Organometallic compound suitable as cocatalyst in polymerization of olefins

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to novel organometallic compounds and to olefin polymerization catalytic systems including such organometallic compounds, and also to a method for polymerization of olefins conduct in presence of said catalytic system. Novel organometallic compound is prepared by bringing into contact (i) compound of general formula I: (I), where Ra, Rb, Rc, and Rd, identical or different, represent hydrocarbon groups; and (ii) Lewis acid of general formula MtR

13
, where Mt represents boron atom and R1, identical or different, are selected from halogen and halogenated C6-C30-aryl groups.

EFFECT: enabled preparation of novel olefin polymerization cocatalysts, which reduce use of excess cocatalyst relative to alkylalumoxanes, do not lead to undesired by-products after activation of metallocene, and form stable catalytic compositions.

14 cl, 1 tbl, 32 ex

 

The scope of the invention

The present invention relates to ORGANOMETALLIC compounds and catalytic systems for polymerization of olefins comprising such ORGANOMETALLIC compounds. The invention also relates to a method for the polymerization of olefins carried out in the presence of the above catalyst system.

Description of the prior art,

Homogeneous catalytic systems based on metallocene complexes known as active in the polymerization of olefins; said complexes can be activated by means of suitable compounds are catalysts.

The first generation of catalysts developed for the homogeneous polymerization of olefins by metallocene consisted of chlorides alkylamine (AlR5CL), in which the substituents R are preferably stands or ethyl; these socializaton are characterized by a low level of activity in the polymerization of ethylene and negligible activity in the polymerization of propylene.

The second generation of joint catalytic systems included the class alkylalkoxy, usually obtained by the reaction of trialkyl-aluminum compound and water in a molar ratio of from 1:1 to 100:1; these alumoxanes are oligomeric linear and/or cyclic compounds represented by the formula:

in the case of a linear oligomeric alumoxanes and

in the case of cyclic oligomeric alumoxanes, in which the substituents R are typically methyl, ethyl or isobutylene groups, n ranges from 4 to 40, and m varies from 3 to 40. Methylalumoxane (MAO) is the most actively used acetalization.

Despite this, alkylalkoxy and, in particular, methylalumoxane (MAO), although they are very active in the catalytic systems based on metallocenes, have a number of intrinsic problems in use, such as high molar relationship alumoxane/metallocen to obtain a satisfactory catalytic activity, their high reactivity towards impurities (moisture, alcohols, etc. and easy Flammability. Moreover, when using MAO failed to isolate characterized metallocene active samples. Thus, some of the research directions in this area include the search for alternative socialization. As socialization for systems based on metallocenes were developed recoordination anions of the type In(C6F5)

-
4
. Specifically, this is the activators are ion-exchange compounds, containing trialkyl or dialkylammonium cation, which reacts irreversibly with metallocenes, and fluorinated arylboronic anion, is able to stabilize the metallocene cation complex and sufficiently labile to allow the substitution of ethylene during the polymerization (see, for example, WO 91/02012). In particular, their advantage is that they are used in relation to the catalyst-acetalization 1:1. Therefore, unlike the above socialization on the basis of aluminum is usually no need to remove a small amount of boron from the final polymer. The preferred activators are three(n-butyl)ammonium tetrakis(pendaftar-phenyl)boron,N, N-dimethylanilinium tetrakis(pentafluorophenyl)boron.

These socializaton possess high catalytic activity, but with a synthetic point of view of industrial production of these acetalization very expensive.

Finally, these anions B(B6F5)

-
4
usually used in the form of the corresponding ammonium salts, thus leading to the obtaining of amine by-product due to activation of metallocenes. In addition, they are characterized by low solubility in the polymerization solvent.

Even the fourth generation of acetalization is In(C 6F5)3. Anion Mew(C6F5)

-
3
obtained after separating Me-from metallocene dimethyl complex, poorly coordinated with electron metal centre, thus leading to a decrease in catalytic activity, and to the same catalytic system is unstable.

Alternative uses (6F5)3was proposed by C. Temme in the Journal of Organometallic Chemistry 488 (1995) 177-182. Bis-cyclopentadienylzirconium processed (6F5)3with the formation of pyrrolidinone and metallocene cation. In this article it is reported that the resulting salt is catalytically active and polimerizuet ethylene, albeit with moderate activity.

In WO 99/64476 disclosed a method of producing polyolefins using a catalytic system comprising a metallocene compound, Lisowski acid-base complex and tri-n-alkylamines connection. As described on page 4 and illustrated in the figures, the appointment lisowska reason is the inhibition of the reaction between the metallocene compounds and Lewis acid. Only adding tri-n-alkylamines connection kata is itihasa system becomes active. This catalytic system is not fully solved the problem of using In(C6F5)3from the point of view that the anion, poorly coordinated with electron metal center, is always a Mew(C6F5)

-
3
and therefore, the active catalytic system is unstable for a long time.

Therefore, there is still a need for alternative easily get socialization, which form a stable catalytic system and is able to show good activity in the polymerization of olefins.

Applicants have discovered there is now a new class of acetalization polymerization of olefins, which reduce the use of excess socializaton compared to alkylalkoxy not produce undesirable by-products after activation metallocene and provide a stable catalytic composition.

The present invention relates to ORGANOMETALLIC compound obtained by introducing in contact

a) compounds having the following formula (I)

where Ra, Rb, Rcand Rdthe same or different from each other, are selected from the group, with the standing of hydrogen, halogen, linear or branched, saturated or unsaturated C1-C10alkyl, C6-C20aryl, C7-C20arylalkyl and C7-C20alcylaryl groups, optionally containing atoms of O, S, N, P, Si or halogen, or two or more adjacent substituent Ra, Rb, Rcand Rdform one or more4-C7rings, optionally containing atoms of O, S, N, P or Si, which can bear substituents; with

b) a Lewis acid of formula (II)

where Mt is a metal belonging to the 13th group of the Periodic table of elements (IUPAC); R1the same or different from each other, are selected from the group consisting of halogen, halogenated6-C20-aryl and halogenated7-C20alcylaryl groups; two groups of R1can also be formed with a single metal condensed ring, such as, for example, 9-perfluorononane connection.

Preferably, Mt represents a or Al, and more preferably represents a Century, the Substituents R1preferably selected from the group consisting of C6F5C6F4H, C6F3H2With6H3(CF3)2, periorbital, heptapteridae, hexaferrite and pendaftar Attila. Most preferably the substituents R1are radicals With6F5.

Preferred ORGANOMETALLIC compounds are those which relate to the following two classes (1) and (2), respectively having the formula (III) and (IV)

Class (1)

ORGANOMETALLIC compounds belonging to the class (1)have the following formula (III)

where Mt is a metal belonging to the 13th group of the Periodic table of elements (IUPAC); R1the same or different from each other, are selected from the group consisting of halogen, halogenated6-C20-aryl and halogenated7-C20alcylaryl groups; two groups of R1can also form with the metal Mt one condensed ring, such as, for example, 9-perfluorononane connection; and the substituents R5, R4, R3and R2the same or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C1-C10alkyl, C6-C20aryl, C7-C20arylalkyl and C7-C20alcylaryl groups, optionally containing atoms of O, S, N, P, Si or halogen, or two or more adjacent substituents R2-R5form one or more4-C 5rings, optionally containing O, S, N, P or Si atoms, preferably, if the substituents R2-R5form one or more rings, R4and R5form one C4-C7aromatic ring, optionally containing atoms of O, S, N or P, which can bear substituents; and R2and R3form one non-aromatic C4-C7ring, optionally containing atoms of O, S, N, P or Si; provided that at least one of R2, R3, R4and R5is other than hydrogen.

Preferably ORGANOMETALLIC compounds of the formula (III) Mt is b or Al, and more preferably is In; the substituents R1the same or different from each other, preferably selected from the group consisting of C6F5C6F4H6F3H2With6H3(CF3)2, periorbital, heptapteridae, hexaferrite and pentaborate; and even more preferably R1is6F5; at least one of the substituents R5and R4preferably is C6-C20aryl, C7-C20arylalkenes and C7-C20alcylaryl group, optionally containing atoms of O, S, N or P, which can bear substituents. A preferred subclass of metalloorganic the ski compounds of the formula (III) are the compounds of formula (V):

where b is a boron atom; the substituents R1, R3and R2have the meanings given above, and the substituents R6the same or different from each other, are selected from the group comprising hydrogen, halogen, linear or branched, saturated or unsaturated C1-C10-alkyl, C6-C20-aryl, C7-C20-arylalkyl and C7-C20alcylaryl group, optionally containing atoms of O, S, N, P, Si or halogen, or two or more adjacent substituents R6form one or more C4-C7rings, optionally containing atoms of O, S, N, P or Si, which can bear substituents; preferably R is selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C1-C10the alkyl. Preferably R2and R3are hydrogen. Another preferred subclass of ORGANOMETALLIC compounds of the formula (III) are the compounds of formula (VI):

where the substituents R1and R6have the above values.

Class (2)

ORGANOMETALLIC compound belonging to the class (2)has the following formula (IV):

where Mt and R1defined as above.

p> The substituents R2', R3', R4'and R5'the same or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C1-C10-alkyl, C6-C20-aryl, C7-C20-arylalkyl and C7-C20-alcylaryl groups, optionally containing atoms of O, S, N, P, Si or halogen, or two or more adjacent substituents R2’, R3’, R4’and R5’form one or more C4-C7rings, optionally containing atoms of O, S, N, P or Si, which can bear substituents; these rings may be aliphatic or optionally may contain a double bond, provided that these rings are not aromatic.

Preferred substituents R2’, R3’, R4’and R5’the same or different from each other, are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C1-C10-Akilov, optionally containing atoms of O, S, N, P, Si or halogen, or two or more adjacent substituents R2’, R3’, R4’and R3’form one or more4-C7rings, optionally containing atoms of O, S, N, P or Si, which can bear substituents; these rings m which may be aliphatic or optionally may contain a double bond, provided that these rings are not aromatic.

A preferred subclass of ORGANOMETALLIC compounds of the formula (IV) are compounds of the formula (VII):

where the substituents R1have the same meaning as described above, and the substituents R2’and R5’the same or different from each other, are C1-C20by alkyl; preferably they are methyl or ethyl groups.

