RU2153502C2 - Metallocene catalyst and method of preparation of polyolefins - Google Patents

Abstract

FIELD: polymerization catalysts. SUBSTANCE: catalyst represents sterilely rigid metallocene compound containing at least two optionally substituted cyclopentadienyl groups as ligands linked to each other through monocyclic annular system, one of cyclopentadienyl groups being annelated to monocyclic system and this ligand system being different from 4-(η⁵-3-alkylcyclopentadienyl)-4,6,6-trimethyl-(η⁵-2- alkyl-4,5-tetrahydropentalene) group and defined by formula I:

, wherein M is IVb group metal; R¹ and R², identical or different, are halogen atoms, C₁-C₁₀-alkyls, or NR $\genfrac{}{}{0ex}{}{\text{13}}{\text{2}}$ , group with R¹³ being C₁-C₁₀-alkyl; R³,R⁴,R⁵,R⁶,R⁷,R⁸ and R⁹, identical or different, are hydrogen atoms, C₁-C₁₀-alkyls, or group -R¹³-SiR $\genfrac{}{}{0ex}{}{\text{13}}{\text{3-}}$ , with R¹³ being as indicated above; R¹⁰ is C₁-C₂₀-alkyl; R¹¹ and R¹², identical or different, are C₁-C₂₀-alkyl, C₆-C₂₀-aryl, or C₂-C₁₂-alkenyl; and n is integer from 1 to 10. Catalyst is applicable in production of polyolefins via polymerization of at least one cycloolefin. EFFECT: enabled production of olefin homopolymers and copolymers with improved physico-chemical properties, especially those with reduced crystallinity, increased impact resistance, elevated transparency, high flowability at processing temperatures, low molecular weight, and reduced melting temperature. 8 cl, 3 tbl, 33 ex

Description

 The invention relates to a technology for producing a polymer of olefins, in particular, to a metallocene catalyst and a method for producing a polymer of olefins.

 A metallocene catalyst for producing an olefin polymer is known, comprising at least one metallocene compound with (substituted) indenyl residues as ligands, in particular isopropylene (cyclopentadienyl) (1-indenyl) dichlorozirconium (see application EP N 0407870, MKI: C 08 F 32/08, 1991).

 A disadvantage of olefin polymers obtained using the known metallocene catalyst, which can be used to produce polymer alloys and molded products, is that their physical and mechanical properties are not entirely satisfactory.

 An object of the present invention is to provide a catalyst by which it is possible to produce a polymer of olefins with improved physicomechanical properties, in particular polyolefins with reduced crystallinity, increased impact strength, increased transparency, high fluidity at processing temperatures, low molecular weight and low melting point.

где М - металл группы IVб Периодической системы,
R¹ и R² одинаковы или различны и означают атом галогена, алкил с 1-10 атомами углерода, или группу NR¹³ ₂, где R¹³ означает алкил с 1 - 10 атомами углерода,
R³, R⁴, R⁵, R⁶, R⁷, R⁸ и R⁹ одинаковы или различны и означают атом водорода, алкил с 1 - 10 атомами углерода, или остаток -R¹³-SiR $\genfrac{}{}{0ex}{}{\text{13}}{\text{3}}$ -, где R¹³ имеет вышеуказанное значение,
R¹⁰ - алкил с 1-20 атомами углерода,
R¹¹ и R¹² одинаковы или различны и означают алкил с 1 - 20 атомами углерода, арил с 6 - 20 атомами углерода, алкенил с 2 - 12 атомами углерода,
n - целое число от 1 до 10.The problem is solved by the proposed metallocene catalyst for producing a polymer of olefins, which is a sterically rigid metallocene compound containing at least two substituted or unsubstituted cyclopentadienyl groups bonded to each other via a monocyclic ring system, and one cyclopentadienyl group is anellated to the monocyclic system, and this ligand system is different from 4 η ⁵ -3-alkyl-cyclopentadienyl) - 4,6,6-trimethyl- (η ⁵ -2-alkyl-4,5-tetrahydropentalene) and is a compound of formula (I)

where M is a metal of group IVb of the Periodic system,
R ¹ and R ^{2 are the} same or different and mean a halogen atom, alkyl with 1-10 carbon atoms, or a group NR ¹³ ₂ , where R ¹³ means alkyl with 1 to 10 carbon atoms,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are the} same or different and represent a hydrogen atom, alkyl with 1 to 10 carbon atoms, or the residue —R ¹³ —SiR $\genfrac{}{}{0ex}{}{\text{thirteen}}{\text{3}}$ - where R ¹³ has the above meaning,
R ¹⁰ is alkyl with 1-20 carbon atoms,
R ¹¹ and R ^{12 are the} same or different and mean alkyl with 1 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, alkenyl with 2 to 12 carbon atoms,
n is an integer from 1 to 10.

 The monocyclic system preferably has 6 ring atoms.

In the above general formula (I), the radicals have the following preferred meanings:
M means zirconium,
R ¹ and R ^{2 the} same mean a halogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are the} same or different and represent hydrogen, alkyl with 1-4 carbon atoms,
R ¹⁰ is alkyl with 1-6 carbon atoms,
R ¹¹ and R ^{12 are the} same or different and mean methyl or phenyl,
n - 2.

 The proposed catalyst can be deposited on a carrier and / or prepolymerized.

Obtaining the proposed metallocene catalyst of the above formula (I) is illustrated by the following reaction scheme. Moreover, M ¹ means a metal of the main group Ia, IIa or IIIa.

Дифульвены формулы (II) получаются из дикетонов (см. Chem. Ber. 114, 1226 (1981); там же 109, 3426 (1976); там же 107, 2453 (1974) или кетоальдегидов по известным из литературы способам (см. J. Org. Chem. 57 (1992) 2504; там же, 49 (1984) 1849; журнал Химия, 46 (1992) 377).

Difulfenes of formula (II) are obtained from diketones (see Chem. Ber. 114, 1226 (1981); ibid. 109, 3426 (1976); ibid. 107, 2453 (1974) or ketoaldehydes by methods known from the literature (see J Org. Chem. 57 (1992) 2504; ibid., 49 (1984) 1849; Journal of Chemistry, 46 (1992) 377).

 The conversion of difulvene (II) to a ligand system of the formula (III) is carried out by reaction with an organometallic compound (such as, for example, methyl lithium, butyllithium, phenyl lithium) or Grignard reagent.

 Salts of formula (III) can be directly converted to the corresponding dianionic compounds of formula (V) by deprotonation, for example, butyl lithium. Hydrolysis of compound (III) leads to the formation of a biscyclopentadiene compound (IV), which is obtained as a mixture of structural isomers and can be purified by chromatography. By doubling the deprotonation of compound (IV), for example with butyl lithium, a dianion compound of the formula (V) is formed.

 The conversion to the metallocene having a bridge of formula (I), as well as the isolation of the desired complexes, are known in principle. For this, the dianion of formula (V) is reacted with an appropriate metal halide, such as, for example, zirconium tetrachloride, in an inert solvent. Metallocenes of formula (I) can also be synthesized directly from difulvenes of structure (II) without isolation of intermediate products.

 Suitable solvents are aliphatic or aromatic solvents, such as, for example, hexane or toluene, ether solvents, such as, for example, tetrahydrofuran or diethyl ether or halogenated hydrocarbons, such as, for example, methylene chloride or halogenated aromatic hydrocarbons, such as, for example, o-dichlorobenzene.

Взаимодействие фульвена (IVa) с металлоорганическими соединениями формулы R¹⁵M¹ (причем R¹³, R¹⁴, R¹⁵, R¹⁶ и R¹⁷ одинаковы или различны и имеют значение радикала R¹⁰; М¹ имеет вышеуказанное значение) приводит к образованию моноанионного соединения (IlIa).Bis-cyclopentadienyl compounds of formula (IV) in which at least one of the residues R ³ to R ⁶ , as well as at least one of the residues R ⁷ to R ⁹ is hydrogen, and at least one of the residues R ³ to R ⁹ is different from hydrogen, can be converted by methods known from the literature to fulvenes of the formula (IVa) or (IVb). This is illustrated by the following reaction scheme, where R ¹³ , R ¹⁴ , R ¹⁶ and R ^{17 are the} same or different and have the meaning of the radical R ¹⁰ :

The interaction of fulvene (IVa) with organometallic compounds of the formula R ¹⁵ M ¹ (wherein R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ^{17 are the} same or different and have the meaning of the radical R ¹⁰ ; M ¹ has the above meaning) leads to the formation of a monoanionic compound (IlIa).

Превращение фульвена (Vlb) приводит, соответственно превращению (IVa), к образованию дианионного соединения (Vb).The use of two equivalents of a compound of the formula R ¹⁵ M ¹ leads directly to the formation of the dianionic compound (Va):

The conversion of fulvene (Vlb) leads, according to the conversion (IVa), to the formation of the dianion compound (Vb).

Бис-циклопентадиенильные анионы формулы (Vb) могут подвергаться взаимодействию с соединениями R_p ¹⁸MX,
где
М - имеет вышеуказанное значение,
X - удаляемая группа, такая как галоген, тозилат, трифторметансульфонат,
R¹⁸ имеет значение радикала R¹⁰, и
p - целое число от 1 до 5.

Bis-cyclopentadienyl anions of the formula (Vb) may be reacted with compounds R _p ¹⁸ MX,
Where
M - has the above meaning,
X is a leaving group such as halogen, tosylate, trifluoromethanesulfonate,
R ¹⁸ has the meaning of R ¹⁰ , and
p is an integer from 1 to 5.

Соединения формулы (VI), при которых по меньшей мере один из остатков R³ до R⁶, а также по меньшей мере один из остатков R⁷ до R⁹ является водородом, могут превращаться до металлоценов согласно изобретению.This is illustrated by the following reaction scheme:

The compounds of formula (VI), in which at least one of the radicals R ³ to R ⁶ , as well as at least one of the radicals R ⁷ to R ⁹ is hydrogen, can be converted to metallocenes according to the invention.

 Salts of compounds of formula (IlIa) can be directly converted to the corresponding dianionic compounds of formula (Va) by deprotonation, for example, butyl lithium. The conversion to the bridged metallocenes of formula (I) is carried out according to the conversion of the compound of formula (V) to the target compound of formula (I).

 A further possibility of preparing the metallocene compounds according to the invention is that monocyclic systems to which the cyclopentadienyl group is anellated, and these monocyclic systems have functional groups which can serve as attachable groups in substitution reactions (such as, for example, bromide or tosylate), are reacted for example with cyclopentadienyl or indenyl lithium compounds.

 The metallocenes of the invention are highly active catalysts for the polymerization of olefins. Depending on the substitution structure of the ligands, metallocenes can be obtained as a mixture of isomers. Metallocenes are mainly used in the form of pure isomers. But the use of the racemate is, in most cases, sufficient.

 However, a pure enantiomer in the (+) - or (-) - form can also be used. Using pure enantiomers, it is possible to obtain an optically active polymer. However, separation of configurational isomeric forms of metallocenes is recommended, since the center (metal atom) responsible for the polymerization in these compounds creates a polymer having other properties. For certain applications, such as soft molded products, this may be desirable.

 The metallocene catalyst according to the invention may also include cocatalyst.

где остатки R¹⁹ одинаковы или различны и означают водород или углеводородную группу с 1 - 20 атомами углерода, такую как алкил с 1 - 18 атомами углерода, арил с 6 - 18 атомами углерода или бензил, а p - целое число от 2 до 50, предпочтительно 10 до 35.In principle, any compound that, due to its Lewis acidity, can convert a neutral metallocene into a cation and stabilize the latter (“labile coordination”) is suitable as a cocatalyst. On top of this, the cocatalyst or the anion formed from it should not enter into further reaction with the formed metallocene cation. As the cocatalyst, an aluminum compound and / or a boron compound are preferably used, in particular aluminoxane is used. Preferred are linear alumoxane of formula (VII) and / or cyclic alumoxane of formula (VIII),

where the residues R ^{19 are the} same or different and mean a hydrogen or hydrocarbon group with 1 to 20 carbon atoms, such as alkyl with 1 to 18 carbon atoms, aryl with 6 to 18 carbon atoms or benzyl, and p is an integer from 2 to 50, preferably 10 to 35.

