RU2154067C2 - Metallocene catalyst and method of preparing copolymer of cycloolefins, molded product and polymeric alloy comprising at least one polymer of cycloolefins - Google Patents

Abstract

FIELD: chemistry of polymers. SUBSTANCE: described is metallocene catalyst for preparing cycloolefin copolymer which is sterilely rigid metallocene compound comprising as ligands at least two substituted or unsubstituted cyclopentadienyl groups bonded together through monocyclic ring system, one cyclopentadienyl group being annealed to monocyclic system, and said system is different from 4-η⁵-3-alkylceclopentadienyl 4,6,6- trimethyl-η⁵-2-alkyl-4,5-tetrahydropentalene) and is essentially compound of formula I:

wherein M is metal of group IV b of Periodic Table; R¹ and R² are the same or different and are halogen atom, alkyl having 1-10 carbon atoms, or group NR $\genfrac{}{}{0ex}{}{\text{13}}{\text{2}}$ , wherein R¹³ is alkyl having 1- 10 carbon atoms, R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are hydrogen atom, alkyl 1-10 carbon atoms, or residue -R¹³-SiR $\genfrac{}{}{0ex}{}{\text{13}}{\text{3}}$ - wherein R¹³ is as defined above, R¹⁰ is alkyl having 1-20 carbon atoms; R¹¹ and R¹² are the same or different and are alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, alkenyl having 2-12 carbon atoms, and n is integer from 1 to 10. Also described are method of preparing cycloolefin copolymer and polymeric alloy comprising at least one cycloolefin polymer. EFFECT: improved physico-mechanical properties of copolymer of cycloolefins, especially polyolefins having greater breaking strength and higher transparency and higher polymerization activity. 11 cl, 34 ex, 1 tbl

Description

 The invention relates to a technology for producing a polymer of olefins and their use in polymer alloys and molded products, in particular to a metallocene catalyst and a method for producing a cycloolefin copolymer, as well as to a polymer alloy and a molded product comprising at least one cycloolefin copolymer.

 A metallocene catalyst is known for producing a cycloolefin copolymer 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).

 The disadvantage obtained by using a known metallocene catalyst of cycloolefin copolymers, which can be used to obtain polymer alloys and molded products, is that their physical and mechanical properties are not entirely satisfactory. The same applies to their polymerization activity.

 An object of the present invention is to provide a catalyst by which it is possible to obtain a copolymer of cycloolefins with improved physicomechanical properties, in particular polyolefins with increased tensile strength and increased transparency, and, in addition, a higher polymerization activity.

где M - металл группы IVб Периодической системы,
R¹ и R² одинаковы или различны и означают атом галогена, алкил с 1-10 атомами углерода, или группу NR₂ ¹³, 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-SiR₃ ¹³-, 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 copolymer of cycloolefins, 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-tetrahydro pentalene) 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 ₂ ¹³ , where R ¹³ means alkyl with 1-10 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 1-10 carbon atoms, or the residue —R ¹³ —SiR ₃ ¹³ -, 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 1-20 carbon atoms, aryl with 6-20 carbon atoms, alkenyl with 2-12 carbon atoms,
n is an integer from 1 to 10.

 The monocyclic system preferably has 6 ring atoms.

A metallocene catalyst of the above formula (I) is preferred 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 1-4 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 inventive metallocene catalyst may be supported and / or prepolymerized.

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

 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 bis-cyclopentadiene compound (IV), which is obtained as a mixture of structural isomers and can be purified by chromatography. By double deprotonation of the compound (IV), for example, butyl lithium, a dianionic 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 such as o-dichlorobenzene.

Bis-cyclopentadienyl compounds of formula (IV) in which at least one of the residues R ³ to R ⁶ and 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 different from hydrogen, can be converted by methods known from the literature to fulvenes of the formula (IVa) or (IVb). This is illustrated by reaction scheme B (see the end of the description), 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 (IIIa).