Non-limiting examples of compounds belonging to formula (I)include pyrrole, ethyl 3,5-dimethyl-2-errorcorrection; tert-butyl-3,4,5-trimethyl-2-pyrrole carboxylate; ethyl 3,4-diethyl-5-methyl-2-pyrrole carboxylate; tertbutyl 4-acetyl-Z,5-dimethyl-2-pyrrole carboxylate; diethyl-3,4-paradisebeach; 2-acylpyrrole; 2,4-dimethylpyrrole; 2,5-dimethylpyrrole; 4,5,6,7-tetrahydroindole; 1,2,5-trimethylpyrrole; 2,4-dimethyl-3-acylpyrrole; 3-acetyl-2,4-dimethylpyrrole; 3-ethyl-2-methyl-1,5,6,7-tetrahydro-4-H-indol-4-one; 2-acetylpyrrole; 2-(trichloroacetyl)pyrrole; 1,5,6,7-tetrahydro-4h-indol-4-one; 2-(TRIFLUOROACETYL)pyrrole; pyrrol-2-carboxaldehyde; indole; 2-methylindol; 3-methylindol; 4-methylindol; 5-methylindol; 6-methylindol; 7-methylindol; 2,3-dimethylindole; 2,5-dimethylindole; 5-Florinda; 4-chlorinda; 5-chlorinda; 6-chlorinda; 5-chloro-2-methylindol; 5-bromoindole; 5-methoxyindol; 4-methoxyindol; 5-acetoxy-2-methylindol; 5,6-Dimitar Jindal; 5-benzyloxyindole; 4-nitroindole; 5-nitroindole; 3-acetylindole; 3-(TRIFLUOROACETYL)indoles; indole-3-carboxaldehyde; 2-methylindol-3-carboxaldehyde; 5-methoxyindol-3-carboxyaldehyde; phenyl-3,3’-dimethyl-2,2’-diindolymethane; 3-indolyl acetate; 4-indolyl acetate; methyl indole-4-carboxylate; methyl 4-methoxy-2-indolocarbazoles; 3-cyanoindole; 5-cyanoindole; 7-azaindole.

Examples of Lewis acids of the formula (II) are:

Tris(pentafluorophenyl)borane;

Tris(heptapteridae)borane;

Tris(2,3,5,6,7,8-hexaferrites)borane;

Tris(2,4,5,6,7,8-hexaferrites)borane;

Tris(3,4,5,6,7,8-hexaferrites)borane;

Tris(2,3,4,6,7,8-hexaferrites)borane;

Tris(2,3,4,5,7,8-hexaferrites)borane;

Tris(2,3,5,6,7,8-hexaplar-4-methylnaphtho)borane;

Tris(2,4,5,6,7,8-hexaplar-3-methyl-naphthyl)borane;

Tris(3,4,5,6,7,8-hexamer-2-methylnaphtho)borane;

Tris(2,3,4,6,7,8-hexaplar-5-methylnaphtho)borane;

Tris(2,3,4,5,7,8-hexaplar-6-methylnaphtho)borane;

Tris(nonaboriginal)borane;

Tris(2,2’,3,3’,5,5’,6,6’-octafluoropentyl)borane;

Tris(3,3’,4,4’,5,5’,6,6’-octafluoropentyl)borane;

Tris(2,2’,4,4’,5,5’,6,6’-octafluoropentyl)borane;

Tris(2,2’,3,3’,4,4’,6,6’-octafluoropentyl)borane;

Tris(2,2’,3,3’,4,4’,5,5’-octafluoropentyl)borane;

Tris(2,2’,3,3’,5,5’,6,6’-octafluoropentyl)borane;

Tris(3,3’,4,4’,5,5’,6,6’-octafluoropentyl)borane;

Tris(2,2’,4,4’,5,5’,6,6’-octafluoropentyl)borane;

Tris(2,2’,3,3’,4,4’,6,6’-acceptor-5,5'-methylbiphenyl)borane;

Tris(2,2’,3,3’,4,4’,5,5’-acceptor-6,6'-methylbiphenyl)borane;

Tris(2,2’,3,3’,5,5’,6,6’-acceptor-4,4’-biphenyl)borane;

Tris(3,3’,4,4’,5,5’,6,6’-acceptor-2,2’-biphenyl)borane;

Tris(2,2’,4,4’,5,5’,6,6’-acceptor-3,3’-biphenyl)borane;

Tris(2,3,4,6-tetrafluorophenyl)borane;

Tris(2,3,5,6-tetrafluorophenyl)borane;

Tris(2,3,5-tryptophanyl)borane;

Tris(2,3,6-tryptophanyl)borane;

Tris(1,3-differenl)borane;

Tris(2,3,5,6-titrator-4-were)borane;

Tris(2,3,4,6-titrator-5-were)borane;

Tris(2,6-debtor-3-were)borane;

Tris(2,4-debtor-5-were)borane;

Tris(3,5-debtor-2-were)borane;

Forbes(pentafluorophenyl)borane;

chlorobis(pentafluorophenyl)borane;

dichloro(pentafluorophenyl)borane;

debtor(pentafluorophenyl)borane;

9-chloro-9-becertified;

9-methyl-9-becertified;

9-pentafluorophenyl-9-becertified

and 9-bromo-9-becertified.

Another objective of the present invention is a catalytic system for polymerization of olefins comprising the product obtained by the introduction of contact:

(A) at least one ORGANOMETALLIC compound of a transition metal except pyrrolidin-bis (η-cyclopentadienyl)methylsilane and

(B) ORGANOMETALLIC compound obtained by introducing in contact

(a) connect the tion, having the following formula (I):

where Ra, Rb, Rcand Rdthe same or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C1-C10alkyl, C6-C20aryl, C7-C20arylalkyl and C7-C20alcylaryl groups, optionally containing atoms of O, S, N, P, Si or halogen, or two or more adjacent substituent Ra, Rb, Rcand Rdform one or more4-C7cycles, not necessarily containing the atoms O, S, N, P or Si, which can bear substituents; with

b) a Lewis acid of formula (II)

where Mt is a metal belonging to the 13th group of the Periodic table of elements (IUPAC); R1the same or different from each other, are selected from the group consisting of halogen, halogenated6-C20-aryl and halogenated7-C20-alcylaryl groups; two groups of R1also can form with the atoms of the metal Mt one condensed ring, such as, for example, 9-perfluorononane connection; and

(C) optionally an alkylating agent.

Preferably the catalytic system for the polymerization of olefins comprises the product of the t, get an introduction to the contact:

(A) at least one ORGANOMETALLIC compound of a transition metal except pyrrolidyl bis(η-cyclopentadienyl)methylsilane,

(B) ORGANOMETALLIC compound belonging to the class (1) (compounds of formula (III), (V) and (VI)) or class (2) (compounds of formulas (IV) and (VII)as described above; and

(C) optionally an alkylating agent.

Transition ORGANOMETALLIC compounds used in the catalytic system of the present invention, are compounds suitable as catalysts for the polymerization of olefins on the basis of the coordination polymerization or polymerization implementation. This class includes the well-known transition metal compounds suitable in the traditional coordination polymerization, Ziegler-Natta and metallocene compounds and compounds of late transition metals, known as suitable for coordination polymerization. They usually include transition metal compounds 4-10 groups in which at least one ligand of the metal can be removed by catalytic activators. Usually, when this ligand is hydrogen or a hydrocarbon group containing from 1 to 20 carbon atoms, optionally containing silicon atoms, ORGANOMETALLIC catalytic connect the group of the transition metal may be used as such, otherwise, you must use an alkylating agent for alkylation of a specified catalyst. The alkylation can be carried out in a separate step or in situ.

The alkylating agent is a compound that can react with ORGANOMETALLIC catalytic transition metal compounds, and to replace the specified ligand, which can be removed alkyl group. Preferably specified alkylating agent selected from the group consisting of R10Li, R10Na, R10K, R10MgU or AIR

10
3-z
Wzor alumoxanes, in which R10may be C1-C10-alkyl, alkenylamine or alcylaryl radicals, optionally containing one or more atoms of Si or Ge, z is 0, 1 or 2, or a non-integer number ranging from 0 to 2; U is chlorine, bromine or iodine, and W represents a hydrogen atom, or chlorine, or bromine, or iodine; non-limiting examples R10are methyl, ethyl, butyl and benzyl; non-limiting examples AlR
10
3
-zWzare trimethylaluminum (TMA), Tris(2,4,4-trimethyl-pentyl)aluminum (TIOA), Tr is(2-methyl-propyl)aluminum (TIBA), Tris(2,3,3-trimethyl-butyl)aluminium, Tris(2,3-dimethyl-hexyl)aluminum, Tris(2,3-dimethyl-butyl)aluminium, Tris(2,3-dimethyl-pentyl)aluminum, Tris(2,3-dimethyl-heptyl)aluminum, Tris(2-methyl-3-ethyl-pentyl)aluminum and Tris (2-ethyl-3,3-dimethyl-butyl). Non-limiting examples of alumoxanes are: methylalumoxane (MAO), Tetra-(isobutyl)alumoxane (TIBAO), Tetra-(2,4,4-trimethyl-pentyl)-alumoxane) (TOAO), Tetra-(2,3-dimethylbutyl) alumoxane (TDMBAO) and Tetra-(2,3,3-trimethylpentyl)alumoxane (TTMWO).

Unlike catalytic system disclosed in WO 99/64476, the catalytic system of the present invention is stable and can be selected.

A preferred class of ORGANOMETALLIC compounds of the transition metal are metallocene compounds belonging to the following formula (VIII)

where (ZR

7
m
)nis a divalent group linking the Cf and A; Z is C, Si, Ge, N or P, and the group R7the same or different from each other, are hydrogen or linear or branched, saturated or unsaturated C1-C20-alkyl, C3-C20-alkyl, C6-C20-aryl, C7-C20-alcylaryl and C7-C20aryl is skillname groups or two R 7may form an aliphatic or aromatic With4-C7ring; CP is a substituted or unsubstituted cyclopentadienyls group, optionally condensed with one or more substituted or unsubstituted, saturated, unsaturated or aromatic rings containing from 4 to 6 carbon atoms, optionally containing one or more heteroatoms;

A represents O, S, NR8PR8in which R8is hydrogen, linear or branched, saturated or unsaturated With7-C20-alkyl, C3-C20-cycloalkyl,6-C20-aryl, C7-C20-alkylaryl or7-C20-arylalkyl or a has the same meaning as Cf;

M is a transition metal belonging to 4, 5 to the group or lantanoides or actinoid groups of the Periodic system of elements (version IUPAC);

the substituents L, equal or different from each other, are monoanionic Sigma ligands selected from the group consisting of hydrogen, halogen, R9, OR9, OCOR9, SR9, NR

9
2
and PR
9
2
in which R9is a linear or branched, saturated or unsaturated With1-C20-alkyl, C3-C20-cycloalkyl,6-C20-aryl, C7-C20-alcylaryl or7-C20-arylalkyl group, optionally containing one or more atoms of Si or Ge; preferably, the substituents L, equal;

m equals 1 or 2 and, in particular, is 1 if Z is N or P, and is equal to 2, if Z is C, Si or Ge;

n is an integer from 0 to 4;

r is 0, 1 or 2; preferably 0 or 1; n is equal to 0, if r equals 0;

p is an integer equal to the oxidation state of the metal M minus r+1; i.e. minus 3 if r=2, minus 2, if r=1, and -1, if r=0, and varies from 1 to 4.

