Transition metal based catalyst systems and methods of producing homopolymers of ethylene or copolymers of ethylene and α-olefins using said systems. RU patent 2507210.

FIELD: chemistry.

SUBSTANCE: invention relates to a transition metal compound of chemical formula (1): [Chemical formula 1] In the present formula, M is Group 4 transition; Cp is a cyclopentadienyl ring bonded with M on a η⁵-type, where the cyclopentadienyl ring can further be substituted with (C1-C20)alkyl or (C6-C30)aryl; Ar is (C6-C14)arylene; R¹¹ and R¹² independently denote a hydrogen atom or (C1-C10)alkyl; n is an integer from 0 to 2; R is (C1-C10)alkyl or (C1-C10)alkoxy; and when n equals 2, individual substitutes R can be identical or different; X¹ and X² independently denotes a halogen atom, (C1-C20)alkyl, (C6-C30)aryl(C1-C20)alkyl or (C6-C30)aryloxy; alkyl, arylalkyl, alkoxy, aryloxy groups, radicals Rⁿ, X¹ and X² and arylene groups Ar can be independently substituted with one or more substitutes selected from a group consisting of (C1-C20)alkyl, (C6-C30)aryl and (C1-C20)alkoxy. The invention also discloses a catalyst composition, a method of producing homopolymers of ethylene or copolymers of ethylene with α-olefin, a homopolymer of ethylene or a copolymer of ethylene with α-olefin.

EFFECT: invention enables to obtain compounds which are suitable as catalysts for producing homopolymers of ethylene or copolymers of ethylene with α-olefin.

13 cl, 1 tbl, 9 ex

The technical field

The present invention relates to the catalytic systems based on transition metals to produce homopolymers ethylene and ethylene copolymers with alpha-olefins. More specifically, it refers to the catalyst on the basis of transition metal Group 4, which differs that catalyst includes surrounded by transition metal 4 Groups derivative of cyclopentadiene and at least one ligand(s)containing group or its derivative, which functions as and serves to stabilize the catalytic system by environment atom of oxygen, which ligand binds with transition metal in ortho-position and has a chemical structure which can be easily replaced by the provision 9, and between ligands no stitching; to the catalytic systems, including the above-mentioned catalyst on the basis of transition metal and or on the basis of boron compounds; and to methods for homopolymers ethylene and ethylene copolymers with alpha-olefins with their use.

The level of technology

According to homopolymers ethylene and ethylene copolymers with alpha-olefins usually employed the so-called catalysts Ziegler-Natta, which consist of titanium compounds or vanadium as the primary catalytic component and connection as component. Although catalytic system Ziegler-Natta had been very active in the polymerization of ethylene, this catalytic system has a disadvantage, namely that of molecular-mass distribution of the resulting polymer is wide due to the presence of irregular center activation of the catalyst, and this can lead to irregular distribution in composition, especially in copolymers of ethylene with alpha-.

Has recently been developed catalytic systems consisting of transition metal compounds 4 Group of the Periodic table of elements, such as titanium, zirconium and hafnium, and as . Because catalytic system is a homogeneous catalyst, has activation center catalyst, it may provide polyethylene having a narrow molecular weight distribution and homogeneous distribution of the composition in comparison with the traditional catalyst Ziegler-Natta. For example, in the European patent publications №320762 and 3726325; laid out by the Japanese patent №Sho 63-092621, Hei 02-84405 and Hei 03-2347 reported that ethylene may be included with a high activity through the activation of metallocene molecules such as Cp 2 TiCl 2 , Cp 2 ZrCl 2 , Cp 2 ZrMeCl, Cp 2 ZrMe 2 , ethylene (IndH 4 ) 2 ZrCl 2 , through the use of as that gives polyethylene, having the molecular mass distribution (Mw/Mn) in the range of 1.5 to 2.0. However, using such a catalytic system difficult to obtain polymers with a high molecular weight. In particular, when the catalytic system is applied in case the solution polymerisation carried out at high temperature 140 C or above, activity suddenly decreases, and β dehydration dominant, so that the system is known to be unsuitable for polymers with high molecular weight (bulk molecular weight Mw) 100,000 or more.

Meanwhile, revealed the so-called geometrically limited catalysts type (also called catalysts with only center activation), in which the transition metals bound in the form of a ring as a catalyst for obtaining polymers with a high molecular weight, with a high catalytic activity in the polymerization of ethylene in or copolymerization of ethylene with alpha-. European patent №0416815 and 0420436 were offered examples amide group is in the form of a ring with one ligand, whereas in the European patent №0842939 were demonstrated illustrative catalysts in which phenolic ligand (as an electron donor) is associated with ligand in the form of a ring. However, there are numerous difficulties in the way of commercial use of these catalysts, because the output of educational procedures ring between the ligand and compound transition metal are very low in the course of synthesis geometrically limited catalyst described above.

On the other hand, examples of catalysts, which are not geometrically constrained, can be found in U.S. patent №6329478 and paved the patent Korea number 2001-0074722. Found that the catalyst with a single activation center that uses connection as a ligand, showed high conversion of ethylene in copolymerization of ethylene with alpha- in the conditions of solution polymerisation at high temperature 140 C or more. US patent # 5079205 reveals examples of catalysts containing ligand, and US patent # 5043408 reveals examples of catalysts containing chelate ligand type. But these catalysts have such a small activity that they can hardly be applied for industrial production of homopolymers ethylene and ethylene copolymers with alpha-, which is carried out at a high temperature.

The description of the invention

Technical problem

In order to overcome the problems of conventional technologies, the authors of the present invention conducted intensive research and found that the catalyst referring to a type of catalysts without stitching between ligands, which includes derivative of cyclopentadiene and at least one ligand(s)containing group or its derivative, which functions as and serves to stabilize the catalytic system environment by an oxygen atom ligand that binds with transition metal in ortho-position and has a chemical structure which can be easily replaced by the provision 9, exhibits excellent catalytic activity in the polymerization of ethylene and olefins. Based on this discovery, invention authors have developed catalysts for obtaining of high molecular mass of homopolymers ethylene and ethylene copolymers with alpha-, possessing high activity during the polymerization process at a temperature of 60 C or more, and came to the present invention.

Thus, the objective of the invention is to create compounds of transition metals, which are suitable as catalysts for obtaining homopolymers ethylene and ethylene copolymers with alpha- containing their catalytic compositions, and offer ethylene and ethylene copolymers with alpha-, which were obtained with the use of such connection or catalytic compositions.

Another object of the invention is to suggest a way of polymerization, in which the catalyst with a single activation center, possessing high activity, apply in the polymerization α-olefins, which allows for cost-effective in terms of commercialization of receipt of homopolymers ethylene and ethylene copolymers with alpha- having different physical properties.

