Metallocen, ligand, catalyst system, the polymerization method

 

(57) Abstract:

The invention relates to the class of heterocyclic metallocenes and containing catalytic systems, as well as the method of polymerization joining the polymerized monomers using a given catalytic system, and these heterocyclic metallocene correspond to the formula (I), YjRiZjjMeQkP1,

where Y represents a coordinating group containing the Central radical with six electrons, directly coordinating IU, which condensed one or more rings containing at least one atom that is not carbon atom and is selected from S; R" represents a divalent bridging communication between the groups Y and Z; Z is a coordinating group having the same meaning as Y; Me represents a transition metal of group 3, 4, 5, 6; Q is halogen or linear or branched C1-C6-alkyl; R represents a counterion; i=0 or 1; j=1-3; jj=0-2; k=1-3 and 1= 0-2. The method allows to obtain polymers with controlled statistics defects. 4 C. and 13 C.p. f-crystals.

The present invention relates to new heterocyclic metallocenes and catalytics alimera low density, polymers of high density, atactic, isotactic and syndiotactic polymers.

More specifically, the present invention relates to a new class of metallocene containing at least one heteroatom in the ring system associated with the Central radical having six electrons and directly coordinating transition metal, where the specified metallocen able to polimerizuet joining the polymerized monomers.

Since the appearance of the work of Ziegler and Natta polymerization of vinyl monomers, as monoolefins and dienes with conjugated double bonds, is performed with the use of catalysts based on transition metals. These catalysts are based on the Central ion or transition metal atom surrounded by a number of coordinated ligands, and modified in many socialization. By regulating the nature of the ligand system, the Central ion or atom of the transition metal and socializaton can be obtained highly active catalytic agents. In addition, can be manufactured catalysts that will allow you to obtain polymers with a high degree of regularity of accession, and in the case of monomers n is emery.

In U.S. patent 3051690 described by way of polymerization of olefins with obtaining high molecular weight polymers with controlled molecular weight by controlled addition of hydrogen to the polymerization system, which includes hydrocarbon insoluble reaction product of the compounds of the Group IVB, VB, VIB and VIII and alkali metal, alkaline earth metal, zinc, earth or rare earth ORGANOMETALLIC compounds. In addition, it is known that some metallocene, such as dialkyl bis(cyclopentadienyl)titanium or zirconium in combination with alkylamines/water acetalization form a homogeneous system of catalysts for polymerization of ethylene.

In the application for patent in Germany 2608863 describes the use of catalysts for polymerization of ethylene consisting of bis(cyclopentadienyl)Citadella, trialkylamine and water. In addition, in the patent application Germany 2608933 described system catalysts for polymerization of ethylene, including the catalyst of General formula (Cp)nZrY4-nwhere n is 1-4, Y represents a hydrocarbon group or metalliance in combination with trialkylaluminium socialization and water (Cf means cyclopentadienyl).

is in in the presence of not containing halogen system of the Ziegler catalysts of General formula (Wed)nMeY4-nwhere n represents an integer from 1 to 4, Me denotes a transition metal, especially zirconium, and Y represents a hydrogen, C1-C5alkyl group, metallofullerene group or other moiety, in combination with alumoxane.

In U.S. patent 5324800 the system described catalysts for the polymerization of olefins, comprising metallocene catalyst of General formula (C5R'm)pR5(C5R'm)Q3-Ror R5(C5R'm)2-MeQ', where (C5R'm) is replaced by the Cf group, and alumoxane.

The polyolefins can be obtained in a variety of configurations in accordance with the way in which each new Monomeric link attached to the growing polyolefin chain. For metilenovyi polyolefins usually there are 4 basic configuration, i.e., atactic, gamestations, isotactic and syndiotactic.

This polymer may include areas for each type of configuration, not with pure or nearly pure configuration.

In contrast, the polymers of the monomers, symmetrically equivalent ethylene (i.e., 1,1-substituents are identical and 2,2-substituents are>Atactic polymers exhibit no regularity orientation of the repeating units in the polymer chain, i.e. the substituents is not regularly located relative to a hypothetical plane containing the polymer backbone (this plane is oriented so that these substituents on pseudosymmetries the carbon atoms are either above or below this plane). Instead, atactic polymers detect statistical distribution of the orientation of the substituents.

In addition, other types of catalysts belonging to the family of metallocene catalysts are the so-called "geometrically employed catalysts", where one of cyclopentadienyls groups is replaced by a ligand-heteroatom, such as amino - or postinvasion. Such catalysts are described in U.S. patents 5453410, 5399635 and 5350723.

In addition to the metallocene catalyst, which produces polyethylene and atactic polyolefins, also known some metallocene that produce polymers with varying levels of stereoregularity or actionspecific, such as isotactic, syndiotactic and gamestations polymers, which have a unique and regularly recurring stereo is.

Isotactic polymers have substituents that are associated with asymmetric carbon atoms, oriented on the same side with respect to the polymer backbone, i.e., all these substituents are located above or below the plane containing the polymer backbone. Isotacticity can be determined by NMR. In standard NMR nomenclature of isotactic pentad written as "mmmm", where "m" represents the "meso"-dyad or sequential monomer units having substituents, oriented on the same side with respect to the polymer skeleton. As is well known in the art, any inversion pseudosymmetries carbon in the chain reduces the degree of isotacticity and crystallinity of the polymer.

In contrast, syndiotactic structure is usually described as a structure that has alternates associated with asymmetric carbon atoms located pseudoenantiomeric, that is, these substituents are oriented alternately and regularly above or below the plane containing the polymer chain. Syndiotactic can also be determined by NMR. In NMR nomenclature syndiotactic the pentad presents "rrrr", where each "r" means "racemachine r-dyads in the chain determines the degree of syndiotactic polymer.

There are also other changes in polymer structures. For example, gamestations polymers are polymers in which the or each second pseudosymmetries carbon atom has his Deputy, oriented on the same side with respect to the plane containing the polymer backbone. Although other pseudosymmetries carbon atoms may have their deputies, oriented disordered either above or below this plane. Since only every second pseudosymmetries carbon atom has an isotactic configuration, uses the term "Hemi".

Isotactic and syndiotactic polymers are crystalline polymers and are not soluble in cold xylene. The crystallinity is characteristic as syndiotactic and isotactic polymers that distinguish them from gamestations and atactic polymers, which are soluble in cold xylene and non-crystalline. Although the catalyst allows you to get all types of polymers (atactic, gamestations, isotactic and syndiotactic), however, it is preferable that the catalyst was produced mainly or Osnovianenko stereochemical defects.

Some catalysts that produce isotactic polyolefins described in U.S. patent 4794096 and 4975403, as well as in the application for the European patent 0537130. Some catalysts that produce syndiotactic polyolefins described in U.S. patents 3258455, 3305538, 3364190, 4852851, 5155080, 5225500 and 5459117.

In addition to the neutral metallocenes known cationic metallocene that produce polymers with different degree of actionspecific. Cationic metallocene catalysts described in the application for the European patent 277003 and 277004. Catalysts that produce gamestations polyolefins described in U.S. patent 5036034.

In addition to homopolymers of monoolefins, polymerization catalysts to obtain copolymers of monoolefins or bifunctional polymers of olefins, or copolymers of bifunctional olefins and monoolefins can be obtained with the use of coordinated metal catalysts, including metallocene catalysts.

Although currently there are many metallocene catalysts, however, the need for new ligand systems and new metallocene catalysts or precursors of catalysts for the polymerization of the GTO. These new ligand systems and catalysts based on them will allow you to develop new methods of producing highly stereoregular or actionspecific polymers, mainly free from defects, polymers with controlled statistics defects and copolymers with adjustable properties, or new methods of regulating the molecular weight and control other properties of the polymers.

The present invention relates to a new class of heterocyclic metallocenes for polymerization of olefins, which can be used to produce polymeric products with desired properties, such as a certain molecular weight, distribution of molecular weight, density, tact and/or terminal unsaturation.

Metallocene of the present invention contain at least one heteroatom in the ring system associated with the Central radical having six electrons and directly coordinating transition metal belonging to Group 3, 4, 5, 6 or to a number of lanthanides or actinides of the Periodic table of elements (version IUPAC).

These metallocene can be used for polymerization joining the polymerized mo is th invention include ORGANOMETALLIC coordination compounds of mono-, di - or trifunctional ligand systems, coordinated with a transition metal complexes, preferably complexes of an element of Group 3, 4 or 5 or with elements of the series of lanthanides of the Periodic table of elements, where the system of ligands includes at least one Central radical with six-electrons associated with one or more radicals containing at least one heteroatom.

Metallocene of the present invention correspond to the formula (I)

YjRiZjjMeQkP1,

where

(1) Y is a coordinating group containing the Central radical with six electrons, directly coordinating Me, which condensed one or more rings containing at least one atom that is not carbon atom selected from b, N, O, Al, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te;

(2) R" represents a divalent bridging communication between the groups Y and Z;

(3) Z represents a coordinating group having the same meaning as Y or Z represents an open pentalateral group, cyclopentadienylsodium group, heterocyclic cyclopentadienylsodium group, nitrogen-containing group, phosphorus-containing Group 3, 4, 5, 6 or to a number of lanthanides or actinides of the Periodic table of elements;

(5) Q represents a linear or branched, saturated or unsaturated alkyl radical, aryl radical, alcylaryl radical, arylalkyl radical or a halogen atom;

(6) P is stable coordinatewise or pseudoscorpionida a counterion;

(7) i is an integer having a value of 0 or 1;

(8) j is an integer having a value of from 1 to 3;

(9) jj is an integer having a value of from 0 to 2;

(10) k represents an integer having a value of from 1 to 3; and

(11) 1 is an integer having a value of from 0 to 2.

In addition, the formula (I) also describes cationic metallocene where 1=1 or 2. These cationic metallocene can be obtained by reaction of ion pairs or compounds of a strong Lewis acid with a neutral metallocene (that is, 1=0) with the formation of cationic metallocene carried out either before or simultaneously with contacting the neutral metallocene with the monomer. Cationic metallocene use the same neutral metallocenes for polymerization joining the polymerized monomers.

Others about the e Y, R, Z, j, i, and jj are the same as defined above;

these ligands can be used as intermediates in obtaining heterocyclic metallocenes of the present invention.

Another object of the present invention is a catalytic system for the polymerization of joining the polymerized monomers containing the reaction product between:

- heterocyclic metallocenes formula (I) and

- suitable acetalization.

The present invention also relates to a method of polymerization joining the polymerized monomers, involving contacting at least one of the above catalytic systems with at least one joining the polymerized monomer. Preferably, metallocene and the monomer in contact with each other in a single reaction zone. Alternatively, metallocene formula (I) can be combined with socialization, such as alkylamine or alumoxane, either before or after contact with metallocene formula (I) monomer.

In addition, metallocene formula (I) can be used for the preliminary polymerization before polymerization bulk mono is homogeneous mixtures of polymers of different types by contacting metallocene formula (I), obtained for each polymer of a certain type from one or more monomers.

The preferred application of the present invention in practice is to obtain polyethylene, copolymers of polyethylene, isotactic, syndiotactic, gamestations or atactic polypropylene, or mixtures thereof, copolymers of polypropylene, as well as polymers and copolymers of other acceding of the polymerized monomers.

In the description of the present invention the following definitions are used:

"The Central radical" means a radical with six electrons, directly coordinating transition metal, such as five-membered ring in cyclopentadiene, indole or fluorine;

"NSO" means a ligand that includes a Central radical with six electrons, associated with radical containing at least one heteroatom;

"CP" means cyclopentadienyls ring;

"NDS" means ring Wed, containing one or more heteroatoms;

"Op" means an outdoor pentadienyl ligand having five atoms in all CIS-configuration and having a six-electrons delocalized over five atoms;

"R" means an anion or a counterion, the box is used to denote a heterocyclic analogues of aromatic ring systems, containing the Central five-membered heterocyclic ring and the condensed ring, for example h-Ind for indene or indianboy ring system containing at least one heteroatom in the six-membered ring of the condensed ring system, h-Flu for fluorenone or fluorenone ring system containing at least one heteroatom in one or both six-membered rings condensed ring system, or h-Pta to pentalenene or pantaleoni ring system containing at least one heteroatom in only one of the condensed five-membered rings Panteleeva ring system; and

The prefix "o-" is used to denote open pentadienyl analogue of the above condensed ring systems.

The applicant has discovered a new class of heterocyclic metallocenes with a wide range of applications for polymers of joining the polymerized monomers; however, these metallocene are two to three coordinated ligands, where at least one of these coordinated ligands has a Central radical with six electrons, directly coordinated with appropriate conversion Michaela group "NSO"). The electrons in the group GCS can be delocalized over all groups.

The present invention relates to metallocene and containing catalytic systems that can be used for polymerization of the accession of the polymerized monomers. In particular, the present invention relates to metallocene and catalytic systems for polymerization of the polymerized vinyl monomers including olefins such as ethylene, propylene and butylene) in order to obtain polymers such as linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and polypropylene (isotactic, syndiotactic, gamestations, atactic polypropylene and mixtures thereof). The resulting polymers are intended for the manufacture of articles by extrusion, injection molding, thermoforming, centrifugal molding, or using other techniques known to experts.

Polymers that can be obtained using metallocenes of the present invention are homopolymers and copolymers of vinyl monomers having from 2 to 20 carbon atoms, and preferably from 2 to 12 carbon atoms; and these vinyl monomers are Predeal and vinylpyridin, may also include various heteroatoms.

Heterocyclic metallocene of the present invention contain one or more mono-, bi - and/or tri-functional ligand, coordinated, forming a complex or otherwise associated with a suitable transition metal, where at least one of these ligands is a ligand NSO, coordinating the transition metal.

Particularly preferred heterocyclic metallocenes of the present invention are metallocene formula (I)

YjRiZjjMeQkP1,

where

(1) Y represents a coordinating ligand containing a Central radical with six electrons, directly coordinating Me, which is linked to a group containing at least one atom that is not carbon atom selected from b, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te;

(2) R" denotes a divalent bridging the relationship between Y and X, and may represent a linear or branched C1-C20-alkanniny radical; bicyclic3-C12radical, aryl radical or diarylethylenes radical, where these radicals optionally containing atoms of silicon, germanium, phosphorus, nitrogen, b is dstanley open pentalateral group, cyclopentadienylsodium group, heterocyclic cyclopentadienylsodium group, nitrogen-containing group, phosphorus-containing group, oxygen-containing group or a sulfur-containing group;

(4) Me is an element belonging to Group 3, 4, 5, 6 or to the series of lanthanides, preferably Lu, La, Nd, Sm, or Gd;

(5) Q represents a linear or branched, saturated or unsaturated alkyl radical, aryl radical, alcylaryl radical, arylalkyl radical or a halogen atom;

(6) P is stable coordinatewise or pseudoscorpionida a counterion;

(7) i is an integer having a value of 0 or 1;

(8) j is an integer having a value of from 1 to 3;

(9) jj is an integer having a value of from 0 to 2;

(10) k represents an integer having a value of from 1 to 3;

(11) l is an integer having a value of from 0 to 2.

A particularly important subclass metallocenes of the present invention represented by formula (III)

YR"ZMeQkP1,

where Y represents a group of the NPC, Z represents a group of non-GCS, and where R", Me, Q, P, k and 1 is defined above, (i=1, j=l, jj=1 in the formula (I)), a YR Z represents a ligand of the present image is pentadienyl)(7-cyclopentadien)-zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

isopropylidene(3-methylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

dimethylsilanol(3-methylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

isopropylidene(3-ethylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

dimethylsilanol(3-ethylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

isopropylidene(3-isopropylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

dimethylsilanol(3-isopropylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

isopropylidene(3-n-butylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

dimethylsilanol(3-n-butylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

isopropylidene(3-tert-butylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

dimethylsilanol(3-tert-butylcyclopentadienyl)(7-cyclopentadien)zirconium dichloride;

isopropylidene(3-trimethylsilylcyanation)(7-cyclopentadien)zirconium dichloride;

dimethylsilanol(3-trimethylsilylcyanation)(7-cyclopentadien)zirconium dichloride;

isopropylidene(ciclopirox)zirconium dichloride;

isopropylidene(3-methylcyclopentadienyl)(7-cyclopentadienyl)zirconium dichloride;

dimethylsilanol(3-methylcyclopentadienyl)(7-cyclopentadienyl)zirconium dichloride;

isopropylidene(3-ethylcyclopentadienyl)(7-cyclopentadienyl)zirconium dichloride;

dimethylsilanol(3-ethylcyclopentadienyl)(7-cyclopentadienyl)zirconium dichloride;

isopropylidene(3-isopropylcyclopentadienyl)(7-cyclopentadienyl)zirconium dichloride;

dimethylsilanol(3-isopropylcyclopentadienyl)(7-cyclopentadienyl)zirconium dichloride;

isopropylidene(3-tert-butylcyclopentadienyl)(7-cyclopentadienyl)zirconium dichloride;

dimethylsilanol(3-tert-butylcyclopentadienyl)(7-cyclopentadienyl)zirconium dichloride;

isopropylidene(cyclopentadienyl)(7-cyclopentadiene)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(7-cyclopentadiene)zirconium dichloride;

isopropylidene(3-methylcyclopentadienyl)(7-cyclopentadiene)zirconium dichloride;

dimethylsilanol(3-methylcyclopentadienyl)(7-cyclopentadiene)zirconium dichloride;

isopropylidene(3-ethylcyclopentadienyl)(7-cyclopentadiene)zirconium dichloride;

dimethylsilanol(3-ethylcyclopentadienyl)(7-cyclopentadiene;

dimethylsilanol(3-isopropylcyclopentadienyl)(7-cyclopentadiene)zirconium dichloride;

isopropylidene(3-tert-butylcyclopentadienyl)(7-cyclopentadiene)zirconium dichloride;

dimethylsilanol(3-tert-butylcyclopentadienyl)(7-cyclopentadiene)zirconium dichloride;

isopropylidene(2-methylthioamphetamine)(2-methylinden)zirconium dichloride;

dimethylsilanol(2-methylthiophenyl)(2-methylinden)zirconium dichloride;

isopropylidene(2-ethylthiophene)(2-atienden)zirconium dichloride;

dimethylsilanol(2-ethylthiophene)(2-atienden)zirconium dichloride;

isopropamide(2-isopropylnaphthalene)(2-isopropylidene)zirconium dichloride;

dimethylsilanol(2-isopropylnaphthalene)(2-isopropylidene)zirconium dichloride;

isopropylidene(2-tert-butylthiophene)(2-tert-butylene)zirconium dichloride;

dimethylsilanol(2-tert-butylthiophene)(2-tert-butylene)zirconium dichloride;

isopropylidene(2-trimethylsilylmethyl)(2-trimethylaniline)zirconium dichloride;

dimethylsilanol(2-trimethylsilylmethyl)(2-trimethylaniline)zirconium dichloride;

isopropylidene (cyclopentadienyl)(thiopental)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(thayil(indenyl)thiopental)zirconium dichloride;

isopropylidene(fluorenyl)(thiopental)zirconium dichloride;

dimethylsilanol(fluorenyl)(thiopental)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-methylthiophenyl)

zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

phenylmethylsulfonyl(cyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-ethylthiophene)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-ethylthiophene)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-n-butylthiophene)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-n-butylthiophene)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-isopropylnaphthalene)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-isopropylnaphthalene)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-phenylthiophene)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-phenylthiophene)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-aftercapture)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-aftercapture)zirconium dichloride;

isopropylidene(trimethylsilylmethyl)zirconium dichloride;