In the metallocene compound of formula (VIII) divalent bridge (ZR

7
m
)npreferably selected from the group consisting of CR
7
2
, (CR
7
2
)2, (CR
2
)3, SiR
7
2
, GeR
7
2
, NR7and PR7, R7have the above values; preferably specified divalent bridge is a Si(CH3)2, SiPh2CH2, (CH2)2, (CH2)3or(CH3)2.

The variable m is preferably equal to 1 or 2; the variable n preferably varies from 0 to 4 and, if n>1, the atoms in Z may be the same or different from each other, such as divalent bridges CH2-O, CH2-S and CH2-Si(CH3)2.

Ligand SR that π-associated with the specified metal M, preferably selected from the group consisting of cyclopentadienyl, mono-, di-, tri - and tetramethylcyclopentadienyl; 4-tertbutylbenzene; 4-adamantilzameshchennykh; in-Danila; mono-, di-, tri and tetramethylbenzene; 2-methylindenyl, 3-tertbutylphenol, 4-phenylindane, 4,5-benzoindole, 3-trimethylsilylethynyl, 4,5,6,7-tetrahydroindene; fluorene, 5,10-dihydroindeno[1,2-b]indol-10-yl; N-methyl- or N-phenyl-5,10-dihydroindeno[1,2-b]indol-10-yl; 5,6-dihydroindeno[2,1-b]in the ol-6-yl; N-methyl - or N-phenyl-5,6-dihydroindeno[2,1-b]indol-6-yl; isopentane-4-yl; tiefenthaler-4-yl; azaindole-6-yl; tiefenthaler-6-yl; mono-, di - and trimethylpentane-4-yl; 2,5-dimethyl-cyclopent[1,2-b:4,3b']-dithiolane.

Group a is O, S, N(R8), in which R8is hydrogen, linear or branched, saturated or unsaturated C1-C20the alkyl, C3-C20cycloalkyl,6-C20the aryl, C7-C20alkylaryl or7-C20arylalkyl, preferably R8is stands, ethyl, n-propylene, isopropyl, n-bootrom, tert-bootrom, phenyl, n-(n-butyl)-phenyl, benzyl, cyclohexyl and cyclododecyl; more preferably R8is tert-bootrom; or a has the same meaning as Ms.

Non-limiting examples, referring to the formula (VIII)are racemic or meso forms (if exist) of the following compounds:

bis(cyclopentadienyl)zirconium dimethyl; bis(indenyl)zirconium dimethyl; bis(tetrahydroindene)zirconium dimethyl; bis-(fluorenyl)zirconium dimethyl; (cyclopentadienyl)(indenyl)zirconium dimethyl; (cyclopentadienyl)(fluorenyl)zirconium dimethyl; (cyclopentadienyl)(tetrahydroindene)zirconium dimethyl; (fluorenyl) (indenyl)zirconium dimethyl; dimethylselenide(indenyl)zirconium dimethyl, dimethylsilane(2-methyl-4-phenyl-ind who yl)zirconium dimethyl, dimethylselenide(4-naphthylidine)zirconium dimethyl, dimethylsilane(2-methylindenyl)-zirconium dimethyl, dimethylsilane(2-methyl-4-tertbutylphenyl)zirconium dimethyl, dimethylsilane(2-methyl-4-ISO-propylidene)zirconium dimethyl, dimethylselenide(2,4-dimethylindole)zirconium dimethyl, dimethylsilane(2-methyl-4,5-benzhydryl)zirconium dimethyl, dimethylselenide(2,4,7-trimethylindium)zirconium dimethyl, dimethylselenide(2,4,6-trimethylindium)zirconium dimethyl, dimethylselenide(2,5,6-trimethylindium)zirconium dimethyl, methyl(phenyl)Silantieva(2-methyl-4,6-diisopropylphenol)zirconium dimethyl, methyl(phenyl)Silantieva (2-methyl-4-isopropylidene)zirconium dimethyl, 1,2-ethylenebis(indenyl)zirconium dimethyl, 1,2-ethylenebis(4,7-dimethyl-indenyl)zirconium dimethyl, 1,2-ethylenebis(2-methyl-4-phenylindane)zirconium dimethyl, 1,4-butanediols(2-methyl-4-phenylindane)-zirconium dimethyl, 1,2-ethylenebis(2-methyl-4,6-diisopropylphenol) zirconium dimethyl, 1,4-batandjieva(2-methyl-4-isopropylidene)zirconium dimethyl, 1,4-butanediols(2-methyl-4,5-benzhydryl)zirconium dimethyl, 1,2-ethylenebis(2-methyl-4,5-benzhydryl)zirconium dimethyl, [4-(η5-cyclopentadienyl)-4,6,6-trimethyl (η5-4,5-tetrahydroindole)]dimethylzirconium, [4-(η5-3’-trimethylsilylcyanation)-4,5,6-trimethyl(η5-4,5-tetrahydroindole)]d is methylsilane, (tert-butylamide)(tetramethyl-η5-cyclopentadienyl)-1,2-amandititita, methylamide(tetramethyl-η5-cyclopentadienyl)-dimethylsilane-dietitian (methylamide)(tetramethyl-η5-cyclopentadienyl)-1,2-ethandiyl-dietitian, (tert-butylamino)-(2,4-dimethyl-2,4-pentadien-1-yl)dimethylsilane-dimethylmethane, bis(1,3-dimethylcyclopentane)zirconium dimethyl, methylene(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl; methylene(3-isopropyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; methylene(2,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; methylene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; methylene-1-(indenyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; methylene-1-(indenyl)-7-(2,5-detrimentaldepending-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; methylene-1-(3-isopropyl-indenyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; methylene-1-(2-methyl-indenyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; methylene-1-(tetrahydroindene)-7-(2,5-dimethylcyclo-pentadienyl-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; methylene(,4-dimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b’]dixital)zirconium dimethyl and dimethyl; methylene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b’]dixital)zirconium dimethyl and dimethyl; methylene-1-(indenyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4, 3-b']dixital)zirconium dimethyl and dimethyl; isopropylidene(3-methyl-cyclopentadienyl)-7-(2,5-dimethylcyclo pentadienyl-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; isopropylidene(2,4-dimethylcyclopentane)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b’]dateopen)zirconium dimethyl and dimethyl; out-propylidene(2,4-diethyl-cyclopentadienyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; isopropylidene(2,3,5-trimethyl-cyclopentadienyl)-7-(2,5-dimethyl-cyclopentadienyl-[1,2-b:4,3-b']dateopen)zirconium dimethyl, and dimethyl; isopropylidene-1-(indenyl)-7-(2,5-dimethylcyclopentane-[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; isopropylidene-1-(2-methyl-indenyl)-7-(2,5-dimethylcyclopentane[1,2-b:4,3-b']dateopen)zirconium dimethyl and dimethyl; dimethylsilanol-1-(2-methyl-indenyl)-7-(2,5-dimethylcyclopentane[1,2-b:4,3-b']dateopen)hafnium dimethyl and dimethyl; dimethylsilanol(3-tert-butyl-cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, dimethylsilanol(3-isopropyl-cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, dimethylsilanol(3-methyl-cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, dimethylsilanol(3-ethyl-cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, 1-2-ethane(3-tert-b is Teal-cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, 1-2-ethane(3-isopropyl-cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, 1-2-ethane(3-methyl-cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, 1-2-ethane(3-ethyl-cyclopentadienyl)(9-fluorenyl)zirconium dimethyl, dimethylselenide-6-(3-methylcyclopentadienyl[1,2-b]-thiophene)dimethyl; dimethylsilane-6-(4-methylcyclopentadienyl-[1,2-b]-thiophene)zirconium dimethyl; dimethylsilane-6-(4-isopropylcyclopentadienyl-[1,2-b]-thiophene)zirconium dimethyl; dimethylsilane-6-(4-tert-butylcyclopentadienyl [1,2-b]-thiophene)zirconium dimethyl; dimethylsilane-6-(3-isopropylcyclopentadienyl-[1,2-b]-thiophene)zirconium dimethyl; dimethylsilane-6-(3-vinylcyclopentane-[1,2-b]-thiophene)zirconium dimethyl; dimethylsilane-6-(2,5-dimethyl-3-phenyl-cyclopentadienyl-[1,2-b]-thiophene)zirconium dimethyl; dimethylselenide-6-[2,5-dimethyl-3-(2-were)cyclopentadienyl-[1,2-b]-thiophene]zirconium dimethyl; dimethylsilane-6-[2,5-dimethyl-3-(2,4,6-trimetilfenil)cyclopentadienyl-[1,2-b]-thiophene]zirconium dimethyl; dimethylsilane-6-[2,5-dimethyl-3-methicillinsensitive-[1,2-b]-thiophene]zirconium dimethyl; dimethylsilane-6-(2,4,5-trimethyl-3-vinylcyclopentane-[1,2-b]-thiophene)zirconium dimethyl; dimethylsilane-6-(2,5-diethyl-3-vinylcyclopentane-[1,2-b]-thiophene)zirconium dimethyl; dimethylsilane-6-(2,5-aminobutiramida 3-vinylcyclopentane-[1,2-b]-thiophene)zirconium dimethyl; demersal diylbis-6-(2,5-decret-butyl-3-vinylcyclopentane-[1,2-b]-thiophene)zirconium dimethyl; dimethylselenide-6-(2,5-ditrimethylol-C-vinylcyclopentane-[1,2-b]-thiophene)zirconium dimethyl; dimethylsilane-6-(3-methylcyclopentadienyl-[1,2-b]-Sila)zirconium dimethyl; dimethylsilane-6-(3-isopropylcyclopentadienyl-[1,2-b]-Sila)zirconium dimethyl; dimethylsilane-6-(3-vinylcyclopentane-[1,2-b]-Sila)zirconium dimethyl; dimethylsilane-6-(2,5-dimethyl-3-vinylcyclopentane-[1,2-b]-Sila)zirconium dimethyl; dimethylsilane-6-[2,5-dimethyl-3-(2-were)cyclopentadienyl-[1,2-b]-Sila]zirconium dimethyl; dimethylsilane-6-[2,5-dimethyl-3-(2,4,6-trimetilfenil)cyclopentadienyl-[1,2-b]-Sila]zirconium dimethyl; dimethylsilane-6-[2,5-dimethyl-3-methicillinsensitive-[1,2-b]-Sila]zirconium dimethyl; dimethylsilane-6-(2,4,5-trimethyl-3-vinylcyclopentane-[1,2-b]-Sila)zirconium dimethyl; [dimethylsilane(tert-butylamino)][(N-methyl-1,2-dihydrocyclopenta[2,1-b]indol-2-yl]titanium dimethyl; [dimethylsilane(tert-butylamino)][(6-methyl-N-methyl-1,2-dihydrocyclopenta[2,1-b]indol-2-yl]titanium dimethyl; [dimethylsilane(tert-butylamino)][(6-methoxy-N-methyl-1,2-dihydrocyclopenta[2,1-b]indol-2-yl]titanium dimethyl; [dimethylsilane(tert-butylamino)][(N-ethyl-1,2-dihydrocyclopenta-[2,1-b]indol-2-yl]titanium dimethyl; [dimethylsilane(tert-butylamino)][(N-phenyl-1,2-dihydrocyclopenta[2,1-b]indol-2-yl]titanium dimethyl; [dimethylsilane(tert-butylamino)][(6-methyl-N-phenyl-1,2-DigitalGlobe the[2,1-b]indol-2-yl]titanium dimethyl; [dimethylsilane(tert-butylamino)][(6-methoxy-N-phenyl-1,2-dihydrocyclopenta [2,1-b]indol-2-yl]titanium dimethyl; [dimethylsilane(tert-butylamino)][(N-methyl-3,4-dimethyl-1,2-dihydrocyclopenta[2,1-b]indol-2-yl]titanium dimethyl; [dimethylsilane(tert-butylamino)][(N-ethyl-3,4-dimethyl-1,2-dihydrocyclopenta[2,1-b]indol-2-Il]titanium dimethyl; [dimethylsilane(tert-butylamino)][(N-phenyl-N,4-dimethyl-1,2-dihydrocyclopenta[2,1-b]indol-2-yl]titanium dimethyl; and the corresponding dichloro-, hydrochlor and dihydrocodiene and appropriate η4-butadiene connection.