In order to solve the tasks of the present invention is one aspect of the present invention relates to the catalyst (presented by the chemical formula (1)) on the basis of transition metal Group 4, which differs in that the catalyst includes surrounded by transition metal 4 Groups derivative of cyclopentadiene and at least one ligand(s)containing group or its derivative (which can easily be replaced by the provision 9), which functions as and serves to stabilize the catalytic system environment by an oxygen atom ligand that binds with transition metal in ortho-position, and between ligands no stitching; to the catalytic systems, which this catalyst on the basis of transition metal and or or on the basis of boron compounds; and to methods for homopolymers ethylene and ethylene copolymers with alpha-olefins with their use.

In the formula M represents the transition metal from Group 4 the Periodic table of elements;

Cf is ring, which is associated with the M η 5-type, or condensed ring containing ring, where ring or condensed ring containing ring, can optionally be replaced by (S1-C20), (C6-C30)Arild, (C2-C20) or (C6-C30)aryl(C1-C20);

Ar is (C6-C14);

R 11 and R 12 independently represent a hydrogen atom, (C1-C10)alkyl or (C6-C13)aryl(C1-C10)alkyl;

n is an integer from 0 to 3; R represents (C1-C10)alkyl, (C3-C10)cycloalkyl, (C6-C13)aryl, (C1-C10)alkyl(C6-C13)aryl, (C6-C13)aryl(C1-C10)alkyl or (C1-C10)alkoxy; when n is 2 or 3, individual deputies R may be similar or different;

X 1 and X 2 independently represent a halogen atom, (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C30)aryl, (C6-C30)aryl(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C30), (C3-C20), (C6-C30), (C1-C20), (C6-C30) , (C1-C20), (C6-C30), (C1-C20), (C6-C30), (C1-C20) or (C6-C30);

Another aspect of the invention, aimed at the solution of the tasks mentioned, refers to a catalytic composition, including such connection of transition metal and or or on the basis of boron compounds.

Another aspect of the invention, aimed at the solving of these tasks, relates to methods of obtaining homopolymers ethylene and ethylene copolymers with alpha-olefins using transition metal compounds or catalytic compositions.

Further, given a more detailed description of the present invention.

Transition metal (M) Group 4 the Periodic table of elements in a chemical formula (1) is a preferable titanium, zirconium, hafnium or.

Cf is ring, which is linked with the Central metal-on η 5-type ring with Deputy(s) or condensed ring containing ring, such as or , with Deputy(s) or without it/them. Specifically, examples Cf include , , , , , , second-, tert-, , , , , , , , , , , and so on.

Group Ar can be a (C6-C14), such as phenylene, naphthalene-1-Il, naphthalene-2-Il, -2-Il and -4-yl. Among them are preferred phenylene or naphthalene-2-Il.

Group R whatever is linear or nonlinear (C1-C10)alkyl, such as methyl, ethyl, n-propyl, isopropyl n-butyl, sec-butyl, tert-butyl n-pentyl, , tert-amyl, n-hexyl, n-octyl and tert-octyl, preferably methyl, ethyl, n-propyl, isopropyl n-butyl, tert-butyl or tert-octyl; (C3 - C10)cycloalkyl, such as cyclohexyl; (C6-C13)aryl or (C1-C10)alkyl(C6-C13)aryl, such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, 2,3,4-trimetilfenil, 2,3,5-trimetilfenil, 2,3,6-trimetilfenil, 2,4,6-trimetilfenil, 3,4,5-trimetilfenil, 2,3,4,5-, 2,3,4,6-, 2,3,5,6-, , , n-, , n-butylphenyl, second-butylphenyl, tert-butylphenyl, n-, , n-, n-, biphenyl and naphthyl, preferably phenyl, naphthyl, biphenyl-2-, 3,5- or 2,4,6-trimetilfenil; (C6-C13)aryl(C1-C10)alkyl, such as benzil, (2-methyphenyl)methyl (3-methyphenyl)methyl (4-methyphenyl)methyl (2,3-dimetilfenil)methyl, (2,4-dimetilfenil)methyl (2,5-dimetilfenil)methyl (2,6-dimetilfenil)methyl (3,4-dimetilfenil)methyl (4,6-dimetilfenil)methyl (2,3,4-trimetilfenil)methyl (2,3,5-trimetilfenil)methyl (2,3,6-trimetilfenil)methyl (3,4,5-trimetilfenil)methyl (2,4,6-trimetilfenil)methyl (2,3,4,5-)methyl (2,3,4,6-)methyl (2,3,5,6-)methyl ()methyl ()methyl, n-)methyl ()methyl, n-butylphenyl)methyl (Deut-butylphenyl), methyl tert-butylphenyl)methyl, n-)methyl ()methyl, n-)methyl and (n-)methyl, preferably benzyl; (C1-C10)aryl(C1-C10)alkyl, such as benzyl, (2-methyphenyl)methyl (3-methyphenyl)methyl (4-methyphenyl)methyl (2,3-dimetilfenil)methyl, (2,4-dimetilfenil)methyl (2,5-dimetilfenil)methyl (2,6-dimetilfenil)methyl (3,4-dimetilfenil)methyl (4,6-dimetilfenil)methyl (2,3,4-trimetilfenil)methyl (2,3,5-trimetilfenil)methyl (2,3,6-trimetilfenil)methyl (3,4,5-trimetilfenil)methyl (2,4,6-trimetilfenil)methyl (2,3,4,5-) methyl (2,3,4,6-)methyl (2,3,5,6-)methyl ()methyl ()methyl, n-)methyl ()methyl, n-butylphenyl)methyl (Deut-butylphenyl)methyl, n-)methyl, , or , preferably benzyl or ; or (C1-C10)alkoxy, such as methoxy, , n-propoxy, , n-, second-, tert-, n-pentoxy, , n- and n-, preferably methoxy or .

Deputy R 11 and R-12 @ group ligand independently represent a hydrogen atom, linear or non-linear (C1-C10)alkyl, such as methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl, preferably methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, n-pentyl, n-hexyl or n-octyl; or (C6-C13)aryl(C1-C10)alkyl, such as benzyl.