Preferably, the radicals R ^{19 are the} same and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.

If the residues R ^{19 are} different, then they preferably mean methyl and hydrogen, or alternatively methyl and isobutyl, and the content of hydrogen or isobutyl in the residues R ^{19 is} preferably from 0.01 to 40%.

 Methods for producing alumoxanes are known. The exact spatial structure of aluminoxanes is unknown (see J. Am. Chim. Soc. (1993) 115, 4971). It is conceivable, for example, that chains and rings combine to form two-dimensional or three-dimensional structures.

 Regardless of the preparation method, all aluminoxane solutions are characterized by a varying content of unreacted starting aluminum compound, available in free form or as an adduct.

 Before being used to carry out the polymerization reaction, the metallocene compound can be preactivated with a cocatalyst, in particular with alumoxane, which can significantly increase its activity. The pre-activation of the metallocene compound is preferably carried out in solution. In this case, the metallocene compound is preferably dissolved in a solution of aluminoxane in an inert hydrocarbon. An inert hydrocarbon is an aliphatic or aromatic hydrocarbon. Toluene is preferably used.

The concentration of alumoxane in the solution is from about 1 wt.% To the saturation limit, preferably from 5 to 30 wt.%, Based on the total amount of the solution. The metallocene can be used in the same concentration, preferably, however, it is used in an amount of from 10 ^-4 to 1 mol per mol of alumoxane. The duration of pre-activation is 5 minutes to 60 hours, preferably 5 to 60 minutes. The operating temperature is from -78 to +100 ^o C, preferably 0 to 70 ^o C.

The metallocene compound is preferably used in a concentration, in terms of a transition metal, of 10 ^-3 to 10 ^-8 , preferably 10 ^-4 to 10 ^-7 mol of a transition metal per dm ^{3 of} solvent or per dm ³ of reactor volume. Aluminoxane is preferably used in a concentration of from 10 ⁻⁶ to 10 ⁻¹ mol, preferably 10 ⁻⁵ to 10 ⁻² mol per dm ^{3 of} solvent or per dm ³ of reactor volume. The other specified cocatalysts are used in approximately equimolar amounts with respect to the metallocene compound. In principle, however, higher concentrations are also possible.

Alumoxane can be obtained in various ways by known methods. One of the methods consists, for example, in that the aluminum-hydrocarbon compound and / or the hydride-aluminum-hydrocarbon compound is reacted with water (in gaseous, solid, liquid or bound form, for example in the form of crystallization water) in an inert solvent (such as e.g. toluene). To obtain aluminoxane with various R ¹⁹ residues, two corresponding aluminum trialkyls are reacted with water.

 A further object of the invention is a method for producing a polymer of olefins by polymerizing at least one olefin on a metallocene catalyst and isolating the resulting polymer, which consists in using a sterically rigid metallocene compound of the above general formula (I) as the metallocene catalyst.

In the proposed method, at least one olefin of the formula R ^a —CH═CH — R ^{b is} preferably homo- or copolymerized, where R ^a and R ^{b are the} same or different and represent a hydrogen atom or a hydrocarbon residue with 1 to 20 carbon atoms, in particular , 1 to 10 carbon atoms, or R ^a and R ^b together with the atoms bonding them form one or more rings. Examples of such olefins are 1-olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, cyclic and acyclic dienes, such as 1,3 -butadiene, isoprene, 1,4-hexadiene, norbornadiene, vinyl norbornene or 5-ethylidene norbornene. Preferably homopolymerization of ethylene or copolymerization of ethylene and one or more 1-olefins with 3-20 carbon atoms such as propylene and / or one or more dienes with 4-20 carbon atoms such as 1,3-butadiene is carried out.

The polymerization is carried out preferably at a temperature of from -60 to +250 ^o C, particularly preferably 50 to 200 ^o C. The pressure is preferably 0.5 to 2000 bar, particularly preferably 5 to 64 bar.

 The polymerization can be carried out continuously or periodically in single or multi-stage in solution, mass, suspension or in the gas phase. Mostly the polymerization is carried out in the gas phase.

 The proposed method can be carried out in the presence of one of the above cocatalysts.

 To remove the catalyst poisons present in the olefin, it is advantageous to purify with an aluminum compound, preferably an aluminum alkyl, such as trimethylaluminum or triethylaluminum. This purification can be carried out, on the one hand, in the polymerization medium itself, or, on the other hand, the olefin is first contacted with an aluminum compound, followed by isolation from the reaction mixture and feeding to the polymerization.

 The proposed method can be carried out in the presence of hydrogen, which serves as a molecular weight regulator and / or to increase the activity of the catalyst. In this case, it is possible to obtain low molecular weight polyolefins.

 The metallocene compound is preferably reacted with a cocatalyst outside the polymerization reactor using a suitable solvent. In this case, application to the carrier can also be carried out.

 In the proposed method, prepolymerization can also be carried out in the presence of a metallocene compound. For prepolymerization, the olefin fed to the polymerization (or one of the olefins fed to the polymerization) is preferably used.

 The catalyst used in the method according to the invention may have a carrier. By applying onto a carrier, it is possible, for example, to control the grain morphology of the resulting polyolefin. In this case, the metallocene compound may undergo interaction first with the carrier, and then with the cocatalyst. You can also first apply the cocatalyst to the carrier, and then co-catalyst is reacted with the metallocene compound. Another option is the application to the carrier of the reaction product of a metallocene compound and cocatalyst. Suitable carriers are, for example, silica gels, alumina, solid aluminoxane or other inorganic carriers, such as, for example, magnesium chloride. A suitable carrier is also a polyolefin in the form of a fine powder.

 A cocatalyst, for example alumoxane, is preferably applied to a carrier such as, for example, silica gels, alumina, solid aluminoxane, other inorganic carriers or also a polyolefin in the form of a fine powder, and then reacted with a metallocene.

 As inorganic carriers, oxides formed by the pyrolytic method by burning elemental halides in an oxygen-hydrogen flame, or obtained as silica gels with a certain particle size distribution and having certain grain forms, can be used.

 Obtaining cocatalyst on a carrier can be carried out, for example, as follows in an explosion-proof stainless steel reactor equipped with a pumping system with a pressure stage of 60 bar, an inert gas supply system, a cooling jacket for temperature control, and a second cooling system for circulating the coolant through the heat exchanger located on the pumping system. The pumping system sucks the contents of the reactor with a pump through a pipe located in the bottom of the reactor and feeds it into the mixer and from there through the discharge pipe through the heat exchanger back to the reactor. The mixer inlet pipe is made with a section tapering over the cross section, causing an increased flow rate, while in the turbulence zone of the specified section in the axial direction and against the direction of the flow stream, a line of narrow cross section is placed through which a certain amount of water can be supplied in strokes in the pressure atmosphere 40 bar of argon. The reaction is monitored by a sampler located on the circulating pumping system.

 In principle, however, other reactors are also suitable.

In the above 16 dm ³ reactor, 5 dm ^{3 of} decane is fed in an inert atmosphere. Add 0.5 dm ³ (= 5.2 mol) of trimethylaluminum at 25 ^o C. After that, 250 g of silica gel brand SD 3216-30 (a commercial product of the company Grace AG, DE), which is pre-dried at 120 ^o C in an argon-blown fluidized bed layer, fed through a funnel for solids to the reactor and homogeneously distributed using a stirrer and pumping system. Water in a total quantity of 76.5 g is fed in portions with a volume of 0.1 cm ³ for 3.25 hours every 15 seconds into the reactor. The pressure caused by argon and the resulting gases is constantly held by a control valve at 10 bar. After supplying the entire amount of water, the pumping system is turned off, and mixing continues for another 5 hours at 25 ^o C.

The supported cocatalyst thus obtained is used as a 10% suspension in n-decane. The aluminum content is 1.06 mmol Al per cm ³ suspension. The precipitated solid contains 31 wt.% Aluminum, and the suspending agent contains 0.1 wt.% Aluminum.

 After this, the metallocene according to the invention is applied to the supported cocatalyst in that the dissolved metallocene is mixed with the cocatalyst. The solvent is removed and replaced with a hydrocarbon in which both the cocatalyst and the metallocene are insoluble.

The reaction to obtain a supported catalyst system is carried out at a temperature of from -20 to +120 ^° C, preferably 0 to 100 ^° C, particularly preferably at 15 to 40 ^° C. The metallocene is reacted with a supported cocatalyst in that the cocatalyst is in the form of 1 to A 40% by weight, preferably 5 to 20% by weight suspension in an aliphatic inert suspending agent such as n-decane, hexane, heptane, diesel fuel is contacted with a solution of metallocene in an inert solvent such as toluene, hexane, heptane, d chloromethane, or finely divided solid metallocene. But it is also possible the interaction of a metallocene solution with a cocatalyst as a solid.

 The reaction is carried out by intensive mixing, for example, stirring at a molar ratio of Al / M from 100: 1 to 10000: 1, preferably from 100: 1 to 3000: 1, for 5-120 minutes, preferably 10 to 60 minutes, particularly preferably 10 - 30 minutes in an inert atmosphere. During the reaction, to obtain a supported catalyst system, in particular when using metallocenes according to the invention having a maximum absorption in the visible region, color changes occur in the reaction mixture, with which you can monitor the progress of the reaction.

 After completion of the reaction, the supernatant is separated, for example, by filtration or decantation. The remaining solid is washed 1 to 5 times with an inert suspending agent, such as toluene, n-decane, hexane, diesel fuel, dichloromethane, to remove soluble substances in the resulting catalyst, in particular to remove unreacted and, therefore, soluble metallocene.

 The supported catalyst system thus obtained can, after vacuum drying, in the form of a powder, or still having a solvent, be resuspended and applied as a suspension in one of the above inert suspending agents to polymerization.

 If the polymerization is carried out in suspension or in solution, then an inert solvent conventional for the Ziegler low pressure method is used. They work, for example, in an aliphatic or cycloaliphatic hydrocarbon, such as, for example, propane, butane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane. In addition, a gasoline fraction or a hydrogenated fraction of diesel fuel can be used. It is also possible to use toluene. Preferably, the polymerization is carried out in liquid monomer.

 Prior to feeding the catalyst, in particular having a catalyst system support (from a metallocene according to the invention and having a cocatalyst carrier, for example, from a metallocene according to the invention and an organoaluminum compound on a polyolefin powder in finely divided form), another alkyl aluminum compound can be added to the reactor, such as, for example , trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum or isoprenylaluminum, which serves to inertize the polymerization system (n example, for the separation present in the olefin catalyst poisons). This compound is added in a concentration of from 100 to 0.01 mmol Al per kg of reactor contents. Triisobutylaluminum and triethylaluminum are preferred at a concentration of from 10 to 0.1 mmol Al per kg of reactor contents. Thus, in the synthesis of a supported catalyst system, the Al / M molar ratio can be selected small.

 When using inert solvents, the monomers are supplied in gaseous or liquid form.

 The polymerization can be of any duration, since the catalyst system used in the method according to the invention differs only in a slight time-dependent decrease in activity.

 The metallocenes used in the process according to the invention are suitable, in particular, for producing polyolefins having reduced crystallinity, increased toughness, increased transparency, high fluidity at a processing temperature, and also a reduced melting temperature.

 The main areas of application of such polyolefins are the formulations of plasticizers and lubricants for hot melt adhesives, coating materials, seals, insulation, or soundproof materials.

 By using hydrogen or increasing the polymerization temperature, low molar mass polyolefins are also available, such as waxes, the hardness or melting point of which can be varied through the comonomer content.