1,2-atanderson(cyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

isopropylidene(3-methylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

dimethylsilanol(3-methylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

isopropylidene(3-ethylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

dimethylsilanol(3-ethylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

isopropylidene(3-isopropylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

dimethylsilanol(3-isopropylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

isopropylidene(3-n-butylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

dimethylsilanol(3-n-butylacetoacetate)(2-methylthiophenyl)zirconium dichloride;

isopropylidene(3-tert-butylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

dimethylsilanol(3-tert-butylcyclopentadienyl)(2-methylthiophenyl)zirconium dichloride;

isopropylidene(3-tert-butylcyclopentadienyl)(7-cyclopent[1,2]thiophene[1,4] cyclopentadiene)zirconium dichloride;

dimethylsilanol(3-tert-butylacetophenone)(7-cyclopent[1,2]thiophene[1,4]cyclopentadiene)zirconium dichloride;

dimethylethyl(EN(3-tert-butylcyclopentadienyl)(7-cyclopent[1,2]thiophene[1,4] cyclopentadiene)zirconium dichloride;

dimethylsilanol(3-tert-butylacetophenone)(7-cyclopent[1,2] thiophene[1,4]cyclopentadiene)zirconium dichloride;

isopropylidene(cyclopentadienyl)(isopentane)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(isopentane)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-methylaziridinyl)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

phenylmethylsulfonyl(cyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-atlasapollo)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-atlasapollo)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-n-butylacetate)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-n-butylacetate)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-isopropylnaphthalene)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-isopropylnaphthalene)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-phenylazophenyl)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-phenylazophenyl)zirconium dichloride;

isopropylidene(cyclopentadienyl)(2-BR> isopropylidene(cyclopentadienyl)(2-trimethylsilylmethyl)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(2-trimethylsilylethynyl)zirconium dichloride;

1,2-atanderson(cyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

isopropylidene(3-methylcyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

dimethylsilanol(3-methylcyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

isopropylidene(3-ethylcyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

dimethylsilanol(3-ethylcyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

isopropylidene(3-isopropylcyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

dimethylsilanol(3-isopropylcyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

isopropylidene(3-n-butylcyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

dimethylsilanol(3-n-butylacetoacetate)(2-methylisophthalic)zirconium dichloride;

isopropylidene(3-tert-butylcyclopentadienyl)(2-methylisophthalic)zirconium dichloride;

dimethylsilanol(3-tert-butylacetophenone)(2-methylisophthalic)zirconium dichloride;

isopropylidene(3-tert-butylcyclopentadienyl)(7-cyclopent[1,2]perryperry[1,4]cyclopentadiene)zirconium dichloride;

dimethylethyl(3-tert-butylacetophenone)(7-cyclopent[1,2] pyrrole[1,4]cyclopentadiene)zirconium dichloride;

isopropylidene(cyclopentadienyl)(oxapentane)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(oxapentane)zirconium dichloride;

isopropylidene(cyclopentadienyl)(brabanthallen)zirconium dichloride;

dimethylsilanol(cyclopentadienyl)(brabanthallen)zirconium dichloride;

isopropylidene(cyclopentadienyl)(phosphopentose)zirconium dichloride and

dimethylsilanol(cyclopentadienyl)(phosphopentose)zirconium dichloride.

Another important subclass metallocenes of the present invention represented by formula (IV)

YR"YMeQkP1,

where the groups Y are the same or different and represent GCS and where R", Me, Q, P, k and 1 are as described above (i=1, j=2 and jj=0 in the formula (I)), a YR Y represents a ligand of the present invention.

Non-limiting examples of such metallocenes are:

isopropylidene(2-methylthiophenyl)zirconium dichloride;

dimethylselenide(2-methylthiophenyl)zirconium dichloride;

isopropylidene(2-ethylthiophene)zirconium dichloride;

dimethylselenide(2-ethylthiophene)zirconium dichloride;
isopropylidene(2-tert-butylthiophene)zirconium dichloride;

dimethylselenide(2-tert-butylthiophene)zirconium dichloride;

isopropylidene(2-trimethylsilylmethyl)zirconium dichloride;

dimethylselenide(2-trimethylsilylmethyl)zirconium dichloride;

isopropylidene(2-soteniliene)zirconium dichloride;

dimethylselenide(2-soteniliene)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-diethyl-1-abapentin-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-diethyl-1-abapentin-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-di-tert-butyl-1-abapentin-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-di-tert-butyl-1-abapentin-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-di-n-butyl-1-abapentin-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-di-n-butyl-1-abapentin-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-di-trimethylsilyl-1-abapentin-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-di-trimethylsilyl-1-userid;

methylphenylethylamine(1-phenyl-2,5-di-methyl-1-abapentin-4-yl)zirconium dichloride;

ethylphenethylamine(1-phenyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

1,2-atanderson(1-phenyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-dimethyl-1-phosphopentose-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-dimethyl-1-phosphopentose-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-diethyl-1-phosphopentose-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-diethyl-1-phosphopentose-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-di-tert-butyl-1-phosphopentose-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-di-tert-butyl-1-phosphopentose-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-di-n-butyl-1-phosphopentose-4-yl)zirconium dichloride;

dimethylselenide(1-phenyl-2,5-di-n-butyl-1-phosphopentose-4-yl)zirconium dichloride;

isopropylidenebis(1-phenyl-2,5-di-trimethylsilyl-1-phosphopentose-4-yl) zirconium dichloride;

dimethylselenide(1-phenyl-2,5-di-trimethylsilyl-1-phosphopentose-4-yl)zirconium dichloride;

diphenylsilanediol(1-phenyl-2,5-dimethyl-1-phosphopentose-4-yl)zirconium dichloride;

methylphenylsiloxane the 1-phosphopentose-4-yl)zirconium dichloride;

1,2-atanderson(1-phenyl-2,5-di-methyl-1-phosphopentose-4-yl)zirconium dichloride;

isopropylidenebis(4-phenyl-2,6-dimethyl-1-thiopental-3-yl)zirconium dichloride;

dimethylselenide(4-phenyl-2,6-dimethyl-1-thiopental-3-yl)zirconium dichloride;

isopropylidenebis(4-phenyl-2,6-diethyl-1-thiopental-3-yl) zirconium dichloride;

dimethylselenide(4-phenyl-2,6-diethyl-1-thiopental-3-yl)zirconium dichloride;

isopropylidenebis(4-phenyl-2,6-di-n-butyl-1-thiopental-3-yl)zirconium dichloride;

dimethylselenide(4-phenyl-2,6-di-n-butyl-1-thiopental-3-yl)zirconium dichloride;

isopropylidenebis(4-phenyl-2,6-di-isopropyl-1-thiopental-3-yl)zirconium dichloride;

dimethylselenide(4-phenyl-2,6-di-isopropyl-1-thiopental-3-yl)zirconium dichloride;

isopropylidenebis(4-phenyl-2,6-di-(3-pyridyl)-1-thiopental-3-yl)zirconium dichloride;

dimethylselenide(4-phenyl-2,6-di-(3-pyridyl)-1-thiopental-3-yl)zirconium dichloride;

isopropylidenebis(4-phenyl-2-methyl-6-(3-pyridyl)-1-thiopental-3-yl)zirconium dichloride;

dimethylselenide(4-phenyl-2-methyl-6-(3-pyridyl)-1-thiopental-3-yl)zirconium dichloride;

isopropylidenebis(4-phenyl-2-methyl-6-(3-chinolin)-1-thiopental-3-yl)zirconium dichloride;

dimethylselenide(4-phenyl-2-methyl-6-(3--3-yl)zirconium dichloride;

dimethylselenide(4-phenyl-2,6-di-trimethylsilyl-1-thiopental-3-yl)zirconium dichloride;

1,2-atanderson(4-phenyl-2,6-dimethyl-1-thiopental-3-yl)zirconium dichloride;

1,3-propanediylbis(4-phenyl-2,6-dimethyl-1-thiopental-3-yl)zirconium dichloride;

isopropylidene(3-methylthiophenyl-4-yl)(1-phenyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

dimethylsilanol(3-methylthiophenyl-4-yl)(1-phenyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

isopropylidene(3-methylthiophenyl-4-yl)(1-methyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

dimethylsilanol(3-methylthiophenyl-4-yl)(1-methyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

isopropylidene (3-methylthiophenyl-4-yl)(1-tert-butyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

dimethylsilanol(3-methylthiophenyl-4-yl)(1-tert-butyl-2,5-dimethyl-1-abapentin-4-yl)zirconium dichloride;

isopropylidene(3-methylthiophenyl-4-yl)(1-methyl-2,5-dimethyl-1-phosphopentose-4-yl)zirconium dichloride;

dimethylsilanol(3-methylthiophenyl-4-yl)(1-methyl-2,5-dimethyl-1-phosphopentose-4-yl)zirconium dichloride;

isopropylidene(3-methylthiophenyl-4-yl)(1-tert-butyl-1,5-dimethyl-1-phosphopentose-4-yl)zirconium dichloride;

dimethylsilanol(3-methylthiofentanyl)(1-phenyl-2,5-dimethyl-1-phosphopentose-4-yl)zirconium dichloride;

dimethylsilanol(3-methylthiophenyl-4-yl)(1-phenyl-2,5-dimethyl-1-phosphopentose-4-yl)zirconium dichloride.

Another subclass metallocenes of the present invention are the compounds of formula (III) or (IV), where i=0 and all other parameters are defined above.

Non-limiting examples of these metallocenes are:

bis(2-methylthiophenyl)zirconium dichloride;

bis(2-methylisophthalic)zirconium dichloride;

bis(2-methylphosphinico)zirconium dichloride;

bis(2-ethylthiophene)zirconium dichloride;

bis(2-atlasapollo)zirconium dichloride;

bis(2-ethylphosphonate)zirconium dichloride;

bis(2-isopropylnaphthalene)zirconium dichloride;

bis(2-isopropylnaphthalene)zirconium dichloride;

bis(2-isopropylnaphthalene)zirconium dichloride;

bis(2-tert-butylthiophene)zirconium dichloride;

bis(2-tert-butylacetate)zirconium dichloride;

bis(2-tert-butylphosphine)zirconium dichloride.

In the description metallocene formula (I), (III) and (IV) the term "associated" with the Central atom is used to refer to a group containing at least one heteroatom, "associated with the Central radical having 6 electrons, means that ukazanno coordinating Me. For example, the heteroatom cannot be a member rings, condensed with the Central radical having six electrons, such as in capitaline, isopentane, dichiarazioneantimafia, districtlocation and diphosphatidylglycerol or the heteroatom may be part of the radical associated with the Central radical having six electrons, such as Deputy heterocyclic radical linked to the Central moiety (for example, group 3-pyridyl-Cf).

In addition, there is another important subclass metallocenes of the present invention, which are capable of producing polymers having varying degrees of tact. Such metallocene usually are bridging metallocene formula (III) and/or (IV) (i.e. containing bridging ligands) having the specific character of the substitution, in which the polymerization process is able to inform this metallocene actionselection, which leads to the formation actionselection polymers.

Basically, actionselection catalysts and even actionspecific catalysts are formed in the case, when in the metallocenes of the formulae (III) and (IV) the group Y and/or Z are the same or different frosting, at least one Deputy is a bulky substituent (that is sterically more bulky than hydrogen, and preferably sterically larger than a methyl group or an aromatic carbon atom, which basically has the same relative steric size as a methyl group). Preferably, these metallocene have a specific overall symmetry. For more information about the action of volume-Deputy can be found in U.S. patent 5459117.

Metallocene formula (III), capable of producing polymers with different degrees of selectivity in respect of isotactic joining of monomer units ("isspecification metallocene"), including almost isspecifically polymers ("isspecification metallocene") must have either C2 or pseudo-C2 symmetry. In isoselective metallocenes neither Y nor Z do not have bilateral or pseudodistance symmetry and both Y and Z have the same volume-Deputy, regardless of the number and type of substituents. Alternatively, in isoselective metallocenes Y or Z, but not both, have bilateral or pseudo-bilateral symmetry, and the group that do not have bilateral symmetry, contains only one volume-Deputy. Similar isoselective metallocene can be obtained from metallocene formula (IV), which replace the polymers with different degrees of selectivity in relation to syndiotactic joining of monomer units ("candicemichelle"), including indiaspecific polymers ("indispositions metallocene") must have either Cs or pseudo-Cs-symmetry. In syndiotactic catalysts both Y and Z have bilateral or pseudodistance symmetry and either Y or Z, but not both, have a volume-deputies, regardless of the number and type of substituents. Similar candicemichelle metallocene can be obtained from metallocene formula (IV) wherein all substituents are present on two groups y

If metallocenes formulas (III) and (IV) that do not have groups of type Cf (i.e. ligands that do not have six-electrons delocalized over five atoms, or all isconfiguration or five-membered ring, such as NR-PR-ABOUT-or S-), the substituents on the group, not a group of type Cf, and the substituents on the group NSO should cause steric hindrance metallocene so that the obtained polymer had a degree of tact. In the case of oxide - or sulfide-bearing metallocenes, where the oxygen atom or sulfur, linked through a divalent bridging group R" with ligand NSO ligand NSO will ensure the regulation of the growth of the polymer chain due to the presence of one or more sometable a heterocyclic ring, condensed with the Central radical having six electrons. The specified class is described by formulas (I), (III) and (IV) where Y is substituted cyclopentadienyls group represented by the following structure:

< / BR>
where the group Rathat may be the same or different, are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C1-C20-alkyl, C3-C20-cycloalkyl,6-C20-aryl, C7-C20-alcylaryl and C7-C20-arylalkyl radicals, and where at least two adjacent groups Randmay form a condensed heterocyclic5-C7ring containing at least one atom that is not carbon atom selected from b, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te;

Rbrepresents hydrogen, halogen, linear or branched, saturated or unsaturated C1-C20-alkyl, C1-C20-CNS, WITH6-C20-aryl, C7-C20-alcylaryl,7-C20-arylalkyl,1-C20-Allexinno group optionally containing a silicon atom, or Rbthe submitted issleduyuschimi formula:

where (i) the atoms X, same or different, can represent N, R, NR9PR9, O or S, if the condensed ring has two heteroatoms, one of X can be O or S and the other X may be N, P, NR9PR9or one of them may be N or P, and the other can be NR9or PR9so that this molecular particle was chemically stable group;

(i) where R9represents a linear or branched C1-C20is a hydrocarbon radical, possibly substituted by one or more halogen, hydroxy-group, alkoxygroup; C3-C12-cyclopentadienyl radical, WITH3-C12-halogencyclopropanes radical, possibly substituted by one or more halogen atoms; C6-C20-aryl radical, WITH7-C20-alcylaryl radical, WITH7-C20-arylalkyl radical, a silicon-containing hydrocarbon radical, a germanium-containing hydrocarbon radical, a phosphorus-containing hydrocarbon radical, a nitrogen-containing hydrocarbon radical, a boron-containing hydrocarbon radical, aluminium-containing hydrocarbon radical, or a halogen atom;

(ii) the groups R are identical or different, can represent more halogen, hydroxy-group, alkoxygroup; C3-C12-halogencyclopropanes radical, optionally substituted by one or more halogen atoms; C6-C20-aryl radical, WITH7-C20-alcylaryl radical, WITH7-C20-arylalkyl radical, a silicon-containing hydrocarbon radical, a germanium-containing hydrocarbon radical, a phosphorus-containing hydrocarbon radical, a nitrogen-containing hydrocarbon radical, a boron-containing hydrocarbon radical, aluminium-containing hydrocarbon radical or a halogen atom; two adjacent groups R, taken together, may form a saturated, unsaturated or aromatic condensed ring;

(iii) n and m denote integers having values from 0 to the maximum number of substituents that may be present in the ring (for example, formulas (a)-(b) n can be 0, 1 or 2); and

(iv) Rand Rdenoting - and-substituents, respectively, which are identical or different, may represent hydrogen, linear or branched C1-C20is a hydrocarbon radical, possibly substituted by one or more halogen atoms, hydroxy-group or alkoxygroup; WITH6-C20-aryl radical, WITH7-C20-alcylaryl radical, WITH7-C20-arylalkyl radical, a silicon-containing hydrocarbon radical, a germanium-containing hydrocarbon radical, a phosphorus-containing hydrocarbon radical, a nitrogen-containing hydrocarbon radical, a boron-containing hydrocarbon radical, aluminium-containing hydrocarbon radical or a halogen atom; two adjacent groups Rand Rtaken together, may form a saturated, unsaturated or aromatic condensed ring;

(v) Raand Rbare the same as defined above.