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

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

Бис-циклопентадиенильные анионы формулы (Vb) могут подвергаться взаимодействию с соединениями R_p ¹⁸MX,
где M - 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 a radical value 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 (IIIa) 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 that can serve as spanning groups in substitution reactions (such as, for example, bromide or tosylate), are interaction, for example, with cyclopentadienyl or indenyl lithium compounds.

 The metallocenes according to the invention are highly active catalysts for the polymerization of cycloolefins. 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, for example, soft molded products, this can be quite 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 1-20 carbon atoms, such as alkyl with 1 to 18 carbon atoms, aryl with 6-18 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 co-catalyst, 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 from 5 minutes to 60 hours, preferably 5 to 60 minutes. The working temperature is from -78 to +100 ^o C, preferably 0 - 70 ^o C.

 Using metallocene, prepolymerization can be carried out, for which purpose the cycloolefin used for polymerization, or one of the cycloolefins used for polymerization, is preferably used.

 The metallocene can be 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.

 In the event that a solvent is added to the reaction mixture, a known inert solvent, such as, for example, aliphatic or cycloaliphatic hydrocarbons, gasoline fractions or hydrogenated diesel oil fractions, or toluene, is used as the solvent.

Metallocenes are preferably used as their racemates. 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. Alumoxane is preferably used in a concentration of 10 ⁻⁴ to 10 ⁻¹ mol, preferably 10 ⁻³ to 10 ⁻² mol per dm ³ of reactor volume, calculated on the aluminum content. In principle, however, higher concentrations are also possible.

 A further object of the invention is a method for producing a cycloolefin copolymer by polymerizing at least one cycloolefin, which consists in using a sterically rigid metallocene compound of the above general formula (I) as a metallocene catalyst.

в которых R²⁰ - R²⁷ одинаковы или различны и означают атом водорода или углеводородный остаток с 1-20 атомами углерода, такой, как алкил с 1-8 атомами углерода или арил с 6-10 атомами углерода, или два или больше из остатков R²⁰ - R²⁷ вместе образуют циклическую систему с 4-40 атомами углерода, причем одинаковые остатки R²⁰ - R²⁷ в различных формулах могут иметь различное значение. Особенно предпочтительными являются циклоолефины формул (X) или (XII), где R²⁰ - R²⁷ одинаковы или различны и означают атом водорода или углеводородный остаток с 1- 20 атомами углерода, в частности, арильный остаток с 6-10 атомами углерода, или алкильный остаток с 1-8 атомами углерода, причем одинаковые остатки R²⁰ - R²⁷ в различных формулах могут иметь различное значение.In the implementation of the proposed method, it is preferable to use one or more polycyclic olefins, in particular, the following formulas (IX) to (XIV),

in which R ²⁰ - R ^{27 are the} same or different and mean a hydrogen atom or a hydrocarbon residue with 1-20 carbon atoms, such as alkyl with 1-8 carbon atoms or aryl with 6-10 carbon atoms, or two or more of R residues ²⁰ - R ²⁷ together form a cyclic system with 4-40 carbon atoms, and the same residues R ²⁰ - R ²⁷ in different formulas can have different meanings. Especially preferred are cycloolefins of the formulas (X) or (XII), where R ²⁰ - R ^{27 are the} same or different and represent a hydrogen atom or a hydrocarbon residue with 1 to 20 carbon atoms, in particular an aryl residue with 6-10 carbon atoms, or an alkyl a residue with 1-8 carbon atoms, and the same residues R ²⁰ - R ²⁷ in different formulas can have different meanings.

где n означает число 2-10.If necessary, in the preparation of cycloolefin copolymers, a monocyclic olefin of the formula (XV) is also used

where n means the number 2-10.

где R²⁸ - R³¹ одинаковы или различны и означают атом водорода или углеводородный остаток с 1-20 атомами углерода, предпочтительно арильный остаток с 6-10 атомами углерода, и алкил с 1-8 атомами углерода. Предпочитается этилен.In addition, in the preparation of cycloolefin copolymers, one or more acyclic 1-olefins are used, preferably having the formula (IV)

where R ²⁸ - R ^{31 are the} same or different and mean a hydrogen atom or a hydrocarbon residue with 1-20 carbon atoms, preferably an aryl residue with 6-10 carbon atoms, and alkyl with 1-8 carbon atoms. Ethylene is preferred.