 On the contrary, by choosing the polymerization conditions it is also possible to obtain high molecular weight polyolefins, which are suitable as thermoplastic materials. The latter are suitable, in particular, for the production of molded products, such as films, plates or large hollow products, such as pipes.

 By choosing the polymerization method and the type of comonomers, as well as the amounts of comonomers, olefin copolymers with elastomeric properties can be obtained, such as, for example, ternary polymers of ethylene, propylene and 1,4-hexadiene.

 The following examples serve to explain the invention in more detail.

 The preparation of metal-organic compounds and their handling is carried out with the exception of air and moisture in an argon atmosphere (Schlenk technique). All solvents required are absolute prior to use by boiling for many hours over a suitable desiccant and subsequent distillation in an argon atmosphere.

The preparation of starting diketones and ketoaldehydes is carried out according to methods known in the literature. Cyclopentadiene and methylcyclopentadiene are obtained by cracking dimers and stored at -35 ^o C.

The determination of the Al / CH ₃ ratio in aluminoxane is carried out by decomposing the sample with sulfuric acid and determining the volume of the gases formed under normal conditions, as well as by complexometric titration of aluminum in the dissolved sample according to Schwarzenbach.

Target compounds are identified by ¹ H-NMR, ¹³ C-NMR and IR spectroscopy.

The indicated melting points of the polymer and the heat of fusion are the results of differential scanning calometry during melting at a heating rate of 10 ^° C./min.

 The methylaluminoxane soluble in toluene used in the comparative examples is supplied by WITCO as a 10% toluene solution. It contains 36 mg Al / ml.

Determination of the content of comonomers is carried out by ¹³ C-NMR according to the method of Randall (see Macromolecules 1994, 27, 2120).

-4,5,6,7-тетрагидроинденил] -дихлорциркония. Циклическая система, которая является мостиком обоих циклопентадиениловых лигандов этого соединения, имеет шесть кольцевых атомов углерода (C4, C5, C6, C7, C8, C9) и три метиловых заместителя. Одна циклопентадиениловая группа однократно анеллирована к циклической системе, вторая находится как заместитель на циклической системе.The following examples illustrate the preparation of the desired products of formula (I) and their starting and intermediate products. For the names of intermediates and target products, the nomenclature of SITEC (International Union of Theoretical and Applied Chemistry) is used. This nomenclature is illustrated by the example of the compound [4- (η ⁵ -4'-methyl-cyclopentadienyl) -4,7,7-trimethyl-

-4,5,6,7-tetrahydroindenyl] dichlorozirconium. The cyclic system, which is the bridge of both cyclopentadienyl ligands of this compound, has six ring carbon atoms (C4, C5, C6, C7, C8, C9) and three methyl substituents. One cyclopentadienyl group is once anellated to the cyclic system, the second is located as a substituent on the cyclic system.

A. Preparation of Bisfulvenes of Formula (II)
Example 1a
Synthesis of 2,5-bis (2,4-cyclopentadiene-1-ylidene) hexane
11.0 g (96.3 mmol) of 2,5-hexanedione and 12.7 g (193 mmol) of cyclopentadiene freshly obtained by cracking are dissolved in 60 ml of methanol, cooled to 0 ^° C. and mixed with 8.60 g (121 mmol) pyrrolidine. After 90 minutes stirring at 0 ^° C., the reaction solution was hydrolyzed with 5 ml of glacial acetic acid and 50 ml of water, subjected to a double extraction, 70 ml of diethyl ether each time, and the combined organic phases were washed with saturated sodium chloride solution, dried over magnesium sulfate and the solvent was removed in a vacuum. 18.0 g (89%) of difulvene are obtained as an oily residue of an orange-red color.

Example 1b
Synthesis of 2,5-bis (cyclopenta-2,4-diene-1-ylidene) undecane
A solution of 3.50 g (19.9 mmol) of 2,5-undecandione in 100 ml of methanol and 10 ml of tetrahydrofuran is cooled to 0 ^o C and mixed with 3.92 ml (3.14 g, 47.5 mmol) freshly obtained by cracking cyclopentadiene. 6.28 ml (5.40 g, 76.0 mmol) of freshly distilled pyrrolidine are added dropwise to the orange-red clear reaction solution over 10 minutes. In this case, the reaction solution is painted dark red for 10 minutes. After this, the reaction solution was allowed to warm to room temperature and was stirred for a further 3 days to complete the reaction. For processing purposes, pyrrolidine is neutralized with 4 ml of glacial acetic acid and hydrolyzed with 100 ml of water. It is extracted twice, each time with 100 ml of pentane, the combined organic phases are washed several times with saturated aqueous sodium chloride and dried over magnesium sulfate. Removal of the solvent in vacuo gives 4.16 g (78%) of crude cyclopentadienylidene as a dark red oil.

 Chromatography on a column containing silica gel deactivated by triethylamine using a mixture of pentane and diethyl ether in a ratio of 100: 1 as eluent gives difulven as an orange-red oil.

B. Synthesis of biscyclopentadienyl anions of formula (V) having a bridge
Example 2
Synthesis of 4- (η ⁵ - cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroilidenyl) -dithium
To a solution of 10.0 g (47.5 mmol) of 2,5-bis- (2,4-cyclopentadiene-1-ylidene) hexane in 150 ml of diethyl ether, 62.4 ml (99.8 mmol) are slowly added dropwise with vigorous stirring. ) 1.60 m. Of an ethereal solution of methyl lithium at 0 ^° C. The reaction solution was allowed to warm to room temperature. After 24 hours stirring, a beige precipitate is obtained. After filtration and repeated washing with pentane, 13.2 g (89%) of dilithium salt are obtained as a beige powder, which is coordinated with the molar equivalent of diethyl ether.

Example 3
Synthesis of 4- (η ^5- cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η ⁵ -4,5,6,7-tetrahydroilidenyl) dilithium
83.4 ml (74.3 mol) of a 0.89 m solution of phenyl lithium in diethyl ether are added dropwise at 0 ^° C. to a solution of 7.10 g (33.7 mmol) of difulven according to Example 1 in 100 ml of diethyl ether. At the same time, after about 5 minutes, a beige precipitation begins. The reaction solution was allowed to warm to room temperature and stirred for a further 12 hours at 25 ^° C. After filtration, repeated washing with pentane and drying under vacuum using an oil pump, 10.3 g (82%) of dilithium salt was obtained as a powder beige color with a high sensitivity to hydrolysis.

Example 4
Synthesis of 4- (η ⁵ - cyclopentadienyl) -4,7-dimethyl-7-6utyl- (η ⁵ -4,5,6,7-tetrahydroilidenyl) dilithium
A solution of 15.0 g (71.3 mmol) of difulven according to example 1, dissolved in 100 ml of diethyl ether, is cooled to -30 ^o C and, with vigorous stirring, slowly mixed with 94 ml (150 mmol) of 1.60 m solution n-butyl lithium in hexane. In this case, a precipitate of lemon yellow is formed. The reaction solution was allowed to warm to room temperature and stirred to complete the reaction for a further 24 hours. After this, the precipitate formed is filtered off, washed repeatedly with pentane and dried in a vacuum created by an oil pump. 29.0 g (91%) of dilithium salt are obtained as a beige powder having a high sensitivity to hydrolysis, with which the molar equivalent of diethyl ether is also coordinated.

B. Synthesis of bridged cyclopentadienes of formula (IV)
Example 5
Synthesis of 4-cyclopentadienyl-4,7,7-trimethyl-4,5,6,7-tetrahydro-1H-indene
To a suspension of 7.35 g (23.5 mmol) of the dilithium salt of Example 2 in 50 ml of diethyl ether are added dropwise at 0 ^° C. 50 ml of degassed water. In this case, the beige suspension immediately disappears and a diethyl ether phase transparent in orange is obtained. Then the phases are separated in a separatory funnel, the aqueous phase is extracted two more times, each time with 25 ml of diethyl ether and the combined organic phases are washed with 20 ml of a saturated solution of sodium chloride. After drying over magnesium sulfate and removal of the solvent in vacuo, 5.1 g (96%) of the hydrolyzed product are obtained as an orange-red oil.

Example 6
Preparation of 4-cyclopentadienyl-4,7-dimethyl-4-phenyl-4,5,6,7-tetrahydro-1H-indene
A yellow suspension of 3.64 g (9.72 mmol) of the dilithium salt of Example 3 in 50 ml of diethyl ether cooled to 0 ^° C. is hydrolyzed by slowly adding 20 ml of degassed water. In this case, the suspension disappears and a clear orange solution is obtained. After twice extraction, each time with 20 ml of diethyl ether, the combined organic phases are washed many times with saturated aqueous sodium chloride and dried over magnesium sulfate. By subsequent removal of the solvent in vacuo, 2.62 g (94%) of the hydrolyzed product are obtained as an orange oil.

Example 7
Preparation of 4-cyclopentadienyl-4,7-dimethyl-4-butyl-4,5,6,7-tetrahydro-1H-indene
Cooled to 0 ^° C, a yellow suspension of 5.00 g (17.33 mmol) of the dilithium salt of Example 4 in 50 ml of diethyl ether is hydrolyzed by the slow addition of 20 ml of degassed water. In this case, the suspension disappears and a clear orange solution is obtained. After twice extraction, each time with 20 ml of diethyl ether, the combined organic phases are washed many times with saturated aqueous sodium chloride and dried over magnesium sulfate. Subsequent removal of the solvent in vacuo gave 4.59 g (96%) of the hydrolyzed product as an orange oil.

D. Synthesis of bridged cyclopentadiene-fulvenine ligands of formula (IVa) by additional introduction of substituents (introduction of various residues R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ )
Example 8a
Synthesis of 4- (3'-isopropylidene-cyclopenta-1,4-dienyl) -4,7,7-trimethyl-4,5,6,7-tetrahydro-1H-indene
7.70 g (34.0 mmol) of the cyclopentadienyltetrahydroindenyl of Example 5 was dissolved in 70 ml of methanol and cooled to 0 ^° C. Then, 2.96 g (51.0 mmol) of acetone and 4.83 were successively added to the orange-red reaction solution. g (68.0 mmol) of pyrrolidine. After stirring for 5 hours at 0 ^° C., stirring was continued for 2 hours at room temperature to complete the reaction, after which the reaction was stopped by adding 4 ml of glacial acetic acid. A red, transparent reaction solution is hydrolyzed with 200 ml of water, and the resulting yellow suspension is subjected to three times extraction with diethyl ether, taken in an amount of 50 ml. After washing the combined organic phases several times with a saturated aqueous solution of sodium chloride and drying over magnesium sulfate, 8.00 g (88%) of the target fulven are obtained as an orange-red waxy precipitate.

Example 8b
Preparation of 4-cyclopentadienyl-4,7-dimethyl-7-allyl-4,5,6,7-tetrahydro-1H-indene
To a solution of 16.8 g (79.8 mmol) of 2,5-bis (2,4-cyclopentadiene-1-ylidene) hexane of Example 1 dissolved in 100 ml of diethyl ether and 50 ml of tetrahydrofuran were added dropwise, stirring vigorously, at 0 ^o C for an hour of 0.60 m. a solution of allyl Grignard reagent (175 mmol) in diethyl ether. After the addition is complete, it is stirred at room temperature overnight, the resulting yellow-orange suspension is cooled to 0 ^° C. and carefully hydrolyzed with an aqueous saturated solution of ammonium chloride. The organic phase is separated, washed three times, each time with 50 ml of a saturated aqueous solution of sodium chloride and dried over magnesium sulfate. After removing the solvent in a vacuum from an oil pump, 17.5 g (87%) of the product are obtained as an orange oil.

D. Synthesis of Dianionic Complexes of Formula (Va)
Example 9a
Synthesis of 4- [3'-tert. butyl- (-η ⁵ -cyclopentadienyl)] - 4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydro-indenyl) dilithium
In the interaction of tetrahydroindenyl fulvene according to example 8 with 2 equivalents of an ethereal solution of methyl lithium at 0 ^o C, after a few seconds an intense yellow precipitate is obtained. Stir for 12 more
hours at room temperature. After filtration, washing with pentane and drying in a vacuum created by an oil pump, a dilithium salt is obtained, which is further converted without prior identification.