X 1 and X 2 independently represent a halogen atom, (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C30)aryl, (C6-C30)aryl(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C30), (C3-C20), (C6-C30), (C1-C20), (C6-C30) , (C1-C20), (C6-C30), (C1-C20), (C6-C30), (C1-C20) or (C6-C30);

examples of the atom include halogen atoms of fluorine, chlorine, bromine and iodine; examples (C1-C20)alkyl include methyl, ethyl, n-propyl, isopropyl n-butyl, sec-butyl, tert-butyl n-pentyl, , amyl, n-hexyl, n-octyl, n-decyl-n-dodecyl, n- and n-, preferably methyl, ethyl, isopropyl, tert-butyl or amyl; examples (C3-C20) include cyclopropane, , , cyclohexyl, and ; examples (Sat-NWB)or aryl (C6-C30)aryl(C1-C20)alkyl include phenyl, naphthyl, , , benzyl, (2-methyphenyl)methyl (3-methyphenyl)methyl (4-methyphenyl)methyl (2,3-dimetilfenil)methyl, (2,4-dimetilfenil)methyl (2,5-dimetilfenil)methyl (2,6-dimetilfenil)methyl (3,4-dimetilfenil) methyl (4,6-dimetilfenil)methyl (2,3,4-trimetilfenil)methyl (2,3,5-trimetilfenil)methyl (2,3,6-trimetilfenil)methyl (3,4,5-trimetilfenil)methyl (2,4,6-trimetilfenil)methyl (2,3,4,5-)methyl (2,3,4,6-)methyl, (2,3,5,6-)methyl ()methyl ()methyl, n-)methyl ()methyl, n-butylphenyl)methyl (Deut-butylphenyl), methyl tert-butylphenyl)methyl, n-)methyl ()methyl, n-)methyl, n-)methyl, n-)methyl, n-)methyl, and , preferably benzyl;

examples (C1-C20)alkoxy include methoxy, , n-propoxy, , n-, second-, tert-, n-pentoxy, , n-, n-, n-, n- and n-, preferably methoxy, , or tert-;

examples (C6-C30) include phenoxy, naphthalene-1-, naphthalene-2-, -2- and -4-, preferably phenoxy or -2-; examples (C3-C20) include , , tri-n-, , tri-n-, three-sec-, tri-tert-, three-, tert-, tri-n-, tri-n- and , preferably or tert-;

examples of amino groups with (C1-C20)alkyl - or (C6-C30)aryl-Deputy(and) include dimethylamino, , di-n-, , di-n-, di-sec-, di-tert-, , tert-, di-n-, di-n-, di-n-, , , , , , and bis-tert-;

examples phosphines with (C1-C20)alkyl - or (C6-C30)aryl-Deputy(and) include , , di-n-, , di-n-, di-sec-, di-tert-, , tert-, di-n-, di-n-, di-n-, , , , , , and bis-tert-, preferably , or ;

examples with (C1-C20)alkyl - or (C6-C30)aryl-Deputy(and) include , , , , 1- and , , and , preferably or .

Examples of halogen, (C1-C10)alkyl, (C3-C20), (C6-C30)aryl, (C6-C30)aryl(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C30), (C3-C20), (C6-C30), (C1-C20), (C6-C30), (C1-C20), (C6-C30), (C1-C20), (C6-C30), (C1-C20) or (C6-C30), which can be further replaced by , , , , alkoxy, , , , , , , , , , or for radicals R n , X 1 and X 2 or group Ar, described above.

Examples (C3-C12) to bind each replacement of the group with related Deputy, which leads to the formation of a ring with the condensed ring or without it, include propylene, butylene, , , , and , preferably butylene; and examples (C3-C12) include , , , , , and , preferably or .

Specifically, the present invention provides compounds of transition metals selected from compounds represented one of the following chemical formula:

where Cf is or ;

M represents the Titan, zirconium, hafnium or;

R 21 R 24 independently represent a hydrogen or (C1-C10)alkyl;

R 31 R 36 independently represent a hydrogen atom, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C6-C13)aryl, (C1-C10)alkyl(C6-C13)aryl, (C6-C13)aryl(C1-C10)alkyl or (C1-C10)alkoxy;

X 1 and X 2 independently represent chloride, methyl pyrrolidone, , benzyl, , or dimethylamino.

More specifically, the compounds of transition metals are different in that they represented one of the following chemical formula:

where Cf is or ; and

Among other things, to create an active catalytic component that can be used to obtain ethylene and a copolymer of ethylene with alpha-, connection of transition metal, represented by the chemical formula (1)can be used preferably with connection or connection of boron or their mixture as that can remove ligands X 1 and X 2 of the complex transition metal, translating the Central metal cation form and acting as (i.e. anion)associated communication. Compositions including connection of the transition metal and , as described above, included in the scope of the present invention.

Boron compounds are suitable as according to the present invention is disclosed in U.S. patent №5198401 and can be selected from compounds represented one of the chemical formulas (2) to (4):

[Chemical formula 2]

B(R 41 ) 3

[Chemical formula 3]

[R 42 ]+[B(R 41 ) 4 ] -

[Chemical formula 4]

[(R 43 ) p ZH] + [B(R 41 ) 4 ] - ,

which is boron atom; R 41 represents phenyl, that can optionally be replaced by three to five deputies selected from fluorine (C1-C20)alkyl with (and) Deputy(s) or without them, or (C1-C20)alkoxy with (and) Deputy (s) or without them; R 42 represents (C5-C7)aroma radical or (C1-C20)alkyl(C6-C20)aryl radical, (C6-C30)aryl(C1-C20)alkyl radical, such as -radical; Z represents an atom of nitrogen or phosphorus; R 43 is (C1-C20)alkyl radical or radical, having two (C1-C10)alkyl-Deputy to the nitrogen atom; and p is an integer, equal to 2 or 3.

Preferred examples include Tris(pentafluorophenyl)borane, Tris(2,3,5,6-tetrafluorophenyl)borane, Tris(2,3,4,5-tetrafluorophenyl)borane, Tris(3,4,5-)borane, Tris(2,3,4-)borane, (pentafluorophenyl)borane tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis (2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-)borate, tetrakis(2,2,4-)borate, (pentafluorophenyl)borate and tetrakis(3,5-)borate. In the form of compounds specific examples include tetrakis(pentafluorophenyl)borate , tetrakis(pentafluorophenyl)borate 1,1′- tetrakis(pentafluorophenyl)borate silver tetrakis(pentafluorophenyl)borate , tetrakis(3,5-)borate, tetrakis(pentafluorophenyl)borate tetrakis(pentafluorophenyl)borate tetrakis(pentafluorophenyl)borate three(n-butyl)ammonium tetrakis(3,5-)borate three(n-butyl)ammonium tetrakis(pentafluorophenyl)borate N,N- tetrakis(pentafluorophenyl)borate N,N- tetrakis(pentafluorophenyl)borate N,N-2,4,6- tetrakis(3,5-)borate N,N- tetrakis(pentafluorophenyl)borate tetrakis(pentafluorophenyl)borate tetrakis(pentafluorophenyl)borate tetrakis(pentafluorophenyl)borate three(methyphenyl) and tetrakis(pentafluorophenyl)borate three(dimetilfenil). Among them are preferred N,N-, and .