 In particular, copolymers of polycyclic olefins, preferably of formulas (IX) and (XI), are prepared using ethylene.

 Particularly preferred polycyclic olefins are norbornene and tetracyclodeodecene, which may be substituted with alkyl of 1-6 carbon atoms. They are preferably copolymerized with ethylene, with copolymers of ethylene and norbornene being of particular importance.

 A polycyclic olefin is used in an amount of from 0.1 to 99.9% by weight, a monocyclic olefin is used in an amount of from 0 to 99.9% by weight, and an acyclic olefin is used in an amount of from 0.1 to 99.9% by weight, each time in terms of the total number of monomers.

 The concentration of the acyclic olefin used depends on its solubility in the reaction medium at particular pressure and temperature.

 Polycyclic olefins, monocyclic olefins and acyclic olefins should also be understood as mixtures of two or more olefins of the corresponding type. That is, according to the proposed method, in addition to polycyclic copolymers, ternary polymers or polymers based on at least four monomers can also be obtained. In addition, copolymers of monocyclic and acyclic olefins can also be prepared by the above method.

 Among monocyclic olefins, cyclopentene, which may be substituted, is preferred.

The proposed method is preferably carried out at temperatures of -78 - 150 ^o C, in particular 0-100 ^o C, and a pressure of 0.01 - 64 bar.

 The polymerization is carried out in the medium of the liquid cycloolefin or in a solution of cycloolefin, moreover, it is advisable that the pressure exceeds 1 bar.

 In the preparation of the copolymers, the molar ratio of the polycyclic olefin to the open chain olefin used can vary widely. Preferably, the molar ratio of cycloolefin to open chain olefin is from 3: 1 to 100: 1. The amount of co-monomer incorporated can be adjusted to almost any extent by selecting the appropriate polymerization temperature, the concentration of catalyst components, the molar ratio and pressure of the open-chain olefin gas. Prefer the content of cyclic components in the range of 20 to 80 mol.%, In particular 40 to 60 mol. %

 The polymerization can also be carried out multistage, and block copolymers can also be obtained.

 The average molecular weight of the resulting polymer can also be adjusted in a known manner by dosing hydrogen, varying the concentration of the catalyst or varying the temperature.

The polydispersity M _w / M _{n of} cycloolefin copolymers has a value from 1.9 to 3.5, that is, it varies only within narrow limits. Due to this, these copolymers are particularly suitable for injection molding.

By the proposed method, it is possible to obtain amorphous copolymers of cycloolefins, not including partially crystalline ethylene polymers. These copolymers are transparent and solid, and they lend themselves to thermoplastic processing. Elongation at break (according to German industry standard DIN 53457) ranges from 50 to 100 MPa, preferably between 55 and 70 MPa. Both during extrusion and injection molding at a temperature of 300 ^° C, neither a decomposition reaction nor a decrease in viscosity is detected.

 The cyclooliphene copolymers obtained according to the invention are particularly suitable for the production of molded products, such as those obtained by extrusion of an article (for example, films, sleeves, pipes, rods and fibers) or obtained by injection molding of an article of any kind and size. The films may be extruded films, calendered sheets, irrigation films, mono- and biaxial oriented films, or multilayer films suitable, in particular, for food packaging or as draft packages. They have a high waterproofing effect and low gas permeability. The cycloolefin copolymers obtained according to the invention are also suitable as additives in other polymer films (in particular polyolefin films, such as polypropylene films or polyethylene films), for example, in order to improve flowability, improve varnishability, influence the modulus of elasticity and obtain opaque films.

