MXPA97007707A - Heterometalic catalysts based on metalocene of group ivb and aluminum hydrides for the polymerization of olefins and dienos conjuga - Google Patents

Abstract

The present invention relates to bis (cyclopentadienyl) hydruroaluminohydride complexes of transition metals of Group IVB of the Periodic Table of Elements as precatalyst component of the catalytic system in the polymerization of olefins and conjugated dienes, to the methods of preparation of polyolefins with the content from 10 to 95% of fragments generated from 1,3 insertion of the monomer and to the methods of preparation of poliedienes with the content of 60 to 95% of 1,4-cis fragments, using said catalytic system. The catalytic system comprises: A) a transition metal bis (cyclopentadienyl) hydruroaluminohydride compound, which has by general formulas (C5H5-y-xRx) Ty (C5H5-y-zRz) MHA1H4, [(C5H5-y-xRx) Ty (C5H5-y-zRz) MHA1H4] 2 or [(C5H5-y-xRx) Ty (C5H5-y-zRZ) MH] 2A1H5, where "M" is Ti, Zr or Hf in its oxidation state +4, ( C5H5-y-xRx) and C5h5-y-zRz) are cyclopentadienyl rings substituted with R or R 'groups (same or different), "x" and "z" can have value from 0 to 5; "and" can have value 0ó1; when "y" is equal to 1, "Ty" is a covalent bridged group. B) a boron compound by formula B (C6H5-kFk) 3 or PB (C6H5-kFk) 4 where "k" can have a value of 0 to 5 and "P" is a cation capable of extracting a hydride atom forming a neut species

Description

HETEROMETALIC CATALYSTS BASED ON METALOCENE OF GROUP IVB AND ALUMINUM HYDRIDES FOR THE POLYMERIZATION OF OLEFINS AND CONJUGATED DIENOS DESCRIPTION The heterometallic compounds mentioned here represent a new variant of the metallocene-based catalysts, also known as single-site catalysts, which are useful in the polymerization of olefins. Apart from an activator (eg methylalumoxane, salts of tetrakis (pentafluorophenyl) boron, tris (pentafluorophenyl) boron, among others), conventional catalysts contain a monometallic component Ü (precatalyst) which is a derivative (chloride, hydride, amide, alkyl, aryl or alkoxide) of metallocene. Said conventional catalysts are applied in obtaining polyolefins "common" whose main chains are formed by incorporation of the two carbon atoms of the double bond of the monomer. In the present invention, the covalent heterometal compounds of transition metal metal bis (cyclopentadienyl) hydruroaluminohydride of Group IVB of the Periodic Table of Elements are detailed as a precatalyst part. Being activated with a boron compound (eg: tris (pentafluorophenyl) boron, salts of Tetrakis (pentafluorophenyl) boron, among others), said heterometallic compounds are catalytically active in the polymerization of olefins and conjugated dienes. Depending on the polymerization temperature and the environment generated by the cyclopentadienyl binders in the transition atom, "common" polymers are obtained in whose main chains the two carbon atoms of the double bond are incorporated (insertion 1,2 or 2, 1) or polymers in whose main chains are incorporated primarily the two double bond carbon atoms and a neighboring allylic carbon atom (primary, secondary or tertiary) of the monomer (insert 1.3). The use of the catalysts referred to in the polymerization of olefins and conjugated dienes has never been reported before, which is the object of the present invention. * bis (cyclopentadienyl) hydruroaluminohydride of transition metals of Group IVB of the Periodic Table of Elements; to its use as a precatalyst component of the catalytic system in the polymerization of olefins and conjugated dienes; to the polyolefin preparation methods generated primarily from the 1.3 insert of the monomer, using the complexes referred to as precatalysts; to the polydiene preparation methods with high content of 1,4-cis fragments, using the complexes referred to as precatalysts.