Aluminum compounds, suitable for use in the present invention, include or connection, presented chemical formula (5) or (6), connection, presented chemical formula (V), or organic aluminum compounds presented chemical formula (8) or (9):

[Chemical formula 5]

(-Al(R 51 )-O-m

[Chemical formula 6]

(R 51 ) 2 Al-(-O(R 51 )-q-R(51 ) 2

[Chemical formula 7]

(R 52 r Al(E) 3-r

[Chemical formula 8]

(R 53 ) 2 AlOR 54

[Chemical formula 9]

R 53 A1(OR 54 ) 2 ,

where R 51 is (C1-C20)alkyl, preferably or methyl isobutyl; m and q independently are integers from 5 to 20; R 52 R 53 independently represent (C1-C20) alkyl; E represents hydrogen atom or halogen; r is an integer from 1 to 3; and R is 54 (C1-C20) alkyl or (C6-C30)aryl.

Specific examples of the compounds of aluminum include compounds such as , modified , ; compounds such as , including , , , and ; chloride , including chloride , chloride , chloride , chloride and chloride ; dichloride , including dichloride , dichloride , dichloride , dichloride and dichloride ; and hydride , including hydride hydride hydride hydride and hydride . Among them is the preferred , more preferably and .

In a catalytic compositions on the basis of transition metal containing of the present invention to obtain homopolymers ethylene and ethylene copolymers with alpha- the ratio between the amounts compounds of transition metal and preferably located in the bands 1:0,1 about 100:10-1000, more preferably 1:of 0.5-5:10 500 V AC calculation of the molar ratio of the Central metal atom Bohr atom aluminium, and in the case of or the ratio of transition metal to or subject to use is 1:50 Hz to 5000 per molar ratio of transition metal (M) to aluminum.

According to another aspect of the present invention method of obtaining polymers of ethylene using catalytic compositions on the basis of transition metal is carried out putting in contact catalyst on the basis of transition metal and ethylene and, on request, of vinyl monomers in the presence of a suitable organic solvent. The catalyst on the basis of transition metal and components can be individually introduced into the reactor or mentioned components can be pre-mixed and loaded into the reactor. Conditions of confusion, such as the procedure for the submission of materials, temperature or concentration, are not specifically limited.

Preferred solvents that can be used in the way, include (C3-C20)hydrocarbons and specifically butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonan, Dean, dodecane, cyclohexane, , benzene, toluene and xylene.

Specifically, upon receipt of ethylene as the monomer used ethylene itself. The right amount of pressure in the method of the present invention is from 1 to 1000 ATM, preferably from 6 to 150 ATM and even more preferably from 10 to 150 ATM. Polymerization effectively carried out at a temperature of 60 C to 250 C, preferably from 80 C up to 200 degrees Celsius.

Upon receipt of copolymers of ethylene and a-olefin (C3-C18)-alpha-olefin can be used as a comonomer ethylene. can be chosen preferably from the group consisting of propylene, 1-butene, 1-, 4-methyl-1-, 1-hexene, 1-Heptene, 1-octene, 1-decene, 1-, 1-, 1-, 1-, 1- and 1-, more preferably from 1-butene, 1-hexene, 1-octene and 1-decene. Preferred pressure of ethylene and temperature polymerization are the same, that in case of receiving homopolymers ethylene. Copolymer obtained the method of the invention, includes at least 50% by weight, preferably from 50% to 99% by weight, more preferably at least 60% by mass, and even more preferably from 60 to 99% by weight of ethylene.

As described above, linear low density polyethylene (LLDPE)obtained using (C4-C10)-alpha-olefin as comonomer, has a density in the range from 0.910 to 0.940 g/l There is a possibility to distribute the way up to the range of polyethylene ultra-low density (VLDPE or ULDPE) or olefin elastomer with density 0,910 g/CC or less. Upon receipt of homopolymers ethylene and its copolymers, according to the invention of the hydrogen can be used as a molecular mass regulator to adjust the molecular mass. The bulk molecular weight (Mw) of the obtained polymers is usually from 80,000 to 500000.

Because catalytic composition, offered by this invention is present in the homogeneous state of the polymerization reactor, it can preferably be used in the method, the solution polymerisation carried out at a temperature higher than the melting point of the relevant polymer. However, as disclosed in U.S. patent №4752597, the catalyst on the basis of transition metal and can be fixed to the disk, such as a porous metal oxides, so that it can be used as a heterogeneous catalytic composition for a method of suspension polymerization or polymerization in the gas phase.

Ensuring advantage effects of the invention Connection of transition metal of the invention or catalytic composition comprising the connection, can be easily derived a simple synthetic procedure with economic benefit. Thanks to its excellent thermal stability catalyst retains a high catalytic activity even at high temperature, high reactivity in the reactions of copolymerization with other olefins, which gives high-yield, high molecular weight polymers.

The best options for carrying out the invention

Below embodiments of the present invention will be described with reference to the accompanying examples and is not intended as limitations of the scope of the invention.

1. Melt flow index (MI)

MI measured according to ASTM D 2839.

2. Density

Density was measured using a gradient tube to determine the density according to ASTM D 1505.

3. Analysis of the melting temperature (Tm)

Tm measured in terms of 2nd heating at a rate of 10 C/min in nitrogen atmosphere through the calorimeter Dupont DSC 2910.

4. Molecular weight and molecular weight distribution of the Molecular mass was measured at 135 C at a speed of 1.0 ml/min in the presence of 1,2,3-trichlorobenzene as a solvent, using PL210 GPC, equipped with a column PL Mixed-BX2+preCol. The molecular mass was calibrated using PL-polystyrene standards.

5. Content (% wt.) α-olefin copolymer α-olefin measured by NMR spectrometer Bruker DRX500 NMR at 125 MHz, using mixed solvent 1,2,4-trichlorobenzene/C 6 D 6 (7/3 by weight), at 120°C mode 13 NMR (reference: Randal, J.. JMS Rev. Macromol. Chem. Phys. 1980, C29, 201).