 An important property of the cycloolefin copolymers obtained by the method according to the invention is their transparency. Therefore, the use of extruded or injection molded products from a cycloolefin copolymer in the field of optics is of particular importance. The refractive index determined using an Abbe refractometer and mixed light, the reaction products described in the following examples of reaction products is in the range of 1.520 to 1.555. Therefore, the refractive index only slightly differs from the refractive index of the crown (n = 1.51), so that the products according to the invention can be used instead of glass for various purposes, for example, as lenses, prisms, carrier plates and film substrates for optical memory, video plates, compact discs, as cover and focusing plates for solar cells, as cover and scattering glasses in the field of powerful optics, as radiation waveguides in the form of fibers or films.

 In a modified form with respect to toughness, the cycloolefin copolymers obtained by the method according to the invention can be used as structural materials in various technical fields.

Obtained by the method according to the invention, the copolymers of cycloolefins can also be used to obtain polymer alloys. Alloys can be obtained in melt or in solution. Each alloy has a combination of component properties that is beneficial for a particular application. For alloys including cycloolefin copolymers obtained by the method according to the invention, preferably the following polymers are used:
polyethylene, polypropylene, copolymers of ethylene and propylene, polybutylene, poly- (4-methyl-1-pentene), polyisoprene, polyisobutylene, natural rubber, poly- (methyl methacrylate), further polymethacrylates, polyacrylates, copolymers of acrylate and methacrylate, polystyrene, copolymers of styrene and acryl-nitrile, bis-phenol-A- polycarbonate, further polycarbonates, aromatic polyester carbonates, polyethylene terephthalate, polybutylene terephthalate, amorphous polyacrylates, polyamide-6, polyamide-66, further polyamides, polyaramides, polyethers ylene, polyoxyethylene, polyurethanes, polysulfones, polyethersulfones, polyvinylidene fluoride.

 The method according to the invention makes it possible to obtain, with high activity, in particular, transparent cycloolefin copolymers having high tensile strength.

The glass transition temperatures Tg indicated in the following examples were determined by differential scanning calometry at a heating rate of 20 ^° C./min. The specified viscosity coefficients were determined according to the German industry standard DIN 53728. The mechanical properties were measured by tensile elongation (according to the German industry standard DIN 50457, 4302).

Нижеследующие примеры служат для более подробного пояснения изобретения.The criterion for the activity of the catalyst is the polymer yield per unit time and mmol of metallocene:

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

 The preparation of organometallic 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 following examples explain not only the preparation of the target products of formula (I), but also their starting and intermediate products. For the name of the intermediate and target products, the nomenclature of SITF (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- (η ⁵ - 4,5,6,7-tetrahydroindenyl] -dichlorozirconium. A cyclic system that It is a 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.

А. Получение бис-фульвенов формулы (II)
Пример 1а
Синтез 2,5-бис-(2,4-циклопентадиен-1-илиден)гексана
11,0 г (96,3 ммоль) 2,5-гександиона и 12,7 г (193 ммоль) свежеполученного путем крекинга циклопентадиена растворяют в 60 мл метанола, охлаждают до 0^oC и смешивают с 8,60 г (121 ммоль) пирролидина. После 90-минутного перемешивания при 0^oC реакционный раствор гидролизуют 5 мл ледяной уксусной кислоты и 50 мл воды, подвергают двухкратному экстрагированию, каждый раз 70 мл диэтилового эфира, а объединенные органические фазы промывают насыщенным раствором хлористого натрия, сушат над сульфатом магния и растворитель удаляют в вакууме. Получают 18,0 г (89%) дифульвена в качестве маслянистого остатка оранжево-красного цвета.

A. Obtaining bis-fulvenes of the 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, extracted twice with 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 gave 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 bridged bis-cyclopentadienyl anions of formula (V)
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-butyl- (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 ^° C and, with vigorous stirring, slowly mixed with 94 ml (150 mmol) of a 1.60 M solution of 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 repeatedly with a saturated aqueous solution of sodium chloride and drying over magnesium sulfate
8.00 g (88%) of the desired 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 according to Example 1 dissolved in 100 ml of diethyl ether and 50 ml of tetrahydrofuran are added dropwise, stirring vigorously , at 0 ^° C. for an hour, a 0.60 M 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. Stirred for another 12 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-tetrahydro-indenyl) 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).