Example 9b
Synthesis of [4 - (- η ⁵ -cyclopentadienyl)] -4,7-dimethyl-7-allyl - (- η ⁵ -4,5,6,7-tetrahydroindenyl) dilithium
10.5 g of the product of example 8b are dissolved in 100 ml of diethyl ether, cooled to 0 ^° C., then 57.6 ml of a solution of n-butyllithium (1.60 molar in hexane, 92.0 mmol) are added dropwise. After stirring for 18 hours at room temperature, a yellow-beige precipitate is obtained, which is filtered off, washed repeatedly with pentane and dried in a vacuum created by an oil pump. The dilithium salt is obtained as a beige solid, with which another molar equivalent of diethyl ether is coordinated. Yield: quantitative.

E. Synthesis of metallocenes of formula (I)
Example 10
Synthesis of 4 - (- η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl) dichlorozirconium
To a suspension cooled to -78 ^° C, 9.58 g (30.7 mmol) of the dilithium compound of Example 2 in 200 ml of toluene are added in portions over 10 minutes 7.50 g (32.2 mmol) of zirconium tetrachloride. After stirring at room temperature for 50 hours, the precipitate was filtered off and the orange filtrate was concentrated to dryness in vacuo. After repeated washing with pentane, 4.38 g (37%) of zirconocene dichloride are obtained as an orange-yellow powder.

For purification, the orange-yellow powder is extracted for several days with pentane in a circulating frit, and after removing the solvent in a vacuum created by an oil pump, 1.70 g (14%) of zirconocene dichloride is obtained as a yellow powder with a melting point of 223 ^o C (decomp. Determined by differential scanning calometry).

Example 11
Synthesis of 4- (η ⁵ cyclopentadienyl) -4,7,7-trimethyl - (- η ⁵ -4,5,6,7-tetrahydro-indenyl) dichlorotitan
A suspension of 5.46 g (17.5 mmol) of the dilithium ether of Example 2 in 200 ml of toluene is cooled to -78 ^° C and mixed with 3.3 g (17.5 mmol) of titanium tetrachloride. In this case, the reaction solution immediately turns dark red. It is stirred for 30 hours at room temperature, filtered off from insoluble matter and the dark red toluene phase is concentrated to dryness in a vacuum created by an oil pump. After repeated washing with pentane, 1.85 g of titanocene dichloride are obtained as a brown-beige powder. The crude product is extracted with pentane for several days in a circulating frit, whereupon removal of the solvent gives 780 mg (13%) of titanocene dichloride as a brown solid with a melting point of 259 ^° C. (decomp. Determined by differential scanning calometry).

¹ H-NMR (200.1 MHz, CDCl ₃ ); δ = 7.06-7.03, 6.94-6.91, 6.82-6.76, 5.87-5.84, 5.82-5.78, 5.62-5.59 (6 xm, 7H, 1-H to 3-H and 2'-H to 5'H); 2.45 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.2 Hz, ³ J (H6 _ax / H5 _eq ) = 6.3 Hz, ³ J (H6 _eq / H5 _eq ) = 2.7 Hz) ; 2.31 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.0 Hz, ³ J (H6 _ax / H5 _ax ) = 14.0 Hz, ³ J (H6 _eq / H5 _ax ) = 6.2 Hz) ; 1.91 (ddd, 1H, 6 _ax -H, ² J (H6 _eq / H6 _ax ) = 14.0 Hz, ³ J (H5 _ax / H6 _ax ) = 14.0 Hz, ³ J (H5 _eq / H6 _ax ) = 6.3 Hz; 1.69 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.0 Hz, ³ J (H5 _ax / H6 _eq ) = 6.2 Hz, ³ J (H5 _eq / H6 _eq ) = 2.7 Hz); 1.86 (s, 3H, 10-H); 1.25 and 1.11 ppm (2 xs, 6H, 11-H and 12-H).

Example 12
Synthesis of [4- (-η ^5- cyclopentadienyl) -4,7,7-trimethyl (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorocirconium from 2,5-bis (2,4-cyclopentadiene-1 -ilidene) hexane
To a solution of 10.0 g (47.5 mmol) of 2,5-bis (2,4-cyclopentadiene-1-ylidene) hexane in Example 1 in 150 ml of toluene is slowly added with vigorous stirring 62.4 ml (99.8 mmol) ) 1.60 m. Of an ethereal solution of methyl lithium at 0 ^° C. After completion of the addition, it is stirred for 24 hours at room temperature, then cooled to -30 ^° C. and 9.32 g (40 mmol) of zirconium tetrachloride are added. After 30 hours stirring at room temperature, it is filtered off from lithium chloride and the filtrate is concentrated to dryness in vacuo. After repeated washing with pentane, 4.02 g (26%) of zirconium dichloride are obtained.

¹ H-NMR (200.1 MHz, CDCl ₃ ) δ = 6.73-6.70, 6.44-6.41, 5.73-5.70 (3 xm, 3H, 1-H to 3-H), 6.70-6.67, 6.53-6.48, 6.08-6.03 5.88-5.82 (4 xm, 4H, 2'-H to 5'-H); 2.42 (ddd, 1H, 5 _eq -H, ² J (H5 _ax H5 _eq ) = 14.8 Hz, ³ J (H6 _ax / H5 _eq ) = 6.0 Hz; ³ J (H6 _eq / H5 _eq ) = 2.2 Hz); 2.30 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.8 Hz, ³ J (H6 _ax / H5 _ax ) = 14.3 Hz, ³ J (H6 _eq / H5 _ax ) = 5.3 Hz; 2.00 (ddd, 1H, 6 _ax -H, ² J (H6 _eq / H6 _ax ) = 14.8 Hz, ³ J (H5 _ax / H6 _ax ) = 14.3 Hz, ³ J (H5 _eq / H6 _ax ) = 6.0 Hz) ; 1.72 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.8 Hz, ³ J (H5 _ax / H6 _eq ) = 5.3 Hz, ³ J (H5 _eq H6 _eq ) = 2.2 Hz; 1.83 (s, 3H, 10-H); 1.33 and 1.10 ppm (2 xs, 6H, 11-H and 12-H).

Example 13
Synthesis of both diastereomers of 4- (η ^5- cyclopentadienyl) - 4,7-dimethyl-7-phenyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorozirconium
To a suspension of 4.37 g (11.7 mmol) of the dilithium salt of Example 3 in 200 ml of toluene, cooled to -78 ^° C, 2.72 g (11.7 mmol) of zirconium tetrachloride are added in portions. The reaction mixture was allowed to warm to room temperature and the orange suspension was stirred for another 20 hours at 20 ^° C. After filtration, the solvent was removed from the filtrate in a vacuum created by an oil pump, and the resulting oily residue, orange-red, was pulverized by vigorous stirring in 20 ml of pentane. Removal of pentane in vacuo gave 2.64 g (50%) of zirconocene dichloride as a yellow-orange powder. Based on the ¹ H-NMR spectrum of the crude product, the ratio of diastereomers is about 8: 1.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 7.24-6.89 (t, 5H, Ph-H); 6.78-6.73, 6.54-6.50, 6.22-6.20, 5.97-5.94 (4 x m, 7H, 1-H to 3-H and 2'-H to 5'-H); 2.30-2.22, 1.92-1.84 (2 xm, 4H, 5-H, 6-H); 1.76, 1.71 ppm (2 xs, 6H, 10-H and 11-H).

Example 14
Synthesis of both diastereomers of 4 - (- η ⁵ - cyclopentadienyl) -4,7-dimethyl-7-butyl- (η ⁵ -4,5,6,7-tetrahydroindenyl) dichlorozirconium
A suspension of 7.80 g (22.0 mmol) of the dilithium salt of Example 4 in 200 ml of toluene is cooled to -78 ^° C, and then 5.10 g (22.0 mmol) of zirconium tetrachloride are added portionwise. The reaction mixture was allowed to warm to room temperature and the yellow-orange suspension was stirred for an additional 48 hours, then filtered off from insoluble matter and the solvent removed in a vacuum created by an oil pump. The resulting red-orange oil is pulverized by vigorous stirring with pentane. 2.72 g (30%) of zirconocene dichloride are obtained, which is purified by extraction with pentane for several days in a circulating frit. The ¹ H-NMR spectrum of the fine yellow precipitate shows two sets of signals in a ratio of 15: 1. From the resulting yellow filtrate, a small amount of crystals can be obtained after storage at -30 ^° C. These crystals of pure zirconocene dichloride diastereomers allow the identification of individual ¹ H-NMR spectrum signals. In this case, the crystals crystallized from the pentane solution correspond to the diastereomer, which is least formed. Crystals can also be obtained from 1.35 g (14%) of a yellow fine powder in that approximately 100 mg of the powder is dissolved in a small amount of methylene chloride and very slow crystallization is carried out by diffusion of pentane into this solution. The main product is another diastereomer.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.73-6.67, 6.52-6.47, 6.41-6.38, 6.08-6.04, 5.87-5.83, 5.76-5.73 (6 xm, 7H, 2'-H 5'-H and 1-H to 3-H); 2.48-2.16 (m, 3H, 5 _eq -H, 5 _ax -H, 6 _ax -H): 1.91-1.84 (m, 1H, 6 _eq -H); 1.83 (s, 3H, 10-H); 1.35-0.85 (3 xm, 6H, ⁿ Bu-CH ₂ ), 1.25 (s, 3H, 11-H); 0.82-0.77 ppm (pt, 3H, ⁿ Bu-CH ₃ ).

Example 15
Synthesis of 4- (η ^5- cyclopentadienyl) -4,7-dimethyl-7-butyl- (η ⁵ -4,5,6,7-tetrahydroindenyl) dichloro-hafnium
1.81 g (5.65 mmol) of hafnium tetrachloride are added to a suspension of 2.00 g (5.64 mmol) of the dilithium salt of Example 4 in 150 ml of toluene cooled to -78 ^° C. The orange suspension was allowed to warm to room temperature and was stirred for another two days to complete the reaction. It is then filtered off from an insoluble matter and the orange-red filtrate is concentrated to dryness in a vacuum of an oil pump. 30 ml of pentane was added to the orange-red residue and stirred vigorously overnight. Removal of the solvent in vacuo gives 700 mg (24%) of hafnocene dichloride as a beige powder. In the ¹ H-NMR spectrum of the crude product, only one diastereomer can be found.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.63-6.58, 6.42-6.39, 6.33-6.30, 5.99-5.96, 5.81-5.78, 5.66-5.63 (6 xm, 7H, 2'-H up to 5 ' -H and 1-H to 3-H): 2.38 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.0 Hz, ³ J (H6 _ax / H5 _eq ) = 5.7 Hz, ³ J (H6 _eq / H5eq) = 3.2 Hz); 2.23 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.0 Hz, ³ J (H6 _ax / H5 _ax ) = 14.4 Hz, ³ J (H6 _eq / H5 _ax ) = 6.8 Hz) ; 1.98 (ddd, 1H, 6 _ax -H, ² J (H6 _eq / H6 _ax ) = 14.4 Hz, ³ J (H5 _ax / H6 _ax ) = 14.4 Hz, ³ J (H5 _eq / H6 _ax ) = 5.7 Hz, 1.85 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6eq) = 14.4 Hz, ³ J (H5 _ax / H6 _eg ) = 6.8 Hz, (H5 _eq / H6 _eq ) = 3.2 Hz), 1.90 (s, 3H, 10-H); 1.27 (s. 3H, 11-H); 1.35-1.07 (3 xm, 6H, ⁿ Bu-CH ₃ ); 0.84-0.76 ppm ( pt, 3H, ⁿ Bu-CH ₃ ).

Melting point: 151 ^o C (determined by differential scanning calometry).