In its most General form the method of the present invention involves the polymerization of joining the polymerized monomer, such as-olefin, taken separately or together with other acceding of the polymerized monomers in the presence of a catalytic system of the present invention, comprising at least one metallocene formula (I) and socialization, such as alumoxane.

In addition, the present invention relates to a method for actionselection and even actionspecific polymers, providing Comte is I, including at least one metallocene formula (III) and/or (IV), where the ligands mentioned metallocenes contain regulatory discretion and the substituents described in this application.

Many metallocene formula (I), (III) and (IV) that, when contacting the monomers capable of forming tactical polymers can produce actionselection and/or actionspecific polymers, require specific replacement, often giving them valid or pseudosymmetry. The term "symmetry" is used mainly to describe metallocenes that generate actionselection polymers, defined below.

The term "bilateral symmetry" means that the ligand, such as a group NSO group PR or group Cf is symmetric with respect to bisecting mirror plane perpendicular to the plane containing the ligand and dividing this ligand into two parts with 2 - and 5-positions, 3 - and 4-positions that are in mirror image relation to each other, respectively (for example, 3,4-dimethyl-Cf or 2,5-dimethyl-Cf). The term "pseudodistance symmetry" means that the 3,4 - and 2,5-substituents are similar, but not identical, tx2">

The term "CS- or pseudo-CS-symmetry" means that the entire metallocene is symmetric with respect bisecting mirror plane passing through the bridge group, and the atoms associated with the bridge group, i.e. the substituents on each coordinated group bridging ligand, which are symmetrically related, are identical or similar. "Cs or pseudo-Cs symmetry also means that the two coordinated groups have bilateral or pseudodistance symmetry. Candicemichelle metallocene have Cs or pseudo-Cs-symmetry and preferably include two coordinated groups connected together divalent bridging communication (i=1 and j+jj= 2 in the formula (I), and the substituents on one coordinated group is sterically larger than the deputies on the other coordinated group. So, for example, ligands (dietetica[3,3,1,0,0]unneutered)-R-(SR), ligands (dietetica[3,3,1,0,0]unneutered)-R(PR), ligand (dietetica[3,3,1,0,0]unneutered)-R-(3,4-di-tert-butyl-Cf) or ligands (dietetica[3,3,1,0,0]unneutered)-R ' -(2,5-dimethyl-Cf) WITH assymmetry or pseudo-Cssymmetry depending on the location of the two ATLA[3,3,1,0,0]unneutered)-R ' -(3-tert-butyl-4-isopropyl-Cf) or related ligands have pseudo-Cs-symmetry. The formation of the corresponding metallocenes of these ligands will lead to catalytic systems, which can lead to the formation of polymers with different degrees of syndiotactic, including polymers with very high degrees of indispositions.

The term "C2- or pseudo-C2-symmetry" means that the ligand has an axle WITH2symmetry passing through the bridge group, and if the system ligands limited to any plane, this axis must be perpendicular to the plane containing the ligand. Isoselective metallocene are, in General, WITH2- or pseudo-C2-symmetry and preferably include two coordinated groups, linked by divalent group (i=1 and j+jj=2 in the formula (I)), where at least one Deputy on one coordinated group is more bulky than the substituent in the same area on the other coordinated group and where only the racemic metallocene are active isoselective connections. So, for example, ligands rat-bis(N-phenyl-5-methyl-1-isopentenyl)R", ligands rat-bis (5-methyl-1-thiapentanal)R" and ligands bis(cyclopent[b]quinoline)R" are C2-symmetry.

Ilinden) have pseudo-C2-symmetry. For producing isoselective metallocene these ligands are subjected to interactions with molecules of the metals, which leads to the formation of a mixture of meso-isomers (which gives atactic polymer) and rat-isomers (which give isoselective polymers). Meso - and rat-isomers can be separated by crystallization or other separation technique, well known to specialists. Synthesis of cyclopent[b]quinoline described in Eisch, J. J.; Gadek, F. J., J. Org.Chem., 1971, 36, 2065-2071.

In addition, isoselective metallocene can be obtained so that they had no inactive meso-forms. Such isoselective metallocene primarily include one bilateral symmetric coordinated group and one asymmetric coordinated group (nedostroennyy or pseudodistance symmetric group).

In accordance with the present invention, by a suitable choice metallocene formula (I) can be also obtained olefin copolymers, in particular copolymers of ethylene and/or propylene and other olefins. The choice metallocenes of the present invention can be used for regulating the content of comonomers, as well as other properties of the polymer, t is="ptx2">

As already noted, metallocene of the present invention include one or more rings containing at least one heteroatom, and associated with the Central radical having six electrons, which directly coordinates the transition metal. Such associated ring include the following classes of radicals:

(i) heteroatom (heteroatoms) contained in the cyclic Deputy associated with one of the Central atoms of the radical;

(ii) heteroatom (heteroatoms) is contained in a ring condensed with the Central radical, but is not endocycles a member of the Central radical; or

(iii) contains heteroatoms in cyclic Deputy, connected with the Central radical and ring condensed with the Central radical. Rings, condensed with the Central radical may be aromatic, non-aromatic, unsaturated and/or unsaturated ring or ring system. In addition, the Central moiety may include phosphine-bratbanane radicals (which are in accordance with the methodology described in Quan, R. W. et al, J. Am.Chem.Soc., 1994, 116, 4489).

Examples of heterocyclic ring systems, which can be associated is In, Sn, Sb or Te; any group containing two or more of these atoms, and preferably any group containing N, O, P or S, or any group containing two or more of these preferred atoms. Non-limiting examples of such compounds are pyrrole, isoperla, pyrazole, isoimidazole, 1,2,3-triazole, 1,2,4-triazole, imidazole, indolizine, thiophene, 1,3-dithiol, 1,2,3-axetil, 1,2-dithiol, thiazole, isothiazol, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxadiazol, 1,2,3,5-oxadiazol, Tinatin, isothionate, isoindole, benzoxazol, anthranol, benzothiophen, natation, furan, isobenzofuran, benzofuran, indole, indazole, purine, carbazole, carboline, isothiazol, isoxazol, oxazol, furazan, tianfuan, pyrazinamidase, propiram, perezalonso, selenatol-benzothiazole, imidazothiazole, frozenocean, iridocorneal, oxalylamino, imidazolidin, predominate-cinoxacin, power-2,4-cyclopentadiene, thepenalty, isopentane and dichiarazioneintegrative.

Additional radicals GCS are, but are not limited to, heterocyclic condensed ring system, in which the heteroatom is not a Central part of the CP-rings, such as compounds represented by formulas (a) Eatom, where the heteroatom is 1-8 positions (numbered according to IUPAC); deletereadonly fluorene, where the heteroatoms are also 1-8 positions; monoethanolamine inden, where the heteroatom is 4-7 positions (IUPAC numbering); and deletereadonly indene, where the heteroatom is also in 4-7 positions. Heterocyclic compounds, including system type TIA - and isopentane, or heterocyclic compounds, including TIA, dithia-, Aza-, diaza -, and taasesitusi have three condensed five-membered ring, where the Central five-membered ring is completely carbon cyclopentadienyls ring.

Obviously, some of these ring systems will not have substituents at the heteroatom. Thus, the ring containing oxygen and sulfur, will not have a Vice associated with atoms of oxygen or sulfur. In addition, in the case of N, P and As, where these atoms are part of a double bond, these rings will not be associated deputies.

The term "open pentadienyl" (abbreviated as Pas) means all structures with six-electrons, which are centrally located in relation to the five related atoms in the fully isconfigurable, but at the same time, these five atom is nationalnoy ring system. Of course, all five atoms must be SP2-hybridized or must be otherwise hybridized that can provide the delocalization of electrons in five centers. One of the possible precursors for the Er-ligands of the present invention is a system, where four atoms are part of two non-conjugate double bonds connected with the Central atom and are separated by this atom and the double bond introduced two electrons in the ligand system, and the Central atom introduces two electrons in this system either directly (as ion pairs of atom N or P), or by loss tsepliaeva group, which leads to the formation of anionic center with respect to the atom or Si. Obviously, that can also be used and other Central atoms, including Ge and As.

Outdoor pentadienyl radical, which can be used in the present invention, includes PRS-ligands of the formula (V)

< / BR>
where G represents a carbon atom, nitrogen atom, silicon atom, or phosphorus atom;

L represents a radical CR3D3', SiR3R3'a radical NR3"the radical PR3', an oxygen atom or a sulfur atom, and L' represents a radical CR4R4'the radical SiR4R3", R4, R4', R4"and R5identical or different, may represent hydrogen, linear or branched C1-C20is a hydrocarbon radical, linear or branched C1-C20-halogenosilanes radical, linear or branched C1-C20-halogenougljovodonika radical, linear or branched C1-C20-alkoxy radical, WITH3-C12-cyclopentadienyl radical, WITH3-C12-halogencyclopropanes radical, WITH6-C20-aryl radical, WITH7-C20-alcylaryl radical, WITH7-C20-arylalkyl radical, the silicon-hydrocarbon radical, a germanium-hydrocarbon radical, a phosphorus-hydrocarbon radical, a nitrogen-hydrocarbon radical, a boron hydrocarbon radical, an aluminum-hydrocarbon radical or a halogen atom;2and R3, R3'or R3"and/or R5and R4, R4'or R4"may form a 4-6-membered ring or condensed 6-20-ring system; R3, R3'or R3"and R4, R4'or R4"can be linked together so that the five-membered atomic centers that make up Central in relation to the five atoms of the ligand with six of delocalized) denote the position of Vice, which will be determined in the following part of the description. Thus, for these metallocenes with divalent bridge, this bridge will be associated with the Central atom, which is indicated as position 1, in accordance with the numbering similar to that used in the cyclopentadiene. In addition, 2 - and 5-positions will be together in some cases referred to as position or proximal position (proximal with respect to the 1-position), while 3 - and 4-positions will be together in some cases referred to as position or distal position.

The present invention also relates to a method for producing polymers and copolymers having different and adjustable properties, including high molecular weight at high temperatures, actionselection (including actionspecific), stereoregularity, narrow or wide distribution of molecular masses, etc., This method involves the polymerization of one or more monomers in the presence of one or more metallocenes of the present invention.

The applicant found that can be obtained metallocene of the present invention that produce stereoregular and stereospecific editactions polyolefins and gamestations polyolefins. These indicated General formula metallocene have, as a key distinguishing features, bridge specifically substituted ligand containing at least one coordinating group NSO.

If metallocenes that produce stereoselective and/or actionselection polyolefins, ligand, which forms metallocene of the present invention, may be substituted in such a way that this metallocen will stereosystem (bridge), stereomotion and stereoselective such that: (1) the substituents on the ligand blocking and/or direct the orientation of the terminal segment of the polymer chain and/or attach the monomer so that each subsequent joining of monomer will be stereospecific, and the degree of stereoselectivity can be adjusted; and (2) bridge group reports the rigidity of the ligand system its rotation or isomerization will be prevented or limited. These metallocene differ in that they have - or distal substituents on the ligands that regulate the orientation of the attachment of the monomer; and, in addition, the configuration metallocene determines actionselection. Metallocene of the present invention can be either Nesteroushkin/metereology/ stereoplaytime or mixtures thereof. Seriousdot reported to metallocenes of the present invention by chemical bridging connection connecting the two coordinated groups with the formation of metallocenes formulas (III) and (IV), that is, where i= 1, jj=1 and j=1 in General formula (I). Bridge group prevents or significantly restricts two coordinated groups in the structural isomerization or rotation.

The applicant was also found that by adjusting the relative steric size metallocenes can be obtained catalysts that contribute steric adjustable defects in the resulting polymers. The applicant was also installed, which can be obtained such catalysts of the present invention that produce gamestations polymers. The applicant was also found that a homogeneous mixture of polymers with different properties can be obtained by polymerization of monomers in the presence of metallocenes of the present invention or by the polymerization of monomers in the presence of catalysts of the present invention in combination with known catalysts.

In the art, the term "metallocene" means ORGANOMETALLIC coordination link is to "sandwich" structure around the Central atom, where all five centers Cf-rings are involved in coordination of the metal. The metal atom may be a transition metal atom or a halide, alkylhalogenide or alkoxide of a transition metal. Such structures are sometimes called "molecular sandwiches" because cyclopentadienyl ligands are oriented above and below the plane containing the Central coordinated metal atom and which is approximately parallel to the planes containing the CP-ring. Similarly, the term "cationic metallocene" means metallocen, in which the Central coordinated metal atoms have a positive charge, i.e. metallocene complex is a cation associated with stable coordinatewise or pseudocordylus anion.

However, in addition to the traditional meaning of the term "metallocene", the concept of "metallocene of the present invention comprises metallocene, in which at least one of the groups coordinating to the Central metal atom or ion, is a ring system containing at least one heteroatom that is associated with the Central radical (Central radical directly coordinating transition metal). The second coordinate of groupola, where the heteroatom is located in the Central ring, the PR-containing ligand or SR-containing ligand, a nitrogen-containing ligand, a phosphorus-containing ligand, oxygen-containing ligand or a sulfur-containing ligand.

The person skilled in the art it is known that the valid values for i, j, k and l depend on the specific ligand and a coordinating metal; it is obvious that these values correspond to known requirements for ORGANOMETALLIC and electronic structure.

Radicals Z, are suitable for use in the present invention, but not limited to, are the following radicals:

(1) hemerocallidaceae ligands, in which the heteroatom is located in the Central radical;

(2) the PR-containing ligands;

(3) cyclopentadienyls or substituted cyclopentadienyls radicals of formula (C5R'iii), where the groups R', which may be the same or different and have values of R, and two adjacent groups R' can be linked together to form with4-C6-ring; (iii represents an integer having values from 0 to 5;

(4) nitrogen - and phosphorus-containing radicals represented by the formula (JR6jjj), where j represents a nitrogen atom or phosphorus, Grupp>1-R5and jjj is an integer having values from 0 to 3;

(5) oxygen - or sulfur-containing radicals represented by the formula (UR7jjj), where U represents an oxygen atom or sulfur; R7has the values defined above for the radicals R1-R5a kkk is an integer having values of 0 or 2.

Structurally suitable bridging groups R", able to tell seriousdot metallocenes of the present invention, include, but are not limited to, linear or branched C1-C20-alkanniny radical, WITH3-C12-dialkylanilines radical, WITH3-C12-cyclopentadienyl radical, WITH6-C20-aryl radical, diarylethylenes radical, diarylethylenes radical, a silicon-containing hydrocarbon radical, depletory serenely radical, a germanium-containing hydrocarbon radical, a phosphorus-containing hydrocarbon radical, a nitrogen-containing hydrocarbon radical, a boron hydrocarbon radical and aluminium-containing hydrocarbon radical.

Other suitable bridging groups R" are ionic links, such as IN(C6F5)2and Al(C6F5slavogorod, cyclic or linear hydrocarbon belonging to the other ORGANOMETALLIC catalyst or carboranes. Indeed, bridging ties can be2-bridges (and C3and so on), which form the backbone of the polymeric carriers (e.g., atactic, syndiotactic and isotactic polymers formed from vinylidene and 9-viniflora and so on), as well as functionalized polystyrene predecessors and all other polymers with integral or branched boron - or Al-containing functional groups that are associated with catalysts, for example, in zwitterionic form. Thus are preferred bridging groups R2C and R2Si, and particularly preferred are dimethylaniline bridge group.

Suitable radicals R, R', R1-R5, Rand Rinclude, but are not limited to, hydrogen atoms, linear or branched C1-C20is a hydrocarbon radical, linear or branched C1-C20-halogenosilanes radicals, linear or branched C1-C20-halogenougljovodonika radicals, linear or branched1-C20-alkoxyalkyl,these radicals, allylamine radicals, arylalkyl radicals, silicon-containing hydrocarbon radicals, germanium-containing hydrocarbon radicals, fosforsoderzhashchie hydrocarbon radicals, nitrogen-containing hydrocarbon radicals, boron-containing hydrocarbon radicals, aluminium-containing hydrocarbon radicals and halogen atoms. Of these preferred radicals are straight or branched C1-C20-alkyl radicals, trialkylsilyl radicals and aryl radicals, the most preferred are straight or branched C1-C10radicals and aryl radicals, and particularly preferred are methyl, ethyl, ISO-propyl, trialkylsilyl, trialkylsilyl and phenyl radicals.

In addition, suitable radicals corresponding to the R, R', R1-R5, Rand Rinclude, but are not limited to, zwitterionic radicals, such as Cf (6F5)-3and Cu-Al(C6F5)-3, CR-Al(CF3)-3, Wed-X-(C6F5)-3and Cf-X-(C6F5)-3where X represents alkenylphenol group or allinoneruby.

Metalna of the present invention and having Me = metal of Group 4, not necessarily must contain an independent and sometimes stereochemical preventing the counterion (i.e., 1=0). These zwitterionic radicals may also be suitable for mono - and dications metallocene formula (I), where Me represents a metal of Group 5 in the oxidation States +5 (Me(V)). They can even be supposedly used to create metallocene ion pair containing metals normal neutral Group 3 in oxidation state +3 (Me(III)). In this case, must be received insoluble heterogeneous system ion pairs to achieve a more accurate size of the polymer particles and morphological control.

The preferred metals, marked Me, include, but are not limited to, the elements of Groups 3, 4, or 5, or the number of elements of the lanthanides of the Periodic table of elements. More preferably, Me represents a metal of Group 4 or 5, and most preferred are titanium, zirconium and hafnium. The preferred elements of the series of lanthanides are elements Lu, La, Nd, Sm and Gd.

Suitable hydrocarbon radicals or halogen denoted by Q include, but are not limited to, linear or branched C1-C20is an alkyl radical, aryl RA is Yong, and more preferably a chlorine atom.