Precatalyst Component 10 The precatalyst component is represented by general phrale (I) where "M" is Ti, Zr or Hf in its formally higher oxidation state (+4, complex d °); 15 (C5H5.y.x.Rx) and (C5H5.y.zR z) are cyclopentadienyl rings substituted with R or R 'groups (same or different), each of which is, independently, a radical selected from hydrocarbon radicals, hydrocarbon radicals where one or more hydrogen or carbon atoms are replaced by heteroatom-containing radicals selected from Groups 20 IIIA-VIIA of the Periodic Table of Elements, from heteroatoms selected from Groups IIIA-VIIA of the Periodic Table of Elements, substituted with hydrogen or hydrocarbon radicals; or (C5H5.y.x.Rx) and (C5H5.y-zR z) are cyclopentadienyl rings in which two vicinal substitutes are bonded forming cycles with the number of carbon atoms from 4 to 20 and thus giving polycyclic cyclopentadienyl binders. saturated or unsaturated; , cyclopentadienyl binders; "y" can have value 0 or 1; when "y" is equal to 1, "Ty" is a covalent, cyclic or acyclic bridged (linear or branched) group selected from hydrocarbon radicals, from hydrocarbon radicals where one or more hydrogen or carbon atoms are replaced by radicals containing heteroatoms selected from the Groups IIIA-VIIA of the Periodic Table of Elements, of heteroatoms selected from Groups IIIA-VIA of the Periodic Table of Elements, substituted with hydrogen or hydrocarbon radicals.

Table 1 includes some representative examples of the cyclopentadienyl binders and bridged "Ty" groups with which the referred heterometallic precatalysts can be constituted. These examples are illustrative and not limiting of benefits and advantages obtained by the practice of the present invention.

The precatalyst component can exist in the form represented by the general formula (I) only when it is dissolved in organic solvents (eg ethyl ether, benzene, toluene, among others) in the range of concentrations less than 10"M. In the range from For concentrations greater than 10"3 M or in solid state, the precatalyst component exists in the dimer form represented by the general formula (II). a a M t "(=? T .. fv = n (G5H5.y.x.x.Rx) and (C5H5.y.zR-z) zirconium methylidene cyclopentadienyl hafnium zJsO-propylidene methylcyclopentadienyl titanium diphenylmethylidene dimethylcyclopentadienyl ethylidene tetramethylcyclopentadienyl cyclohexylidene pentamethylcyclopentadienyl 4-piperidinylidene tert-butylcyclopentadienyl 4-tetrahydropyranylidene 1 -tert-butyl-3 -metilciclopentadienilo dimetilsililideno trimethylsilylcyclopentadienyl dietilsililideno l-trimethylsilyl-3-methylcyclopentadienyl difenilsililideno di-fert-butylcyclopentadienyl 15 terametildisililideno dimetilborilciclopentadienilo terametildisiloxano borilideno metilborilideno tetrahydroindenyl fluorenyl indenyl octahydrofluorenyl fenilborilideno 20 methylimine tert-butilindenilo ethylimine trimetilsililindenilo w-butylimine tert -butyltetrahydroindenyl oxo trimethylsilyltetrahydroindenyl sulfide 2.7-dimesityloctahydrofluorenyl When storing the heterometallic complexes referred to (in the solution or in the solid), these release an equivalent of the aluminum hydride leaving the precatalyst component in the form represented by the general formula (III) All the precatalyst forms represented by the general formulas (I-III) are active in the polymerization of olefins and conjugated dienes. The subsequent decomposition of the precatalyst leads to the formation of inactive species in the polymerization of olefins and conjugated dienes.

The preparation of the precatalyst solution consists (as Example IE) of the addition of two equivalents of lithium aluminum tetrahydride (solution in ethyl ether) to the corresponding metallocene dichloride solution in ethyl ether followed by evaporation 15 of solvent. Then an aromatic solvent (eg benzene, toluene) is added and the resulting suspension is filtered leaving a solution containing the compound of interest.

Activating Component The activating component is a boron compound by general formula B (C6Hs_kFk) 3 or PB (C6Hs.kFk) 4 where the subscript "k" can have a value of 0 to 5 and "P" is a cation capable of removing an atom hydride forming a neutral species that does not have a Lewis basic functionality (eg B (C6F5) 3, CPh3B (C6F5) 4).

Preparation of Catalyst (Catalytic System) The preparation of the catalytic system consists (as described in Example IB) in the addition of an equivalent of the activating component (solution in toluene) to the precatalyst component (solution in toluene) in the temperature range of 0 to 25 ° C. The solution of the catalytic system has a bright orange color.

It should be noted that the precatalysts, activators and catalysts referred to are highly sensitive to air and to pro-active substances (water, alcohols, acids, etc.) and that is why the use of a technique (argon-vacuum) that guarantees an inert atmosphere is required, as well as strict purification of the gas (eg argon), solvents and monomers required.