Example 16
Synthesis of both diastereomers of 4- (η ^5- cyclopentadienyl) -4,7-dimethyl-7-butyl- (η ⁵ -4,5,6,7-tetrahydroindenyl) dichlorotitan
If 5.95 g (16.8 mmol) of the dilithium salt of Example 4 is suspended in 120 ml of toluene, then when adding 3.18 g (16.8 mmol) of titanium tetrachloride at -78 ^° C, the beige suspension immediately turns dark -Red color. The suspension is stirred for another 36 hours at room temperature, after which it is separated from the precipitate and the dark red filtrate is concentrated to dryness in a vacuum created by an oil pump. This gives 1.54 g (24%) of both diastereomers of titanocene dichloride as a brown-red powder. According to the ¹ H-NMR spectrum of the crude product, the ratio of both diastereomers is 8: 1. If the brown-red powder is extracted with pentane for several days in a circular frit, then a brown precipitate forms from the filtrate. Moreover, in the ¹ H-NMR spectrum, it can be established that the pentane solution includes both isomers in a ratio of 1: 1 (150 mg, 2.3%), while brown powder (720 mg, 11%) is almost pure diastereomer.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 7.06-6.96, 6.95-6.92, 6.82-6.74, 5.89-5.85, 5.83-5.79, 5.64-5.61 (6 xm, 7H, 2'-H 5'-H and 1-H to 3-H); 2.40-2.27, 1.89-1.75 (2 xm, 4H, 5 _eq- H 5 _ax -H, 6 _ax -H, 6 _eq -H); 1.86 (s, 3H, 10-H); 1.35-0.89 (m, 6H, ⁿ Bu-CH ₂ ); 1.21 (s, 3H, 11-H); 0.84-0.77 ppm (pt, 3H, ⁿ Bu-CH ₃ ).

Melting point: 134 ^o C (determined by differential scanning calometry).

Example 17
Synthesis of {4- (3 '- [tert-butyl- (η ^5- cyclopentadienyl)] -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)} dichlorocirconium
A suspension of 2.84 g (7.71 mmol) of the dilithium salt of Example 9a in 150 ml of toluene is cooled to -78 ^° C. After adding 1.79 g (7.71 mmol) of zirconium tetrachloride in a reaction mixture, the reaction mixture is allowed to warm to room temperature and stirred for another 48 hours. It is then separated from the insoluble matter, the orange toluene phase is concentrated in a vacuum created by an oil pump, and the resulting orange-red oil is pulverized by vigorous stirring in pentane. This yields 787 mg (23%) of the regioisomeric zirconocene dichlorides as an orange-yellow powder. According to a ¹ H-NMR spectrum, the crude product includes both diastereomers in a 1: 1 ratio. By extracting an orange-yellow powder with pentane in a circulating frit, 370 mg (11%) of zirconocene dichlorides are obtained in a 1: 1 ratio.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.76-6.72, 6.69-6.65, 6.53-6.50, 6.43-6.32, 5.99-5.97, 5.88-5.82, 5.72-5.61 (7 xm, 12H, 1-H , 2-H, 3-H, 2'-H, 4'-H, 5'-H): 2.37-2.33, 2.10-1.85, 1.75-1.62 (3 xm, 8H, 5-H and 6-H) ; 1.82, 1.81 (2 xs, 6H, 10-H); 1.33 (bs, 6H, 11-H or 12-H); 1.31, 1.25 (2 xs, 18H, ⁿ Bu-CH ₃ ); 1.12, 1.09 ppm (2 xs, 6H, 11-H or 12-H).

J. Synthesis of metallocene-dialkyl complexes
Example 18
Synthesis of 4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl) zirconium dimethyl
To a suspension of 1.03 g (2.66 mmol) of zirconocene dichloride of Example 10 in 50 ml of diethyl ether was added dropwise 3.30 ml (5.33 mmol) of 1.60 m methyl ether of a lithium solution at -78 ^° C. the mixture was allowed to slowly warm to room temperature in the bath of the cooling mixture and was further stirred for another 5 hours at room temperature. The solvent was removed in vacuo and the colorless residue was extracted three times with pentane taken in an amount of 50 ml. The combined pentane solutions are concentrated and stored at -25 ^° C for crystallization. After separation of the solvent and drying in a vacuum using an oil pump, 700 mg (76%) of zirconocentimethylmethyl are obtained as a colorless crystalline powder.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.58-6.50, 6.38-6.34, 5.91-5.87, 5.47-5.53, 5.34-5.31 (5 xm, 7H, 1-H to 3-H and 2'- H to 5'-H); 2.18 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.0 Hz, ³ J (H6 _ax / H5 _eq ) = 5.9 Hz, ³ J (H6 _eq H5 _eq ) = 3.1 Hz; 2 09 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.0 Hz, ³ J (H6 _eq / H5 _ax ) = 14.0 Hz, ³ J (H6 _eq / H5 _ax ) = 5.31 Hz; 1.80 (ddd, 1H, 6 _ax -H, ² J (H6 _eq / H6 _ax ) = 14.0 Hz, ³ J (H5 _ax / H6 _ax ) = 14.0 Hz, ³ J (H5 _eq / H6 _ax ) = 5.9 Hz; 1.57 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.0 Hz, ³ J (H5 _{ax /} H6eq) = 5.3 Hz, ³ J (H5 _eq / H6 _eq ) = 3.1 Hz; 1.53 (s, 3H, 10-H); 1.19, 1.12 (2 xs, 6H, 11-H and 12-H), 0.26 and 0.34 ppm (2 xs, 6H, 13- CH ₃ and 14-CH ₃ ).

Melting point: 114 ^o C (determined by differential scanning calometry).

Example 19
Synthesis of both diastereomers of 4- (η ^5- cyclopentadienyl) -4,7-dimethyl-7- (2-propen-1-yl) - (η ⁵ -4,5,6,7-tetrahydroindenyl) dichlorotitan
2.45 g (7.24 mmol) of the dilithium compound of Example 9b are dissolved in 80 ml of tetrahydrofuran, the resulting clear orange solution is cooled to -78 ^° C and mixed with 2.42 r (7.24 mmol) of titanium tetrachloride adduct and bis tetrahydrofuran. In this case, the reaction mixture immediately turns dark red. The reaction mixture was allowed to warm to room temperature and stirred for another 2 days. After removing the solvent in vacuo, a brown powder is obtained. By extracting the crude product with pentane in a circulating frit, 0.22 g (9%) of both allyl titanocenes are obtained as a brown powder. According to ¹ H-NMR spectrum, the product contains both diastereomers in a 2: 1 ratio.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 7.05-7.01, 6.94-6.91, 6.85-6.80, 6.75-6.73, 5.87-5.79, 5.63-5.61 (6 xm, 2'-H to 5'-H and 1-H to 3-H); 5.63-5.40, 5.15-4.80 (2 xm, vinyl-CH and vinyl-CH ₂ ); 2.38-2.17, 2.10-2.06, 1.86-1.77 (3 xm, 5-H, 6-H, allyl-CH ₂ ): 1.85 (s, 10-H); 1.24, 1.10 ppm (2 xs, 11-H).

Example 20
Synthesis of both diastereomers of [4- (η ^5- cyclopentadienyl) -4,7-dimethyl-7- (2-propen-1-yl) - (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorozirconium
7.56 g (22.3 mmol) of the dilithium compound of Example 9b are suspended in 200 ml of toluene and cooled to -78 ^° C. 5.21 g (22.3 mmol) of zirconium tetrachloride are added in portions. The reaction mixture was left to stand for 30 minutes at -78 ^° C, after which it was allowed to warm to room temperature for 4 hours and was stirred for a further 12 hours. The resulting orange suspension is filtered on a G4 frit, the residue is washed twice with toluene, taken in an amount of 30 ml, and the filtrate is concentrated to dryness in a vacuum created using an oil pump. An orange-red oil is obtained, which is transferred to powder by adding 50 ml of pentane and subsequent intensive mixing. After removal of the solvent in vacuo, 5.04 g (55%) of yellow-orange powder allyl zirconocenes are obtained. By repeatedly extracting the crude product with 100 ml of pentane in a circulating frit, 2.34 g (26%) of allyl zirconocene are obtained as a yellow powder. Melting point: 99 ^o C (determined by differential scanning calometry). According to spectrum ¹ H-NMR, the product contains both diastereomers in a ratio of 1.5: 1.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.73-6.67, 6.55-6.47, 6.41-6.38, 6.08-6.04, 5.94-5.80, 5.76-5.72 (6 xm, 2'-H to 5'-H and 1-H to 3-H); 5.62-5.41, 5.20-4.83 (2 xm, vinyl-CH and vinyl-CH ₂ ); 2.55-2.17, 2.09-2.05, 1.97-1.69 (3 xm, 5-H, 6-H, allyl-CH ₂ ); 1.83 (s, 3H, 10-H); 1.27, 1.09 ppm (2 xs, 11-H (cis isomer) and 11-H (trans isomer)).

Example 21
Synthesis of both diastereomers [4- (η ^5- cyclopentadienyl) -4,7-dimethyl-7- (3- (9-borabicyclo) nonyl-B) propyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorozirconium
210 g (0.51 mmol) of the allyl zirconocene dichlorides of Example 20 are dissolved in 50 ml of toluene and mixed at room temperature with 62 mg (0.51 mmol) of 9-borabicyclononil. It is stirred for 36 hours at room temperature, the solvent is removed in vacuo and the resulting orange-yellow oil is mixed with 30 ml of diethyl ether. The clear solution is concentrated to 10 ml and cooled for several hours to -30 ^° C, whereby 208 mg (78%) of diastereomers are obtained as an orange-yellow powder with a melting point of 74 ^° C (determined by differential scanning calometry).

Example 22
Synthesis of {4- [3'-isopropyl- (η ^5- cyclopentadienyl)] 1-4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)} dichlorocirconium
a) Synthesis of 4- (3'-isopropyl-cyclopentadienyl) -4,7,7-trimethyl-4,5,6,7-tetrahydro-1H-indene
To a suspension of 2.17 g (57.3 mmol) of lithium aluminum hydride in 100 ml of diethyl ether was added dropwise at room temperature a solution of 6.11 g (22.9 mmol) of tetrahydroindenyl fulvene according to Example 8a in 20 ml of diethyl ether. After a strong, but not very exothermic reaction, the orange suspension is heated under reflux for another three hours. Then it is cooled in an ice bath to 0 ^° C. and carefully hydrolyzed with ice water. The resulting white bulky precipitate was extracted twice with diethyl ether, taken in an amount of 50 ml, and the combined organic phases were washed with an aqueous solution of sodium chloride. After drying over magnesium sulfate and after removal of the solvent in vacuo, 5.63 g (92%) of the isopropyl substituted ansa ligand are obtained as an orange oil. Also in this case, the product consists of a large number of isomers due to double bond, so that only a rough classification of signal groups in the ¹ H-NMR spectrum is possible.