Examples of hydrocarbon radicals are methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl and phenyl. Examples alkilinity radicals are methylene, ethylene, propylene and isopropylidene. Examples of halogen atoms are fluorine, chlorine, bromine and iodine, and preferred is chlorine. Examples alkylidene radicals are methylidene, ethylidene and propylidene. Examples of nitrogen-containing radicals are amines, such as alkylamines followed, arylamine, arylalkylamine and al kilrenny.

Suitable coordinatewise anions corresponding to R in the General formula include, but are not limited to, [BF4]-B(PhF5)4[W(PhF5)6]-, [Mo(PhF5)6]-(where PhF5is pentafluorophenyl), [ClO4]-, [SnO6]-, [PF6]-, [SbR6]' and [AlR4]', where each R independently represents Cl, C1-C5is an alkyl group (preferably methyl group), aryl group (e.g. phenyl or substituted phenyl group) or a fluorinated aryl and alkyl groups.

Actionselection metal is otlichautsya fact, they have symmetry or pseudosymmetry associated with ligand or metallocenes. As previously established, metallocene, including two ligand and a2- or pseudo-C2-symmetry, or having one bilateral symmetric ligand, and one unsymmetrical ligand, and at least one volume-the Deputy or pseudo--Deputy (if metallocenes with groups that are not Cf, such as geometrically difficult amine or phosphine anionic ligands) produce polymers with varying degrees of isotacticity. In contrast, metallocene, including two ligand and as- or pseudo-Cs-symmetry, produce polymers with varying degrees of syndiotactic. These ligands, preferably, are the bridge, but there are two remotecopy metallocene, which can produce polymers with varying actionselection or polymers with varying degrees of regularity in the nature of the attachment of monomers, such as regularity attach type "head to tail" or "tail to head".

Of these metallocenes of the present invention, the most preferred are titanocene, redstapler few examples metallocenes of the present invention, where:

(1) Y in the ligand YR"Z correspond to the formulas (a)-(s), where Ris the volumetric Deputy or where the substituent R in combination with a ring atom in position relative to the carbon atom associated with R, forms a volume-Deputy; or

(2) two groups Y in the ligand YR"Z, which may be identical or different, correspond to the formulae (a)-(s), where Ris the volumetric Deputy or where the substituent R in combination with a ring atom in position relative to the carbon atom associated with R, forms a volumetric Deputy.

Some examples metallocenes of the present invention are metallocene where:

(1) Y in the ligand YR"Z correspond to the formulas (a)-(s), where Z is Cf-radical; Y and Z are bilateral symmetric, and only one of Y and Z has two volume-Deputy; or

(2) two groups Y in the ligand YR"Z, which may be the same or different, are bilateral symmetric and correspond to the formulas (a)-(s), where only one of the group Y has two volume-Deputy.

Another important subclass metallocenes of the present invention are metallocene able Produzione is directly obtained from the polymerization reaction of propylene without requiring additional stages of separation or subsequent polymerization and which have good mechanical properties and can be successfully used as elastomeric materials and as compatible components to obtain mixtures of amorphous and crystalline polyolefins.

These metallocene are nesostykovki metallocene corresponding to the formula (I), where i=0, j=1, jj=1 (i.e. containing two remotecopy ligand), and has a specific character substitution, which receive polypropylene with isotactic and atactic blocks in one polymer chain, or a mixture of isotactic and atactic polymer chains having elastomeric properties.

In the formula (I) Y and Z, which may be identical or different, preferably represent namashikaye ligands corresponding to the formula (hh')

< / BR>
where X, R, n and m are the same as defined above.

These metallocene are not hard and after isomerization, the symmetry of the catalysts alternates from chiral to achiral geometric configuration; alternating geometric configuration in the metallocenes of the present invention can be eliminated by choosing the appropriate volume remotecopy ligands Y and Z, as well as selection of suitable polymerization conditions.

Examples of the above metallocenes are, but are not limited to:

bis(4-phenyl-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-phenyl-2,6-diethyl-thiopental)CL-thiopental)zirconium dichloride;

bis(4-phenyl-2,6-di-n-butyl-thiopental)zirconium dichloride;

bis(4-phenyl-2,6-di-tert-butyl-thiopental)zirconium dichloride;

bis(4-phenyl-2,6-di-trimethylsilyl-thiopental)zirconium dichloride;

bis(4-(2-pyridyl)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(3-pyridyl)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(8-chinolin)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(3-chinolin)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(5-pyrimidyl)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(2-furanyl)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(2-piroli)-2,6-dimethyl-thiopental)zirconium dichloride:

bis(4-(3, 5dimethylphenyl)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(3,5-diethylphenyl)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(3,5-dimethylsilane)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-methyl-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-phenyl-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(triptoreline)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-naphthyl-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-(1-indenyl)-2,6-dimethyl-thiopental)zirconium dichloride;

bis(4-phenyl-2,6-dimethyl-asaint the-azaindole)zirconium dichloride;

bis(4-phenyl-2,6-di-isopropyl-azaindole)zirconium dichloride;

bis(4-phenyl-2,6-di-n-butyl-azaindole)zirconium dichloride;

bis(4-phenyl-2,6-di-tert-butyl-azaindole)zirconium dichloride;

bis(4-phenyl-2,6-di-trimethylsilyl-azaindole)zirconium dichloride;

bis(4-(2-pyridyl)-2,6-dimethyl-azaindole)zirconium dichloride;

bis{4-(3-pyridyl)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(8-chinolin)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(3-chinolin)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(5-pyrimidyl)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(2-furanyl)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(2-pyrrolyl)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(3, 5dimethylphenyl)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(3,5-diethylphenyl)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(3,5-dimethylsilane)-2,6-dimethyl-azaindole)-zirconium dichloride;

bis(4-methyl-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-phenyl-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(triptoreline)-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-naphthyl-2,6-dimethyl-azaindole)zirconium dichloride;

bis(4-(1-indenyl)-2,6-dimethyl-and the,6-diethyl-phosphopentose)zirconium dichloride;

bis(4-phenyl-2,6-dipropyl-phosphopentose) zirconium dichloride;

bis(4-phenyl-2,6-di-isopropyl-phosphopentose)zirconium dichloride;

bis(4-phenyl-2,6-di-n-butyl-phosphopentose)zirconium dichloride;

bis(4-phenyl-2,6-di-tert-butyl-phosphopentose)zirconium dichloride;

bis(4-phenyl-2,6-di-trimethylsilylacetamide)zirconium dichloride;

bis(4-(2-pyridyl)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(3-pyridyl)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(8-chinolin)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(3-chinolin)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(5-pyrimidyl)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(2-furanyl)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(2-pyrrolyl)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(3, 5dimethylphenyl)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(3,5-diethylphenyl)-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(3,5-dimethylsilane)-2,6-dimethyl-phosphopentose)-zirconium dichloride;

bis(4-methyl-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-phenyl-2,6-dimethyl-phosphopentose)zirconium dichloride;

bis(4-(triptoreline)-2,6-dimethyl-phosphopentose)Zirconia dig Stalin)zirconium dichloride.

Indeed, metallocene can be adapted for specific applications using a variety of methods of controlling the properties such as relative stereoselectivity and/or stereospecificity, molecular weight and other important properties of polymers. Metallocene containing ligands having a bridge connection with one carbon atom, are more stereospecific than their silicon bridge analogues used for syndiotactic specific catalysts; metallocene with carbon bridge connection are mostly less stereospecificity than silicon bridge counterparts isspecifically catalysts. The higher steric requirements of the substituents, the more stereospecific is metallocen. Differences in steric requirements for conformational constraints and stereoregular-Deputy can be used to optimize the orientation of the end of the chain. The presence of substituents in the position should also lead to an increase in molecular weight of the polymer. The present invention relates both to a neutral metallocene and the cationic metallocenes, as indicated by the subscript 1 referring to the anion P, there is allocine are cationic, as evidenced by the inclusion of the anion in the General formula.

Metallocene of the present invention can be also obtained for polymers with very high rates of tact depending on the necessary tact. To obtain actionspecific polymers from metallocenes of the present invention are important characteristics of the substituents on the bridging ligands. For example, the term "steric requirements" or "steric size of the substituents may relate to the regulation of steric characteristics metallocene so that the location of substituents provided control over the stereochemistry of each subsequent addition of monomer.

If necessary, it can also be appropriately located deputies with their own steric properties on the corresponding atom (atoms) carbon metallocene of the present invention, which should serve as a conformational restrictions of the terminal segment of the chain (preferably located in the "mouth" of the ligand), and which should also inform the solubility (the separation of the ion pair to improve catalytic activity and stereospecificity) and/or nerest who are stereosystem, have conformational restrictions on the end of the chain and have advantages compared with metallocene without such conformational restrictions.

In previous studies it was shown that, for example, methyl Deputy under-Cf-position C5-ring bicentenial catalysts, increases the molecular weight of the isotactic polypropylene obtained by using a catalyst based on Et[Ind]2ZrCl2. Similarly, the methyl substituents on C6-ring ingenious ring system reduces stereospecificity depending on the position isomerism.

Additionally, the accession of methyl, t-Bu, OMe - Ph-Deputy to the coordinating groups of the ligand and to the bridging group R" affects steritest, solubility and electronic environment of the catalysts for syndiotactic and isotactic specific polymerization.

By introducing other sterically larger-substituents and/or other sterically smaller-substituents can be obtained actionselection options metallocenes of the present invention in order of the messages produced polymers of any degree of tact. For example, the EU mately, actionspecific metallocenes will be reduced compared to metallocene having two tert-butyl and two bromide.

Of course, to maintain its strict neutrality cationic metallocene require the presence of anion R. Anion R in the General formula is preferably compatible coordinatewise or pseudocordylus anion which either does not coordinated with the cation of metallocene, or only loosely coordinated with the cation and, in addition, remains quite unstable, so that it can be easily displaced by a neutral Lewis base, such as Monomeric link. Compatible coordinatewise or pseudoachondroplasia anions defined as anions, which stabilize cationic metallocene, but which do not transfer an electron or equivalent electrons to the cation with the production of neutral metallocene and a neutral by-product coordinatewise or pseudoachondroplasia anion.

Used the size of the counterion R also depends on the volume or steric requirements of the ligands. In addition to size, good for anions or counterions are important and other characteristics, such as stability and swasey electron cation of metallocene, and the strength of bonding with the cation must be weak enough not to interfere with the coordination of the monomer and the chain growth.

The preferred method of producing cationic metallocenes of the present invention (1=1 or 2) involves the reaction of ion pairs in ncoordinates solvent metallocene formula (I), where 1=0. So, for example, tetrakis(pentafluorophenyl)boronate triphenylarsine or similar ion pair may be subjected to reaction with a neutral metallocene of the present invention in a solvent such as toluene, to obtain the corresponding cationic metallocene. This method of obtaining well-known in the art and described, for example, in U.S. patent 5225550.

The preferred application of the present invention is its use in the polymerization of alpha-olefins, preferably ethylene and propylene, to obtain a high degree of linear polyethylene of low, medium and high density, as well as atactic, isotactic, syndiotactic, gamestations polypropylene or mixtures thereof. However, metallocene of the present invention can be used to obtain gamestations, isotactic or syndiotactic the specific or hemisections polymers of 1-butene, 1-pentene, 1-hexene and styrene can be obtained using metallocenes of the present invention.

Joining the polymerized monomers, suitable for use in the present invention are Ethylenediamine monomers or any other organic molecule having a terminal vinyl group (CH2=CH), such as a-olefins (e.g. propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten), vinylchloride (for example, viniferin and vinyl chloride), vinylidene (for example, styrene, alkylated styrene, halogenated styrene and halogenosilanes styrene), diene (for example, 1,3-butadiene and isoprene). Polyethylene and polypropylene are probably the most practical application, and in the present application will be described in detail obtaining polyethylene and/or polypropylene polymers, but it should be noted that the present invention can be also applied to all acceding the polymerized monomers. These catalysts can also be used for the polymerization of dienes with elastomers through 1,4-addition instead of 1,2-addition. Obviously, these catalysts can also be used to vary otoshimono with conjugated double bonds.

The polymerization procedure using metallocenes of the present invention carried out by known methods such as a method described in U.S. patent 4892851.

In the catalytic systems of the present invention metallocene of the present invention are used in combination with various socialization. Although many of them are active, but they can be activated after adding various socialization. Socialization, which can be used in the present invention are usually alumoorganic compounds such as trialkylaluminium, trialkylaluminium, halides dialkylamide or dihalogenide alkylamine. Particularly suitable alkylamines compounds are trimethylaluminum and triethylaluminum (TEAL), the latter is the most preferred. In the method of the present invention can also be used methylalumoxane (MAO), especially for neutral metallocene in quantities greatly in excess of the stoichiometric equivalent.

Alumoxane are polymeric aluminum compounds that can be represented by the General formula (R-Al-O)nthat meet the, where R represents a C1-C5is an alkyl group such as methyl, ethyl, propyl, butyl and pentyl, and n represents an integer from 1 to 20. Most preferably, when R is methyl, and n=4.

Basically, in the manufacture of alumoxanes of trialkylamine and water receive a mixture of linear and cyclic compounds. Alumoxane can be obtained in various ways. They can be obtained, preferably, by contacting water with a solution trialkylamine, such as, for example, trimethylaluminum in an appropriate organic solvent such as benzene or an aliphatic hydrocarbon. For example, alkylamine process water in the form of a moist solvent, in an alternative method alkylamine may be subjected to contact with a hydrated salt such as hydrated copper sulfate. Alumoxane, preferably produced in the presence of hydrated copper sulfate: a dilute solution of trimethylaluminum in toluene is treated with copper sulfate represented by the General formula CuSO45H2O. the Ratio of copper sulfate to the trimethylaluminum is, preferably, about 1 mole of copper sulfate on 4-5 moles of trimethylaluminum. This reaction prosleeves the manage in the range from 0.5:1 to 10000:1, and preferably 5:1 to 1,000:1. Solvents used in the preparation of catalytic systems of the present invention are, preferably, inert hydrocarbons, particularly hydrocarbons, inert in relation to metallocenes.

These solvents are well known in the art and such solvents are, for example, isobutane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene and xylene. For more regulation and more accurate molecular weight of the polymer can be varied concentration alumoxane: higher concentration alumoxane in the catalytic system of the present invention results in more high molecular weight polymer product.

Since in accordance with the present invention, it is possible to obtain high-viscosity polymer products at a relatively high temperature, temperature is not the limiting parameter, as it was previously produced metallocene/alumoxane catalyst. Therefore, the catalytic systems described in this application, suitable for the polymerization of olefins in solution, in suspension or in the gas phase, and the polymerization can be about Elah from -60oWith up to 280oWith, and preferably in the range of 50oWith up to 160oC. In the method of the present invention uses pressure, which are usually used for these purposes, specialists, and preferably in the range from 1 to 500 atmospheres or higher.

When polymerization in solution alumoxane, preferably dissolved in a suitable solvent, typically in an inert hydrocarbon solvent such as toluene and xylene, molar relationship for about 510-3M But can be used in larger or smaller amounts. Soluble metallocene of the present invention can be used in heterogeneous catalytic systems on the medium by applying a specified metallocenes on carriers of catalysts known in the art, such as silicon dioxide, aluminum oxide and polyethylene. The solid catalyst system in combination with alumoxane can be successfully used for polymerizatio in suspension and gas-phase polymerization of olefins.

After polymerization and deactivation of the catalyst, the polymer may be isolated by known methods to remove the deactivated catalysts and mortar. The solvents can be evaporated from polimernogo other suitable forms. The polymer may be added pigments, antioxidants and other additives known to the specialists.

The polymer product obtained by the method of the present invention has srednevekovoy molecular weight ranging from about 500 to about 1400000, and preferably from about 1,000 to 500,000. The distribution of molecular masses (Mw/Mn) is preferably in the range from 1.5 to 4, but can be obtained and higher values. These polymers contain unsaturation end of the chain to 1.0 molecule. Wider distribution Mw can be achieved through the use of two or more metallocenes of the present invention in combination with alumoxane. The polymers obtained by the method of the present invention can be molded in a wide range of products, known as polymeric products derived from the joining of the polymerized monomers.

Metallocene of the present invention can be obtained by methods known in the art and described in U.S. patent 4892851 and active cationic metallocene can be obtained simply by turning neutral metallocene in cationic state in accordance with known methods described in EP 0277003 and 0277004, or by reaction with Boronina precursors for the production of the active anionic metallocenes of the present invention, where alcohol proton reacts with the amine alkyl groups on the coordinating metal atoms with the formation of cationic metallocene and alkoxide(PhF5)3-anion.

Metallocene of the present invention can be also transformed into a heterogeneous catalytic system on the media by applying katalizatorov on the media including, but not limited to, silicon dioxide, aluminum oxide, magnesium dichloride and polystyrene pellets. Metallocene on the media can inform the obtained polymer bulk density, as described in U.S. patent 4935474 and 4530914 and in EP 0427697 and 0426638.

Metallocene of the present invention can also be chemically linked to the carrier by attaching functional groups with ion pairs or centers of the Lewis acid or the centers of the base Lewis to the ligands and/or media. Join the media can also be performed by using a large (oligomeric or polymeric) insoluble anions as counterions.

Metallocene of the present invention can be used to obtain polymers with a small, medium or large molecular weight, polymers of low, medium and high density, elastomers, nelena, but all-olefins such as 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten and CH2=CH(CH2)p-Si(CH3)3where p=1-4. In addition, metallocene of the present invention can be polymerized alone or in a mixture of all acceding of the polymerized monomers, including vinyl monomers and diene monomers.

For each secondary specialist should be obvious that metallocene of the present invention, which can be obtained using bioselective catalysts can be selected in the meso-form, which is asymmetric, and in rat-form, which is selective for isotactic polymers. Stereospecific rat-metallocene can be separated from the meso-form by crystallization. From Bercaw and others (J. Ann.Cherry Soc., 1992, 1, 14, 7607 J. E. Bercaw & E. B. Coughlin.) it is known that rat-metallocene separated from unwanted nonspecific meso stereoisomers can be obtained by attaching a suitable volumetric substituents, such as Si(Me)3for atoms of the ligand in the nodal position bridging atom.

