JP2002527446A - Metallocenes with fixed bridges - Google Patents

Abstract

  (57) [Summary] Metallocenes with fixed crosslinking can be used as catalyst components for the production of polyolefins.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to metallocenes with fixed crosslinks and to a process for their preparation, and to their use as catalyst components for the production of polyolefins, excluding cyclic polyolefins.

[0002] Polyolefin production methods using soluble metallocenes in combination with aluminoxanes or other cocatalysts and the Lewis acidity of the cocatalysts allow the conversion of uncharged transition metal compounds to cations, Is known from the literature (EP-A129368, EP-A351392,
EP-A 416 815).

[0003] Metallocenes are of great interest not only for the polymerization or oligomerization of olefins. Metallocene can be hydrogenated, epoxidized, isomerized, C-C
It has also been used as a binding catalyst (Chem. Rev. 1992, 92, 965-994).

[0004] The use of soluble metallocene compounds based on the combination of bis (cyclopentadienyl) zirconium dialkyls or dihalides with oligomeric aluminoxanes has given rise to industrial importance due to unbalanced and unsatisfactory product properties Low,
An atactic polymer is obtained. Furthermore, certain olefin copolymers cannot be obtained. The polymerization properties of the metallocene compound can be controlled by the ligand system. Zirconocene dichloride derivatives in which two substituted cyclopentadienyl groups are linked to each other, for example by a methyl, ethyl or dimethylsilyl bridge, allow these conformations to be fixed for isomer-specific polymerization of olefins. It can be used as a catalyst (EP-A 316 155).

The object of the present invention is in particular the development of metallocenes having fixed bridges and a process for their preparation.

The present inventors have found that this object has been achieved by a bridged metallocene complex having a fixed bridge, and can be achieved by the following production method.

The present invention therefore provides an organometallic compound of formula I.

[0008]

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[Where M is a metal of Group 3, 4, 5, or 6 of the periodic table or a lanthanide;
Or actinide, R¹, R⁵May be the same or different, and each represents a hydrogen atom or C₁~ C_{4 0} Group, e.g., methyl, ethyl, tert-butyl, cyclohexyl, or octyl
Chill, C₂~ C₂₅Alkenyl, C₃~ C_FifteenAlkyl alkenyl, C₆~ C_{2 4} Aryl, C₅~ C₂₄Heteroaryl (eg pyridyl, furyl or quino
Lil), C₇~ C₃₀Arylalkyl, C₇~ C₃₀Alkyl aryl,
Chemical C₁~ C₂₅Alkyl, fluorinated C₆~ C₂₄Aryl, fluorinated C₇~ C₃₀A
Reel alkyl, C₇~ C₄₀Arylalkenyl, C fluoride₇~ C₃₀Archi
Ruaryl, C₁~ C₁₂Alkoxy or C₁~ C₁₂Amino or SiR ⁶ Group (however, R⁶May be the same or different and each represents a hydrogen atom or C₁~
C₄₀Group, preferably C₁~ C₂₀Alkyl, C₁~ C₁₀Fluoroalkyl
, C₁~ C₁₀Alkoxy, C₆~ C₂₀Aryl, C₆~ C₁₀Fluoroant
, C₆~ C₁₀Aryloxy, C₂~ C₁₀Alkenyl, C₇~ C₄₀A
Reel alkyl, C₇~ C₄₀Alkylaryl or C₈~ C₄₀Aryla
Represents lukenyl. ) Or two or more groups R¹Or R⁵Is a group R¹Or R⁵ And the atoms of the cyclopentadienyl ring to which they are attached may be substituted.
C₄~ C₂₄May be linked to each other in such a way as to form a ring,