[Example 1]

Synthesis (dichloro)() (2-(9′,9′--2′-yl)phenoxy)titanium (IV)

Synthesis of 2-bromo-9,9′-

In three-neck round-bottom flask 1000 ml downloaded the 2- (25 g, 102,0 mmol), (43,4 g, 306,0 mmol) and DHS (300 ml) and the mixture is stirred in nitrogen atmosphere, in order to achieve full dissolution. The mixture slowly solution was added dropwise tert-butoksida potassium (32,1 g, 285,6 mmol), dissolved in DMSO (4 00 ml). Mixture was stirred at room temperature for 12 hours at 80 C for 1 hour and then again cooled to ambient temperature. The reaction mixture is mixed with water (1000 ml) and the mixture were extracted with n-hexane. The organic layer is washed three times with distilled water, dried over magnesium sulfate (MgSO 4 ) and evaporated using a rotary evaporator for evaporation of the solvent. Cleaning by column chromatography on silica gel (eluent: n-hexane) and recrystallization again from n-hexane was given 2-bromo-9,9′- (27.0 g, exit to 96.6%) in the form of a white solid.

1 H-NMR (CDCl 3 ) δ=1,65 (s, 6N), 7,35-7,39 (m 2N), 7,44-7,50 (m 2N), 7,58-7.62 mm (m 2N), 7,72-7,73 (m, 1H) ppm

Synthesis of 2-(2′-methoxyphenyl)-9,9′-

The flask was downloaded by 2-bromo-9,9′- (27.0 g, 98,8 mmol), 2- acid (18.0 g, 118,6 mmol), acetate palladium (0.13 g, 0.6 mmol), triphenylphosphine (0,94 g, 3.6 mmol) and potassium phosphate (40,9 g, 177,9 mmol), added a mixture of water (70 ml) and (150 ml) and the mixture was heated in boiling under reflux for 6 hours. After cooling the mixture to a temperature of the environment it introduced the aqueous solution of ammonium chloride (150 ml) and diethyl ether (200 ml). The organic layer is separated, and the rest were extracted with diethyl ether. The combined organic layer was dried over magnesium sulfate and evaporated to remove volatile substances. Cleaning by column chromatography on silica gel (eluent-hexane) has given 2-(2′-methoxyphenyl)-9,9′- (28,0 g, exit 94,0%) as a solid.

1 H NMR (CDCl 3 ) δ=1,56 (s, 6N), 3,88 (C, 3H), 7,04-7,06 (d, 1H), 7,08-7,11 (t, 1H), of 7.33-7,39 (m, 3H), USD 7.43-7,45 (d, 1H), 7,47-of 7.48 (d, 1H), 7,56-7,58 (d, 1H), 7,63 (1H), 7,76-7,840 (t, 2N) ppm

Synthesis of 2-(9′,9′--2′-yl)phenol

To a solution of 2-(2′-methoxyphenyl)-9,9′- (25.0 g, 83,2 mmol) in metilenhloride (4 00 ml) solution was added dropwise boron (100 ml) (1 M in metilenhloride) at -78 C and at a slow rise in temperature up to the temperature of the environment mixture reacted within three hours. Then to a mix added a mixture of ice (150 g) and diethyl ether (300 ml). The organic layer is separated, and the water layer were extracted with diethyl ether. The combined organic layer was dried over magnesium sulfate and evaporated to remove volatile substances. Cleaning by column chromatography on silica gel (eluent: mixture of hexane and methylene chloride) has given 2-(9′,9′--2′-yl)phenol (18.0 g, exit to 75.5%) in the form of a white solid.

1 H-NMR (CDCl 3 ) δ=1,55 (s, 6N), 7,04-7,07 (m 2N), 7,30-7,40 (m, 4N), 7,47-7,50 (m 2N), 7,55 (1H), 7,78-7,80 (d, 1H), the 7.85-7,87 (d, 1H) ppm

Synthesis (dichloro)() (2-(9′,9′--2′-yl)phenoxy)titanium (IV)

To a solution of 2-(9′,9′--2′-yl)phenol (5,0 g, 17,1 mmol) in toluene (200 ml) slowly injected n- (2,5M in hexane, 6.9 ml) at -78 C and mixture was stirred at room temperature for 12 hours. After cooling the reaction mixture to -78°C slowly added to the solution ()titanium (IV) (4.7 grams of 16.3 mmol) in toluene (100 ml), and the reaction was performed at ambient temperature for 12 hours. Upon completion of the reaction, the reaction mixture was filtered through filter and removed from it solvent. Recrystallization step was carried out from the treated toluene, hexane at -35°C. Solid filtered and dried at low pressure, getting (dichloro)()(2-(9′,9′--2′-yl)phenoxy)titanium (IV) (5.6 g output: 63,9%) in the form of red solid.

1 H NMR (C 6 D 6 ) δ=1,61 (s, 6N), 1,77 (, 15N), 7.03 is-7,05 (t, 1H), 7,16-7,19 (t, 1H), 7,32-7,34 (m 2N), 7,37-7,39 (d, 1H), 7,42-7,44 (d, 1H), 7,46-7,47 (d, 1H), 7,71-7,77 (m, 3H), 7,82-7,84 (d, 1H) ppm

Mass-spectrum (APCI mode, m/z): 539,4.

[Example 2]

Synthesis (chlorine)() (bis(2-(9′,9′--2′-yl)phenoxy))titanium (IV)

To a solution of 2-(9′,9′--2′-yl)phenol (5,0 g, 17,1 mmol) in toluene (200 ml) slowly injected n- (2,5M in hexane, 6.9 ml) at -78 C and mixture was stirred at room temperature for 12 hours. After cooling the reaction mixture to -78°C slowly added to the solution ()titanium (IV) (2.3 g, 8.0 mmol) in toluene (100 ml), and the reaction was performed at 80 C for 12 hours. Upon completion of the reaction, the reaction mixture was filtered through filter and removed from it solvent. Recrystallization step was carried out from the treated toluene, hexane at -35°C. Solid filtered and dried at low pressure, getting (chlorine)()(bis(2-(9′,9′--2′-yl)phenoxy))titanium(IV) (3.5 g, output: 55,8%) in the form of orange solid.

1 H-NMR (C 6 D 6 ) δ=1,54 (s, 6N), 1,61 (s, 6N), 1,65 (, 15N), 7,01-7,04 (t, 2N), 7,21-7,24 (t, 2N), 7,33 of 7.36 (m, 4N), 7,39 with 7.41 (t, 4N), 7,44-7,46 (m 2N), the 7.65 (C, 2H), 7,73-7,757 (t, 2N), 7,82-of 7.88 (m, 4H) ppm

Mass-spectrum (APCI mode, m/z): 789,3.