Metallocene of the present invention can be used alone or in mixture with other metallocene catalysts, TiCl3

Metallocene of the present invention affect the rate of termination reactions by elimination of the hydride. So getting a new ligand conduct to regulate the molecular weight of the polymer. These metallocene can be used to achieve a certain molecular mass, and therefore for the molecular mass distribution of mixed molecules of these catalysts and catalysts of any other class. This gives advantages to achieve certain polymer properties in HDPE, LLDPE, PP, s-PP, etc. Similarly, Deputy limiting to butene and hexene. The impact of new ligands on the relationship of the reaction ability of the catalysts can be used to obtain reaction mixtures with different compositions, procedures alternation, distributions and/or molecular-mass distributions. Metallocene of the present invention allow to obtain higher quality polypropylene and copolymers of propylene-ethylene with a high toughness in the form of reaction mixtures or intermediate reaction products obtained by the polymerization, including polymerization in the fluidized bed and gas-phase polymerization under stirring.

Metallocene of the present invention can also be used to produce copolymers of olefins and copolymers of olefins and dienes with various degrees of actionspecific.

The following describes the General method of obtaining metallocenes of the present invention. In this way it is important that metallocen was "clean", because the use of metallocenes with impurities can lead to the production of low molecular weight amorphous polymers.

Basically, getting metallocene provides for the formation and secretion of the ligand (with bridge or emoticonos link), which can Bion, and then the reaction with a halide or alkyliden metal by the end of the complex.

The procedure of synthesis, mainly carried out in the atmosphere of inert gas with a security camera with gloves or using technology Slanka. The synthesis process mainly involves the following stages: 1) obtain a halogenated or alkylated metal compound; 2) obtain ligand; 3) synthesis of the complex; and (4) purification of the complex.

Synthesis of bridged ligands of the present invention having a substituted group, Cf, can be made by contacting the appropriate substituted fulvene with a suitable substituted cyclopentadienylsodium anionic ring under reaction conditions sufficient to produce bridge structure, resulting in a gain ligands or WITH2or Csor pseudo-C2or pseudo-Cs-symmetry. Fulvin is a cyclopentadiene ekzoticheskoy methylene group in the 1-position cyclopentadiene rings. Carbon ekzoticheskogo methylene is in the 6-position of fulvene. Because this carbon may eventually become a bridging group R" in the formula (I), preferred is the cue, the resulting bridge group is a tertiary carbon atom.

Fulvene that can be used to obtain ligands of the present invention have substituents at the 3 - and 4-positions Q and are mainly 6,6-disubstituted, and other arrangements may be substituted or unsubstituted, as shown below:

< / BR>
where R p is the Deputy to the received Cf-ring and where T, T' and ekzoticeski carbon (C6 in fulvene) are precursors of structural bridging group R".

As mentioned previously, the preferred method of turning neutral metallocene in cationic metallocene, which can be used in the present invention, provides for the reaction of neutral metallocene with boronate triphenylarsine. The preferred reagena is tetrakis(pentafluorophenyl)boronate triphenylarsine.

The catalysts of the present invention can also be used to obtain a pre-polymerized catalysts in accordance with known methods, such as the method described in U.S. patent 3893989, 4200171, 4287328, 4316966 and 5122583. Pre-polymerized catalysts can be polyclinic electron donor.

Preferred pre-cured metallocene of the present invention have a mass ratio of polymer/metallocene, approximately 0.1-100; especially preferred is a ratio less than 10. This synthesis is usually carried out at room temperature or lower in low-boiling solvents that easily evaporate in vacuum.

Experimental part

PFC means polyphosphoric acid, the synthesis of which is described in the work of F. D. Popp & W. E. McEwen, Chem. Rev., 58, 321 (1958); F. Uhlig & H. R. Snyder, Advances in Organic Chemistry, 1, 35 (1960).

EXAMPLE 1. Synthesis dichloride bis(2-methylthiofentanyl) zirconium

A. Synthesis of 4,5-dihydro-5-methyl-6N-cyclopent(b)thiophene-6-it.

[Below is a modification of the method first described O. Meth-Cohn, S. Gronowytz, Acta Chemica Scandinavica, 20 (1966) 1577-1587].

The solution containing thiophene (65,7 g, 781 mmol), methacrylic acid (66,56 g, 773 mmol) and methylene chloride (50 ml) for 1 hour was added dropwise to a solution of PFC (obtained above), keeping the temperature at 50oC. the Reaction mixture was stirred for another 2 hours, and then poured into 1 l of ice (obtained in 2-liter separating funnel and the organic layer was collected using a solution of methylene chloride in hexagenia water (2x250 ml). The organic layer was collected by the same method, and then dried with magnesium sulfate, was filtered and was dried in vacuo, resulting in a received 93,5 g dark brown, slightly viscous oil. After distillation of the substance was received at 52.2 g (1 mbar, 92-98oS) of the target product. Yield=44%. 1H-NMR: DCl3million days; a 7.85 (d, 1H), 6,95 (d, 1H), 2,4-3,3 (m, 2H), 1,25 (m, 3H).

b. Synthesis of 5-methyl-1-tupenterprise

(Below is a modification of the method first described Hendrich Volz & Heinrich Kowarsch, Tet. Lett., 48 (1976) 4375].

Absolute ethanol (300 g) was treated with intensive flow of gaseous hydrochloric acid until saturation. Then added toluene-4-sulfamerazine (64 g, 343 mmol) in the form of dry powder, resulting in the formed white suspension. After that for 30 minutes was added dropwise 4,5-dihydro-5-methyl-6N-cyclopent(b)thiophene-6-he (52,2 g, 343 mmol). The solution became clear liquid straw color, and then formed a white precipitate, which was collected by filtration. The residue is washed with THF (800 ml) and then dried in vacuum. Output: 100 g (91.5 per cent).

C. Synthesis of 5-methyl-1-Capitalina

5-Methyl-1-tainturieri (12.8 g, 40 mmol) suspended in dietyour in diethyl ether, 62,5 ml). The temperature was raised to room temperature and stirring continued for 16 hours, after which the color was dark purple. Then was added dropwise deoxygenating saturated aqueous solution of ammonium chloride (2 ml) and stirring continued for another 15 minutes, after which the solution has gained a yellow color. Then the suspension was filtered through a Frit with an average pore size and the solids re-washed with fresh diethyl ether (250 ml). Then diethyl ether in the filtrate was removed in vacuo, and provided a dark brown oil (of 1.62 g, 30%). Mass spectrum (typical, first isomer; m/e (RA): 136(11,4), 134(100), 121(25), 77(12).

d. Synthesis dichloride bis(2-methylthiofentanyl)zirconium

The zirconium tetrachloride (800 mg, 3.4 mmol) was added as a dry powder to 5-methyl-1-capitalistically salt (400 mg, 3.6 mmol) and then was added pentane (50 ml) and THF (5 ml) to give a suspension. The suspension was stirred for another 16 hours after which the solvents were removed in vacuum and received a bright yellow free flowing powder (1 g). The sample used for polymerization without further purification.1H-NMR (THF-d8): million D., of 7.4 (m, 1H), 7,0 (m, 1H), 5,9 (s, 1.5 H) and 5.7 (s, 1H), 2,l (s, 3H).

EXAMPLE 2. Polymerization of ethylene dichloride bis(2-matoesian using fortified outside magnetic stirrer. In the glass 10 ml vessel was added the catalyst (20 mg) and MAO (2.5 ml, 10% wt. in toluene). In a solution of toluene used as a solvent for polymerization, was added 2.5 ml MAO. Into a reaction vessel containing toluene/MAO, through a tube added to the solution containing the catalyst/MAO. The reaction vessel was purged of residual nitrogen was replaced with ethylene. In the reaction vessel was added to the ethylene pressure was maintained at 3 bar for 8 minutes, after which the reaction was suppressed by adding 5 ml of distilled water. Then the contents of the reaction vessel were poured into obezbolivaiuscii solution containing Hcl (4n., 120 ml) and methanol (80 ml). The organic layer was dried in vacuum at low heat (50oC, 3 hours).

Yield: 2.5 g; [] THN=3,47 (DL/g).

EXAMPLE 3. Polymerization of propylene with dichloride bis(2-methylthiofentanyl) zirconium

Polymerization of propylene was carried out in glass 500 ml reaction vessel with stirring using fortified outside magnetic stirrer. In the glass 10 ml vessel was added the catalyst (20 mg) and MAO (5.0 ml, 10% wt. in toluene). The reaction vessel was purged of residual nitrogen and was replaced by propylene. In the reaction vessel was added propylene and the pressure maintained at 3 to the reaction vessel were poured into obezbolivaiuscii solution containing 120 ml of 4n. HCl and 80 ml of methanol. The organic layer was dried in vacuum at low heat (70oC, 1 hour). Yield: 13.5 g of viscous oil. [] THN=0,18 (DL/g).

EXAMPLE 4. The synthesis of the dichloride dimethylsilane(2-methylthiofentanyl)zirconium

A. Getting 5-methyl-1-Capitalina

The synthesis was carried out by the method described in Example 1C.

b. Synthesis dimethylsilane(2-methylthiofentanyl)

5-Methyl-1-thiapentanal (1,62 g, to 11.9 mmol) was dissolved in 30 ml of diethyl ether and the temperature was lowered to -78oC. Then was added dropwise motility (11,9 mmol, 1.6 M solution in diethyl ether, 7,4 ml). The contents of the flask were heated to room temperature and stirring was continued for 3 hours. In a separating flask the clear (0,77 g, 5.9 mmol, 0,78 ml) was dissolved in 20 ml of THF and the temperature was lowered to -78oC. To the stirred solution was added dropwise to the suspension containing the anion of 5-methyl-1-Capitalina. Then the contents of the flask were heated to room temperature. The sample was taken for analysis, extinguished a saturated solution of aqueous ammonium chloride, dried with magnesium sulfate, filtered, concentrated in vacuo, and then analyzed (20549-47S; the purity of 37.6%, as determined by GC-MS). Mass SP is altepeter)zirconium

The solution containing dimethylsilanol(2-methylthiofentanyl) (1.78 g, 5,95 mmol) in diethyl ether (obtained above) at -78oWith, were treated with methyllithium (11,9 mmol, 1.6 M solution in diethyl ether, 7,4 ml). The contents were heated to room temperature and stirring continued for 16 hours. The solvents were removed in vacuum and the solid was repeatedly washed with fresh pentane (g ml). Then added zirconium tetrachloride in the form of a dry powder and pentane. After that, the pentane evaporated and was replaced by toluene and the solution was stirred over night. The solids were filtered and the filtrate was dried in vacuum. Output: 1,49 g (54%).

EXAMPLE 5. Polymerization of propylene dichloride with dimethylsilane(2-methylthiofentanyl)zirconium

Polymerization of propylene was carried out in glass 500 ml reaction vessel with stirring using fortified outside magnetic stirrer. In the glass 10 ml vessel was added the catalyst (20 mg) and MAO (5.0 ml, 10% wt. in toluene). The reaction vessel was purged of residual nitrogen and was replaced by propylene. In the reaction vessel was added propylene and the pressure maintained at 3 bar for 60 minutes, after which the reaction was suppressed by adding 5 ml of distilled water. Then the soda the ski layer was dried in vacuum at low heat (70oC, 1 hour). Output: a 19.6 g of a white free flowing polymer, [] THN=0,49 (DL/g).

EXAMPLE 6. Synthesis dichloride isopropylidene [cyclopentadienyl-(7-cyclopentadien)]zirconium

A. Synthesis of 7H-cyclopent[1,2-b: 4,3-b']dithiolene

7H-cyclopent[1,2-b: 4,3-b']dateopen (called in the following examples cyclopentadiene) was synthesized by the method first described A. Kraak et al., Tetrahedron, 1968, 24, 3381-3398.

b. Isopropylidene(7H-cyclopentadien)(cyclopentadiene)

The solution cyclopentadiene (1.0 g, 5,62 mmol) in ether (15 ml) was cooled to -78oAnd was treated with n-butyllithium (of 5.75 mmol, 2.3 ml of 2.5 M solution in hexane). After 2 hours stirring at 0oWith added during 30 minutes a solution of 6,6-diethyltoluene (0,60 g, 5,62 mmol) in ether (5 ml). The temperature was maintained at 0oC for 1 hour, and then the contents were heated to 25oC and was stirred for 16 hours. The reaction was stopped by adding a saturated solution of NH4Cl (15 ml). The organic layer was separated, washed with saturated salt solution (g ml) and dried MgSO4. After filtration the solvent was removed by evaporation on a rotary evaporator to obtain an oily residue. The product crystallized from a mixture of methane(d, 2H), 7,10 (d, 2H), 6,l-6,8 (m, 3H), 3,1(m, 2H), 1,18, of 1.29 (2s, 6H). Mass spectrum: C17H16S2PM=284.

C. Dichloride, isopropylidene[cyclopentadienyl-(7-cyclopentadien)]zirconium

A solution of isopropylidene(7H-cyclopentadiene)(cyclopentadiene) (540 mg, 1.9 mmol) in THF (20 ml) was cooled to -78oAnd was treated with n-butyllithium (4.0 mmol, 1.6 ml of 2.5 M solution in hexane). The contents of the reaction vessel was slowly heated to 0oC and stirring was continued for 4 hours to obtain a dark red solution. The solvents were removed in vacuum atoAnd the rest resuspendable in ether (15 ml) at -78oC. and Then through a tube was added ZrCl4(0,443 g, 1.9 mmol) in suspension in pentane (10 ml) and the contents of the reaction vessel was slowly heated to room temperature with stirring for 16 hours. The precipitated crude product was collected in a sealed Frit, washed with ether and pentane and dried in vacuum (yield: 1.0 g). A sample of the target compounds used in the tests polymerization, was obtained by extraction with toluene at 50oC. Proton NMR (CD2Cl2) million D. 7,42 (d, 2H), 7,21 (d, 2H), 6,44 (t, 2H), of 5.84 (t, 2H), 2.05 is (s, 6H).

EXAMPLE 7. Polymerization of ethylene dichloride isopropylidene[Tiziana vessel under stirring by means of a built outside magnetic stirrer. In the glass 10 ml vessel was added the catalyst (10 mg), and then added MAO (2.5 ml, 10% wt. in toluene). To a solution of toluene used as a solvent for polymerization, was added 2.5 ml MAO. Into a reaction vessel containing toluene/MAO, through a tube added to the solution containing the catalyst/MAO. The reaction vessel was purged of residual nitrogen was replaced with ethylene. In the reaction vessel was added to the ethylene pressure was maintained at 3 bar for 8 minutes, after which the reaction was suppressed with 5 ml of distilled water. Then the contents of the reaction vessel were poured into obezbolivaiuscii solution containing Hcl (4n. 120 ml) and methanol (80 ml). The organic layer was washed with water and the polymer solids were collected by filtration and washed with fresh methanol. The polymer was dried in vacuum at low heat (50oC, 3 hours).

Yield: 4.3 g; FDS.elm tree. (THN)=3,7 (DL/g).

EXAMPLE 8. Polymerization of propylene dichloride with isopropylidene[cyclopentadienyl-(7-cyclopentadien)]zirconium

Polymerization of propylene was carried out in glass 500 ml reaction vessel with stirring by means of a built outside magnetic stirrer. In the glass 10 ml vessel was added the catalyst (20 mg) and MAO (5.0 ml, 10% masala propylene and the pressure maintained at 3 bar within 60 minutes then the reaction was suppressed with 5 ml of distilled water. Then the contents of the reaction vessel were poured into obezbolivaiuscii solution containing 120 ml of 4n. HCl and 80 ml of methanol. The organic layer was washed with water, and the solvents were removed on a rotary evaporator. The viscous polymer was dried in vacuum at low heat (50oC, 1 hour). Output: 30 g of polymer; the FDS.elm tree. (THN)=0,30 (DL/g).

EXAMPLE 9. Synthesis dichloride isopropylidene[(tert-butyl-cyclopentadienyl)-(7-cyclopentadien)]zirconium

A. Synthesis of 7H-cyclopent[1,2-b: 4,3-b']dithiolene

7H-cyclopent[1,2-b; 4,3-b']dateopen (referred to in subsequent examples cyclopentadiene) was synthesized by the method first described A. Kraak and other Tetrahedron, 1968, 24, 3381-3398.

b. Obtain 3-tert-butyl-6,6-diethyltoluene

Dry acetone (99,3 mmol, 5,77 g, 7.3 ml) and tert-butylcyclopentadienyl (50,6 mmol, of 6.17 g) was mixed in a drip funnel and was added at room temperature in ethanol solution (10 ml) of KOH (10,3 mmol, of 0.58 g), stirring in nitrogen atmosphere. After stirring over night the Golden solution was diluted with ether, washed with 2n. HCl, water and dried with sodium sulfate. Sample raw organic fraction (7,4 g) were taken for analysis (GC-MS), which indicated 90% conversion of the (m, 2H).