If a is N(R8), suitable for use in the catalytic complexes of the invention a class of metallocene complexes (A) includes the well-known catalysts with fixed geometry, described in EP-A-0416815, EP-A-0420436, EP-A-0671404, EP-A-0643066 and WO-A-91/04257.

According to a preferred execution of the invention, the group a has the same meaning as Cf, and is preferably a substituted or unsubstituted cyclopentadienyl, indenolol, tetrahydroindene (2,5-dimethyl-cyclopent[1,2-b:4,3-b']-dithiolene).

Suitable metallocene complexes which can be used in the catalytic system according to the present invention, is described in WO 98/22486, WO 99/58539, WO 99/24446, USP 5556928, WO 96/22995, EP-485822, EP-485820, USP 5324800 and EP-A-0129 368.

The metal M preferably represents Ti, Zr or Hf and more before occhialino Zr.

The substituents L are preferably identical and are selected from the group consisting of halogen, R9, OR9and NR

9
2
; where R9is C1-C7alkyl, C6-C14aryl or C7-C14arylalkyl group, optionally containing one or more atoms of Si or Ge; more preferably the substituents L selected from the group consisting of-Cl, -Br, -Me, -Et, -n-Bu, -sec-Bu, -Ph, -Bz, -CH2SiMe3, -OEt, -OPr, -OBu, -OBz and NMe2even more preferably, L is the stands.

The integer n ranges from 0 to 4, and it preferably is 1 or 2.

If n=0 and r=1, And can have the same value as Cf; Cf and preferably are pentamethyl cyclopentadienyls, indenolol or 4,5,6,7-tetrahydroindole group.

Non-limiting examples of these metallocene complexes are:

(Me3Cf)2l2(Me4Cp)2MCl2(Me5Cp)2MCl2
(EtMe4Cp)2MCl2[(C6H5)IU4Wed]2l2(Et5Cp)2MCl2
(Ind)2MCl2(H4nd) 2MCl2(Me4Cp)(Me5Cp)MCl2-
[(Si(CH3)3Cp]2MCl2(Me5Wed)l3(Ind)MCl3
(H4Ind)MCl3

and appropriate-NMe2M(OMe)2-MN2, -l, -MMeOMe, -MMeOEt, -MMeOCH2Ph-MMeOPh, -M(OEt)2, -MCl(OMe), -MCl(OEt), -MPh2, -MBz2, -MMeCl, -MPhCl, -M(NMe2)2and-M(NMe2)OMe derivatives, in which Me= methyl, Et= ethyl, CP= cyclopentadienyl, Ind= indenyl, H4Ind=4,5,6,7-tetrahydroindene, PH=phenyl, BZ=benzyl and M is preferably Zr.

If n=1 or 2 and r=1, Cf and the same or different from each other, are preferably cyclopentadienyl, tetramethyl-cyclopentadienyl, indenolol, 4,5,6,7-tetrahydroindene, 2-methyl-4,5,6,7-tetrahydroindene, 4,7-dimethyl-4,5,6,7-tetrahydroindene, 2,4,7-trimethyl-4,5,6,7-tetrahydroindene, or fluoroaniline groups; (ZR

7
m
)n(preferably represent Me2Si, Me2C, CH2or C2H4. Non-limiting examples of metallocene complexes of the formula (II)in which n=1 or 2 and r=1, are:

and appropriate MMe 2, -M(OMe)2-M(OEt)2-MCl(OMe), -MCl(OEt), -MPh2, -MBz2, -MMeCl, -MPhCl, -M(NMe2)2and-M(NMe2)OMe derivatives, in which Me, Cp, Ind, Flu, Ph, Bz, H4Ind and M have the meanings specified above.

Suitable metallocene complexes (A) are bicentenary metallocene with bridge groups, as described, for example, in USP 5145819 and EP-A-0485823.

For more metallocene complexes suitable for the catalytic system according to the invention, are classes of heterocyclic metallocenes described in WO 98/22486 and WO 99/24446. Among these metallocenes particularly preferred are those which are listed on page 15, line 8 to page 24, line 17; page 25 line 1 to page 31 line 9; and page 58 the second to last line to page 63 line 20 in WO 98/22486. Other preferred metallocenes are those that are bridging ligands listed on page 11 line 18 to page 14, line 13 MO 99/24446.

Another class of catalytic ORGANOMETALLIC transition metal compounds are complexes of late transition metals of the formula (IX) or (X)

in which M3is a metal belonging to 8,9,10 or 11 group of the Periodic table of elements (new notation IUPAC);

LaJW is aetsa bidentate or tridentate ligand of the formula (XI):

where:

In is C1-C50bridging group connecting the E1and E2not necessarily containing one or more atoms belonging to groups 13-17 of the Periodic table;

E1and E2the same or different from each other, are elements belonging to the 15th or 16th group of the Periodic table, and are associated with the specified metal Ma;

the substituents Ra1the same or different from each other, are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C1-C20alkyl, C3-C20cycloalkyl, C6-C20aryl, C7-C20alcylaryl and C7-C20arylalkyl radicals, optionally containing one or more atoms belonging to groups 13-17 of the Periodic table of elements (such as the atoms of In, Al, Si, Ge, N, P, O, S, F and Cl); or two substituent Ra1attached to the same atom E1or E2form a saturated, unsaturated or aromatic C4-C7ring having from 4 to 20 carbon atoms; maand naindependently equal to 0, 1 or 2 depending on the valency of E1and E2so as to satisfy the valency of E1and E2; qais the charge of the bidentate or tridentate is Uganda, so to satisfy the oxidation state of MaX

a
p
aor MaAndaand compound (IX) or (X) were generally neutral;

Xathe same or different from each other, are monoanionic Sigma ligands selected from the group consisting of hydrogen, halogen, Ra, ORa, S2CF3, OCORa, SRa, -NR

a
2
and PR
a
2
groups in which the substituents Raare linear or branched, saturated or unsaturated, C1-C20alkyl, C3-C20cycloalkenyl,6-C20aryl, C7-C20alcylaryl or7-C20arylalkyl radicals, optionally containing one or more atoms belonging to groups 13-17 of the Periodic table of elements (new notation IUPAC), such as atoms, N, P, Al, Si, Ge, O, S and F; or two Xagroups form metallacycles ring containing from 3 to 20 carbon atoms; the substituents Xapreferably one of the same;

Rais an integer from 0 to 3, so that the target compound (IX) or (X) was generally neutral; andais π-allyl or π-benzyl group.

Non-limiting examples of complexes of late transition metals are those described in WO 96/23010, WO 97/02298, WO 98/40374 and SOC. 120:4049-4050, 1998. Brookhart et al., J. Am. Chem. Soc. 1995, 117, 6414 and Brook-hart et al., J. Am. Chem. Soc. 1996, 118, 267, Brookhart et al., J. Am. Chem. Soc. 1998, 120, 4049, Gibson et al., Chem. Commun. 1998, 849, WO 96/27439 and Chem. Ber./Recl. (1997), 130(3), 399-403.

The next objective of the present invention is a method for the polymerization of one or more olefins in the presence of the above catalyst system.

ORGANOMETALLIC compound according to the invention have good activity as socialization in ways polymerization of olefins. In addition, they are easy to get, and they do not lead to the separation of undesirable side products after activation metallocene. In addition, they are stable and provide a stable catalyst composition in the polymerization conditions.

ORGANOMETALLIC compound according to the invention is easily obtained by the reaction of approximately stoichiometric amounts of the compounds of formula (I):

where Ra, Rb, Rcand Rdthe same as described above; with a Lewis acid of formula (II)

where Mt and R1above.

The reaction between the said Lewis acid and a compound of formula (I) is preferably carried out in an aprotic solvent, more preferably in a polar aprotic solvent (such as toluene, diethyl ether or CH2Cl2), at room temperature, the reaction can also be carried out in the presence of a small amount of water, preferably equal to or less than one molar equivalent with respect to the Lewis acid. The acidity of the Lewis acid must be high enough to cause the migration of hydrogen from the N atom to atom in αor β-position of the pyrrole ring.

The molar ratio of ORGANOMETALLIC compound (b) and ORGANOMETALLIC catalytic transition metal compounds (A), calculated as the molar ratio between the metal Mt Lewis acid and metal catalytic ORGANOMETALLIC compound of a transition metal, preferably ranges from 10:1 to 1:10, more preferably from 2:1 to 1:2 and still more preferably about 1:1.

According to the invention compound (b) may in an appropriate case, include a mixture of two or more ORGANOMETALLIC compounds according to the invention. Moreover, the component (b) may be used in combination with other joint socialization known in the art, such as alumoxane connection.

The catalytic system according to the invention may also include one or more aluminum compounds of the formula AlR

10
3-z
Wzacting as an absorber, in which R10may be C1-C10-alkyl, alkenylamine or alcylaryl radicals, optionally containing one or more atoms of Si or Ge, z represents 0, 1 or 2 or is not an integer variable in the range from 0 to 2; U is an atom of chlorine, bromine or iodine, and W is hydrogen, chlorine, bromine or iodine; non-limiting examples of aluminum compounds are trimethylaluminum (TMA), Tris(2,4,4-trimethyl-pentyl)-aluminum (TIOA), Tris(2-methyl-propyl)aluminum (TIBA), Tris(2,3,3-trimethyl-butyl)aluminium, Tris(2,3-dimethyl-hexyl)aluminum, Tris(2,3-dimethyl-butyl)aluminium, Tris(2,3-dimethyl-pentyl)aluminum, Tris(2,3-dimethyl-heptyl)aluminum, Tris (2-methyl-3-ethyl-pentyl)aluminum and Tris(2-ethyl-3,3-dimethyl-butyl).