[Example of getting 3]

Synthesis (dichloro)()(2-(9'--2′-yl)phenoxy)titanium (IV)

Synthesis of 2-(2′-methoxyphenyl)-9-

The flask was downloaded by 2-bromo-9- (10,0 g, 40,8 mmol), 2- acid (7.4 g, 49,0 mmol), acetate palladium (0,055 g, 0,245 mmol), triphenylphosphine (0.44 g, 1.4 mol) and potassium phosphate (2.0 g, 95.5 per mmol), added a mixture of water (33 ml) and (100 ml) and the mixture was heated in boiling under reflux for 6 hours. After cooling the mixture to a temperature of the environment it introduced the aqueous solution of ammonium chloride (100 ml) and diethyl ether (150 ml). The organic layer is separated, and the rest were extracted with diethyl ether. The combined organic layer was dried over magnesium sulfate and evaporated to remove volatile substances. Cleaning by column chromatography on silica gel (eluent-hexane) has given 2-(2′-methoxyphenyl)-9- (10,0 g, exit 90,0%) as a solid.

1 H-NMR (CDCl 3 ) δ=3,87 (C, 3H), 3,98 (C, 2H), 7,04-7,05 (d, 1H), 7,07-7,10 (t, 1H), 7,32-7,42 (m, 4N), 7,57-7,59 (d, 2N), 7,74 (1H), 7,83-7,86 (t, 2N) ppm

Synthesis of 2-(9'--2′-yl)phenol

To a solution of 2-(2′-methoxyphenyl)-9- (10,0 g, 36.7 per mmol) in metilenhloride (200 ml) solution was added dropwise boron (44 ml) (1M in metilenhloride) at -78 C and at a slow rise in temperature up to the temperature of the environment mixture reacted within three hours. Then to a mix added a mixture of ice (150 g) and diethyl ether (200 ml). The organic layer is separated, and the water layer were extracted with diethyl ether. The combined organic layer was dried over magnesium sulfate and evaporated to remove volatile substances. Cleaning by column chromatography on silica gel (eluent: mixture of hexane and methylene chloride) has given 2-(9'--2′-yl)phenol (7,0 g, exit 73,8%) in the form of a white product.

1 H NMR (CDCl 3 ) δ=3,96 (C, 2H), 7,00-7,02 (m 2N), 7,25-7,35 (m, 3H), 7,39-7,42 (t, 1H), 7,47-7,49 (d, 1H), 7,56-7,58 (d, 1H), of 7.64 (1H), 7,81-7,83 (d, 1H), of 7.88-7,89 (d, 1H) ppm

Synthesis (dichloro)()(2-(9'--2′-yl)phenoxy)titanium (IV)

To a solution of 2-(9'--2′-yl)phenol (4.4 grams of 17.0 mmol) in toluene (200 ml) slowly injected n- (2,5M in hexane, 6.9 ml) at -78 C and mixture was stirred at room temperature for 12 hours. After cooling the reaction mixture to -78°C slowly added to the solution ()titanium (IV) (4.7 grams of 16.3 mmol) in toluene (100 ml), and the reaction was performed at ambient temperature for 12 hours. Upon completion of the reaction, the reaction mixture was filtered through filter and removed from it solvent. Recrystallization step was carried out from the treated toluene, hexane at -35°C. Solid filtered and dried at low pressure, getting (dichloro)()(2-(9'--2′-yl)phenoxy)titanium (IV) (5.6 g output: 71,0%) in the form of red solid.

1 H-NMR (C 6 D 6 ) δ=1,72 (, 15N), 3.94 in (C, 2H), 7,05-7,18 (m 2N), of 7.36-7,38 (m 2N), 7,44-7,46 (m 2N), of 7.48-7,50 (d, 1H), the 7.65 at 7.66 (d, 1H), 7,81-7,82 (d, 1H), of 7.88-7,87 (d, 1H), 7,98 (1, 1H) ppm

Mass-spectrum (APCI mode, m/z): 511,3. [Example of getting 4]

Synthesis (dichloro)()(2-tert-butyl-6-(9′,9′--2′-yl)-4-)titanium (IV)

Synthesis of 9′,9′--2′- acid In three-neck round bottom flask 500 ml dissolved 2- (30 g, 105,1 mmol) in THF (250 ml) and slowly dropwise at -78°C in an atmosphere of nitrogen added n- (2,5M solution in hexane) (44,1 ml, 110,4 mmol). After mixing under the ambient temperature of the mixture was cooled to -78°C and slowly was added dropwise to her (22,8, 157,7 mmol). Then the mixture was stirred at room temperature for 12 hours and was poured into a mixture of 2N aqueous hydrochloric acid (300 ml) and ice (300 g). After stirring for 2 hours mixture was extracted with diethyl ether. The organic layer is washed three times with distilled water, dried over anhydrous magnesium sulfate (MgSO 4 ) and evaporated using a rotary evaporator for evaporation of the solvent. Recrystallization of n-hexane and ethyl acetate (10:1) gave a 9′,9′--2′- acid (16.0 g, output: 64,0%) in the form of a white product.

1 H NMR (CDCl 3 ) δ=1,71 (s, 6N), USD 7.43-7,57 (m, 3H), of 7.88-7,96 (m 2N), 8,39-8,40 (m 2N) ppm

Synthesis of 1-bromo-3-tert-butyl-2-methoxy-5-

In three-neck round-bottom flask 500 ml downloaded the 2-bromo-6-tert-butyl-4- (20,0 g, 82.3 per mmol, potassium hydroxide (9.7 g, 164,5 mmol) and DMSO (dimethyl sulfoxide) (100 ml) and the mixture is cooled to 0 C). After a slow introduction in it (23,4 g, 164,5 mmol) the resulting mixture was stirred at room temperature for 12 hours. Then the reaction mixture was poured into ice (2 00 g) and the resulting mixture was stirred for 30 minutes. After adding diethyl ether organic layer was separated, and the rest were extracted with diethyl ether. The combined organic layer was dried over magnesium sulfate and evaporated to remove volatile components. Recrystallization of a mixture of hexane and dichloromethane gave 1-bromo-3-tert-butyl-2-methoxy-5- (17,5 g, output: 82,8%).

1 H-NMR (CDCl 3 ) δ=1,41 (, 9), 2,38 (C, 3H), 3,82 (C, 3H), 7,04 (1H), 7,13 (1H), ppm

Synthesis of 2-(3-tert-butyl-2-methoxy-5-methyphenyl)-9′,9′-

In the flask downloaded 1-bromo-3-tert-butyl-2-methoxy-5- (9.0 g, 35,0 mmol), 9′,9′--2′-Il- acid (10,0 g, 42,0 mmol), acetate palladium (0.024 g, 0,105 mmol), triphenylphosphine (0,19 g, 0,63 mmol) and potassium phosphate (14.5 g, 63,0 mmol), added a mixture of water (25 ml) and (150 ml) and the mixture was heated in boiling under reflux for 6 hours. After cooling the mixture to a temperature of the environment it introduced the aqueous solution of ammonium chloride (100 ml) and diethyl ether (150 ml). The organic layer is separated, and the rest were extracted with diethyl ether. The combined organic layer was dried over magnesium sulfate and evaporated to remove volatile substances. Cleaning by column chromatography on silica gel (eluent-hexane) gave 3-tert-butyl-2-methoxy-5-methyphenyl-9′,9′- (12.0 g, exit 93,0%) as a solid.