C. Synthesis of isopropylidene(3-tert-butylcyclopentadienyl)-(7H-cyclopentadiene).

The solution cyclopentadiene (4.9 mmol, 0.87 g) in dry ether was cooled to -78oAnd was treated with n-butyllithium (4.9 mmol, 1,95 ml of 2.5 M solution in hexane). The reaction mixture was heated to 0oC and was stirred for 4 h and Then was added dropwise a solution of 3-tert-butyl-6,6-diethyltoluene (4.9 mmol, 0,79 g) in ether (10 ml) was stirred for 2 h at 0oC and then for 16 h at room temperature. The reaction was suppressed by the slow addition of a saturated solution of NH4Cl (10 ml). The aqueous layer was separated, washed with ether and discarded. The organic fractions were combined, dried MgSO4, was filtered and was evaporated to education oils. This oil was again dissolved in methanol/acetone, and the product was led by cooling on dry ice. Yield: 800 mg, 48%.

d. Dichloride, isopropylidene[tert-butylcyclopentadienyl-(7-cyclopentadien)]zirconium

Isopropylidene[tert-butylcyclopentadienyl-(7-cyclopentadien)] (800 mg, 2.4 mmol) was dissolved in THF (20 ml). The temperature was lowered to -78oWith and was added dropwise n-utility (4.8 mmol, 1,92 ml of 2.5 M solution in hexane). The solution, which stalonetray temperature. After cessation of gas evolution (2 hours) the solution was continued to stir for 1 h, and then THF was removed under pressure. The solids were washed with pentane and dried in vacuum. Then added ZrCl4(2.5 mmol, 0.56 g) and the mixture of solids suspended in pentane (50 ml) and was stirred for 16 hours Then pentane decantation and the product was dried under vacuum, resulting in a received 1,21 g light brown free flowing powder. The product (1.2 g) suspended in 30 ml Me2Cl2. After filtering and drying in vacuum was allocated 150 mg of the complex.1H-NMR million d: 7,40 (d, 2H), 7,22 (m, 2H), 6.30-in (t, 1H), 5,85 (t, 1H), 5,65 (t, 1H), 2,0 (s, 6H), 1,2 (s, 9H).

EXAMPLE 10. Polymerization of propylene dichloride with isopropylidene[tert-butylcyclopentadienyl-(7-cyclopentadien)]zirconium

Polymerization of propylene was carried out in glass 250 ml reaction vessel equipped with installed outside a magnetic stirrer, sensor internal temperature and bath to create an external temperature. The reactor was loaded with toluene (100 ml) and MAO (3 ml, 10% wt. in toluene from Witco Corp., 4,7% of the mass. Al). The content was maintained in thermostat, a stirring, at a temperature of 50oC. Then was added the desired number of calibrated solution metallocen/th and the temperature of the monomer is maintained constant during the whole cycle. The reaction was stopped after 1 hour by reducing the pressure and add 5 ml of oxidized methanol. The contents of the reactor quantitatively transferred into a solution of oxidized methanol intensive stirring for several minutes, and then separated organic fraction. After thorough washing with water, the solvents were removed by evaporation on a rotary evaporator. The polymer was dried in vacuum at low heat. Yield: 28 g of the polymer; C. C.=0,3 (DL/g), so pl.: 128oWith, mrrm: 2,9% mol.

EXAMPLE 11. Synthesis dichloride bis(4-phenyl-2,6-dimethylthiophenol)zirconium

A. Obtaining 3,4-bischloromethyl-2,5-dimethylthiophene

In a round bottom 2-liter flask equipped drip 100 ml funnel and mechanical stirrer, was added 2,5-dimethylthiophene (253,6 g of 2.26 mmol) and Hcl (41,3 g, 1.13 mol, 94,5 ml 37% of the mass. solution). Gaseous Hcl was added in a slow stream for 5 minutes and then was added dropwise a solution containing (water) formaldehyde (69,1 g, 2.3 mol, 172 ml 37% of the mass. solution). In the process of adding (1 hour 20 minutes) the temperature was maintained in the range -15oWith 0oC. After complete addition, the content was stirred for another 1 hour. The reaction mixture was suppressed by addition of N2O (400 ml) and the organic is om, containing PA2CO3, water, dried with magnesium sulfate, filtered, and then the solvent was removed in vacuo, resulting in a received 349,0 g of the reaction product. After purification by vacuum fractional distillation under pressure of 190 mtorr (mm RT.CT.) received they accounted for 60,54 g of the desired product.

b. Synthesis of 4-phenyl-2,6-dimethylthiophenol-4-ol

In a round bottom 2-liter flask equipped with a mechanical stirrer, was added magnesium powder (29 g, 1.2 mol) and covered THF (20 ml). Then the chips are activated 5 iodine crystals and dibromethane (1.5 ml). After activation is completed, THF was removed and replaced with fresh THF. Then was added dropwise a solution containing 3,4-bis-chloromethylstyrene (42.8 g, 205 mmol) in THF (1 l) and stirring was continued for another 18 hours To quickly stir the solution was added dropwise a solution containing methylbenzoate (29 g, 213 mmol) dissolved in THF (220 ml) and the mixture was stirred for 5 hours, the Reaction mixture was suppressed by adding a mixture of THF/water, then add H2O (200 ml) and the organic fraction was collected with the use of dry diethyl ether. The organic layer was dried MgSO4was filtered and the solvents were removed in vacuo, resulting in a received 61,9 g bright orange is pentalene

In a round bottom 2-liter flask, equipped with reflux condenser, was placed alcohol for dehydration (45,9 g) dissolved in toluene (100 ml). Then added monohydrate paratoluenesulfonyl acid (1.6 g) and 1 g of amberlite (mberlite IR-120). The contents were heated under reflux for 4 h, after which the flask and its contents were left to cool to room temperature. The organic layer was collected, again washed with H2O and dried MgSO4. After filtration the solvent was removed by evaporation on a rotary evaporator and received is 41.45 g of dark brown oil.

d. Synthesis dichloride bis(4-phenyl-2,6-dimethylthiophenol)zirconium

In a 100 ml round-bottom flask equipped with a rod for mixing and lateral diversion was added 80% of the compound (2.8 g, 10 mmol) containing 4-phenyl-2,6-dimethyl-3-ene(b)thiophene. The complex was dissolved in dry diethyl ether (50 ml) and then dropwise at room temperature was added n-utility (12.5 mmol, 5 ml of 2.5 M solution). The mixture was stirred for 1 h, which formed a bright orange solid precipitate, which was collected by removing the solvent in vacuo. Then added zirconium tetrachloride (of 1.16 g, 5 mmol) and the solids suspended in singing, washed with fresh pentane and dried in vacuum. Part of the solids collected in this way was dissolved in toluene and then filtered. The toluene was removed under vacuum and collected 1,38 g dark red glassy free flowing solids.

1H-NMR: million D.: 7,25 (m, 10H), 5,78 (s, 4H), 2,44 (s, 6H).

EXAMPLE 12. Polymerization of propylene with dichloride bis(4-phenyl-2,6-dimethylthiophenol)zirconium

In a glass 250 ml reaction vessel was loaded with 100 ml of toluene. Then was added a solution containing dichloride bis(4-phenyl-2,6-dimethylthiophenol)zirconium (5 mg) and MAO (5 ml, 10% wt. in toluene). The reaction vessel was tightly closed and the pressure was raised to 4 bar by feeding gaseous propylene. The temperature was controlled within 40oC for polymerization.

After 1 h the reaction vessel was purged with nitrogen and the solution is extinguished aqueous solution containing 30% vol. HCl (37% wt.) and 30% methanol. After filtering soluble in toluene substances, the solvent was removed in vacuum. Yield: 300 mg of the polymer; % mass. = 75,4; =512 (NMR).

EXAMPLE 13. Getting the dichloride dimethylsilane(1-phenyl-2,5-dimethyl-1-abapentin-4-yl)zirconium

A. Synthesis of 1-phenyl-2-methylpyrrole I

Utility (0,700 mol, 280 TMEDA (0,700 ml, 106 ml) in hexane (80 ml) and was stirred for 3 hours, the Suspension was diluted in 300 ml of THF and slowly added itmean (0,771 mol, 48 ml), maintaining the temperature between 35 and 40oC. After stirring at room temperature for 16 h was added 250 ml of water and the organic layer was separated. The aqueous layer was extracted with ether (CH ml) and the combined organic fractions were dried MgSO4. After filtration, evaporation of solvents and TM EDA received 107 g of light brown oil (yield 98%, purity +95%, GC-analysis).1H-NMR (DCl3): 7,29-7,44 (m, 5H), to 6.80 (m, 1H), 6,23 (m, 1H), between 6.08 (m, 1H), 2,24(s, 3H).

b. Synthesis of 1-phenyl-5-methyl-2-errorcorrecting II

l3(0,375 mol, 35 ml) was added dropwise to 37 ml of DMF and was stirred for 10 minutes the Temperature was lowered to 0oWith and was added dropwise a mixture of compound I (55 g, ~ 0,340 mol) and DMF (7 ml). A viscous solution was slowly heated to 50oC and was stirred for 1 h After cooling to room temperature, the flask was opened to air and downloaded 350 g of crushed ice. Then carefully added 20% of the mass. NaOH solution (430 ml), the mixture was immediately heated to 90-95oC and was stirred for 10 minutes, the Flask was placed in an ice-water bath and after cooling the product overide dried MgSO4. After filtration, the solvent evaporated and obtained 38 g of light brown solid (yield 60%).1H-NMR showed that the crude product is a mixture of 1-phenyl-5-methyl-2-paracervical and 1-phenyl-2-methyl-3-errorcorrecting in the ratio of about 4:1. By a spectroscope pure 1-phenyl-5-methyl-2-errorcorrecting was obtained by recrystallization from ether.

The presence of the two isomers was confirmed using NMR NOESY experiment.

1H-NMR (CDCl3) 1-phenyl-5-methyl-2-errorcorrecting: 9,26 (s, 1H, Ru-SLEEP), the 7.43 (m, 3H, AGN), 7,22 (m, 2H, AGN), of 7.00 (d, 1H, Runes), 6,12 (d, 1H, Runes), 2,04 (s, 3H, RUSN3), so pl. 85oC.

1H-NMR (CDCl3) 1-phenyl-2-methyl-3-errorcorrecting: 9,88 (s, 1H, Rusan), the 7.43 (m, 3H, AGN), 7,22 (m, 2H, AGN), of 6.68 (d, 1H, Runes), 6,62 (d, 1H, Runes), 2,39 (s, 3H, RUSN3).

C. Synthesis of ethyl -(1-phenyl-2-methylpyrrole-5-yl)methacrylate (III)

Triethyl 2-phosphonopropionic (93,3 mmol, 20 ml) was diluted in THF (15 ml) and slowly added to NaH (130 mmol, and 3.16 g) in THF (40 ml) at 0oC. After the evolution of gas has ceased, stirring is continued at room temperature for 30 minutes the Temperature was lowered to -10oWith and was added dropwise a solution of compound (II) (8 is formed on the thick sludge which were separated using a magnetic stirrer. Then carefully added a saturated solution of NH4Cl (50 ml) to dissolve the precipitate. After evaporation of THF, the crude product was extracted with ether (CH ml), washed with brine, dried MgSO4, filtered and evaporated to obtain a brown oil. Output: 22,5 g (96,5%) by a spectroscope pure product.

1H-NMR: (DCl3): 7,41(m, 3H, ArH), to 7.15 (m, 3H, ArH (2 N s) + Runs(CH3) (CO2Et), 6,60 (d, 1H, Runes), 6,12 (d, 1H, PyH), Android 4.04 (q, 2H, och2CH3), is 2.09 (s, 3H, Russ (CH3) (CO2Et), from 2.00 (s, 3H, RUSN3), of 1.12 (t, 3H, och2CH3).

d. Synthesis of ethyl -(1-phenyl-2-methylpyrrole-5-yl)isobutyrate (IV)

A solution of compound (III) (10 g, 37 mmol) in ethanol (50 ml) was stirred under hydrogen pressure of 3.5 bar at room temperature with 300 mg 10% Pd on coal within 1 h After evaporation of the filtered Golden solution was obtained ethyl -(1-phenyl-2-methylpyrrole-5-yl)isobutyrate in the form of a yellow syrup (9.4 g, purity 95% (GC)).

1H-NMR (DCl3): the 7.43 (m, 3H, ArH), 7.23 percent (m, 2H, ArH), of 5.92 (m, 2H, Runes), of 4.00 (q, 2H, och2CH3), 2,70 (m, 1H, RUSN2CH (CH3) (CO2Et), the 2.46 (m, 2H, PyCH2-SN), a 2.00(s, 3H, RUSN3), to 1.21 (t, 3H, och2CH3), of 1.05 (d, 3H, the ethyl -(1-phenyl-2-methylpyrrole-5-yl)somaclonal acid (V)

A mixture of the compound (IV) (9.4 g of the crude oil, approx. 33 mmol) and reagent Clausen (18 ml) was heated at 90-95oC for 1 h, After cooling to room temperature the solution was diluted with 15 g of crushed ice and acidified to pH 1-2 by addition of 6N Hcl. The brown oily residue was dissolved in ether; washed with saline, dried MgSO4, was filtered and was evaporated to obtain waxy solids. After grinding solids with pentane were obtained 6.6 g of compound V in the form of a reddish-brown powder (yield 84.7 per cent).

1H-NMR (CDCl3): the 7.43 (m, 3H, ArH), 7,21 (m, 2H, ArH), of 5.92 (m, 2H, Runes), of 2.72 (dd, 1H, PyCH2CH (CH3) (CO2Et), the 2.46 (m, 2H, PyCH2CH), from 2.00 (s, 3H, RUSN3), of 1.05 (d, 3H, PyCH2CH(CH3)).

f. Synthesis of 1-phenyl-5,6-dihydro-2,5-dimethylcyclopentane[b]azafen-4-it (VI)

The solution (V) (25 mmol, 6.0 g) in dichloroethane (45 ml) was slowly added to 100 g of 87% PFC at 85-90oC and was stirred for 3 hours the Mixture was cooled to room temperature, then added 200 g of crushed ice and continued to stir until complete dissolution of the PFC. The lower organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic fractions were washed TO2WITH

1H-NMR (DCl3): 7,44 (m, 3H, ArH), 7.23 percent (m, 2H, ArH), 6,12 (s, 1H, Runes), 2,90 (m, 2H, RUSN2), 2,32 (d, 1H, RUSN3CH-(CH3)CO-), of 2.09 (s, 3H, RUSN3), to 1.19 (d, 3H, PyCH2CH(CH3WITH-). MS (EI) (Rel. intensity): 223 ([M+-2], 4), 205(4), 149(100), 121(3), 104(5), 93(3), 76(5). So pl. 106oC.

g. Synthesis of gerazancecin (VII)

The ketone (VI) (31 mmol, 7.0 g), p-toluensulfonate (36 mmol, 6.7 g) and monohydrate p-toluensulfonate acid (6.3 mmol, 1.2 g) was dissolved in 50 ml of absolute ethanol and was stirred for 24 h at 65oC. After cooling to room temperature and standing for several hours the precipitated product was collected on a filter funnel, washed with ether and dried in vacuum (yield 5.0 g). The solvent was removed from the filtrate and a further 1.2 g of the product were led from ether/toluene solution of the oily residue. Total yield: 6.2 g (51%) of a light grey powder.

1H-NMR (DCl3): 7,80 (d, 2H, AGN), 7,39 (m, 3H, AGN), 7,17 (m, 4H, AGN), 6,23 (s, 1H, Runes), 3,25 (tt, 1H, PyCH2CH(CH3)CN-), 2,89 (d, 1H, PyCH2), to 2.35 (s, 3H of RUSN3), 2,24 (d, 1H, PyCH2), 2,10 (s, 3H, Me), and 1.15 (d, 3H, PyCH2CH(CH3)CN-); so pl. 156oWith (Raleigh in 20 ml of THF, was cooled to 0oAnd was treated with 2.1 equivalents of utility (to 10.6 ml of 2.5 M BuLi in hexane). The mixture was slowly heated to room temperature and was added 10 ml of THF to obtain a dark solution. After 2 hours formed a residue, to which was added ether (approx. 30 ml) to precipitate the product. The solids were collected on a closed filter funnel, washed with ether and dried in vacuum (7.5 g).1H-NMR of the crude product, protonated raw Dl3indicated the presence of a mixture of two isomers. Solids suspended in hexane (100 ml) and treated with saturated solution of NH4Cl. The hexane layer was separated, dried gS4, was filtered and was evaporated to obtain an oil (yield: 1.0 g, purity 85%, GC/MS). Proton NMR of the oil showed the presence of a single isomer.

1H-NMR (DCl3): Isomer 1 - 7,33 (m, 5H, ArH), 5,96 (s, 1H), 5,86 (s, 1H), 3.15 in (s, 2H, CH2WITH5-rings), of 2.21 (s, 3H, RUSN3), 2,04 (s, 3H, CH3the S-5). The isomer 2 - 7,33 (m, 5H, ArH), 6,ll(s, 1H), to 5.85 (s, 1H), 3.15 in (s, 2H, CH2WITH5-ring) to 2.18 (s, 3H, RUSN3), from 2.00 (s, 3H, CH3the S-5). m/e (EI) (Rel. the intensity): 209 (100), 194(27), 167(5), 117(4), 91(5), 77(13).

(i) Synthesis dimethylsilane(4-phenyl-2,5-dimethyl-4-isopentene) (IX)

1-Phenyl-Ř utility (3 ml of 2.5 M solution in hexane). The solution was heated to room temperature and was stirred for 2 hours the Precipitated lithium salt was collected on a closed filter funnel, washed with pentane and dried in vacuum. Salt (700 mg) was dissolved in THF (40 ml) was cooled to -78oAnd using a gas tight syringe was injected 0.2 ml (1,63 mmol) of dichlorodimethylsilane. The solution was heated to 55oC and was stirred for 16 hours the Solvent was removed in vacuum and the crude product used without further purification (ligand was obtained as a mixture of isomers).

1H-NMR (DCl3): 7,42 to 7.62 (m, 10H, ArH), 6,45, 6.42 per, 6,21 (3s, 4H), 5,86 (s, 1H), 3,62 (s, 2H,), 2,48, 2,45, 2,43, 2,41 ( 4s, 12H), -0,06, -0,08, -0,11 (3s, 6H).

13C-NMR (CD2Cl2) 129,4, 126,4, 126,1 (Ar), 117,9, 104,6 (olefinic CH), 42,5 (SN) and 18.0 (CH3), AND 14.3 (CH3), -7,1, is 7.3, to-7.6 (Si-CH3). m/e (EI) (Rel. the intensity): 474(29), 266(100), 251(11), 208(21), 192(13), 77(5).

