

17. The catalytic system on the media under item 16, in which garnisongasse catalytic connection with the element of group 15 and a metallocene catalyst compound with a bulky ligand, if it is contained, are in contact with the activator with the formation of a reaction product, which is then put in contact with the media.

18. The catalytic system on the media under item 16, in which the activator is an aluminium-containing the Lewis acid corresponding to the formula

RnAl(rl)3-n,

where R denotes monoanionic ligand;

ArHal is a halogenated aromatic With6or bulbocapnine, in which two or more rings (or condensed ring systems) are directly connected with each other or among themselves;

n denotes a number from 1 to 2, preferably n is 1.



 

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