Polymerization Process The polymerization method consists in adding to a polymerization reactor the monomer solution in toluene and then the catalyst solution in toluene. The reactor must be provided basically with a temperature controlled system and a stirring system. The procedure basically consists of adding the monomer solution in the required quantities and waiting for it to reach the desired temperature. Once I know reach the temperature, the catalyst is added quickly and the system is allowed to polymerize for a certain time dependent on the polymerization temperature.

An alternative method is to add the precatalyst solution to a polymerization reactor, wait for it to reach the programmed temperature (in the range of 0 to 25 25 ° C). Once the temperature is reached, an activator equivalent is added and the color of the solution is expected to turn bright orange. Subsequently, the monomer previously added to the required temperature is added and the system is allowed to polymerize for a determined time dependent on the polymerization temperature.

The monomer can be added in bulk or in solution. In case the monomer is a gas, the pressure of the latter can be varied in the range of 10 psi to 2,000 psi. The preferred solvent. -. Polymerization time is preferably from 1 minute to 24 hours. The polymer is recovered by conventional methods.

Monomers The catalysts referred to are useful for the polymerization of alpha-olefins and conjugated dienes. The alpha-olefins that can be used are of the general formula CH2 = CHCHXY, where "X" and "Y" are independently: a hydrogen atom; a linear, branched or cyclic hydrocarbon radical, saturated or unsaturated; a linear, branched or cyclic hydrocarbon radical, saturated or unsaturated, wherein one or more hydrogen or carbon atoms are replaced by radicals containing heteroatoms selected from Groups IIIA-VIIA of the Periodic Table of Elements; heteroatoms selected from Groups III A-VII A of the Periodic Table of Elements, substituted with hydrogen or hydrocarbon radicals.

Some illustrative examples of the alpha-olefins are propylene, 1-butene, 1-hexene, iso-butene, allylbenzene, 3-chloropropylene.

Some illustrative examples of conjugated dienes are butadiene, isoprene, cyclopentadiene, trimethylsilylcyclopentadiene.

Resulting polymers With this method, using only a minimum concentration of catalyst (0.2 μmol / mL), polymers with molecular weight (Mw) are obtained up to 1.5 x 10 with a polydispersity no greater than 3.2. or merc e to a-o e ness.

Depending on the polymerization temperature and the environment generated by the cyclopentadienyl binders in the transition atom, the polymers obtained using the catalysts referred to may have structures generated from insertions 1,2 (or 2,1) of the monomer (Scheme 1). , a), or polymers generated from 1.3 insertions of the monomer (Scheme 1, b), or random co-polymers in which the two types of monomer insertion are represented (Scheme 1, c). Scheme 1 represents the three types of polymers described above that are obtained in the case of a monomer of the general formula CH2 = CHCHXY.

CH2 = CHCHXY a) b) c) Scheme 1 In some experiments (examples No. 2,4,5), polymers have been obtained whose characteristics and properties have been similar to those obtained with conventional single site catalysts (Scheme 1, a). In those experiments (examples No. 3,6,9,11-14) where polymers generated from 1,3 inserts have been obtained, the content of fragments - (CH2-CH2-CXY) - varies in a range of 20 to 95 % (calculated by NMR spectroscopy of 13C and 1H).

Polymerization of conjugated dienes n unc nea empera ura e po mer zac nye am in which cyclopentadienyls in the transition atom, the polymers obtained using the catalysts referred to, may contain the fragments generated by insertion 1,4-cis- in the range of 60 to 95% (examples No. 7,8,10) (calculated by NMR spectroscopy of C and H). In case the monomer is a cyclopentadiene (substituted or unsubstituted) the resulting polymer can contain up to 95% of repeating units where subscript "m" can have value from 0 to 3 and R "is a hydrocarbon or trialkylsilyl radical.

In accordance with the above, a series of polymerization experiments were carried out, of which 15 examples are described below. Said examples are not limiting of the benefits and advantages obtained by the practice of the present invention.

Example IA. To the solution of rac-C2H4 (H4lnd) 2ZrCl2 (0.15 mMol) in ethyl ether (100 ml) added the solution (3 ml) of LiAlH4 in ethyl ether (0.1 M) at room temperature with vigorous stirring. The mixture was allowed to react for 30 min and the solvent was evaporated under high vacuum. To the solid residue was added 100 mL of toluene, the suspension was allowed to stir for 30 min and the insoluble products were separated by filtration. The resulting solution is colorless.