(ii) Synthesis of the dichloride dimethylsilane(4-phenyl-2,5-dimethyl-4-isopentenyl)zirconium (X).

The product IX (1.1 g) was dissolved in ether (20 ml) was cooled to -78oAnd was treated with 4.8 mmol utility (1.9 ml of a 2.5 M solution in hexane). The solution was heated to room temperature and was stirred for 16 hours Besieged dianion collected in a closed of filtroval is stirred with 0.32 g ZrCl4was cooled to -78oAnd was treated with 20 ml of cold dichloromethane (-78oC). The contents of the flask was slowly heated to room temperature, was stirred for 4 h and filtered. The filtrate was evaporated to obtain a brown free flowing powder which was used without further purification in the tests of the polymerization.

EXAMPLE 14. Polymerization of propylene dichloride with dimethylsilane(4-phenyl-2,5-dimethyl-4-azaindole-4-yl)zirconium

Polymerization of propylene was carried out in glass 250 ml reaction vessel equipped with installed outside a magnetic stirrer, sensor internal temperature and bath to create an external temperature. In this reaction vessel was loaded with 100 ml of toluene. 10 mg of compound X in 5 ml of toluene was mixed with 3 ml of MAO (10 wt%. solution in toluene from Witco Corp., 4,7% of the mass. A1) and loaded into the reaction vessel, stirring at 25oC. the Pressure in the reaction vessel drove up to 4 bar using propylene and the temperature was raised to 50oC. the Polymerization was stopped after 1 hour by reduction of pressure and injection of 5 ml of acidified methanol. The contents of the reaction vessel was transferred into acidified methanol solution under intensive paramasivan and the polymer was dried in vacuum at low heat.

Output = 15 g free flowing powder (Mw= 47000, so pl. DSK=153oC, 13C-NMR Pintada "mrrm"=0,6% mol).

EXAMPLE 15. Synthesis dichloride dimethylsilane(2-methylthiophenyl)(2-methylinden)zirconium

A. Synthesis dimethylsilane(2-methylthiophenyl)chloride

In a 500 ml round-bottom flask, equipped with a side-wall, a rod for mixing and drip 125 ml funnel, was added to 31.9 g (100 mmol) of asymmetric topintercasino dissolved in THF (70 ml). Then was added dropwise N-utility (250 mmol, 100 ml of 2.5 M solution in hexane). After complete addition, the reaction mixture was stirred for another 5 hours. Then the reaction was suppressed by adding 250 mmol of water (4.5 ml H2O in 50 ml of Et2O). The organic layer was collected using Et2O, dried with magnesium sulfate, filtered, and then evaporated on a rotary evaporator, resulting received a dark brown oil.

Results: - area, %

BTR - 7,6

RM=136 - 79,6

ATR - 12,8

In a 250 ml round-bottom flask, equipped with a side-wall, a rod for mixing and addition of 60 ml funnel, was added olefin (10 g, of 73.5 mmol)(obtained above), dissolved in THF (15 ml). Then was added dropwise N-utility (73,5 mmol, of 29.4 ml of 2.5 M rastvorye substance was washed with pentane. In dividing 500 ml flask, equipped with a drip 125 ml funnel, was obtained a clear (19.3 g, 150 mmol, 18.2 ml, 1.5 EQ.), dissolved in THF (30 ml). The above anion was dissolved in THF (125 ml) and was added dropwise to a solution of silane. After complete addition, the reaction mixture was stirred for 30 minutes and then the solvents were removed in vacuum. Was the orange oil from orange solids.

b. Synthesis dimethylsilane(2-methylindenyl)(2-methylthioinosine)

In a 250 ml round-bottom flask, equipped with a side-wall, a rod for mixing and addition of 60 ml funnel, was added 2-methylinden (13 g, 100 mmol, the product manufactured Boulder), dissolved in THF (20 ml). Then was added dropwise N-utility (100 mmol, 40 ml of 1.6 M solution in hexane) at room temperature. After complete addition, the flask contents were stirred for another 2 hours. Then dropwise at room temperature was added a solution containing dimethylsilane(2-methylthiophenyl)chloride in THF (30 ml). Stirring was continued for 1 h, after which the reaction was suppressed by adding 30 ml of 30% mixture of water/THF, concentrated on a rotary evaporator and the sample was analyzed.

The results of GC, reactionwas)

ATR - 4,1%

Mass spectrum (m/e (RA)): 322(34), 193(100), 187(37), 159 (37), 128(26).

Subsequent purification of this substance is carried out by recrystallization from dichloromethane/Meon. The solid was isolated by the same method, and then dried on a rotary evaporator.

Results: - area, %

BTR - 0,7

RM=130 - 10,2

MTR - 27,6

RM=322 - 48,5

RM=328 - 6,3

ATR - 6,4

C. Synthesis dichloride dimethylsilane(2-methylthiophenyl)(2-methylinden)zirconium

In a 250 ml flask, equipped with a side-wall and a rod for stirring, was added ligand dimethylsilane(2-methylindenyl)(2-methylthiophenyl) (3.1 g, 9.6 mmol) dissolved in THF (70 ml). The temperature was lowered to -30oWith and was added dropwise n-utility (20 mmol, 8 ml, 2.5 M in hexane). The reaction mixture was stirred for 2 h, after which the solvent was removed in vacuo, and dianion collected in a similar way, washed with fresh pentane and dried in vacuum. This dianion were placed in a drying Cabinet and added ZrCl4(2,23 g, 9.6 mmol) in the form of a dry powder. Then the solids suspended in fresh pentane (70 ml) and was stirred for 16 h then the solvent decantation and the solid was dried in vacuum. These solids restoran. The solids were again dried in vacuum, and then dissolved in toluene and filtered. The toluene was removed under vacuum and provided 1.6 g of a dark brown free flowing solids.

EXAMPLE 16. Polymerization of propylene dichloride with dimethylsilane(2-methylthiophenyl)(2-methylinden)zirconium

In a glass 250 ml reaction vessel were placed toluene (100 ml), catalyst (40 mg) and MAO (8 ml, 10% wt. in toluene). The reaction vessel was tightly closed, then blew propylene and the pressure was raised to 4 bar. The passage of the polymerization reaction was controlled at 60oC for 1 h Then the reaction vessel was purged with nitrogen and added acid methanol solution for clearing the contents of the reactor. The organic layer was collected, washed with water and dried in vacuum. Yield: 38 g of a white free flowing non-adhesive polymer.

In a glass 250 ml reaction vessel were placed toluene (100 ml), catalyst (5 mg) and 5 ml of MAO (10 wt%. in toluene). The reaction vessel was tightly closed, then blew propylene and the pressure was raised to 4 bar. The passage of the polymerization reaction was controlled at 60oC for 1 h Then the reaction vessel was purged with nitrogen and used acidic methanol plants is yhod: 13 g of a white free flowing non-sticky polymer: % m=84,6, Mn=1132 (NMR end group).

EXAMPLE 17. Getting dichloride dimethylsilane(2-methylthiofentanyl)(1-phenyl-2,5-dimethyl-1-isopentanol)zirconium

A. Getting thio(C)Penta-4-methyl-5-dimethylsilicone

In a 250 ml round-bottom flask, equipped with a side-wall, a rod for mixing and addition of 25 ml funnel, were placed 6,18 g (to 45.4 mmol, 6 ml) 2-methylthioinosine (2-Meter), dissolved in 30 ml of diethyl ether. The temperature of the solution was lowered to -78oWith and added 50 mmol n-utility (20 ml, 2.5 M solution in hexane). The solution was heated to room temperature, and then stirred for another 2 hours. Formed in the reaction flask yellow solid residue (the anion of the lithium salt of 2-M) was cooled to -78oC. To the stirred reaction mixture was added dropwise a solution containing 11.7 g (91 mmol) of a clear, dissolved in 20 ml of diethyl ether. The contents of the flask were heated to room temperature and stirred for another 18 h and Then the crude reaction mixture was filtered, the solvents were removed in vacuum and was given a dark orange oil. Output: 10,45:1H-NMR CD2Cl2(main isomer): (million D.: a 7.2 (d, 1H), and 7.1 (d, 1H), 6,7 (m, 1H), 3,6 (s, 1H), 2,3 (s, 3H), 0,4 (s, 3H), 0,3 (s, 3H).

b. On agenoy side-wall and a rod for mixing, added 1.86 g (6.4 mmol) of the lithium salt of 1-phenyl-2,5-dimethyl-1-isopentene (obtained previously), dissolved in 30 ml of diethyl ether. Then slowly at room temperature was added a solution containing of 1.46 g (6.4 mmol) thio(C)Penta-4-methyl-5-dimethylsilicone dissolved in 30 ml of diethyl ether, and stirring was continued for another 48 hours Then the reaction was suppressed with a solution containing 10% water/THF, the organic layer was collected, dried with magnesium sulfate, filtered and the solvents were removed in vacuum. Output: 3,23 g of dark brown oil:1H-NMR CD2Cl2(main isomer): (million D.: 7,5 (m, 5H), 7,28 (d, 1H), and 7.1 (d, 1H), 7,0 (d, 1H), 6,9 (m, 1H), 5,9-6,3 (m, 1H), 3,0-3,3 (3s, 4H), to 2.1-2.3 (m, 6N), 1,5 (s), 0,2 (m, 6N).

C. Obtaining dichloride dimethylsilane(2-methylthiofentanyl)(1-phenyl-2,5-dimethyl-1-isopentanol)zirconium

In a 250 ml round-bottom flask, equipped with a side-wall and a rod for stirring, was added 2.8 g (7 mmol) of ligand (dimethylsilane(2-methylthiophenyl)(1-phenyl-2,5-dimethyl-1-isopentane), obtained as described above) dissolved in 50 ml of diethyl ether. Then was added dropwise n-utility (14 mmol, 6 ml of 2.5 M solution in hexane) and the crude reaction mixture was stirred another 2 hours at room temperature. Then the solvent was removed the g, 7 mmol) as a solid and the resulting mixture of solids suspended in 70 ml of fresh pentane. The contents of the reaction flask was stirred over night. The solvent was evaporated, the solids thus collected, suspended in toluene, filtered, and the toluene was removed in vacuo, resulting in a received 660 mg of a light brown free flowing solid (mixture of isomers, RAC/meso).

EXAMPLE 18. Polymerization of propylene with dimethylsilane(2-methylthiofentanyl)(1-phenyl-2,5-dimethyl-1-isopentanol)zirconium

In a glass 250 ml reaction vessel was placed 100 ml of toluene, 5 mg of catalyst and 5 ml of MAO (10%). The reaction vessel was tightly closed, purged with propylene, and then increased the pressure up to 4 bar. The polymerization reaction was carried out for 1 h at 50oC. Then the reaction vessel was purged with nitrogen and the contents of the reaction vessel extinguished acidic solution of methanol. The organic layer was collected, washed with water, and then dried in vacuum. Output: 22,8 g of polymer.

Synthesis dimethylsilane(tert-butylamide)(N-methyl-2-methyl-5,6-dihydroindeno[2,1-b]indol-6-yl)dimethylsilane

< / BR>
(a) Synthesis of 2-methyl-5,6-dihydrothieno[2,1-b]indole

All operations were carried out is panel, RPE Carlo Erba (99%); 2-indanol, Chemische Fabrik Berg (98%); p-tolylhydrazine hydrochloride, Aldrich (98%).

In a glass reaction vessel (Buchi) with a capacity of 1 l, equipped with three magnetic stirrer and connected to a thermostat for temperature control, uploaded 85,0 g of 2-indanone (Mm=132,16, to 0.63 mol), 102,0 g p-McC6H4NHNH2HCl (Mm= 158,63, to 0.63 mol) and 0.5 l i-D. The thick suspension was heated to 80oWith about 30 minutes and under stirring, the suspension was darkened and became dark brown. The mixture was stirred for 1 hour at 80oC and then cooled to room temperature within 30 minutes.

Suspension decantation using a siphon in 1.2 l of water containing 1.5 EQ. Panso3thus the thin-dispersed product is dark green (not observed no heat). The suspension is then filtered on a G3 Frit, washed with water, dried in air under conditions of moderate vacuum, and then in a rotary evaporator at 80oAnd, finally, under conditions of high vacuum (mechanical pump).

Received 121,2 g of the desired product with a yield of 87.3% (purity 99.6 percent according to GC).

1H-NMR (DCl3, , M. D.): 2,52 (s, 3H, CH3); 3,70 (s, 2H, CH2); 7,01-7,66 (m, 7H, Ar); 8,13 (Shir.s, 1H, N-H).4
Cl. The formed solid substance was separated by filtration and dried in vacuum to obtain 9.5 g of the target microcrystalline solid brown color in its purest form with the release of 86,3% (purity according to GC to 98.2%).

1H-NMR (DCl3, , M. D.): 2,52 (s, 3H, CH3); 3,68 (s, 2H, CH2); of 3.78 (s, 3H, N-CH3); 7,02-to 7.64 (m, 7H, Ar).

(c) Synthesis chlorodimethyl(N-methyl-2-methyl-5,6-dihydroindeno-[2,1-b]indol-6-yl)selama

9,5 ml of 2.5 M solution of n-BuLi in hexane-holding (23.75 mmol) was added dropwise to a solution of 5.1 g (N-methyl-2-methyl-5,6-dihydroindeno-[2,1-b]indole, obtained as described above (purity of 98.2%, Mm=233,32, 21,46 mmol; indenolol; n-BuLi= 1: 1,1) in 70 ml of THF, pre-cooled to -78oC. the value of 6 hours. Then it was again cooled to -78oC and added dropwise to a solution of dichlorodimethylsilane (Mm=129,06, d=1,264, and 2.6 ml, 21,43 mmol; indenolol: Me2SiCl2=1:1) in 20 ml of THF, pre-cooled to -78oC. after the addition was finished the reaction mixture was allowed to warm to room temperature and was stirred overnight. The solvents are evaporated under reduced pressure to get sticky solid brown color, which according to analysis1H-NMR was the target product with a small amount of by-products. This product is used in the next stage without additional purification.

1H-NMR (DCl3, , M. D.): -0,13 (s, 3H, Si-CH3); to 0.48 (s, 3H, Si-CH3); 2,53 (s, 3H, CH3); 3,44 (s, 1H, CH); 3,88 (s, 3H, N-CH3); 6.90 to-7,71 (m, 7H, Ar).

(d) Synthesis of 6[dimethylsilane(tert-butylamino)N-methyl-2-methyl-5,6-dihydroindeno[2,1-b]indole

3,96 g Chlorodimethyl(N-methyl-2-methyl-5,6-dihydroindeno-[2,1-b] indol-6-yl)silane (Mm=325,92, 12, and 15 mmol), obtained as described above was dissolved in 50 ml of toluene and was added at -78oTo a solution of t-BuNH2(3.0 ml, Mm=73,14, d= 0,696, 28,55 mmol) in 20 ml of toluene. After the addition was finished the reaction mixture was allowed to warm to room temperature and the AC is monia. The filtrate was concentrated under vacuum to obtain 3,49 g of the desired product as a black sticky substance (crude yield 79,2%).

1H-NMR (DCl3, , M. D.): -0,15 (s, 3H, Si-CH3); -0,04 (s, 3H, Si-CH3); to 1.23 (s, N, t-Bu); 2,52 (s, 3H, CH3); 3,44 (s, 1H, CH); 3,86 (s, 3H, N-CH3); 6.90 to-7,71 (m, 7H, Ar).

(e) Synthesis dimethylsilane(tert-butylamino)(N-methyl-2-methyl-5,6-dihydroindeno[2,1-b]indol-6-yl)dimethylsilane

to 25.3 ml of 1.6 M solution of MeLi in diethyl ether (40,48 mmol) was added dropwise at room temperature to a solution 3,49 g of 6-[dimethylsilane(tert-butylamino)]N-methyl-2-methyl-5,6-dihydroindeno [2,1-b]indole (Mm=362,60, 9,62 mmol), obtained as described above, in 45 ml of Et2O. the Reaction mixture was stirred overnight; the solution became more and more muddy and the formed suspension black. Then at room temperature was slowly added to 1.05 ml of TiCl4(Mm=189,71, d=l,730, 9,62 mmol) in 40 ml of pentane and the resulting mixture was stirred over night. The solvents were removed under reduced pressure to obtain a black sticky substance, which was extracted with 50 ml of toluene. The extract is then concentrated with getting to 3.02 g of the desired product in the form of a black powder (crude yield = 71,6%).

3); of 1.41 (s, N, t-Bu); of 2.45 (s, 3H, CH3); of 3.12 (s, 3H, N-CH3); 6.90 to-7,94 (m, 7H, Ar).

1. Synthesis dimethylallyl{ (2-methyl-1-indenyl)-7-(2,5-dimethylcyclopentane[1,2-b:4,3-b']-dateopen)}zirconiated (metallocen 1)

1.1 Synthesis of 2-methyl-4-bromothiophene

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1 mol of 2-thiophenecarboxaldehyde was added to 2.5 mol of powdered ll3with stirring, keeping the temperature below 40oC. after the addition was curing liquid complex, then carefully added dropwise with stirring to 1.2 mol of bromine. Upon completion of the addition the stirring became impossible due to the complete curing of the mixture. This solid substance was injected into a mixture of ice (0.5 kg) and hydrochloric acid (100 ml, 32%) was then added 300 ml of CH2CL2. The organic phase was separated and the solvent was removed. The resulting substance (4-bromo-2-thiophenecarboxaldehyde) was dissolved in 700 ml of di(ethylene glycol) and the resulting solution was treated with 5.5 mol of hydrazine hydrate is added. The resulting mixture was boiled under reflux for 30 minutes After cooling to room temperature was added a 2.75 mol of potassium hydroxide. After gas evolution ceased, began the distillation and collected what was and was distilled at 60oC./10 mm. RT.article Yield 52%.

1H-NMR (DCl3, , M. D.): of 6.99 (d, 1H, H); 6,69 (kV, 1H, H)); 2,48 (d, 3H, CH3).