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-ylidene) hexane
To a solution of 10.0 g (47.5 mmol) of 2,5-bis- (2,4-cyclopentadiene-1-ylidene) hexane according to Example 1 in 150 ml of toluene is added slowly with vigorous stirring 62.4 ml (99.8 mmol) 1.60 M of an ethereal solution of methyl lithium at 0 ^° C. After the addition is complete, it is stirred for 24 hours at room temperature, then it is 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.

Example 13
Synthesis of both diastereomers of 4- (η ⁵ - cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorocirconium
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 (m, 5H, Ph-H); 6.78-6.73, 6.54-6.50, 6.22-6.20, 5.97-5.94 (4xm, 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 (2xs, 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 the 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 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 ).

Example 15
Synthesis of 4- (η ⁵ - cyclopentadienyl) -4,7-dimethyl-7-butyl- (η ⁵ - 4,5,6,7-tetrahydro-indenyl) 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 / 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 xm, 6H, ⁿ Bu-CH ₂ ); 0.84-0.76 million d. (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 circulating frit, 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 an 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 to 5'-H and 1-H to 3-H); 2.40-2.27, 1.89-1.75 (2x m, 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. In this case, 787 mg (23%) of the regioisomeric zirconocene dichlorides are obtained as an orange-yellow powder. According to 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 in a 1: 1 ratio are obtained.

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).

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 is added dropwise 3.30 ml (5.33 mmol) of 1.60 M methyl lithium ether solution at -78 ^° C. The reaction mixture allowed to slowly warm to room temperature in the bath of the cooling mixture and additionally 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 ) = 5.3 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 (2xs, 6H, 11-H and 12-H), 0.26 and 0.34 ppm (2xs, 6H, 13- CH ₃ and 14-CH ₃ ).

Mp: 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 g (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 (2xs, 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 96 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. Removal of the solvent in vacuo gives 5.04 g (55%) of yellow-orange powder allyl zirconocenes. 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 (2xs, 11-H (cis isomer) and 11-H (transisomer).

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 to -30 ^° C over several hours, whereby 208 mg (78%) of the 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)] - 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 analysand is 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.

b) Synthesis of {4- [3'-isopropyl- (η ⁵ - cyclopentadienyl)] - 4,7,7-trimethyl- (η ⁵ - 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 methyl lithium solution 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 effects 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 examination of ¹ H-NMR of the toluene phase shows that both diastereomers are in this phase in a 1: 1 ratio. By adding 2 ml of pentane and storage in a refrigerator at -20 ^° C, a yellow solid (1.42 g) is precipitated, in which one of the diastereomers is enriched (8: 1 ratio). In the toluene phase, another diastereomer (1.62 g) is enriched in inverse proportion; 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 4R ^* - {4- [3'-isopropyl- (η ⁵ - cyclopentadienyl)] -4 diastereomer, 7,7-trimethyl- (η ⁵ - 4,5,6,7-pR ^* -tetrahydroindenyl)} dichlorosirconium.

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)] - 4,7,7-trimethyl- [2-isopropyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl)]} dichlorozirconium
a) Synthesis of 4- (3'-isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (2-isopropyl-4,5,6,7-tetrahydro-1H-indene)
Option I
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 sequential 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 30 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 a 1.60 M ether solution of methyl lithium. 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.

e) {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 bis-isopropyl from step B of variant I or II in 20 ml of pentane was added dropwise 2.00 ml (3.22 mmol) of a 1.60 M methyl lithium ether solution at 0 ^° C. The reaction 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 ansa-zirconocene diastereomers are obtained 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, 2x 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, 4x ⁱ Pr-CH ₃ ).