Example IB To the solution prepared as in Example IA, a solution of B (C6F5) 3 (0.15 mMol) in toluene (4 mL) was added at 0 ° C with vigorous stirring. In 2 min the color of the solution turned bright orange. or you can go to a or menc ona or prep r IB. Example 2. Polymerization of propylene (15 psi) with the catalyst. { rac-C2H4 (H4lnd) 2ZrAlH4} +. { HB (C6F5) 3} "(30 μmol) was carried out in toluene (20 mL) at 0 ° C for 2 hours After a precipitation with acidified methanol, 1.5 g of polymer having a molecular weight (Mw) of 3.3 x 10 and a polydispersity were obtained. (Mw / Mn) of 2.67 The microstructure of the polymer is isotactic polypropylene.

Example 3. Polymerization of propylene (15 psi) with the catalyst. { rac-C2H4 (H4Ind) 2ZrAlH4} +. { HB (C6F5) 3} "(30 μmol) was carried out in toluene (20 mL) at 25 ° C for 2 hours After a precipitation with acidified methanol, 1.2 g of polymer having a molecular weight (Mw) of 1.5 x 10 and a polydispersity were obtained. (Mw / Mn) of 2.33 The microstructure of the polymer is random co-polymer of isotactic polypropylene (90%) and polyethylene (10%).

Example 4. Polymerization of propylene (15 psi) with the catalyst. { (1, 3-C5H3Me2) 2ZrAlH4} +. { HB (C6F5) 3} "(30 μmol) was carried out in toluene (20 mL) at 0 ° C for 2 hours After a precipitation with acidified methanol, 2.7 g of polymer having a molecular weight (Mw) of 0.5 x 104 and a polydispersity were obtained. (Mw / Mn) of 3.45 The microstructure of the polymer is atactic polypropylene.

Example 5. The polymerization of 1 -hexene (2 g) with the catalyst. { rac-C2H4 (H4Ind) 2ZrAlH4} +. { HB (C6F5) 3} "(30 μmol) was carried out in toluene (20 mL) at 0 ° C for 24 hours After a precipitation with acidified methanol, 0.9 g of polymer having a molecular weight (Mw) of 1.0 x 10 and a polydispersity were obtained. (Mw / Mn) of 1.83 The microstructure of the polymer is isotactic polyhexen.

Example 6. The polymerization of 1 -hexene (2 g) with the catalyst. { (1, 3-C5H3Me2) 2ZrAlH4} +. { HB (C6F5) 3} (30 μmol) was carried out in toluene (20 mL) at 0 ° C for 24 hours After a precipitation with acidified methanol, 0.6 g of polymer having a molecular weight (Mw) of 0.7 x 104 and a polydispersity were obtained. (Mw / Mn) of 2.09.The microstructure of the polymer is polyhexene with the content of fragments - (CH2-CH (n-C4H9)) - of 78% and the content of fragments - (CH2-CH2-CH (n-C3H7 )) - of 22%.

Example 7. 10 The polymerization of cyclopentadiene (2 g) with the catalyst. { (1, 3-C5H3Me2) 2ZrAlH4} +. { HB (C6F5) 3} "(30 μmol) was carried out in toluene (20 mL) at 0 ° C for 24 hours After a precipitation with acidified methanol, 0.4 g of polymer having a molecular weight (Mw) of 2.2 x 10 and a polydispersity was obtained. (Mw / Mn) of 3.2 The microstructure of the polymer is polycyclopentadiene with 1,4-cis incorporation monomer of 81% and incorporation 1.2 of 19%.

Example 8. The polymerization of cyclopentadiene (2 g) with the catalyst. { SiMe2 (H8Flu) 2ZrAlH4} +. { HB (C6F5) 3} "(30 μmol) was carried out in toluene (20 mL) at 0 ° C for 24 hours After a precipitation with acidified methanol, 1.6 g of polymer having a molecular weight (Mw) of 3.7 x 104 and a polydispersity (Mw / Mn) of 2.39 The microstructure of the polymer is polycyclopentadiene with 1.4-cis incorporation of the monomer of 95% and incorporation 1.2 of 5%.