Another example of compounds that can act as the absorber are alumoxane compounds containing at least one group of the type:

where the substituents R11that may be the same or different and, above.

In particular, alumoxane formula:

can be used in the case of linear compounds in which the n1is 0 or an integer from 1 to 40 and the substituents R15described above, or alumoxane formula:

can be used in the case of cyclic compounds in which the n2is an integer from 2 to 40 and the substituents R11defined above.

Examples of alumoxanes, suitable as absorbents according to the present invention, are methylalumoxane (MAO), Tetra-(isobutyl)alumoxane (TIBAO), Tetra-(2,4,4-trimethyl-pentyl) alumoxane) (TOAO), Tetra-(2,3-dimethylbutyl)-alumoxane (TDMBAO) and Tetra-(2,3,3-trimethylpentyl)alumoxane (TTMWO).

Particularly interesting alumoxane are those described in WO 99/21899.

The catalytic system according to the invention can be obtained prior to its introduction into the polymerization reactor or in situ in the reactor by bringing into contact with the above-described components (A), (b) and optionally (C).

According to a variant implementation of the invention components (A), (B) and optionally (C) initially introduced into contact and then injected into the reactor, which were separately introduced aluminum compound AlR

10
3-z
Wzor alumoxane. Alternatively, components (A), (b) and optionally (C) and specified aluminum compound AlR
10
3-z
Wzor specified alumoxane can be brought into contact with each other prior to their introduction into the reactor.

The catalysts of the present invention can be used on inert substrates. This can be achieved by deposition of a specified catalytic ORGANOMETALLIC compounds of the transition metal (S) or the product of its reaction with the ORGANOMETALLIC compound (b) and optionally with an alkylating agent (C), or specified ORGANOMETALLIC compound, and subsequently specified catalytic ORGANOMETALLIC compound of a transition metal, before or after optional processing specified alkylating agent in an inert substrate, such as silicon dioxide, aluminum oxide, copolymers of styrene/divinylbenzene, polyethylene or polypropylene.

Thus, the obtained solid substance can be appropriately used in the polymerization in the gas phase.

The catalysts of the present invention can be used in the polymerization of olefins.

Thus, according to the following objectives, and the acquisition is proposed a method of polymerization of one or more olefins, comprising bringing into contact one or more olefins in the polymerization conditions in the presence of the above catalyst system.

The olefins which can be polymerized in the method of the present invention, are, for example, α-olefins of the formula CH2=CHR, in which R is hydrogen or C1-C20alkyl radical.

The catalysts according to the present invention can appropriately be used when homopolymerization ethylene, in particular to obtain HDPE (high density polyethylene) and copolymerization of ethylene, in particular to obtain LLDPE. Suitable comonomers in the ethylene copolymers are α-olefins of the formula CH2=R’, in which R’ is a linear, branched or cyclic With1-C20is an alkyl radical or cycloolefine. Examples of such olefins are propylene, 1-butene, 1-penten, 4-methyl-1-penten, 1-hexene, 1-octene, allyl-cyclohexane, cyclopentene, cyclohexene, norbornene and 4,6-dimethyl-1-hepten.

Additional suitable comonomers in these ethylene copolymers are polyene, especially paired or unpaired, linear or cyclic diene, such as 1,4-hexadiene, isoprene, 1,3-butadiene, 1,5-hexadiene and 1,6-heptadiene.

When the ORGANOMETALLIC compound, which TS the lute of the present invention, used as socializaton in the copolymerization of ethylene, they, in General, create a polymer with a higher molecular weight compared to alumoxane, especially methylalumoxane.

The catalysts according to the invention can suitably be used when homopolymerization propylene, in particular in the production of isotactic polypropylene.

In addition, the catalysts according to the invention can suitably be used when obtaining elastomeric copolymers of ethylene with α-olefins of the formula CH2=CHR, in which R’ is C1-C10alkyl radical, such as propylene, 1-butene, 4-methyl-1-penten, 1-hexene and 1-octene; these copolymers may optionally contain a small proportion of units derived from a polyene.

According to another implementation variant, the catalysts according to the present invention used to obtain cycloolefinic polymers. Monocyclic and polycyclic olefin monomers can be either homopolymerization or copolymerization with linear olefinic monomers.

The polymerization processes of the present invention can be carried out in the liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in gas phase. Specified hydrocarbon solvent may be the or aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane).

The polymerization temperature preferably varies from 0°, 250°; HDPE and LLDPE, it is preferably between 20°150°and in particular between 40°s and 90°; elastomeric copolymers it is preferably between 0°200°and particularly preferably between 20°and 100°C. Molecular the weight of the polymers can be easily changed by changing the polymerization temperature, the type or concentration of the catalytic components or by using molecular weight regulators such as hydrogen.

Molecular weight distribution can be changed by using mixtures of different metallocene complexes or by carrying out the polymerization in several stages, which differ depending on the polymerization temperature and/or concentration of molecular weight regulators.

The output of polymerization depends on the purity ORGANOMETALLIC catalyst compounds of the transition metal in the catalyst, so the connection can be used as it is, or can be cleaned before using.

The following non-limiting examples are provided for illustration.

General methodology and identification

All operations were carried out in the atmosphere is e nitrogen using conventional methods with the use of line Slanka. Solvents were purified by degassing N2and by passing over activated (8 hours, blowing N2, 300° (C) Al2O3and kept in a nitrogen atmosphere. Indole (Aldrich, purity 98% or Fluka purity 99%), 2-methylindol (Aldrich, purity 98%), 3-methylindole (Aldrich, purity 98%), pyrrole (Aldrich, purity 98%), 2,4-dimethylpyrrole (Aldrich, purity 97%), 2,5-dimethylpyrrole (Aldrich, purity 98%), 2-acylpyrrole (Aldrich, purity 90%), 4,5,6,7-tetrahydroindole (Aldrich, purity 98%), l3(Aldrich, 1.0 M solution in heptane) and(C6F5)3(Boulder Scientific Company) was used in the supplied form. 2-methyl-5,6-dihydroindeno[2, 1-b] indole was synthesized in the laboratory of the applicants according to the method described in patent WO 99/24446. The melting temperature of the compounds were obtained using capillary Electrochemical device.

1H-NMR and13C-NMR

Proton and carbon spectra of the compounds were obtained on a spectrometer Bruker DPX 200, operating in the mode of the Fourier transform at room temperature when 200,13 MHz and 50,33 MHz, respectively. The samples were dissolved in Dl3, CD2CL2or C6D6. As the standard used residual peak l3or CHDCl2or6BUT5in1H spectrum (to 7.25 ppm, 5,35 to 7.15 ppm and ppm, respectively) and the peak of the solvent in13With range (53,80 ppm CD2Cl2and 128,00 ppm for C6D6). P the otonic spectrum was obtained with the pulse 15° and 2-second delay between pulses; for each spectrum collected 32 pass. The carbon spectrum of the received pulse 45° and 6-second delay between pulses; for each spectrum collected about 512 times. CD2Cl2(Aldrich, purity 99.8% atom D) used in the supplied form, while Dl3(Aldrich, purity 99.8% atom D) and C6D6(Aldrich, purity 99% atom D) before using dried over activated 4molecular sieves. Obtaining samples was performed in a nitrogen atmosphere using standard inert atmosphere techniques.

Synthesis of ORGANOMETALLIC compounds of boron

Example 1

N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]3H-indole (a-2)

Method (a)

Indole (99%, 1.07 g, MM (molecular mass) = 117,15, 9.0 mmol) was dissolved in 10 ml of CH2Cl2and were loaded into a 50 ml vessel Slanka in nitrogen atmosphere. The solution In(C6F5)3(4.61 in) MM = 511,99, 9.0 mmol) in 25 ml of CH2Cl2was added at room temperature under stirring. While adding the color of the solution immediately changed from yellow to amber-yellow; the heat was not observed. The reaction mixture was stirred at room temperature for 1 hour, then the solvent was removed under vacuum to obtain the product to be autogo solid (5.32 g). Output=94,4%.

1H NMR (CD2Cl2that δ, ppm): 4,30 (AB system, 2H, H3N3); 7,39-7,72 (m, 4H, Ar); 8,83 (d, 1H, JHF=5,0 Hz, H2)

13With NMR (CD2Cl2that δ, ppm): 42,18 (C3); 118,26 (SN); 125,35 (SN); 129,16 (SN); 129,20 (SN); 133,07 (); 147,97 (); 175,43 (C2) (peak assigned based on the DEPT experiment).

TPL=amount of 203.9°-206,7°C.

Method b)

A solution of indole (99%, 0,72 g, MM = 117,15, 6.05 mmol) in 5 ml of Et2O was added at -20°C in nitrogen atmosphere to a suspension of(C6F5)3(99.4%of 3.13 g, MM = 511,99, between 6.08 mmol) in 20 ml of ethyl ether in a 50 ml vessel Slanka. While adding the color of the solution changed from whitish to yellow. The reaction mixture was then left to warm to room temperature and was stirred for 2 hours with final formation of a yellow solution.1H NMR analysis showed that the reaction was completed after 1 hour stirring at room temperature. The solvent was evaporated under vacuum obtaining in the quality of the product is a light yellow solid (yield 100%).

1H NMR (Dl3that δ, ppm): 4,22 (extended AB system, 2H, H3N

'
3
); 7,34-7,66 (m, 4H, Ar); 8,77 (d, 1H, JHF=5,0 Hz, H2).

Example 2

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]3-methyl-3H-ind is La (A-4)

A solution of 3-methylindole (98%, 0,92 g, MM = 131,18, 6,87 mmol) in 10 ml dichloromethane was added at room temperature in a nitrogen atmosphere to a solution In(C6F5)3(BSC-382-4-0128, 99.4 per cent, of 3.53 g, MM = 511,99, 6,85 mmol) in 15 ml of dichloromethane in a 50 ml vessel Slanka. Heat was not observed. While adding the color of the solution changed from light yellow to yellow. After 30 min stirring at room temperature1H NMR analysis showed the presence of traces of unreacted 3-methylindole) are studied. Then, to complete the reaction was added to 0.23 g (0.45 mmol) of Tris(2,3,4,5,6-pentafluorophenyl)borane. After stirring overnight the solvent was removed under vacuum to obtain the product of white powder (yield 100%).