-4,5,6,7-тетрагидроинденил)}дилития
4,21 г (15,7 ммоль) замещенного изопропилом лиганда растворяют в 70 мл диэтилового эфира и добавляют каплями при 0^oC 21,6 мл (34,5 ммоль) 1,60 м. раствора метиллития. Раствор быстро обесцвечивается с образованием белого осадка. После окончания прикапывания перемешивают еще в течение дальнейших 15 часов при комнатной температуре. Затем осадок отфильтровывают и два раза промывают диэтиловым эфиром, взятым в количестве по 15 мл. Получают 5,20г (93%) крайне чувствительной к воздействию воздуха дилитиевой соли в качестве порошка бежевого цвета, включающей один молярный эквивалент диэтилового эфира.b) Synthesis of {4- [3'-isopropyl- (η ^5- cyclopentadienyl)] - 4,7,7-trimethyl-

-4,5,6,7-tetrahydroindenyl)} dilithium
4.21 g (15.7 mmol) of the isopropyl substituted ligand are dissolved in 70 ml of diethyl ether and 21.6 ml (34.5 mmol) of a 1.60 m solution of methyl lithium are added dropwise at 0 ^° C. The solution quickly decolours to form a white precipitate. After completion of the dropping, the mixture is stirred for a further 15 hours at room temperature. Then the precipitate is filtered off and washed twice with diethyl ether, taken in an amount of 15 ml. Receive 5.20 g (93%) of extremely sensitive to the action of air dilithium salt as a beige powder, including one molar equivalent of diethyl ether.

c) Synthesis of {4- [3'-isopropyl- (η ^5- cyclopentadienyl)] - 4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)} dichlorocirconium
To a suspension of 5.20 g (14.7 mmol) of dilithium salt in 200 ml of toluene cooled to -78 ^° C, 3.40 g (14.6 mmol) of zirconium tetrachloride are slowly added. The resulting beige suspension was stirred for 24 hours at room temperature, the insoluble matter was separated, and the transparent orange residue was concentrated to approximately 50 ml in a vacuum created by an oil pump. Spectroscopic analysis of ¹ H-NMR of the toluene phase shows that both diastereomers are in this ratio in a 1: 1 ratio. A yellow solid (1.42 g) is precipitated by adding 2 ml of pentane and storing in a refrigerator at -20 ^° C. which is enriched in one of the diastereomers (8: 1 ratio). In the toluene phase, another diastereomer (1.62 g) is enriched in inverse proportion: the total yield is 49%.

If you dissolve approximately 100 mg of the precipitated yellow powder in methylene chloride, then after subsequent slow diffusion of pentane into this solution, crystals are obtained which are the 4R ^* - {4- [3'-isopropyl- (η ^5- cyclopentadienyl)] - 4 diastereomer, 7,7-trimethyl (η ⁵ -4,5,6,7-pR ^* -tetrahydroindenyl)} dichlorozirconium.

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.79-6.75, 6.48-6.38, 6.24-6.21, 5.99-5.95, 5.56-5.54, 5.44-5.41 (6 xm, 6H, 1-H, 2-H , 3-H, 2'-H, 4'-H, 5'-H): 2.91 (s, 1H, ⁱ Pr-CH, ³ J ( ⁱ Pr-CH ₃ / ⁱ Pr / CH) = 6.9 Hz); 2.41 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.5 Hz, ³ J (H6 _ax / H5 _eq ) = 6.2 Hz, ³ J (H6 _eq / H5 _eq ) = 2.8 Hz) ; 2.28 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.5 Hz, ³ J (H6 _ax / H5 _ax ) = 14.5 Hz, ³ J (H6 _eq / H5 _ax ) = 5.6 Hz) ; 2.01 (ddd, 1H, 6 _ax -H, ² J (H6 _eq H6 _ax ) = 14.5 Hz, ³ J (H5 _ax / H6 _ax ) = 14.5 Hz, ³ J (H5 _eq / H6 _ax ) = 6.2 Hz; 1.72 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.5 Hz, ³ J (H5 _ax H6 _eq ) = 5.6 Hz, ³ J (H5 _eq / H6 _eq ) = 2.8 Hz; 1.78 ( s, 3H, 10-H); 1.32, 1.11 (2 xs, 6H, 11-H and 12-H); 1.24, 1.09 ppm (2 xd, 6H, ⁱ Pr-CH ₃ , ³ J ( ⁱ Pr-CH / ⁱ Pr-CH ₃ ) = 6.9 Hz.

Melting point: 193 ^o C (determined by differential scanning calometry).

Example 23
Synthesis of {4 [3'-isopropyl- (η ^5- cyclopentadienyl) 1-4,7,7-trimethyl- (2-isopropyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)]} dichlorocirconium
a) Synthesis of 4- (3'-isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (2-isopropyl-4,5,6,7-tetrahydro-1H-indene)
Option 1
Stage A
2-isopropylidene-4- (3'-isopropylidene-cyclopenta-1 ', 4'-dienyl) -4,7,7-trimethyl- (4,5,6,7-tetrahydro-2H-indene)
8.32 g (34.2 mmol) of monofulvene according to Example 8a are dissolved in a mixture of 50 ml of methanol and 20 ml of pentane, and the resulting clear orange-red solution is cooled to 0 ^° C. By successive addition of 2.61 g (3.31 ml) , 45.0 mmol) of acetone and 6.08 g (7.10 ml, 85.5 mmol) of pyrrolidine, the reaction solution turned dark red after 36 minutes. After stirring for 7 days at room temperature, 5 ml of glacial acetic acid, 150 ml of water and 50 ml of pentane are successively added to the reaction mixture.

 After extracting the aqueous phase twice with pentane, the combined organic phases are washed several times with saturated aqueous sodium chloride and dried over magnesium sulfate. After removing the solvent in a vacuum created by an oil pump, 9.04 g (86%) of the indicated difulvene is obtained as a red oil. A portion of the red oil is mixed with pentane and chromatographed on a silica gel (60 mesh grain; product from Merck, DE) column pretreated with triethylamine. A mixture of pentane and triethyl ether in a ratio of 100: 5 (total yield <10%) is used as a solvent.

Stage B
4- (3'-isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (2-isopropyl-4,5,6,7-tetrahydro-1H-indene)
3.03 g (80.0 mmol) of lithium aluminum hydride in 100 ml of diethyl ether are fed into a three-necked flask with an intensive cooling refrigerator and a dropping funnel, and 6.47 g (21.1 mmol) of the step obtained are added with vigorous stirring at room temperature. A difulvene dissolved in 50 ml of diethyl ether. Upon completion of the addition, the reaction mixture was heated under reflux for 5 hours and then carefully hydrolyzed with 100 ml of water. In this case, a gray precipitate of alumina and a yellow phase of diethyl ether are obtained. The latter is decanted, the gray precipitate is extracted several times with diethyl ether, and the combined phases of diethyl ether are washed with a saturated aqueous solution of sodium chloride. After drying over magnesium sulfate and removing the solvent in vacuo, 6.25 g (96%) of recovered difulvene are obtained as an orange-red oil, which can be processed without further purification.

Option II
Stage A
2,5-bis [(isopropyl) cyclopenta-2,4-dien-1-ylidene] hexane
To a solution of 2.78 ml (2.71 g, 23.8 mmol) of 2,5-hexanedione and 4.00 g (47.6 mmol) of isopropylcyclopentadiene in 50 ml of methanol are added dropwise at 0 ^° C. 5.90 ml (5 07 g, 71.3 mmol) of freshly distilled pyrrolidine. In this case, the reaction solution immediately turns dark red. After stirring for a further 15 hours at 0 ^° C, excess pyrrolidine is neutralized by adding a solution of 2 ml of glacial acetic acid in 100 ml of water. Extracted twice with diethyl ether, taken in an amount of 100 ml, the combined organic phases are washed several times with saturated aqueous sodium chloride and dried over magnesium sulfate. Removal of the solvent in vacuo gives 5.20 g (75%) of difulvene as a dark red oil.

 Purification of difulven is carried out by chromatography on a column containing silica gel deactivated by triethylamine, used as a mixture with pentane in a ratio of 1: 100. A mixture of pentane and diethyl ether in a ratio of 1: 1 is used as an eluent. 1.72 g (25%) of difulvene are obtained as red oil.

Stage B
a) 4- (3'-isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (2-isopropyl-4,5,6,7-tetrahydro-1H-indene
600 mg (2.04 mmol) of substituted bis-isopropyl difulvene from step A are dissolved in 10 ml of diethyl ether and slowly mixed at 0.degree ^. C. with 2.55 ml of 1.60 m. Methyl lithium ether solution. The reaction mixture was allowed to warm to room temperature. After 24 hours, an orange suspension was obtained, which was cooled to 0 ^° C. and then hydrolyzed with 10 ml of water. After extraction with diethyl ether in an amount of 20 ml and drying over magnesium sulfate, 520 ml (82%) of the expected product are obtained as an orange oil.

b) {4- [3'-isopropyl- (η ⁵ -cyclopentadienyl)] - 4,7,7-trimethyl- [2-isopropyl (η ⁵ -4,5,6,7-tetrahydroindenyl)} dichlorozirconium
To a solution of 500 g (1.61 mmol) of the compound substituted with bisisopropyl from step B of variant I or II in 20 ml of pentane was added dropwise 2.00 ml (3.22 mmol) of 1.60 m of an ethereal solution of methyl lithium at 0 ^° C. the mixture was allowed to warm to room temperature, and after 12 hours a cloudy orange suspension was obtained, which was cooled to -78 ^° C and mixed with 373 mg (1.61 mmol) of zirconium tetrachloride. After stirring for 24 hours at room temperature, the insoluble matter is filtered off and the solvent removed in vacuo. 300 mg (40%) of both diastereomers are obtained.
ansa zirconocene as an orange powder. In the ¹ H-NMR spectrum, resonance signals of both diastereomers were detected in a 1: 1 ratio (determined using isopropyl groups).

¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.44-6.41, 6.24-6.15, 5.95-5.91, 5.68-5.60, 5.33-5.29, 5.18-5.17 (6 xm, 10H, 2'-H, 4 ' -H, 5'-H, 1-H and 3-H); 3.13-2.83, 2.46-2.16, 2.08-1.93, 1.78-1.72 (4 xm, 12H, 2 x ⁱ Pr-CH and 5-H and 6-H); 1.76, 1.72 (2 xs, 6H, 10-H): 1.28-1.07 ppm. (m, 36H, 11-H, 12-H, 4 x ⁱ Pr-CH ₃ ).

Example 24
Synthesis of {4- [3'-trimethylsilyl- (η ^5- cyclopentadienyl) 1-4,7,7-trimethyl- [2-trimethyl-silyl- (η ⁵ -4,5,6,7-tetrahydroindenyl) 1} dichlorozirconium
a) Synthesis of 4- (3'-trimethylsilyl-cyclopentadienyl) -4,7,7-trimethyl- (2-trimethyl-silyl-4,5,6,7-tetrahydro-1H-indene)
A solution of 6.81 g (21.8 mmol) of the dilithium ether of Example 9 in 50 ml of tetrahydrofuran is cooled to 0 ^° C. and 5.50 ml (4.74 g, 43.6 mmol) of trimethylsilyl chloride are added dropwise with stirring. The reaction mixture was allowed to warm to room temperature overnight, the resulting turbid orange suspension was hydrolyzed by adding 50 ml of degassed water, and then extracted with petroleum ether. After drying over magnesium sulfate and removal of the solvent in vacuo, 6.54 g (81%) of a red-orange oil is obtained.

b) Synthesis of {4- [3'-trimethylsilyl- (η ^5- cyclopentadienyl)] - 4,7,7-trimethyl- [2-trimethyl-silyl (η ⁵ -4,5,6,7-tetrahydroindenyl)]} dility
To a solution of 3.30 g (8.90 mmol) substituted with bistrimethyl-silyl compound from step a) cooled to 0 ^° C in 40 ml of pentane, 11.1 ml (17.8 mmol) of 1.60 m ether solution are added dropwise with stirring. methyl lithium. In this case, a white precipitate is obtained upon evolution of gas. To complete the reaction, stirring is continued for another 24 hours at room temperature, after which the white precipitate is filtered off and washed with pentane. After drying in a vacuum created by an oil pump, 2.60 g (76%) of dilithium salt are obtained as a white pyrophoric residue.

c) Synthesis of {4- [3'-trimethylsilyl- (η ^5- cyclopentadienyl)] - 4,7,7-trimethyl- [2-trimethylsilyl (η ⁵ -4,5,6,7-tetrahydroindenyl)]} dichlorozirconium
To a suspension of 2.60 g (6.79 mmol) substituted by bistrimethyl-silyl dilithium salt from step b) cooled to -78 ^° C in 100 ml of toluene, 1.58 g (6.79 mmol) of zirconium tetrachloride are added in portions. The reaction mixture was allowed to warm to room temperature, and after 24 hours stirring, an orange suspension was obtained. After separation of the insoluble matter and thickening to dryness, red oil is obtained. By adding 20 ml of pentane and subsequent processing, 1.54 g (43%) of both ansa-zirconocene diastereomers are obtained as an orange powder. Melting point: 151 ^o C (decomp., Determined by differential scanning calometry).