Example 24
Synthesis of {4- [3'-trimethylsilyl- (η ⁵ - cyclopentadienyl)] - 4,7,7-trimethyl- [2-trimethyl-silyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl)]} dichlorozirconium
a) Synthesis of 4- (3'-trimethylsilyl-cyclopentadienyl) -4,7,7-trimethyl- (2-trimethylsilyl-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-trimethylsilyl (η ⁵ - 4,5,6,7-tetrahydroindenyl)]} dility
To a solution of 3.30 g (8.90 mmol) substituted by bis-trimethylsilyl compound from step a) cooled to 0 ^° C. in 40 ml of pentane, 11.1 ml (17.8 mmol) of 1.60 M methyl lithium ether are added dropwise with stirring . 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) of the substituted bis-trimethylsilyl 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. In these examples, the physicomechanical properties of the products are determined by the above industry standard terms.

Example 25
In an autoclave with a capacity of 1.5 dm ³ , previously thoroughly washed with ethene, 600 cm ^{3 of a} 85 wt.% Solution of norbornene in toluene are fed. By repeatedly pressing ethene (18 bar), the solution is saturated with ethene. After that, 5 cm ^{3 of a} toluene solution of methylaluminoxane (19.1 wt.% Solution of ethylaluminoxane with a molecular weight of 1300 g / mol determined by the cryoscopic method) is fed countercurrently and stirred for 30 minutes at 70 ^° C. After preliminary activation lasting 15 minutes a solution of 1.0 mg of 4- (η ⁵ - cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorocirconium in 5 cm ^{3 of a} toluene solution of methylaluminoxane is added. (In the case of controlling molecular weight with hydrogen, hydrogen can be pressed here).

With stirring (750 rpm) polymerized for an hour at 70 ^o C, and the ethene pressure by additional supply is kept at 18.0 bar.

After the reaction time, the polymerization mixture is released into the vessel and immediately fed into 5 dm ^{3 of} acetone, stirred for 10 minutes, and then the precipitated product is filtered off. The filter cake is washed three times alternately with 10% hydrochloric acid and acetone. Finally, it is washed with water until neutral, the precipitate is suspended in acetone and filtered again. The polymer thus purified was dried for 15 hours at 80 ^° C. in vacuo (0.2 bar).

After drying, 224 g of a colorless polymer having a glass transition temperature of 179 ^° C., a viscosity coefficient of 52 cm ³ / g, a tensile strength of 59 MPa and an elongation at break of 3.1% are obtained. Activity A ^* is 80512 g of polymer / h • mmol.

Example 26 (comparative example)
Example 25 is repeated with the difference that isopropylene (cyclopentadienyl) (1-indenyl) dichlorozirconium is used as the metallocene compound. Obtain 89 g of a polymer having a glass transition temperature of 150 ^o C, a viscosity coefficient of 57 cm ³ / g, a tensile strength of 61 MPa and an elongation at break of 3.3%. Activity A ^* is 34,000 g polymer / h • mmol.

Example 27
In an autoclave with a capacity of 1.5 dm ³ , previously thoroughly washed with ethene, 600 cm ^{3 of a} 85 wt.% Solution of norbornene in toluene are fed. By repeatedly pressing ethene (18 bar), the solution is saturated with ethene. After that, 5 cm ^{3 of a} toluene solution of methylaluminoxane (10.1 wt.% Ethylaluminoxane solution with a molecular weight of 1300 g / mol, determined by cryoscopy) is fed countercurrently and stirred for 30 minutes at 80 ^o C. After preliminary activation lasting 15 minutes a solution of 1.0 mg of 4- (η ⁵ - isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorocirconium in 5 cm ^{3 of a} toluene solution of methylaluminoxane is added. (In the case of controlling molecular weight with hydrogen, hydrogen can be pressed here).

With stirring (750 rpm) they polymerize for one hour, the ethene pressure being kept at 17.8 bar by means of an additional feed, and the temperature is kept at 80 ^o C.

After the reaction time, the polymerization mixture is released into the vessel and immediately fed into 5 dm ^{3 of} acetone, stirred for 10 minutes, and then the precipitated product is filtered off. The filter cake is washed three times alternately with 10% hydrochloric acid and acetone. Finally, it is washed with water until neutral, the precipitate is suspended in acetone and filtered again. The polymer thus purified was dried for 15 hours at 80 ^° C. in vacuo (0.2 bar).