1 H-NMR (CDCl 3 ) δ=1,47 (, 9), and 1.56 (C, 6N), 2,30 (C, 3H), 3,90 (C, 3H), 6,89 (1H), 7,23 (1H), 7,36 with 7.41 (m, 3H), 7,46-7,50 (m 2N), 7,78-7,81 (m 2N) ppm

Synthesis of 2-tert-butyl-6-(9′,9′--2′-yl)-4-

To a solution of 3-tert-butyl-2-methoxy-5-methyphenyl-9′,9′- (22,0 g, 73.2 per mmol) in metilenhloride (500 ml) solution was added dropwise boron (88 ml) (1 M in metilenhloride) at -78 C and at a slow rise in temperature up to the temperature of the environment mixture reacted within three hours. Then to a mix added a mixture of ice (200 g) and diethyl ether (300 ml). The organic layer is separated, and the water layer were extracted with diethyl ether. The combined organic layer was dried over magnesium sulfate and evaporated to remove volatile substances. Cleaning by column chromatography on silica gel (eluent: mixture of hexane and methylene chloride) has given 2-tert-butyl-6-(9′,9′--2′-yl)-4- (18.0 g, exit to 85.9%) in the form of a white solid.

1 H-NMR (CDCl 3 ) δ=1,53 (, 9), 1,60 (s, 6N), 2,23 (C, 3H), 4,70 (, 1H (HE)), 6,69 (1H), 7,32 is 7.40 (m, 4N), 7,42 (1H), 7,47-7,49 (d, 1H), 7,77-7,89 (d, 1H) ppm

Synthesis (dichloro)()(2-tert-butyl-6-(9′,9′--2′-yl)-4-)titanium (IV)

To a solution of 2-tert-butyl-6-(9′,9′--2′-yl)-4- (5,0 g, 14.0 mmol) in toluene (200 ml) slowly injected n- (2,5M in hexane, 5.6 ml) at -78 C and mixture was stirred at room temperature for 12 hours. After cooling the reaction mixture to -78°C slowly added to the solution ()titanium (IV) (4.7 grams 13.3 mmol) in toluene (100 ml), and the reaction was performed at ambient temperature for 12 hours. Upon completion of the reaction, the reaction mixture was filtered through filter and removed from it solvent. Recrystallization step was carried out from the treated toluene, hexane at -35°C. Solid filtered and dried at low pressure, getting (dichloro)()(2-tert-butyl-6-(9′,9′--2′-yl)-4-)titanium (IV) (5.5 g, output: 66,7%) in the form of red solid.

1 H-NMR (C 6 D 6 ) δ=1,51 (s, 6N), 1,70 (, 9), 2,10 (, 15N), 2,42 (C, 3H), 7,30-7,39 (m, 5H), 7,50-7,52 (d, 1H), 7,59-7,60 (1H), 7,73-7,77 (m 2N) ppm

Mass-spectrum (APCI mode, m/z): 609,5.

Example 1

Copolymerization of ethylene with 1- conducted in reactor of periodic action, as described below.

Into a reactor from stainless steel on 2000 ml, which was sufficiently dried and purged with nitrogen, download, cyclohexane (1140 ml) and 1-octene (60 ml). Then he added 54,2 mm mortar (11,1 ml) in toluene modified -7 (modified MAO-7, 7% of the mass. solution Al Isopar, from Akzo Nobel). Then the temperature of the reactor increased up to 140 C and consistently added to the reactor (chlorine)()(bis(2-(9′,9′--2′-yl) phenoxy)) titanium (IV) (5 mm solution in toluene) (0.4 ml), which was synthesized according to example 2, and 10 mm solution (99%, Boulder Scientific) in toluene (0.6 ml). By ethylene pressure in the reactor was established on 30 kg/cm 2 at a constant submission for the conduct of polymerization. After one minute, the reaction was achieved maximum temperature 1. After 1 minute of added to 100 ml of ethanol, containing 10%. aqueous hydrochloric acid to repay polymerization. The mixture is then mixed with 1.5 liters of ethanol within 1 hour and the reaction product is filtered and separated. Such a reaction product is dried in a vacuum furnace at 60 degrees C for 8 hours, receiving 38.0 g polymer. Polymer had a melting point of 91.5°C, melt flow index 22,0 and density 0,8944 g/l According to the results of gel-chromatographic analysis of polymer had the bulk molecular weight (Mw) 51200 g/mol molecular mass distribution (Mw/Mn) 2,26 and content 1-octene 17,9% by mass.

Example 3

Copolymerization of ethylene with 1- conducted in reactor of periodic action, as described below.

Into a reactor from stainless steel on 200 ml, which was sufficiently dried and purged with nitrogen, download, cyclohexane (91 ml) and 1-octene (8 ml). Then he added 54,17 mm solution of (5.5 ml) in toluene modified -7 (modified MAO-7, 7% of the mass. solution Al Isopar, from Akzo Nobel). Then the temperature of the reactor increased up to 140 C and consistently added to the reactor (dichloro)()(2-(9'--2′-yl)phenoxy)titanium (IV) (5 mm solution in toluene) (0,98 ml), which was synthesized in example 3, and 4,07 mm solution (99%, Boulder Scientific) in toluene (0,74 ml). By ethylene pressure in the reactor was established on 30 kg/cm 2 at a constant submission for the conduct of polymerization. After one minute, the reaction was achieved maximum temperature 166,5°C. After 1 minute of added 10 ml of ethanol, containing 10%. aqueous hydrochloric acid to repay polymerization. The mixture is then mixed with 150 ml of ethanol within 1 hour and the reaction product is filtered and separated. Such a reaction product is dried in a vacuum furnace at 60 degrees C for 8 hours, receiving 4.5 g polymer. Polymer had a melting point 79,9°C, melt flow index 73, density 0,8823 g/CC and content 1-octene 23,2% by mass.

Examples 4-8

Copolymerization of ethylene with 1- conducted in continuous action reactor as described below.