 The following examples explain in more detail the method according to the invention.

Example 25
Methylaluminoxane is supplied as a cocatalyst to a 500 ml polymerization reactor, dissolved in 250 ml of toluene and cooled to -50 ^° C. Propene is passed through a gas supply pipe, and excess propene can escape through the bubble counter. Once there is the desired amount of liquid propene (approximately 39 to 35 ml), the monomer supply is stopped. Then set the desired polymerization temperature. Then add a solution of the catalyst a) -c) indicated in table 1 in a small amount of toluene. After the required polymerization time has elapsed, the reaction is terminated by adding 500 ml of methanol hydrochloride, and excess propene evaporates when the solution is boiled intensively. The polymer is isolated by separating the toluene phase and extracting the water-methanol phase with diethyl ether. The combined toluene and ethyl phases are concentrated to dryness in vacuo.

 Data on the parameters of the experiment and the results achieved with this are shown in table 1.

Example 26
In a steel autoclave with a volume of 2 dm ³ with polished surfaces of the walls, gas-phase polymerization of ethylene is carried out. The fluidized bed is created mechanically by means of a twin-screw mixer capable of moving along the walls using 10 g of polyethylene powder. Co-catalyst (2 mmol of triisobutylaluminum in 2 cm ^{3 of} isopentane) and 1 g of 4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl) are successively added through a burette; dichlorozirconium (25.8 mmol Zr) on a SiO ₂ carrier. Then polymerization is carried out for 1 hour at 8 bar of partial pressure of ethylene at a temperature of 80 ^o C. The reaction is stopped by depressurizing the autoclave. Obtain 36 g of polyethylene, respectively, activity of 3.6 kg of polyethylene / g of metallocene. The viscosity coefficient of the polymer is 70 ml / g.

Example 27
A dry reactor with a volume of 1.5 dm ^{3 is} washed with nitrogen and filled at ^20.degree. C. 0.75 dm.sup.3 ^{of a} dearomatized gasoline fraction with a boiling range of 100 to 120.degree ^. C. Then the gas space of the reactor is washed to a nitrogen-free state by 5-fold pressing 2 bar propylene and pressure reducing. 3.75 dm ^{3 of a} toluene methylaluminoxane solution (5 mmol Al, n = 18) was then added. With stirring, the reactor is heated to 30 ^o C, and at a stirrer speed of 500 rpm, monomers are added (the partial pressure of ethylene and propylene, as well as the amount of 5-ethylidene-2-norbornene in cm ³ , see table 2).

0.125 mg of metallocene 4- (η ⁵ -3'-methylcyclopentadienyl) -4,7,7-tri-methyl- (η ⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)] dichlorocirconium is dissolved in 1.25 cm ^{3 of a} toluene solution of methylaluminoxane (1.67 mmol Al, n = 18) and the resulting solution was left to stand for 15 minutes to complete the reaction, after which the solution was fed to the reactor, the medium to be polymerized was brought to 50 ^° C and kept under this cooling temperature for an hour. Then, by adding 2 ml of isopropanol, the polymerization is stopped, the polymer is precipitated by lowering the contents of the reactor into acetone and dried in vacuum at 80 ^° C (the polymer is stabilized with Irganox 1010, 0.1% by weight). The parameters of the experiment and the results achieved with this are shown in table 2.

Example 28
In an autoclave with a capacity of 1.5 dm ³ , which is subjected to thorough thorough washing with argon, 600 cm ^{3 of a} solution of 180 cm ^{3 of} styrene (distilled under reduced pressure) in toluene are fed. By repeatedly pressing argon (1 bar), the solution is saturated with argon. In a reactor thus prepared, a countercurrent flow of 10 cm ^{3 of a} toluene solution of methylaluminoxane (10.1 wt.% Solution of methyl aluminoxane with a molecular weight of 1300 g / mol by cryoscopic determination) is provided. A solution of 10 mg of 4- (η ⁵ -3'-isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl), dichlorocirconium in 10 cm ³ of a methylaluminoxane toluene solution is added after preliminary 15-minute activation. (In the case of regulating the molecular weight with hydrogen, hydrogen can be pressed here.) With stirring (750 rpm), the polymerization is carried out for two hours at a temperature of 70 ^o C. Then the polymerization mixture is released into the collector and 5 dm ^{3 of} ethanol are immediately added, stirred for 10 minutes, and the precipitated product is filtered. The filter cake is washed three times, alternately with 10% hydrochloric acid and ethanol. Then it is washed with water until neutral, the residue is suspended in ethanol and filtered again. The polymer thus purified was dried for 15 hours at 80 ^° C. in vacuo (0.2 bar).

After drying, 5.2 g of polymer are obtained having a glass transition temperature of 102 ^° C.

Example 29
In an autoclave with a capacity of 1.5 dm ^3, which is subjected to thorough thorough washing with ethene, 600 cm ^{3 of a} solution of 180 cm ^{3 of} styrene (distilled under reduced pressure) in toluene are fed. By repeatedly pressing ethene (1 bar), the solution is saturated with ethene. To the reactor thus prepared, a countercurrent flow of 10 cm ^{3 of a} toluene solution of methylaluminoxane (10.1 wt.% Solution of methylaluminoxane with a molecular weight of 1300 g / mol by cryoscopic determination) is provided. A solution of 10 mg of 4- (η ⁵ -3'-isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl) dichlorocirconium in 10 cm ³ of a methylaluminoxane toluene solution is added after preliminary 15 minute activation. (In the case of controlling molecular weight with hydrogen, hydrogen can be pressed here). With stirring (750 rpm) the polymerization is carried out at a temperature of 70 ^o C for one hour, and by additional supply of ethene pressure is kept at 1 bar. Then the polymerization mixture is discharged into the collection tank, 5 dm ^{3 of} ethanol is added, stirred for 10 minutes, and then the precipitated product is filtered. The filter cake is washed three times, alternately with 10% hydrochloric acid and ethanol. Then it is washed with water until neutral, the residue is suspended in ethanol and filtered again. The polymer thus purified was dried for 15 hours at 80 ^° C. in vacuo (0.2 bar). After drying, 21 g of a colorless polymer having a glass transition temperature of -24 ^° C. and a viscosity coefficient of 30 cm ³ / g are obtained.

Example 30
To obtain a catalyst solution, 10 ml of metallocene a) are dissolved (see Example 25) in 10 ml of a toluene methylaluminoxane solution and stirred for 15 minutes. 900 ml of diesel fuel (boiling range 100-120 ^o C) are fed into an inertized reactor with a stirrer with a capacity of 1.5 dm ³ and heated to 70 ^o C. The catalyst solution is added and ethylene polymerization is carried out at 750 rpm (7 bar) after which the pressure in the reactor is released, the polymer is filtered from the suspension, washed with acetone and dried for 12 hours in a vacuum oven. 39.2 g of polyethylene are obtained with a viscosity coefficient of 72 cm ³ / g.

Example 31
Example 25 is repeated in the application of the following metallocenes 1 to 5.

1: [4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorozirconium
2: [4- (η ^5- cyclopentadienyl) -4,7-dimethyl-7-butyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorozirconium
3: [4- (η ^5- cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorozirconium
4: [4- (η ⁵ -3-methyl-cyclopentadienyl) -4,7,7-dimethyl- (η ⁵ -4,5,6,7-tetrahydro-indenyl)] dichlorozirconium
5: [4- (η ⁵ -th.-Butyl-cyclopentadienyl) -4,7,7-dimethyl- (η ⁵ -4,5,6,7-tetrahydro-indenyl)] dichlorocirconium
Data on the parameters of the experiment and the results achieved with this are shown in table 3.

Example 32
In a laboratory autoclave in a nitrogen atmosphere serves 500 ml of diesel fuel (boiling range 100 - 120 ^o C), 20 ml of hexene and 10 ml of 10 weight. % solution of methylaluminoxane in toluene was fed under nitrogen and heated to 70 ^° C. with stirring at a speed of 700 rpm. 10 mg of metallocene N 5 is dissolved in 1 ml of 10 wt.% - toluene methylaluminoxane solution. The polymerization is started by adding a solution of metallocene and metalloaluminoxane and napressivka 4 bar of ethylene. After 15 minutes, the polymerization is stopped by feeding CO ₂ and the contents of the reactor are added to 200 ml of methanol hydrochloric acid. The mixture is stirred for 5 hours to remove aluminum, then the polymer is filtered off, washed with water and acetone and dried to determine the yield for 12 hours in vacuum at 80 ^o C.

4.8 g of a copolymer of ethylene and 1-hexene are obtained with a viscosity coefficient of 70 cm ³ / g. To remove the residual comonomer, a sample in an amount of 1 g is dissolved in diesel fuel during heating (boiling range 100-120 ^o C), then precipitated, filtered, washed with acetone and dried again in vacuum at 80 ^o C. According to the data of differential scanning calometry melting point is 110.5 ^o C, and according to 13 C-NMR the content of hexene is 4.6 mol.%.

Example 33
The experiment of Example 25 was repeated using 10 mg of the metallocene [4- (η ⁵ -3-isopropyl-cyclopentadienyl) -4,7,7-dimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] -dichlorocirconium. 4 g of a copolymer with a viscosity coefficient of 22 cm ³ / g are obtained, which, after cleaning, has a melting point of 102 ^° C. determined by differential scanning calometry. According to 13 C-NMR, the content of hexene is 7.1 mol%.

Physico-chemical characteristics of the compounds of examples 11 - 20, 22, 23
The compound of example 11
¹ H-NMR (200.1 MHz, CDCl ₃ ); δ = 7.06-7.03, 6.94-6.91, 6.82-6.76, 5.87-5.84, 5.82-5.78, 5.62-5.59 (6 xm, 7H, 1-H to 3-H and 2'-H to 5'H); 2.45 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.2 Hz, ³ J (H6 _ax / H5eq) = 6.3 Hz, ³ J (H6 _eq / H5eq) = 2.7 Hz); 2.31 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.0 Hz, ³ J (H6 _ax / H5 _ax ) = 14.0 Hz, ³ J (H6 _eq / H5 _ax ) = 6.2 Hz) ; 1.91 (ddd, 1H, 6 _ax -H, ² J (H6 _eq / H6 _ax ) = 14.0 Hz, ³ J (H5 _ax / H6 _ax ) = 14.0 Hz, ³ J (H5 _eq / H6 _ax ) = 6.3 Hz) ; 1.69 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.0 Hz, ³ J (H5 _ax / H6 _eq ) = 6.2 Hz, ³ J (H5 _eq / H6 _eq ) = 2.7 Hz); 1.86 (s, 3H, 10-H); 1.25 and 1.11 ppm (2 xs, 6H, 11-H and 12-H).

Compound of Example 12
¹ H-NMR (200.1 MHz, CDCl ₃ ); δ = 6.73-6.70, 6.44-6.41,5.73-5.70 (3 xm, 3H, 1-H to 3-H), 6.70-6.67, 6.53-6.48, 6.08-6.03, 5.88-5.82 (4 xm, 4H, 2 '-H to 5'-H); 2.42 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.8 Hz, ³ J (H6 _ax / H5 _eq ) = 6.0 Hz; ³ J (H6 _eq / H5 _eq ) = 2.2 Hz) ; 2.30 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.8 Hz ³ J (H6 _ax / H5 _ax ) = 14.3 Hz, ³ J (H6 _eq / H5 _ax ) = 5.3 Hz; 2.00 (ddd, 1H, 6 _ax -H, ² J (6 _eq H6 _ax ) = 14.8 Hz, ³ J (H5 _ax / H6 _ax ) = 14.3 Hz, ³ J (H5 _eq / H6 _ax ) = 6.0 Hz); 1.72 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.8 Hz, ³ J (H5 _ax / H6 _eq ) = 5.3 Hz, ³ J (H5 _eq / H6 _eq ) = 2.2 Hz ); 1.83 (s, 3H, 10-H); 1.33 and 1.10 ppm (2 xs, 6H, 11-H and 12-H).