1H NMR (CD2Cl2that δ, ppm): 1,61 (USS, 3H, CH3); or 4.31 (USS, 1H, NC); 7,35-to 7.67 (m, 4H, Ar); 8,69 (d, 1H, JHF=5.3 Hz, H2).

1H NMR (C6D6that δ, ppm): 0,65 (USS, 3H, CH3); 2,74 (USS, 1H, NC); 6,62-6,84 (m, 3H, Ar); 7,53 to 7.62 (m, 1H, Ar); to $ 7.91 (USS, 1H, H2 of the first diastereoisomer); 7,97 (USS, 1H, H2second diastereoisomer).

13With NMR (C6D6that δ, ppm): 11,72 (CH3); 46,97 (C3); 111,18 (SN); 117,99 (C7); 123,76 (SN); 128,97 (SN); 138,32 (Sa); 146,52 (Sa); 179,29 (C2).

Complex 3-methyl-3H-indol·In(C6F5)3shows two diastereoisomers at 10� With CD2Cl2. The ratio of these two diastereoisomers is 55:45 in 10°CD2Cl2.

Example 3

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2-methyl-ZN-indole (a-3)

A solution of 2-methylindole (98%, of 0.67 g, MM = 131,18, free 5.01 mmol) in 10 ml dichloromethane was added at room temperature in a nitrogen atmosphere to a solution In(C6F5)3(99,4%, 2,60 g, MM = 511,99, of 5.05 mmol) in 15 ml of dichloromethane in a 50 ml vessel Slanka. Heat was not observed. While adding the color of the solution changed from light orange to orange.1H NMR analysis in CD2Cl2showed quantitative conversion of the original 2-methylindole after 1 h stirring at room temperature. After 4 h stirring at room temperature, the reaction mixture became light pink suspension. Stirring was continued overnight and then the suspension was filtered through a G3 Frit. The residue on the Frit was a white solid and according to1H NMR analysis in C6D6was specified product (2.16 g, yield 67.0 per cent). The final complex is not fully dissolved in CD2Cl2but were completely dissolved in C6D6.

1H NMR (C6D6that δ, ppm): 1,70 (m, 3H, CH3); 2,46 (AB system, 2H, J=25,63 Hz, N

'
3
); 6,64-6,83 (m, 3H, Ar); to 7.61-of 7.69 (m, 1H, Ar).

13With NMR (C6D6that δ, ppm): 18,77 (DD, JCF=9,20 Hz, JCF=2,50 Hz, CH3); 46,88 (C3); 117,74 (DD, JCF=7,66 Hz, JCF=1,84 Hz, C7); 123,83 (AG); 127,75 (AG); 128,15 (AG); 130,79 (Sa); 150,44 (l, JCF=3.98 Hz, Sa); 189,36 (C2).

TPL=204,3°-204,5°C.

Example 4

Synthesis of N-(tricorbraun)3H-indole (A-20)

A solution of indole (99%, 1,79 g, MM = 117,15, 15,13 mmol) in 20 ml of dichloromethane was added within 5 min at -20°C in nitrogen atmosphere to a solution of l3(1M in heptane, 15 ml, 15.0 mmol) in 15 ml of dichloromethane in a 100 ml vessel Slanka. At the end of the add was formed yellow suspension. The reaction mixture was stirred at -20°C for 15 min and then left to warm to room temperature. The color of the suspension was slowly changed from yellow to pink.1H NMR analysis showed that the reaction had ended after 1 hour stirring at room temperature. After 4 h stirring at room temperature the suspension was filtered on a G4 Frit and the residue was dried to obtain a pink powder, which according to the1H NMR analysis in CD2Cl2was a given product (2,79 g, yield 79.4 per cent).

1H NMR (CD2Cl2that δ, ppm): 4,27 (USS, 2H, H3N

'
3
); 7,42-7,81 (m, 3H, Ar); of 8.37-to 8.41 (m, 1H, Ar); 9,44-9,48 (m, 1H, H2).

1H NMR (C2D2Cl4that δ, ppm): 4,19 (USS, 2H, H3N

'
3
); 7,29-7,72 (m, 3H, Ar); 8,35-to 8.41 (m, 1H, Ar); 9,38-9,48 (m, 1H, H2).

TPL=184,8-185,6°C.

Synthesis of N-(tricorbraun)3H-girondolo also conducted using the same above conditions, but by adding a solution of trichloride boron in heptane to the solution of indole in dichloromethane, to obtain the same results.

Example 5

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2H-4,5,6,7-tetrahydroindole (A-13)

A solution of 4,5,6,7-tetrahydroindole (98%, 0.65 g, MM = 121,18, the 5.25 mmol) in 3 ml dichloromethane was added at room temperature in a nitrogen atmosphere to a solution In(C6F5)3(99,4%, 2,69 g, MM = 511,99, the 5.25 mmol) in 15 ml of dichloromethane in a 25 ml vessel Slanka. There was a slight evolution of heat. The reaction mixture was stirred for 30 min at room temperature and then the solvent was evaporated in vacuum to obtain a white powder as product (yield 100%).

1H NMR (CD2Cl2that δ, ppm): 7,34 (USM, 1H, H3); 4,85 (extended AB system, 2H, H2, H2’); 3,4-1,02 (USS, 8H, H4, H4’, H5, H5’, N6, N6’, N7, H7’).

13With NMR (CD2Cl2that δ, ppm): 21,74 (C5 and C6); 23,87 (C4); 29,76 (C7); 66,39 (d, C2, JCF=10.4 Hz); 140,78 (Sa); 147,02 (C3); 186,25 (Sa).

Example 6

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2-methyl-6,10b-dihydroindeno [2,1-b] indole (A-21)

2-methyl-5,6-dihydroindeno[2,1-b]indole (1.77 g, MM = 219,29, 8.1 mmol) was dissolved in 10 ml of CH2Cl2and were loaded into a 50 ml vessel Slanka in nitrogen atmosphere. The solution In(C6F5)3(4,14 g, MM = 511,99, 8.1 mmol) in 25 ml of CH2CL2was added at room temperature under stirring. During the addition the color of the solution immediately changed from green to dark brown; the heat was not observed. The reaction mixture was stirred for 1 h at room temperature, then the solvent was removed under vacuum to obtain a brown solid as the product (5,90 g). Output = 100%.

1H NMR (CD2Cl2that δ, ppm): to 2.46 (s, 3H, CH3); of 3.78 (d, 1H, J=20,1 Hz, CH2); to 4.23 (DD, 1H, J=20,1 Hz, J=3.0 Hz, CH2); 5,86 (s, 1H, N); 7,16-of 7.69 (m, 7H, Ar).

13With NMR (CD2Cl2that δ, ppm): 21,33 (CH3); 35,72 (d, CH2, J=10,8 Hz); 62,88 (CH2); 117,88 (m); 124,04; 125,31; 125,80; 129,18; 129,48; 129,98; 133,20; 134,07; 139,25; 141,19; 149,24 (d, J=4, 2 Hz); 200,03 (peak assigned based on the DEPT experiment).

TPL=160,5°-166,1&x000B0; C.

Example 7

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]5H-pyrrole (a-1).

Method (a)

Yellow-orange solution of pyrrole (98%, 0.35 g, MM = 67,09, 5,11 mmol) in 10 ml dichloromethane was added at room temperature in a nitrogen atmosphere to a yellow-orange solution In(C6F5)3(99.4%of 2.64 g, MM = 511,99, 5,12 mmol) in 40 ml of dichloromethane in a 100 ml vessel Slanka. Heat was not observed. Thus obtained yellow reaction mixture was stirred for 2 h at room temperature and then the solvent was removed under vacuum to obtain white-light yellow powder as product (yield 100%).

1H NMR (CD2Cl2that δ, ppm): 4,71 (USS, 2H, H5N

'
5
); 6,94 (DK, 1H, J=5,48 Hz, J=1.08 Hz, H3); of 7.90 (DK, 1H, J=5,48 Hz, J=1.08 Hz, H4); 8,58 (m, 1H, J=1.08 Hz, H2);

13With NMR (CD2Cl2that δ, ppm): 66,72 (m5); 128,61 (C3); 156,98 (C4); 172,04 (C2).

NOESY (CD2Cl2): δ1H/δ1H=4,71/Of 7.90 (H5/H4), Of 7.90/6,94 (N4/N3), 6,94/8,58 (H3/H2).

1H NMR (C6D6that δ, ppm): 3,70 (USS, 2H, H5N

'
5/td>
); 5,62 (DK, 1H, J=6,16 Hz, J=1.08 Hz, H3); 6,51 (DK, 1H, J=6,16 Hz, J=1.08 Hz, H4); 7,51 (m, 1H, J=1.08 Hz, H2);

13With NMR (C6D6that δ, ppm): 65,76 (m, C5); 127,38 (C3); 155,67 (C4); 171,38 (C2).

NOESY (C6D6): δ1H/δ1H=3,70/6,51 (H5/H4), 6,51/5,62 (N4/N3), 5,62/7,51 (H3/H2).

TPL=187,0°-189,6°C.

Method b)

Light yellow solution In(C6F5)3(1,182 g, MM = 511,99, 2,31 mmol) in 8 ml of toluene was added at room temperature to a yellow solution of pyrrole (98%, 0,158 g, MM = 67,09, 2,30 mmol) in 2 ml of toluene in a nitrogen atmosphere in a 25 ml vessel Slanka. Heat was not observed. Thus obtained yellow reaction mixture was stirred for 2 h at room temperature and then the solvent was removed under vacuum to obtain a yellow powder as product (1,255 g, 99.5%purity, yield 93,8%).

Example 8

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2,4-dimethyl-5H-pyrrole (5)

Yellow-orange solution of 2,4-dimethylpyrrole (97%, 0,564 g, MM = 95,15, of 5.75 mmol) in 5 ml dichloromethane was added at room temperature in a nitrogen atmosphere to pale yellow solution In(C6F5)3(99.4%of 3,267 g, MM = 511,99, 6,34 mmol) in 20 ml of dichloromethane in a 50 ml vessel Slanka. Heat was not observed. The yellow reaction mixture was stirred for 20 h at room temperature and analyzer the Wali 1H NMR at different points in time. The final yellow solution was dried in vacuum to obtain a dark yellow powder as product (yield 100%).

1H NMR (CD2Cl2that δ, ppm): 2,20 (t, 3H J=2,74 Hz, CH32); to 2.29 (d, 3H, J=1,57 Hz, CH34); 4,82 (broad AB system, 2H, H5N

'
5
); 6,41 (K, 1H, J=1,57 Hz, H3).

1H NMR (C6D6that δ, ppm): 1.14 in (d, 3H, J=1,74 Hz, CH34); of 1.41 (t, 3H, J=2,74 Hz, CH32); 4,20 (CL, 2H, H5N5); 5,06 (SHK, 1H, J=1,47 Hz, H3).