After drying, 16.0 g of a colorless polymer having a glass transition temperature of 145 ^° C., a viscosity coefficient of 156 cm ³ / g, a tensile strength of 64 MPa and an elongation at break of 3.3% are obtained. Activity A ^* is 68300 g of polymer / h • mmol.

Example 28
In an autoclave with a capacity of 1.5 dm ^3, previously thoroughly washed with ethene, 600 cm ^{3 of a} 50 wt.% Solution of norbornene in toluene are fed. By repeatedly pressing ethene (18 bar), the solution is saturated with ethene. After this, 5 cm ^{3 of a} toluene solution of methylaluminoxane (10.1 wt.% Solution of ethylaluminoxane with a molecular weight of 1300 g / mol, determined by cryoscopy) is fed countercurrently and stirred for 30 minutes at 80 ^o C. After preliminary activation lasting 15 minutes add a solution of 0.2 mg of 4- (η ⁵ - isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorocirconium in 5 cm ^{3 of a} toluene solution of methylaluminoxane. (In the case of controlling molecular weight with hydrogen, hydrogen can be pressed here).

With stirring (750 rpm) they polymerize for one hour, the ethene pressure being kept at 17.8 bar by means of an additional supply and the temperature at 70 ^o C.

After the reaction time, the polymerization mixture is released into the vessel and immediately fed into 5 dm ^{3 of} acetone, stirred for 10 minutes, and then the precipitated product is filtered off. The filter cake is washed three times alternately with 10% hydrochloric acid and acetone. Finally, it is washed with water until neutral, the precipitate is suspended in acetone and filtered again. The polymer thus purified was dried for 15 hours at 80 ^° C. in vacuo (0.2 bar).

After drying, 98 g of a colorless polymer having a glass transition temperature of 184 ^° C., a viscosity coefficient of 114 cm ³ / g, a tensile strength of 61 MPa and a relative elongation at break of 3.1% are obtained. Activity A ^* is 104500 g of polymer / h • mmol.

Example 29
In an autoclave with a capacity of 1.5 dm ³ , previously thoroughly washed with ethene, 600 cm ^{3 of a} 50 wt.% Solution of norbornene in toluene are fed. By repeatedly pressing ethene (18 bar), the solution is saturated with ethene. After this, 5 cm ^{3 of a} toluene solution of methylaluminoxane (10.1 wt.% Solution of ethylaluminoxane with a molecular weight of 1300 g / mol, determined by cryoscopy) is fed countercurrently and stirred for 30 minutes at 80 ^o C. After preliminary activation lasting 15 minutes a solution of 1.0 mg of 4- (η ⁵ -isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorocirconium in 5 cm ^{3 of a} toluene methylaluminoxane solution is added. (In the case of controlling molecular weight with hydrogen, hydrogen can be pressed here.)
With stirring (750 rpm) they polymerize for one hour, the ethene pressure being kept at 17.8 bar by means of an additional supply and the temperature at 50 ^o C.

After the reaction time, the polymerization mixture is released into the vessel and immediately fed into 5 dm ^{3 of} acetone, stirred for 10 minutes, and then the precipitated product is filtered off. The filter cake is washed three times alternately with 10% hydrochloric acid and acetone. Finally, it is washed with water until neutral, the precipitate is suspended in acetone and filtered again. The polymer thus purified was dried for 15 hours at 80 ^° C. in vacuo (0.2 bar).

After drying, 31 g of a colorless polymer having a glass transition temperature of 121 ^° C., a viscosity coefficient of 203 cm ³ / g, a tensile strength of 65 MPa and an elongation at break of 3.3% are obtained. Activity A ^* is 13,200 g of polymer / h • mmol.

Example 30
In an autoclave with a capacity of 1.5 dm ^3, previously thoroughly washed with ethene, 600 cm ^{3 of a} 50 wt.% Solution of norbornene in toluene are fed. By repeatedly pressing ethene (18 bar), the solution is saturated with ethene. After that, 5 cm ^{3 of a} toluene solution of methylaluminoxane (10.1 wt.% Solution of ethylaluminoxane with a molecular weight of 1300 g / mol, determined by cryoscopy) is fed countercurrently and stirred for 30 minutes at 80 ^o C. After pre-activation for 15 minutes add a solution of 0.83 mg of 4- (η ⁵ - isopropyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorozirconium in 5 cm ^{3 of a} toluene methylaluminoxane solution. (In the case of controlling molecular weight with hydrogen, hydrogen can be pressed here).