Compound of Example 13
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 7.24-6.89 (t, 5H, Ph-H); 6.78-6.73, 6.54-6.50, 6.22-6.20, 5.97-5.94 (4 xm, 7H, 1-H to 3-H and 2'-H to 5'-H); 2.30-2.22, 1.92-1.84 (2 xm, 4H, 5-H, 6-H); 1.76, 1.71 ppm (2 xs, 6H, 10-H and 11-H).

Compound of Example 14
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.73-6.67, 6.52-6.47, 6.41-6.38, 6.08-6.04, 5.87-5.83, 5.76-5.73 (6 xm, 7H, 2'-H to 5'-H and 1-H to 3-H); 2.48-2.16 (m, 3H, 5 _eq -H, 5 _ax -H, 6 _ax -H); 1.91-1.84 (m, 1H, 6 _eq -H); 1.83 (s, 3H, 10-H); 1.35-0.85 (3 xm, 6H, ⁿ Bu-CH ₂ ); 1.25 (s, 3H, 11-H); 0.82-0.77 ppm (pt, 3H, ⁿ Bu-CH ₃ ).

The compound of example 15 (trans isomer)
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.63-6.58, 6.42-6.39, 6.33-6.30, 5.99-5.96, 5.81-5.78, 5.66-5.63 (6 xm, 7H, 2'-H up to 5 ' -H and 1-H to 3-H); 2.38 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.0 Hz, ³ J (H6 _ax / H5 _eq ) = 5.7 Hz, ³ J (H6 _eq / H5 _eq ) = 3.2 Hz) ; 2.23 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.0 Hz, ³ J (H6 _ax H5 _ax ) = 14.4 Hz, ³ J (H6 _eq / H5 _ax ) = 6.8 Hz); 1.98 (ddd, 1H, 6 _ax -H, ² J (H6 _eq H6 _ax ) = 14.4 Hz, ³ J (H5 _ax H6 _ax ) = 14.4 Hz, ³ J (H5 _eq / H6 _ax ) = 5.7 Hz; 1.85 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.4 Hz, ³ J (H5 _ax H6 _eq ) = 6.8 Hz, ³ J (H5 _eq H6 _eq ) = 3.2 Hz); 1.90 (s, 3H, 10-H); 1.27 (s, 3H, 11-H); 1.35-1.07 (3 x m, 6H, ⁿ Bu-CH ₂ ); 0.84-0.76 ppm ( pt, 3H, ⁿ Bu-CH ₃ ).

Melting point: 151 ^o C (determined by differential scanning calometry).

Compound of Example 16
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 7.06-6.96, 6.95-6.92, 6.82-6.74, 5.89-5.85, 5.83-5.79, 5.64-5.61 (6 xm, 7H, 2'-H 5'-H and 1-H to 3-H); 2.40-2.27, 1.89-1.75 (2 xm, 4H, 5 _eq -H, 5 _ax -H, 6 _ax -H, 6 _eq -H); 1.86 (s, 3H, 10-H); 1.35-0.89 (m, 6H, ⁿ Bu-CH ₂ ); 1.21 (s, 3H, 11-H); 0.84-0.77 ppm (pt, 3H, ⁿ Bu-CH ₃ ).

Melting point: 134 ^o C (determined by differential scanning calometry).

Compound of Example 17
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.76-6.72, 6.69-6.65, 6.53-6.50, 6.43-6.32, 5.99-5.97, 5.88-5.82, 5.72-5.61 (7 xm, 12H, 1-H , 2-H, 3-H, 2'-H, 4'-H, 5'-H); 2.37-2.33, 2.10-1.85, 1.75-1.62 (3 xm, 8H, 5-H and 6-H); 1.82, 1.81 (2 xs, 6H, 10-H); 1.33 (bs, 6H, 11-H or 12-H); 1.31, 1.25 (2 xs, 18H, ^t Bu-CH ₃ ); 1.12, 1.09 ppm (2 xs, 6H, 11-H or 12-H).

Compound of Example 18
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.58-6.50, 6.38-6.34, 5.91-5.87, 5.47-5.53, 5.34-5.31 (5 xm, 7H, 1-H to 3-H and 2'- H to 5'-H); 2.18 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.0 Hz, ³ J (H6 _ax / H5 _eq ) = 5.9 Hz, ³ J (H6 _eq / H5 _eq ) = 3.1 Hz; 2.09 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.0 Hz, ³ J (H6 _eq / H5 _ax ) = 14.0 Hz, ³ J (H6 _eq / H5 _ax ) = 5.3 Hz); 1.80 (ddd, 1H, 6 _ax -H, ² J (H6 _eq / H6 _ax ) = 14.0 Hz, ³ J (H5 _ax / H6 _ax ) = 14.0 Hz, ³ J (H5 _eq H6 _ax ) = 5.9 Hz; 1.57 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.0 Hz, ³ J (H5 _ax / H6 _eq ) = 5.3 Hz, ³ J (H5 _eq / H6 _eq ) = 3.1 Hz; 1.53 (s, 3H, 10-H); 1.19, 1.12 (2 xs, 6H, 11-H and 12-H), 0.26 and 0.34 ppm (2 xs, 6H, 13-CH ₃ and 14-CH ₃ ).

T. pl. : 114 ^o C. (determined by differential scanning calometry).

Compound of Example 19
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 7.05-7.01, 6.94-6.91, 6.85-6.80, 6.75-6.73, 5.87-5.79, 5.63-5.61 (6 xm, 2'-H to 5'-H and 1-H to 3-H); 5.63-5.40, 5.15-4.80 (2 xm, vinyl-CH and vinyl-CH ₃ ); 2.38-2.17, 2.10-2.06, 1.86-1.77 (3 xm, 5-H, 6-H, allyl-CH ₂ ); 1.85 (s, 10-H); 1.24, 1.10 ppm (2 xs, 11-H).

Compound of Example 20
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.73-6.67, 6.55-6.47, 6.41-6.38, 6.08-6.04, 5.94-5.80, 5.76-5.72 (6 xm, 2'-H to 5'-H and 1-H to 3-H); 5.62-5.41, 5.20-4.83 (2 xm, vinyl-CH and vinyl-CH ₂ ); 2.55-2.17, 2.09-2.05, 1.97-1.69 (3 xm, 5-H, 6-H, allyl-CH ₂ ); 1.83 (s, 3H, 10-H); 1.27, 1.09 ppm (2 xs, 11-H (cis isomer) and 11-H (trans isomer)).

Compound of Example 22
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.79-6.75, 6.48-6.38, 6.24-6.21, 5.99-5.95, 5.56-5.54, 5.44-5.41 (6 xm, 6H, 1-H, 2-H , 3-H, 2'-H, 4'-H, 5'-H); 2.91 (s, 1H, ⁱ Pr-CH, ³ J ( ⁱ Pr-CH ₃ / ⁱ Pr / CH) = 6.9 Hz); 2.41 (ddd, 1H, 5 _eq -H, ² J (H5 _ax / H5 _eq ) = 14.5 Hz, ³ J (H6 _ax / H5 _eq ) = 6.2 Hz, ³ J (H6 _eq / H5 _eq ) = 2.8 Hz) ; 2.28 (ddd, 1H, 5 _ax -H, ² J (H5 _eq / H5 _ax ) = 14.5 Hz, ³ J (H6 _ax / H5 _ax ) = 14.5 Hz, ³ J (H6 _eq / H5 _ax ) = 5.6 Hz) ; 2.01 (ddd, 1H, 6 _ax -H, ² J (H6 _eq / H6 _ax ) = 14.5 Hz, ³ J (H5 _ax / H6 _ax ) = 14.5 Hz, ³ J (H5 _eq / H6 _ax ) = 6.2 Hz; 1.72 (ddd, 1H, 6 _eq -H, ² J (H6 _ax / H6 _eq ) = 14.5 Hz, ³ J (H5 _ax H6 _eq ) = 5.6 Hz, ³ J (H5 _eq / H6 _eq ) = 2.8 Hz; 1.78 (s, 3H, 10-H); 1.32, 1.11 (2 xs, 6H, 11-H and 12-H); 1.24, 1.09 ppm (2 xd, 6H, ⁱ Pr-CH ₃ , ³ J ( ⁱ Pr-CH / ⁱ Pr-CH ₃ ) = 6.9 Hz.

Melting point: 193 ^o C (determined by differential scanning calometry).

Compound of Example 23
¹ H-NMR (200.1 MHz, CDCl ₃ ): δ = 6.44-6.41, 6.24-6.15, 5.95-5.91, 5.68-5.60, 5.33-5.29, 5.18-5.17 (6 xm, 10H, 2'-H, 4 ' -H, 5'-H, 1-H and 3-H); 3.13-2.83, 2.46-2.16, 2.08-1.93, 1.78-1.72 (4 xm, 12H, 2 x ⁱ Pr-CH and 5-H and 6-H); 1.76, 1.72 (2 xs, 6H, 10-H); 1.28-1.07 ppm (m, 36H, 11-H, 12-H, 4 x ⁱ Pr-CH ₃ ).

Claims (8)

1. A metallocene catalyst for producing an olefin polymer, which is a sterically rigid metallocene compound containing at least two substituted or unsubstituted cyclopentadienyl groups bonded to each other via a monocyclic ring system, wherein one cyclopentadienyl group is anellated to the monocyclic system, and this system ligands other than 4- (η ⁵ -3-alkyl-cyclopentadienyl) -4,6,6-trimethyl- (η ⁵ -2-alkyl-4,5-tetrahydropentalene) and is a compound of formula I

where M is a metal of group IVb of the Periodic system;
R ¹ and R ^{2 are the} same or different and mean a halogen atom, alkyl with 1 to 10 carbon atoms or a group NR ₂ ¹³ , where R ¹³ means alkyl with 1 to 10 carbon atoms;
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are the} same or different and mean a hydrogen atom, alkyl with 1 to 10 carbon atoms, or the residue —R ¹³ —SiR ₃ ¹³ -, where R ¹³ has the above meaning;
R ¹⁰ is alkyl with 1 to 20 carbon atoms;
R ¹¹ and R ^{12 are the} same or different and mean alkyl with 1 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, alkenyl with 2 to 12 carbon atoms;
n is an integer from 1 to 10.  2. The metallocene catalyst according to claim 1, in which the monocyclic ring system of a sterically rigid metallocene compound has six ring atoms. 3. The metallocene catalyst according to claim 1 of formula I, in which M - means zirconium; R ¹ and R ^{2 are the} same and mean a halogen atom; R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are the} same or different and represent hydrogen, alkyl with 1 to 4 carbon atoms; R ¹⁰ is alkyl with 1 to 6 carbon atoms, R ¹¹ and R ^{12 are the} same or different and mean methyl or phenyl, n = 2.  4. The metallocene catalyst according to one or more of claims 1 to 3, which is supported on the carrier and / or prepolymerized.  5. A method for producing a polymer of olefins by polymerizing at least one olefin on a metallocene catalyst and isolating the obtained polymer, characterized in that the sterically rigid metallocene compound according to claim 1 is used as the metallocene catalyst. 6. The method according to p. 5, characterized in that the polymerization is subjected to at least one olefin of the formula R ^a -CH = CH - R ^b , where R ^a and R ^{b are the} same or different and mean a hydrogen atom or a carbon residue from 1 to 20 carbon atoms or R ^a and R ^b together with their bonding atoms form at least one ring.  7. The method according to PP. 5 and 6, characterized in that the process is carried out in the presence of cocatalyst.  8. The method according to claim 7, characterized in that aluminoxane is used as a cocatalyst.

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