As a catalyst, with the only center activation used (dichloro)()(2-(9′,9′--2′-yl)phenoxy)titanium(IV) (synthesized according to the example 1). Used quantity of the catalyst are shown in table 1. Ti is a catalyst in the only center activation, Al - as and In - , respectively. The catalyst was administered after it dissolved in toluene, receiving concentration of 0.2 g/L. the Synthesis was performed using the 1-octene as comonomer. Conversion in the reactor was determined by gas chromatography analysis of the technological flow after the reaction. Molecular mass (for catalyst with a single activation center) was monitored as a function of temperature reactor and content of 1-octene. Conditions are shown in table 1.

[Table 1]

Example 4

Example 5

Example 6

Example 7

Example 8

Flow rate only solution (kg/h)

The number of ethylene

Proportion of 1-octene (1-octene/ethylene)

The number of Ti (mmol/kg)

The Ratio Of Al/Ti

The Ratio B/Ti

The reaction temperature (C)

Conversion (%)

- Ti Ti in the catalyst with a single activation center

Al: as

In: as

Example 9

Copolymerization of ethylene with 1- conducted in reactor of periodic action, as described below.

Into a reactor from stainless steel on 2 00 ml, which was sufficiently dried and purged with nitrogen, download, cyclohexane (91 ml) and 1-octene (8 ml). Then he added 54,17 mm solution of (5.5 ml) in toluene modified -7 (modified MAO-7, 7% of the mass of the solution Al Isopar, from Akzo Nobel). Then the temperature of the reactor increased up to 140 C and consistently added to the reactor (dichloro)()(2-tert-butyl-6-(9′,9′--2′-yl)-4-)titanium (IV) (5 mm solution in toluene) (0,98 ml), which was synthesized according to the example of 4, and 4,07 mm solution (99%, Boulder Scientific) in toluene (0,74 ml). By ethylene pressure in the reactor was established on 30 kg/cm 2 at a constant submission for the conduct of polymerization. After one minute, the reaction was achieved maximum temperature 168,5°C. After 1 minute of added 10 ml of ethanol, containing 10%. aqueous hydrochloric acid to repay polymerization. The mixture is then mixed with 150 ml of ethanol within 1 hour and the reaction product is filtered and separated. Such a reaction product is dried in a vacuum furnace at 60 degrees C for 8 hours, receiving 4.8 g polymer. Polymer had a melting point 70,2°, melt flow index 65, density 0,8801 g/CC and content 1-octene 23,0% by mass.

As you can see from the examples 1-9, according to the invention the polymers having a great bulk molecular mass, may be obtained in conditions of high temperature (at 140 C or above) with small molecular weight distribution. In particular, you can successfully get copolymers low density of ethylene-1-octene.

Connection of transition metal of the invention or catalytic composition comprising the connection, can be easily derived a simple synthetic procedure with economic advantage. Thanks to its excellent thermal stability catalyst retains a high catalytic activity even at high temperature, high reactivity in the reactions of copolymerization with other olefins, which gives high-yield, high molecular weight polymers. Thus, the catalyst has a high practical usefulness for the industry than the already known traditional catalysts with only center activation or type. Therefore, catalytic composition based on transition metal according to the present invention may usefully be applied in obtaining homopolymers ethylene and a copolymer of ethylene with alpha- having different physical properties.

Although the present invention is described with reference to the examples above, specialist conventional qualification in the field of technology to which the invention can make various changes, not deviating from the essence or the scope of the invention, which is defined supplied by the claims. Thus, any potential change or modify these examples invention will not deviate from the method of the present invention.

1. Connection of transition metal, represented by the chemical formula (1):

where the formula M represents the transition metal from Group 4 the Periodic table of elements; Cf is ring, which is associated with the M η 5-type where ring can optionally be replaced by (S1-C20) or (C6-C30)Arild; Ar is (C6-C14); R 11 and R 12 independently represent a hydrogen atom or C1-C10)alkyl; n is an integer from 0 to 2; R represents (C1-C10)alkyl or (C1-C10)alkoxy; and when n is set to 2, individual deputies R may be similar or different; X 1 and X 2 independently represent a halogen atom, (C1-C20)alkyl, (C6-C30)aryl(C1-C20)alkyl or (C6-C30); alkyl group, , alkoxy, radicals R n , X 1 and X 2 and group Ar can be replaced by one or more Deputy(s)selected from the group consisting of (C1-C20)alkyl, (C6-C30)and aryl (C1-C20)alkoxy.

2. Connection of transition metal of claim 1, wherein Ar selected from the group consisting of , and fluorene.

3. Connection of transition metal in paragraph 2, which was selected from compounds represented one of the chemical formulas (1-1) (1-6):

where Cf is a or ; M represents the Titan, zirconium, hafnium or; R 21-R 24 independently represent a hydrogen or (C1-C10)alkyl; R 31-R 36 independently represent a hydrogen atom (C1-C10)alkyl or (C1-C10)alkoxy; X 1 and X 2 independently represent chloride, methyl or .

4. Connection of transition metal in clause 3, which is chosen from the following connections:

where Cf is a or ; and X 1 and X 2 can be independently selected from the group consisting of chloride, bromide or .

7. Catalytic composition based on transition metal to obtain homopolymers ethylene and ethylene copolymers with alpha- 6, in which or selected from modified , , , or or their mixtures.

8. Catalytic composition based on transition metal to obtain homopolymers ethylene and ethylene copolymers with alpha- indicated in paragraph 5, in which the ratio of transition metal or and on the basis of boron compounds in the range of 1:0.5 to about 5:10 500 V AC calculation of the molar ratio of transition metal (M):boron atom atom aluminium.

9. Catalytic composition based on transition metal to obtain homopolymers ethylene and ethylene copolymers with alpha- on item 8, in which on the basis of boron compounds selected from N,N- or or their mixtures.

10. The method of obtaining homopolymers ethylene and ethylene copolymers with alpha- using catalytic compositions on the basis of transition metal according to claim 5, which α-olefin is one or more connection(s)selected(s) from propylene, 1-butene, 1-, 1-hexene, 1-Heptene, 1-octene, 1-decene, 1-, 1-, 1-, 1- and 1-, and the content of ethylene copolymer of ethylene with equal to from 50 to 99% by weight.

11. The method of obtaining homopolymers ethylene and ethylene copolymers with alpha- to 10, in which the pressure of ethylene monomer in the reactor is from 6 to 150 ATM and temperature polymerization is from 60 to 250 C to C.

12. Homopolymer ethylene and a copolymer of ethylene with alpha- obtained using the catalyst on the basis of transition metal on any one of claims 1 to 4.

13. Homopolymer ethylene and a copolymer of ethylene with alpha- obtained using catalytic compositions on the basis of transition metal according to the clause 5.