Example 9. The polymerization of 1 -hexene (2 g) with the catalyst. { CMe2 (3-SiMe3-H4Ind) 2ZrAlH4} +. { HB (C6F5) 3} (30 μmol) was carried out in toluene (20 mL) at 0 ° C for 24 hours After a precipitation with acidified methanol, 1.7 g of polymer having a molecular weight (Mw) of 3.9 x 10 and a polydispersity were obtained. (Mw / Mn) of 2.99. The microstructure of the polymer is polyhexene with the content of fragments - (CH2-CH (n-C4H9)) - of 13% and the content of fragments - (CH2-CH2-CH (n-C3H7)) - 87%.

Example 10. The polymerization of butadiene (2 g) with the catalyst. { CMe2 (3-SiMe3-H4Ind) 2ZrAlH4} +. { HB (C6F5) 3} "(30 μmol) was carried out in toluene (20 mL) at 25 ° C for 0.5 hours After a precipitation with acidified methanol, 1.9 g of polymer having a molecular weight (Mw) of 4.5 x 10 and a polydispersity were obtained. (Mw / Mn) of 2.54 The polymer microstructure is polybutadiene with 1, 4-c and 85% monomer incorporation and 1.2, 15% incorporation.

Example 11. Polymerization of 1-butene (15 psi) with the catalyst. { SiMe2 (2-Me-H4Ind) 2ZrAlH4} +. { HB (C6F5) 3} "(30 μmol) was carried out in toluene (20 mL) at 0 ° C for 0.5 hours After a precipitation with acidified methanol, 3.8 g of polymer having a molecular weight (Mw) of 1.5 x 10 and a polydispersity were obtained. (Mw / Mn) of 2.13 The microstructure of the polymer is polybutene with the content of fragments - (CH2-CH (C2H5)) - of 6% and the content of fragments - (CH2-CH2-CH (CH3)) - of 94% Example 12. The polymerization of 1 -hexene (2 g) with the catalyst. { SiMe2 (2-Me-H4Ind) 2ZrAlH4} +. { HB (C6F5) 3} (30 μmol) was carried out in toluene (20 mL) at 0 ° C for 2 hours After a precipitation with acidified methanol, 1.7 g of polymer having a molecular weight (Mw) of 4.6 x 104 and a polydispersity were obtained. (Mw / Mn) of 2.76 The microstructure of the polymer is polyhexene with the content of fragments - (CH2-CH (n-C4H9)) - 5% and the content of fragments - (CH2-CH2-CH (n-C3H7 )) - of 95%.

Example 13. The polymerization of 1 -hexene (2 g) with the catalyst. { SiMe2 (2-Me-H4Ind) 2ZrAlH4} +. { B (C6F5) 4} '(30 μmol) was carried out in toluene (20 mL) at 25 ° C for 1 hour. After a precipitation with acidified methanol, 1.9 g of polymer having a w ecu ar weight was obtained. x and one po spers a w n of 2.93. The microstructure of the polymer is polyhexene with the content of fragments - (CH2-CH (n-C4H9)) - of 7% and the content of fragments - (CH2-CH2-CH (n-C3H7)) - of 93%. Example 14. 5 The polymerization of allylbenzene (2 g) with the catalyst. { SiMe2 (2-Me-H4Ind) 2ZrAlH4} +. { HB (C6F5) 3} (30 μmol) was carried out in toluene (20 mL) at 0 ° C for 6 hours After a precipitation with acidified methanol, 1.5 g of polymer having a molecular weight (Mw) of 1.2 x 105 and a polydispersity were obtained. (Mw / Mn) of 1.62 The polymer microstructure is poly (allylbenzene) with the content of fragments 10 - (CH2-CH (CH2Ph)) - 5% and the content of fragments - (CH2-CH2-CH (Ph )) - of 95%. *

Claims (15)

We claim:

1. A catholytic system comprising: A) a bis (cyclopentadienyl) hydruroaluminohydride transition metal compound of the Group IVB of the Periodic Table, represented by the general formulas where "M" is Ti, Zr or Hf in its formally higher oxidation state (+4, complex d °); (C5H5.y.x.Rx) and (C5H5.y.zR z) are cyclopentadienyl rings substituted with R or R 'groups (same or different), each of which is, independently, a radical selected from hydrocarbon radicals; of hydrocarbon radicals where one or more hydrogen or carbon atoms are replaced by radicals containing heteroatoms selected from Groups IIIA-VIIA of the Periodic Table of Elements; of heteroatoms selected from Groups IIIA-VIIA of the Periodic Table of Elements, substituted with hydrogen or hydrocarbon radicals; or 5 5.x and xy 5 5.yz z are still years old in which their neighbors are united forming cycles with the number of carbon atoms from 4 to 20 and thus giving polycyclic cyclopentadienyl binders saturated or unsaturated; * the subscripts "x" and "z" can have a value of 0 to 5, denoting the level of substitution of the 5 cyclopentadienyl binders; "y" can have value 0 or 1; when "y" is equal to 1, "Ty" is a covalent, cyclic or acyclic (linear or branched) bridged group selected from hydrocarbon radicals; of hydrocarbon radicals where one or more hydrogen or carbon atoms are replaced by radicals containing heteroatoms selected from the groups IIIA-VIIA of the Periodic Table of Elements; of heteroatoms selected from Groups IIIA-VIA of the Periodic Table of ^ Elements, substituted with hydrogen or hydrocarbon radicals. 15 B) a boron compound by formula B (C6H5-kFk) 3 or PB (C6H5.kFk) where the subscript "k" can have a value of 0 to 5 and "P" is a cation capable of removing a hydride atom forming a neutral species that does not have a basic Lewis function.

2. The catalyst system of claim No. 1 wherein said saturated or unsaturated polycyclic cyclopentadienyl binders are selected from the group of tetrahydroindenyl or octahydrofluorenyl.

3. The catalytic system of claims No. 1 and 2 wherein said heteroatoms constituting the substituents R and R 'are selected from the Group IVA of the Periodic Table 25 of Elements.

4. The catalytic system of claims No.1-3 wherein said heteroatoms constituting the covalent bridged group k'Ty "are selected from the Group IVA of the Periodic Table of Elements.

5. The catalyst system of claims No.1-4 wherein the molar ratio of component A to component B is 1: 1. I

6. The use of the catalytic system of claims No.1-5 in the polymerization of olefins.

7. The use of the catalytic system of claims No.1-5 in the polymerization of monomers of general formula CH2 = CH-CHXY, where "X" and "Y" are independently: a hydrogen atom; a linear, branched or cyclic hydrocarbon radical, saturated or unsaturated; A linear, branched or cyclic, saturated or unsaturated hydrocarbon radical, wherein one or more hydrogen or carbon atoms are replaced by heteroatom-containing radicals selected from Groups IIIA-VIIA of the Periodic Table of Elements; # heteroatoms selected from Groups IIIA-VIIA of the Periodic Table of Elements, substituted with hydrogen or hydrocarbon radicals.

8. The method of preparing the polymers whose main chains consist of fragments formed by the insertion 1.2 (or 2.1) and of fragments formed by the insertion 1.3 of the monomer described in claim No. 7, wherein the method of preparation comprises the use of the catalyst system of claims No. 1-5 in the polymerization 20 of monomers described in claim No. 7.

9. The use of the catalytic system of claims No. 1-5 in the polymerization of monomers described in claim No. 7 for the polymer preparation of claim No. 8 wherein the content of fragments formed by the insertion 1,3 of the 25 monomer is from 0.1 to 20%.

10. The use of the catalytic system of claims No. 1-5 in the polymerization of monomers described in claim No. 7 for the polymer preparation of claim No. 8 wherein the content of fragments formed by the insertion 1,3 of the

The monomer is from 20 to 50%. . use s ema ca e co e ns re v n cac ons o. - in a pore monomers described in claim No. 7 for the preparation of polymers of claim No. 8 wherein the content of fragments formed by the 1.3 insertion of the monomer is 50 to 80%.

12. The use of the catalytic system of claims No. 1-5 in the polymerization of monomers described in claim No. 7 for the preparation of polymers of claim No. 8 wherein the content of fragments formed by the 1,3 insertion of the monomer It is not less than 95%.

13. The use of the catalytic system of claims No. 1-5 in the polymerization of conjugated dienes. *

14. The method of preparing polybutadienes with the content of 1,4-cis fragments not less than 85% and fragments 1,2 not greater than 15%, wherein the method of preparation comprises the use of the catalyst system of claims No. 1 -5 in the polymerization of butadienes.

15. The method of preparation of polycyclopentadienes with the content of repetitive fragments not less than 95%, wherein the method of preparation comprises the use of the catalytic system of claims No. 1-5 in the polymerization of cyclopentadienes of general formula C5H6.mR "m, where subindice" m "may have value from 0 to 3 and R "is a hydrocarbon or trialkylsilyl radical.