1.2 Synthesis of 2-methyl-4-formylthiophene

< / BR>
To mix the solution 44,26 g 2-methyl-4-bromothiophene (0.25 mol) in 300 ml of simple ether was added at -70 With a 1.6 M solution of n-BuLi (164 ml, 0.26 mol). The resulting solution was maintained under stirring at -60oWITH -70oC for 30 min and then was treated with a 27.4 g of dimethylformamide (of 0.37 mol) in 100 ml of ether. The mixture was allowed to warm to room temperature, then neutralized with 10% aqueous solution of NH4Cl, washed with 10% aqueous solution of N3RHO4and finally with water until neutral pH. The organic phase was collected, evaporated and distilled at 110oC./10 mm RT.article The output of 22.3 g (71%). Specified in the title compound was described1H-NMR spectroscopy.

1.3 Synthesis of 2,2'-dimethyl-4,4'-dithienylethene

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To a solution of 31.3 g of 2-methyl-4-bromothiophene (0,177 mol) in 150 ml ether at -70oWith under stirring was added 113 ml of a 1.6 M solution of n-BuLi (0.18 mol). The resulting solution was kept under stirring at -60oWITH -70oC for 30 min and then added to 22.3 g of 2-methyl-4-formylthiophene (0,177 mol) in 100 ml of ether. Mixture Doudou. The organic phase was separated and evaporated. Received the crude product of bis(2-methyl-4-thienyl)methanol (or 2,2'-dimethyl-4,4'-dithienylethene).

To a suspension of 10 g of LiAlH4(0,266 mol) in 100 ml ether was slowly added to a suspension of 35.5 g ll3(0,266 mol) in 100 ml of ether. The resulting mixture was treated with a solution of the carbinol (obtained as described above) in 100 ml of ether. The reaction mixture is boiled under reflux for another 1 hour, cooled to room temperature and then was added 100 ml of ethyl acetate. Then the mixture was treated with 300 ml of water and 300 ml of ether. The organic phase was collected, washed with water, dried MgSO4and was evaporated. The residue was distilled at -90oWITH -110oC/0.5 mm RT.article The output of 23.2 g (63%). Specified in the title compound was described1H-NMR spectroscopy.

1.4 Synthesis of 2,6-dimethyl-4H-cyclopent[1,2-b:4,3-b']-dithiolane (or 2,6-dimethyl-4H-thieno[3',2':2',3]-the cyclopent[b]thiophene)

< / BR>
1.04 g of 2,2'-Dimethyl-4,4'-dithienylethene (5 mmol) was dissolved in 30 ml of ether at -70oWith under stirring was added 9 ml of a 1.6 M solution of n-BuLi (14.4 mmol) and 1,74 g TMEDA (15 mmol). The resulting mixture was allowed to warm to room temperature, was stirred for 1 hour, again cooled to -70oAnd was treated with 2.7 g CuC is water. The organic phase was collected and passed through a column of silica gel. The resulting solution was evaporated to obtain 0.34 g of the product. The output is 34%. Specified in the title compound was described1H-NMR spectroscopy.

1.5 Synthesis dimethylallyl { (2-methyl-1-indenyl)-7-(2,5-dimethylcyclopentane[1,2-b:4,3-b']-dateopen)}zirconiabased

< / BR>
A solution of 2.4 M n-BuLi in hexane (7,20 ml, 18,00 mmol) was added at -20oWith the solution 3,93 g (2-methyl-1-indenyl)-7-(2,5-dimethylcyclopentane[1,2-b: 4,3-b'] dateopen)-dimethylsilane (Mm= 392,66, 90,4% according to GC-MS, 8,15 mmol, n-BuLi:ligand = 2:1 based on the purity of the ligand 90,4%) in 30 ml of ether. The resulting mixture was stirred for another 1 hour at 0oC and 30 minutes at room temperature, which led to the formation of a dark brown suspension. The suspension was again cooled at -20oAnd added to it a suspension 1,91 g ZrCl4(Mm=233,03, 8.20 mmol, Zrl4:ligand = 1:1 based on the purity of the ligand 90,4%) in 50 ml of pentane, pre-cooled to -20oC. the Reaction mixture was stirred at -20oC for 1 hour, then allowed to warm to room temperature and was stirred overnight. The obtained orange-pale brown suspension was evaporated in vacuum and the residue was washed .1H-NMR analysis showed the presence of the desired catalyst together with unidentified adduct coordination (possibly ZrCl4(Et2O)2or LiCl(EtO)). The powder is very quickly washed with 15 ml of 4N Hcl, then water (30 ml), then EtOH (20 ml) and Et2O. After drying, got 3.50 g of pure catalyst in powder form orange. The yield of pure product = 77,7%.

1H-NMR (CD2Cl2, , M. D.): 1,20 (s, 3H, Si-CH3); to 1.35 (s, 3H, Si-CH3); 2,39 (d, 3H, CH3, J=0,59); of 2.45 (d, 3H, CH3, J=1.2 Hz); 2,62 (d, 3H, CH3, J= 1.2 Hz); 6,66 (kV, 1H, CH, J=1.2 Hz); for 6.81 (Shir.s, 1H, CH); 6.87 in (DDD, 1H, CH, J= 0,98 Hz, J=6,65 Hz, J=9.0 Hz); 7,21 (DDD, 1H, CH, J=0,98 Hz, J=6,65 Hz, J=8,61 Hz); was 7.45 (dt, 1H, CH, J=0,98 Hz, J=8,61 Hz); 7,73 (DQC, 1H, CH, J=0,98 Hz, J=9.0 Hz).

2. Obtain di(2,5-dimethyl-7H-thieno[1,2-b: 4,3-b'] -cyclopent[b]thiophene-7-yl)dimethylchlorosilane (metallocen 2)

2.1. Synthesis of di(2,5-dimethyl-7H-thieno[1,2-b:4,3-b']-cyclopent[b]thiophene-7-yl)dimethylsilane

A solution of 1.03 g (5 mmol) of 2,5-dimethyl-cyclopentadiene[1,2-b:4,3-b']-dithiolane in 20 ml ether was treated at -70oFrom 1.13 ml of a 1.6 M solution of BuLi (5 mmol). The resulting mixture was stirred for another 30 minutes at 0oWith, again cooled to -70oC and then was treated with 0.32 g (2.5 mmol) clear 10 ml simple EPE is Cl. The organic phase was separated, the solvent was removed and the residue was recrystallized from hexane. The output of 1.66 (71%). Specified in the title compound were analyzed by the method of1H-NMR spectroscopy.

2.2. Obtaining di-(2,5-dimethyl-7H-thieno[1,2-b:4,3'-b']-cyclopent[b]thiophene-7-yl)dimethylchlorosilane

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A suspension of 1.41 g (3.0 mmol) of (2,5-dimethyl-7H-thieno-[3',2':3,4]the cyclopent[b] thiophene-yl)dimethylsilane in 20 ml of ether was treated with 3.75 ml (6.0 mmol) of 1.6 M BuLi at -70oC. the Mixture was allowed to warm to room temperature and then at the same temperature was added 0.7 g (3 mmol) ZrCl4. The reaction mixture was stirred while boiling under reflux for 3 hours. The red precipitate was filtered, washed twice with ether, and dried. The output of 1.47 g (80%).

3. Receiving (2,5-dimethyl-7H-thieno[1,2-b:4,3-b']-cyclopent[b]thiophene-7-yl)(N-9-fluorenyl)dimethylchlorosilane (metallocen 3)

3.1. Synthesis of (2,5-dimethyl-7H-thieno[1,2-b:4,3-b']cyclopent[b]-thiophene-7-yl)(N-9-fluorenyl)dimethylsilane

A solution of 1.03 g (5 mmol) of 2,5-dimethylcyclopentane[1,2-b:4,3-b']dithiolene in 20 ml simple ether was treated at -70oWith 3,13 ml of 1.6 M BuLi (5 mmol). The resulting mixture was stirred for another 30 minutes at 0oWith, again cooled to -70oC and C is I to room temperature, then was treated with saturated aqueous NH4Cl. The organic phase was separated, the solvent was removed and the residue was recrystallized from hexane. Yield 1.28 g (60%). Specified in the title compound were analyzed by1H-NMR and13C-NMR spectroscopy.

3.2. Receiving (2,5-dimethyl-7H-thieno[1,2-b:4,3-b']cyclopent[b]thiophene-7-yl)(N-9-fluorenyl)dimethylchlorosilane

< / BR>
A suspension of 1.28 g (3.0 mmol) of (2,5-dimethyl-7H-thieno[3',2':3,4]cyclopent[b] thiophene-7-yl)(N-9-fluorenyl)-dimethylsilane in 20 ml of ether was treated with 3.75 ml (6.0 mmol) of 1.6 M BuLi at -70oC. the Mixture was allowed to warm to room temperature and obtained a yellowish precipitate deliciious salt. Salt was twice washed with ether and dried. Thus obtained salt is suspended in 20 ml of CH2CL2at -70oC and then was treated with 0.7 g (3 mmol) ZrCl4at the same temperature. The reaction mixture was allowed to warm to room temperature, then was stirred for 1 hour at boiling under reflux. Red crystalline precipitate was filtered, washed twice CH2CL2and dried. The output of 1.31 g (90%).

POLYMERIZATION

The copolymerization of propylene/butene

1 mmol of Al(i-Bu)3(1M R is stainless steel, fitted shirt with a set temperature 58oWith, so to get 50/50 mol%. in the liquid phase, and then, under nitrogen pressure, through the ampoule, stainless steel autoclave was injectively toluene solution containing a mixture of catalyst/socializaton (0.5 mg metallocene 1, 0.45 mmol MAO, in 3 ml of toluene), the temperature is quickly increased to the polymerization temperature, and polymerization was carried out at constant temperature for 1 hour. Received of 26.5 g of essentially amorphous polymer, which had a characteristic viscosity (I. V.)=to 2.29 DL/g, glass transition temperature (Tg)= -13,6oAnd the content of butene = 27,7% wt. (22,3% mol.).

Copolymerize propylene/ethylene

1 mmol of Al(i-VI)3(1M solution in hexane), propylene and ethylene were loaded at room temperature into an autoclave of 1 l stainless steel, equipped with a jacket, at the specified temperature 58oWith, so as to obtain the composition of the liquid phase of 288 g of propylene and 1.5 g of ethylene (0,42% wt.) in the liquid phase, and then, under nitrogen pressure, through the ampoule, stainless steel autoclave was injectively toluene solution containing a mixture of catalyst/socializaton (0.3 mg of metallocene 1, 0.27 mmol MAO, in 3 ml of toluene), Cerretani temperature and pressure (25 bar-g), feeding ethylene (total absorption 13.3 g). Received 52.7 g essentially amorphous polymer, which had I. V.=to 2.29 DL/g and an ethylene content = 6,3% wt. (9,2% mol.).

Copolymerization of ethylene/1-hexene

Glass autoclave with a capacity of 260 ml, equipped with a magnetic stirrer, a temperature sensor and a line feed of ethylene, cleaned and gave it a stream of ethylene at 35oC. at room temperature, the autoclave was loaded with 5 ml of 1-hexene and heptane to achieve a volume of 140 ml of the Catalytic system was prepared separately in 10 ml of heptane by sequential introduction of MAO (0.33 mmol) and metallocene 2, dissolved in 3 ml of toluene. After 5 minutes of stirring the solution was injected into the autoclave under a stream of ethylene. The reactor was closed, the temperature was raised to 70oWith and install a pressure of 4.5 bar. The total pressure was maintained constant by feeding ethylene. After 10 minutes the polymerization was stopped by cooling, degassing the reactor and the introduction of 1 ml of methanol. The obtained polymer was washed with acidic solution of methanol, then with methanol and dried in a vacuum oven at 60oC. the Yield was 3.3 g, activity 725,3 (kg/Zr), the characteristic viscosity of the polymer to 3.5 DL/g

Copolymerization of ethylene/propylene is second mixer, a thermometer and a pipeline for supplying monomers. After purging with nitrogen in the reactor is maintained in a thermostatic bath, loaded with 100 ml of toluene and the solution of TOO. At the temperature of polymerization was filed gaseous mixture of ethylene/propylene (60% wt. ethylene) at a constant discharging a flow rate of 1.5 l/min and a pressure of 1.1 ATM. After 2 minutes was added to 3.45 mmol of metallocene 2, dissolved in 5 ml of toluene in the presence of 34 Ámol TIOA to start the polymerization. During polymerization the temperature was maintained in the range of 0.2oC. the Polymerization was stopped after 15 minutes by adding 1 ml of methanol and the copolymer was recovered by precipitation in methanol/Hcl, filtering, washing with methanol and drying at 50oWith under reduced pressure. Yield 0.3 g, activity 3,81 (kg/Zr), the characteristic viscosity of the polymer of 1.0 DL/g

Gas-phase polymerization of ethylene/1-octene

100 g of the Polypropylene having a characteristic viscosity for 1.49 DL/g, bulk density 0,363 g/cm3and porosity determined by the mercury method, 0,375 cm3/g, was loaded into the reactor with a capacity of 4.2 l through the opening in the upper part of the reactor in an atmosphere of propane (pressure = 1 bar) at room temperature, without any pen is price 3, TIOA and MAO (Al/Zr= 200 mol/mol; MAO/TOU: 1:5) was dissolved in such a quantity of toluene to obtain a total volume of 10 ml, and stirred at room temperature for 10 minutes. Then the reactor was injectible solution of the catalyst by using a slight excess pressure of nitrogen. The suspension in the reactor was stirred for 10 minutes at 40oC. Then present in the reactor liquid was subjected to instantaneous evaporation. The reactor was loaded 25 g of ethylene 4,20 g 1-octene, at the same time bringing the temperature up to 75oC. the Final pressure was 6 bar, during the polymerization reaction pressure was maintained constant by continuously feeding ethylene. In the course of polymerization was continuously added dropwise to 50%on. solution of 1-octene in pentane. After a period of time, the polymerization was stopped by rapid degassing of the monomers. The polymer was collected and immersed in 800 ml of methanol, then was filtered and dried in vacuum for 2 hours at a temperature of 60oC. Yield 90 g, the activity of 4.5 (kg/g cat.), the characteristic viscosity of the polymer 2,46 DL/g

1. Metallocen General formula (I)

YjRiZjjMeQkP1< / BR>
where (1) Y is a coordinating group containing the multiple rings, containing at least one atom that is not carbon atom and selected from N, S;

(2) R" represents a divalent bridging communication between the groups Y and Z;

(3) Z represents a coordinating group having the same meaning as Y or Z is cyclopentadienylsodium group or nitrogen-containing group;

(4) Me is an element belonging to group 3, 4, 5, 6 of the Periodic table of elements, such as zirconium or titanium;

(5) Q represents a linear or branched, saturated WITH1-C6alkyl radical or a halogen atom;

(6) P is stable gecoordineerde or pseudonocardiaceae a counterion;

(7) i is an integer having a value of 0 or 1;

(8) j is an integer having a value of 1-3;

(9) jj is an integer having a value of 0-2;

(10) k represents an integer having a value of 1-3;

(11) l is an integer having a value of 0-2.

2. Metallocen under item 1, characterized in that it Y contains a heterocyclic ring condensed with the specified Central radical having six electrons.

3. Metallocen under item 2, characterized in that it Y is driving us crazy, selected from the group consisting of hydrogen, linear or branched saturated or unsaturated WITH1-C6-alkyl, C6-C15-aryl, C7-C15-alcylaryl and C7-C15-arylalkyl radical and where at least two adjacent groups Randform a condensed heterocyclic5-C7ring containing at least one atom that is not carbon atom and selected from N and S;

Rbrepresents hydrogen, linear or branched, saturated or unsaturated C1-C6is an alkyl group, or Rbrepresents a divalent bridging group R".

4. Metallocen under item 1, characterized in that it Y contains at least two heteroatoms.

5. Metallocen under item 1, where i= 1, a Z is the same as y

6. Metallocen under item 1, where i= 1, j= 1, and Z represents CR-containing group, nitrogen-containing group.

7. Metallocen under item 1, where i= 1, j= 1, jj= 1, and at least one Deputy or Y or Z is a volume group that sterically larger than a hydrogen atom or fluorine.

8. Metallocen under item 1, where i= 1, j= 1, both Y and Z are bilateral or pseudobacteremia SIM is n by p. 1, where i= 1, j= 1, jj= 1, one or both of Y and Z are not bilateral or pseudonatural symmetric and Y or Z have at least one Deputy larger than hydrogen.

10. Metallocen on p. 9 with CS- or pseudo-CS-symmetry.

11. The ligand of General formula (II)

YjRiZjj,

where (1) Y is a coordinating group containing the Central radical with six electrons, which condensed one or more rings containing at least one atom that is not carbon atom and selected from N and S;

(2) R" represents a divalent bridging communication between the groups Y and Z;

(3) Z represents a coordinating group having the same meaning as Y or Z is cyclopentadienylsodium group.

(4) (i is an integer having a value of 1;

(5) j is an integer having a value of 1;

(6) jj is an integer having a value of 1.

12. Catalytic system for the polymerization of joining the polymerized monomers containing product of the reaction between the metallocene compound of formula (1) according to any one of paragraphs. 1-11 and appropriate socialization, which is alumac sterowanie catalytic system p. 13 with at least one joining the polymerized monomer.

14. The method according to p. 13, providing for the engagement of metallocene contained in the specified catalytic system, with a suitable acetalization either before or after contact of the specified metallocene with the monomer.

15. The method according to p. 13, comprising the following stages: a) contacting a specified catalyst system with a small amount specified acceding of the polymerized monomer with education prepolymerized catalyst; (b) contacting prepolymerized catalyst obtained in stage (a), with the specified accession of the polymerized monomers.

16. The method according to p. 13, characterized in that the polymerized monomers are alpha-olefins.

17. The method according to p. 16, wherein the alpha-olefins are selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene.

 

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