With stirring (750 rpm) polymerized for an hour, and the pressure of ethene by additional supply is kept at 18.0 bar, and the temperature at 90 ^o C.

After the reaction time, the polymerization mixture is released into the vessel and immediately fed into 5 dm ^{3 of} acetone, stirred for 10 minutes, and then filtered
precipitated product. The filter cake is washed three times alternately with 10% hydrochloric acid and acetone. Finally, it is washed with water until neutral, the precipitate is suspended in acetone and filtered again. The polymer thus purified was dried for 15 hours at 80 ^° C. in vacuo (0.2 bar).

After drying, 45 g of a colorless polymer having a glass transition temperature of 130 ^° C., a viscosity coefficient of 107 cm ³ / g, a tensile strength of 62 MPa and an elongation at break of 3.2% are obtained. Activity A ^* is 24,200 g of polymer / h • mmol.

Example 31
Example 25 is repeated with the difference that 0.92 mg of 4- (η ⁵ -benzylcyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorocirconium is used. The polymerization temperature is 90 ^o C. Get 31 g of a polymer having the following properties: Tg = 141 ^o C, viscosity coefficient = 80 cm ³ / g, tensile strength = 63 MPa, elongation at break = 3.6%, A ^* = 18900 g of polymer / h • mmol.

Example 32
Example 25 is repeated with the difference that 1.0 mg of 4- (η ⁵ - cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) bis (dimethylamino) zirconium is used . Get 180 g of a polymer having the following properties: Tg = 169 ^o C, viscosity coefficient = 54 cm ³ / g, tensile strength = 59 MPa, elongation at break = 3.2%, A ^* = 71,900 g of polymer / h • mmol.

Example 33
Example 25 is repeated with the difference that 1.1 mg of 4- (η ⁵ - tert-butyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ - 4,5,6,7-tetrahydroindenyl) dichlorozirconium is used. Obtain 33 g of a polymer having the following properties: Tg = 124 ^o C, viscosity coefficient = 228 cm ³ / g, tensile strength = 64 MPa, elongation at break = 3.8% A ^* = 27400 g of polymer / h • mmol .

Example 34
On a twin-screw extruder, the polymer of Example 25 is converted at 260 ^° C. to the alloys indicated in the following table. This table provides data on the mechanical properties of the polymer and polymer alloys.

Claims (10)

1. A metallocene catalyst for producing a cycloolefin copolymer, which is a sterically rigid metallocene compound containing at least two substituted or unsubstituted cyclopentadienyl groups as ligands bonded to each other via a monocyclic ring system, with one cyclopentadienyl group being anellated to the monocyclic system, and this system ligands is different from 4- (η ⁵ -3-alkyl-cyclopentadienyl) -4,6,6-trimethyl- (η ⁵ -2-alkyl-4,5-tetragidropentalena) and a compound Fur uly (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 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 mean a hydrogen atom, alkyl with 1 to 10 carbon atoms, or the residue —R ¹³ —SiR ¹³ ₃ -, 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, 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 are 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 of producing a copolymer of cycloolefins by polymerizing at least one cycloolefin 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 claim 5, characterized in that the process is carried out in the presence of cocatalyst.  7. The method according to claim 6, characterized in that aluminoxane is used as a cocatalyst.  8. A polymer alloy comprising at least one copolymer of cycloolefins obtained by the method according to claims 5 to 7.  9. A molded product comprising at least one copolymer of cycloolefins obtained by the method according to claims 5 to 7.  10. A molded product comprising a polymer alloy according to claim 8. Priority on points:
12/21/1993 according to claims 1 to 4;
12/24/1993 according to claims 5-10.

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