13With NMR (CD2Cl2that δ, ppm): 14,56 (CH34); is 18.40 (CH32); 70,32 (C5); 128,65 (C3); 169,60 (C4); 185,40 (C2).

NOESY (CD2Cl2): δ1H/δ1H=4,82/2,29 (H5/CH34), to 2.29/6,41 (CH34/N3), 6,41/2,20 (H3/CH32).

TPL=209,2-211,8°C.

Example 9

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2,5-dimethyl-5H-pyrrole (6)

Pink solution of 2,5-dimethylpyrrole (98%, 0,313 g, MM = 95,15, up 3.22 mmol) in 8 ml dichloromethane was added at room temperature in a nitrogen atmosphere to pale yellow solution In(C6F5)3(99.4%of 1,659 g, MM = 511,99, up 3.22 mmol) in 15 ml of dichloromethane in a 25 ml vessel Slanka. Heat was not what was distributed. The reaction mixture was stirred for 5 h at room temperature and analysed by1H NMR at different points in time. The final light orange solution was dried in vacuum to obtain a yellow powder as product (1,878 g, yield 96.1 per cent). According to NMR analysis, the product was a mixture of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2,5-dimethyl-5-hidropetrol (90%) and N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2,5-dimethyl-3-hidropetrol (10%).

N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2,5-dimethyl-5-hidropetrol:

1H NMR (CD2Cl2that δ, ppm): 1,23 (Ust, 3H, J=7,14 Hz, CH35); of 2.20 (d, 3H, J=2,84 Hz, CH32); 5,41 (USS, 1H, H5); 6,62 (DD, 1H, J=5,48 Hz, J=1,17 Hz, H3); to 7.67 (m, 1H, J=5,48 Hz, H4).

1H NMR (C6D6that δ, ppm): 0.50 in (m, 3H, CH35); of 1.29 (d, 3H, J=2,74 Hz, CH32); 4,70 (USS, 1H, H5); at 5.27 (DD, 1H, J=5, 38 Hz, J=1,17 Hz, H3); 6,21 (DM, 1H, J=5,38 Hz, H4).

13With NMR (CD2Cl2that δ, ppm): 15,94 (l, JCF=15.3 Hz, CH35); 19,36 (Usc, CH32; 77,02 (l, JCF=15.3 Hz, CH5); 130,31 (C3); 161,43 (C4); 185,86 (l, JCF=3,70 Hz, C2).

NOESY (CD2Cl2): δ1H/δ1H=5,41/1,23 (H5/CH35), 2,20/6,62 (CH32/N3), 6,62/to 7.67 (H3/N4); to 7.67/5,41 (H4/N5).

N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2,5-dimethyl-3-hydro is Errol:

1H NMR (CD2Cl2that δ, ppm): 2,03 (OST 3H, CH3); 2,44 (m, 3H, J=2,05 Hz, CH3); 3,71 (extended AB system, 2H, J=26,8 Hz, H3N

'
3
); 6,10 (USS, 1H, H4).

1H NMR (C6D6that δ, ppm): 1,53 (OST 3H, CH3); 1,61 (USS, 3H, CH3); 2,09 (extended AB system, 2H, J=27,1 Hz, H3N

'
3
); 4,98 (USS, 1H, H4).

Example 10

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-2-ethyl-5H-pyrrole (7)

The orange solution of 2-acylpyrrole (90%, 0,367 g, MM = 95,15, 3,47 mmol) in 5 ml dichloromethane was added at room temperature in a nitrogen atmosphere to pale yellow solution In(C6F5)3(99.4 per cent, of 1.80 g, MM = 511,99, to 3.49 mmol) in 15 ml of dichloromethane in a 25 ml vessel Slanka. During the addition the color of the solution immediately changed from orange to dark orange; the heat was not observed. The reaction mixture was stirred over night at room temperature:1H NMR analysis showed the presence of approximately 11% mole. unreacted 2-acylpyrrole. Then, to complete the reaction was added 0.21 g (0.41 mmol) of Tris (2,3,4,5,6-pentafluorophenyl)borane is. After several minutes of stirring the solvent was removed under vacuum to obtain a white powder as product (yield 100%).

1H NMR (CD2Cl2that δ, ppm): from 0.88 (t, 3H, J=7,43 Hz, CH3); 2,67 (USM, 2H, CH2); 4,99 (extended AB system, J=25,24 Hz, 2H, H5N5’); to 6.88 (dt, 1H, J=5,58 Hz, J=1,27 Hz, H3); to 7.77 (d, 1H, J=5,58 Hz, H4).

1H NMR (C6D6that δ, ppm): 0,075 (t, 3H, J=7,43 Hz, CH3); 2,00 (m, 2H, J=7,43 Hz, CH2); 4,14 (extended AB system, J=25,14 Hz, 2H, H5N5’); 5,54 (dt, 1H, J=5,48 Hz, J=1,27 Hz, H3); of 6.31 (d, 1H, J=5, 48 Hz, H4).

13With NMR (CD2Cl2that δ, ppm): 9,80 (CH3); 25,48 (CH2); 68,36 (m5); 130,30 (C3); 154,37 (C4); 189,38 (C2).

Example 11

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-imidazole (A-9)

A colorless solution of imidazole in 5 ml of dichloromethane was added at room temperature in a nitrogen atmosphere to pale yellow solution In(C6F5)3(99.4 per cent, of 1.80 g, MM = 511,99, to 3.49 mmol) in 15 ml of dichloromethane in a 25 ml vessel Slanka. During the addition the color of the solution immediately changed from orange to dark orange; the heat was not observed. The reaction mixture was stirred for 1 h at room temperature, then the solvent was removed under vacuum to obtain a white powder is CA (2,60 g) as product (yield 100%).

1H NMR (CD2Cl2that δ, ppm): 7,18-7,24 (m, 2H, H4and H5), 8,08 (s, 1H, H2); of 10.05 (USS, 1H, NH).

13C NMR (CD2Cl2that δ, ppm): 117,83 (C5); 126,69 (C4); 136,24 (C2).

TPL=214,9°-217,8°C.

Example 12

Synthesis of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-pyrrolidine (A-10)

The solution pyrrolidine (99,5%, 0.34 g, MM = 71,12, 4,78 mmol) in 3 ml dichloromethane was added at room temperature in a nitrogen atmosphere to a solution of Tris(2,3,4,5,6-pentafluorophenyl)borane (BSC 382-4-0128, 99.4%of the 2,44 g, MM = 511,99, 4.77 mmol) in 15 ml of dichloromethane in a 50 ml vessel Slanka. There was a slight evolution of heat. The reaction mixture was stirred for 30 min at room temperature and then the solvent was evaporated in vacuum to obtain a white powder as product (yield 100%).

1H NMR (CD2Cl2that δ, ppm): 6,30 (USS, 1H, NH); 3,44-of 3.54 (m, 2H, H2and H5); 2,68-of 2.86 (m, 2H, H2and H5); 1,84-of 2.09 (m, 4H, HCand H4).

13With NMR (CD2Cl2that δ, ppm): 50,37 (C2and C5); 23,86 (C3and C4).

Synthesis of metallocene complexes

Synthesis of bis(indenyl)Zirconia dimetil

29,6 ml of 1.6 M solution of MeLi in Et20 (by 47.4 mmol) was added at room temperature to a solution of 3 g of indene (23,7 mmol, Aldrich, 91,8%) in 30 ml Et2O during the approximately 5 minutes (exothermic reaction). The mixture was stirred for 30 minutes to obtain an orange solution.

2.76 g ZrCl4(11,84 mmol) suspended in 30 ml of pentane. Suspension ZrCl4the pentane was quickly added to the Li salt solution in Et2O (exothermic reaction). The resulting reaction mixture was stirred for 2 hours and then dried under reduced pressure. The obtained pale-brown solid was extracted with 100 ml of pentane (Soxhlet, 4.5 hours) and then the filtrate was evaporated to dryness under reduced pressure to obtain 3.2 g (77% yield) of light yellow solid, which was identified1H NMR as pure chemical Ind2ZrMe2.

1H NMR (C6D6that δ, ppm): -0,78 (s, 6N, Zr-SN3), 5,62 (t, 2H, CP-H(2)), 5,80 (d, 4H, Cf(H(1,3)); 6,87-6,92 (m, 4H, Ar), 7,19-of 7.23 (m, 4H, Ar).

Synthesis of bis(indenyl)hafnium of dimetil

32,4 ml of MeLi 1.6 M in Et20 (51,8 mmol) was added at -80°to a solution of 3 g of indene (Aldrich, 92%, with 23.7 mmol) in 30 ml Et2O, for about 10 minutes. The reaction mixture gave to slowly warm to room temperature and was stirred for 4 hours. After this time the solution became orange from light yellow. 1,4 ml of TiCl4(Aldrich, 99%, 12.8 mmol) was dissolved in 30 ml of pentane. Both the mixture was cooled to -80°C and a solution of TiCl4quickly added to the Li salt solution. The reaction mixture was let to rise slowly to room is based temperature and was stirred overnight with final receipt of the dark brown suspension. Then the solvents were removed under reduced pressure. The obtained brown solid was extracted with pentane to to conventional Soxhlet extractions (Soxhlet). The filtrate was evaporated to dryness under reduced pressure to obtain 2.2 g of a dark-green powder (56% yield).

1H NMR (C6D6that δ, ppm): -0,93 (s, 6N, Hf-CH3), to 5.57 (t, Cu-N(2) 2N), 5,69 (d, 4H, Cf(H(1,3)); 6,87-6,92 (m, 4H, Ar), 7,19-of 7.23 (m, 4H, Ar).

Obtaining the catalytic systems according to the invention

The catalytic system 1

Bis(indenyl)zirconium dimethyl (1.0 g, MM = 351,60, 2,84 mmol), obtained as described above in the synthesis of 4, was dissolved in 20 ml of toluene in a 100 ml vessel Slanka in nitrogen atmosphere. A solution of 1.8 g of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-3-girondolo (MM=629,14, of 2.86 mmol), obtained as described above, in 20 ml of toluene was added at room temperature under stirring. In the process of adding was observed methane and minor amounts of heat. The reaction mixture was stirred at room temperature for 1 hour and 30 minutes and then the solvent was removed under vacuum to obtain 2,74 g of an orange-red powder.

1H NMR (C6D6that δ, ppm): -0,82 (s, 3H, Zr-SN3), 4,20 (s, 1H, CH); of 5.05 (USS, 1H, CH); 5,20 (t, 1H, J=2,9 Hz, CH); 5,35 is 5.38 (m, 1H, CH); 5,52-of 5.55 (m, 1H, CH); to 5.66 (t, 1H, J=2.5 Hz, CH); of 5.83 (t, 1H, J=3,4 Hz, CH); 6,37-7,14 (m, 11N, AG); 7,53 (USS 1H, CH); of 7.96 (d, 1H, J=8,3 Hz, CH).

13 6D6that δ, ppm): 50,48 (CH3); 79,69 (SN); 100,96 (SN); 101,29 (SN); 103,15 (SN); 106,70 (SN); 115,39 (SN); 117,27 (SN); 118,78 (CH); 122,78, 123,82; 124,82, 125,03; 125,25; 125,37; 125,79; 126,44; 126,49; 126,79; 127,01; 135,94 (C); 145,62 (); 155,91 (SN) (peak assigned based on the DEPT experiment). The remaining Quaternary carbons were not wholly attributed as possibly superimposed on the peak from C6D6.

The catalytic system 2

Bis(indenyl)hafnium dimethyl (0.50 g, MM = 438,87, to 1.14 mmol), obtained as described above was dissolved in 3 ml of toluene, 15 ml of the vessel Slanka in nitrogen atmosphere. The solution to 0.72 g of N-[Tris(2,3,4,5,6-pentafluorophenyl)borane]-3-girondolo (Mm = 629,14, to 1.14 mmol), obtained as described above, in 4 ml of toluene was added at room temperature under stirring. In the process of adding was observed methane and minor amounts of heat. The reaction mixture was stirred at room temperature for 3 hours, then the solvent was removed under vacuum to obtain a red powder as product (1.20 g).

1H NMR (C6D6that δ, ppm): -0,85 (s, 3H, Hf-CH3); 3,74 (s, 1H, CH); 4,99 (USS, 1H, CH); 5,20 (USS, 1H, CH); 5,28 (t, 1H, J=2.5 Hz, CH); 5,38 (Ust, 1H, CH); the ceiling of 5.60 (Ust, 1H, CH); 5,80 (t, 1H, J=3.0 Hz, CH); 6,36-7,14 (m, 11N, AG); 7,62 (USS 1H, CH); of 7.95 (d, 1H, J=7.9 Hz, CH).

Polymerization

Analysis of polymer

Carbon spectra were recorded at 120°With the spectrometers Bruker DPX-400 or Brker DPX-200, working in the mode of the Fourier transform when 100,61 and 50,33 MHz, respectively. The samples were dissolved in C2D2Cl4at concentrations of 8% wt./about.

Spectra were obtained with 90° pulses and 12 second delay between pulses. For each spectrum collected about 1500 or 3000 times depending on the spectrometer. Peak Sδδ carbon (29,9 ppm) was used as reference. The nomenclature is given according to Carman C.J., R.A. Harrington; Wilkes C.E. Macromolecules, 1977, 10, 536, the assignment of the peaks according to Randall J.C. Macromol. Chem. Phys., 1989, p.29, 201 and Tritto I., Z. Fan, P. Locatelli, M. Sacchi, Camurati, I., Galim-berti M., Macromolecules 1995, 28, 3342, and triad distribution determined according Kakugo, M., Naito y, Mizunuma, K., Miyatake T., Macromolecules 1982, 15, 1150.

Characteristic viscosity was measured in tetrahydronaphtalene (THN) at 135°C.

The molecular weight of the polymers was determined from the viscosity values.

Polymerization Example 1

Polymerization of ethylene

A polymerization test was carried out in a 1 l autoclave made of stainless steel, thermostatted using H2About/pair and cleaned by blowing of ethylene at 80°C. While purging with ethylene were loaded into the reactor 513 ml of technical hexane and 1 mmol of TIBA, the temperature was brought to 80°and the reactor was ventolinbuy to remove residual nitrogen, then created excessive pressure ethylene up to 9.5 barg.) (950 kPa). to 3.52 mg catalytic system 1, receiving the Noi, as described above, dissolved 1.76 ml of toluene, was injectively into the reactor by means of excess pressure of ethylene through the steel vessel and the partial pressure of ethylene stabilized at the level of 9.6 bar(abs) (960 kPa) (Ptotal11 bar(abs) (1100 kPa)).

The polymerization was carried out at 80°C for hours maintaining a constant partial pressure of ethylene, and then stopped by the injection of CO in the reactor and releasing unreacted ethylene.

The polymer was separated by filtration and dried under reduced pressure at 60°C, thus obtaining the 36.1 g of polyethylene having a characteristic viscosity of 4.3 DL/g

Polymerization: Examples 2-20

At 4.25 l chemical reactor with a stirrer made of stainless steel at 30°loaded With 2 l of hexane, and then TIBA in hexane (amount shown in table 1) as the absorber. Then the reactor was filed under the pressure of propylene and ethylene to achieve a composition of 1.2 wt.% ethylene and 22.8 wt.% propylene and then the temperature of the reactor was raised to 50°C.

The catalytic complex was obtained by rapid mixing 5 mg (bis-indenyltitanium)-dichloride in 5 ml of toluene, one equivalent of socializaton dissolved in toluene (MAO used 500 equivalents), and, if necessary, 2 ml of triisobutylaluminum (TIBA) in hexane, as shown in the table.

The polymerization was started engineering is the design of toluene solution, containing a solution of catalyst/socializaton in toluene in an autoclave by means of excess pressure of ethylene, the temperature was then maintained at 50°and ethylene is continuously fed into the reactor in order to hold a constant pressure. After adding 40 g of ethylene polymerization was stopped by injection of CO in the reactor, ventilation and cooling of the reactor (inactive experiments were stopped after 60 min). Amorphous copolymer of ethylene/propylene was isolated from the hexane solution by precipitation in acetone, followed by drying under reduced pressure at 70°C for 4 hours.

Characteristics of the copolymers are presented in the table.

1. ORGANOMETALLIC compound obtained by bringing into contact

a) compounds having the following formula (I):

(I)

where Rand, Rb, Rcand Rdthe same or different from each other, are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C1-C10alkyl groups, or two or more adjacent substituents Rand, Rb, Rcand Rdform one or more4-C7rings, optionally containing N atoms, which can bear substituents; with

b) luisas the second acid of formula (II):

where Mt represents a boron atom; R1the same or different from each other, are selected from the group consisting of halogen and halogenated6-C20-aryl groups.

2. ORGANOMETALLIC compound according to claim 1, in which the substituents R1selected from the group consisting of fluorine, C6F5C6F4H, C6F3H2C6H3(CF3)2performfinish, heptapteridae, hexaferrite and pentaverate.

3. ORGANOMETALLIC compound according to claim 1, having the formula (III)

(III)

where Mt represents a boron atom; R1the same or different from each other, are selected from the group consisting of halogen and halogenated6-C20-aryl groups; and the substituents R5, R4, R3and R2the same or different from each other, are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated, C1-C10-alkyl groups, or two or more adjacent substituents R2-R5form one or more4-C7rings, optionally containing N atoms; provided that at least one of R5, R4, R3and R2different from hydrogen is.

4. ORGANOMETALLIC compound according to claim 3, in which the substituents R1the same or different from each other, are selected from the group consisting of fluorine, C6F5With6F4H, C6F3H2With6H3(CF3)2performfinish, heptapteridae, hexaferrite and pentaborate; the substituents R5and R4together form an aromatic C5-C7ring, optionally containing N atoms, which can bear substituents.

5. ORGANOMETALLIC compound according to claim 3 or 4, having the formula (V)

(V)

where the substituents R1, R3and R2have the meanings defined in claim 3 or 4, and the substituents R6represent hydrogen or linear or branched, saturated or unsaturated With1-C6is an alkyl group.

6. ORGANOMETALLIC compound according to claim 3 or 4, having the formula (VI)

(VI)

where the substituents R1and R6have the meanings given in claim 5.

7. ORGANOMETALLIC compound according to claim 1 or 2, having the following formula (IV):

where Mt and R1have the meanings given in claims 1 or 2;

the substituents R2’, R3’, R4’and R5’one is the same or different from each other, selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C1-C10-alkyl groups, or two or more adjacent substituent R2’, R3’, R4’and R5’form one or more4-C7rings, optionally containing N, which can bear substituents; these rings may be aliphatic or optionally may contain a double bond, provided that these rings are not aromatic.

8. ORGANOMETALLIC compound according to claim 7, having formula (VII):

where

the substituents R1have the meanings defined in claim 1 or 2, and the substituents R2’and R5’the same or different from each other, are C1-C20the alkyl.

9. Catalytic system for polymerization of olefins comprising the product obtained by bringing into contact:

(A) at least one ORGANOMETALLIC compound of a transition metal except pyrrolidin-bis(η-cyclopentadienyl)methylsilane and

(B) ORGANOMETALLIC compound defined as indicated in claim 1; and

(C) optionally alkylating agent.

10. The catalytic system according to claim 9, in which the ORGANOMETALLIC compound (B) has the formula (III):

(III)

where Mt, R1, R5, R4, R3and R2defined as in item 3.

11. The catalytic system according to claim 9, in which the ORGANOMETALLIC compound (B) has the formula (IV):

where Mt, R1, R2', R3', R4'and R5'defined as in item 7.

12. The catalytic system according to any one of p-11, in which the catalytic ORGANOMETALLIC transition metal compound has the following formula:

(Cf)(Cf)rMLp

where CP is a substituted or unsubstituted cyclopentadienyls group, optionally condensed with one or more substituted or unsubstituted, saturated, unsaturated or aromatic rings containing from 4 to 6 carbon atoms; M is a transition metal belonging to group 4 of the Periodic system of elements (version IUPAC); the substituents L, equal or different from each other, are monoanionic Sigma ligands selected from linear or branched, saturated or unsaturated With1-C20-alkyl groups;

r is 0, 1 or 2;

p is an integer equal to the oxidation state of the metal M minus r+1.

13. The method of obtaining the ORGANOMETALLIC compound according to any one of claim 2 to 8, including the step of the reaction in aprot nom solvent, in approximately stoichiometric amounts of the compounds having formula (I)

(I)

where Rand, Rb, Rcand Rddefined in claim 1; with a Lewis acid of formula (II)

where Mt and R1defined in claim 1.

14. How homopolymerization of ethylene or copolymerization of ethylene and one or more alpha-olefins, namely, homopolymerization or copolymerization carried out by bringing into contact of ethylene and, optionally, one or more alpha-olefins in the liquid phase or in the gas phase at the temperature of polymerization in the range from 0 to 125°and in the presence of a catalytic system according to any one of p-12.



 

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SUBSTANCE: claimed polymer or copolymer may be obtained using comonomers selected from at least one monomer of group including olefine, (meth)acrylic alkyl esters, cyclopentadiene, cyclohexene, cyclohexadiene, optionally substituted norbornene, dicyclopentadiene, optionally substituted tetracyclododecenes, alkylated in nuclear styrene, alpha-methylstyrene, divinylbenzene, vinyl ester, vinyl ether, vinyl acetate, vinyl acid, (meth)acrylonitrile, maleic anhydride. Polymer contains more than 50.1 % and less than 74 % of isotactic diads.

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The invention relates to the field of chemical technology
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