M represents 0, 1, 2, 3 or 4; p represents 0, 1, 2, 3 or 4;²And R³May be the same or different, and each represents a hydrogen atom or C₁~
C₄₀Groups such as methyl, ethyl, tert-butyl, cyclohexyl, or
Cutil, C₂~ C₂₅Alkenyl, C₃~ C_FifteenAlkyl alkenyl, C₆~ C ₂₄ Aryl, C₅~ C₂₄Heteroaryl, C₇~ C₃₀Arylalkyl,
For example pyridyl, furyl or quinolyl, C₇~ C₃₀Alkyl aryl,
Chemical C₁~ C₂₅Alkyl, fluorinated C₆~ C₂₄Aryl, fluorinated C₇~ C₃₀A
Reel alkyl, C₇~ C₄₀Arylalkenyl, C fluoride₇~ C₃₀Archi
Ruaryl, C₁~ C₁₂Alkoxy or C₁~ C₁₂Amino or SiR ⁶ Group (however, R⁶May be the same or different and each represents a hydrogen atom or C₁~
C₄₀Group, preferably C₁~ C₂₀Alkyl, C₁~ C₁₀Fluoroalkyl
, C₁~ C₁₀Alkoxy, C₆~ C₂₀Aryl, C₆~ C₁₀Fluoroant
, C₆~ C₁₀Aryloxy, C₂~ C₁₀Alkenyl, C₇~ C₄₀A
Reel alkyl, C₇~ C₄₀Alkylaryl or C₈~ C₄₀Aryla
Represents lukenyl. ) Or two or more groups R¹Or R⁵Is a group R¹Or R⁵ And the atoms of the cyclopentadienyl ring to which they are attached may be substituted.
C₄~ C₂₄May be linked to each other in such a way as to form a ring;⁴Is NR⁷R⁸Group ｛where R⁷And R⁸May be the same or different
, Each hydrogen atom or C₁~ C₄₀Groups (eg, methyl, ethyl, tert-butyl
, Cyclohexyl, or octyl, C₂~ C₂₅Alkenyl, C₃~ C_FifteenA
Alkenylalkenyl, C₆~ C₂₄Aryl, C₅~ C₂₄Heteroaryl, for example
Pyridyl, furyl or quinolyl, C₇~ C₃₀Arylalkyl, C₇~ C ₃₀ Alkyl aryl, fluorinated C₁~ C₂₅Alkyl, fluorinated C₆~ C₂₄Ants
, Fluoride C₇~ C₃₀Arylalkyl, C₇~ C₄₀Arylalkenyl
, Fluoride C₇~ C₃₀Alkylaryl, C₁~ C₁₂Alkoxy or C₁~
C₁₂Amino) or a group R⁷And R⁸Is an optionally substituted C₄~ C_{2 4} They may be connected to each other to form a ring. Represents n, 0 represents 1, 1, 2, 3 or 4; X may be the same or different;₁~ C₁₀Alkyl group
, C₁~ C₁₀Alkoxy group, C₆~ C₁₀Aryl group, C₆~ C₁₀Aryl
Oxy group, C₂~ C₁₀Alkenyl group, C₇~ C₄₀Arylalkyl group, C₇ ~ C₄₀Alkylaryl group, C₈~ C₄₀Aryl alkenyl group, OH group or
Represents a halogen atom. ]

The organometallic compound of the present invention will be described, but this does not limit the present invention. 9-N, N-dimethylamino-trans-6,9-bis (cyclopentadienyl)
Butadienyldichlorotitanium, 9-N-pyrrolidino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorohafnium, 9-N, N-dimethylamino-trans-6,9-bis (cyclopentane Dienyl)
Butadienyl dichlorohafnium, 9-N, N-dimethylamino-trans-6,9-bis (cyclopentadienyl)
Butadienyldichlorozirconium, 9-N-morpholino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium, 9-N-pyrrolidino-trans-6,9-bis (cyclopentadienyl) Butadienyldichlorozirconium, 9-N, N-diethylamino-trans-6,9-bis (cyclopentadienyl)
Butadienyldichlorozirconium, 9-N, N-ethylpropylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium,

9-N, N-methyl-tert-butylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium 9-N, N-diethylamino-trans-6,9-bis ( Cyclopentadienyl)
Butadienyldichlorotitanium, 9-N, N-ethylpropylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorotitanium, 9-N, N-methyl-t-butylamino-trans- 6,9-bis (cyclopentadienyl) butadienyldichlorotitanium, 9-N, N-diethylamino-trans-6,9-bis (cyclopentadienyl)
Butadienyldichlorohafnium, 9-N, N-ethylpropylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorohafnium, 9-N, N-methyl-t-butylamino-trans- 6,9-bis (cyclopentadienyl) butadienyldichlorohafnium, 9-N, N-dimethylamino-trans-6,9-bis (indenyl) butadienyldichlorozirconium, 9-N-morpholino-trans- 6,9-bis (indenyl) butadienyldichlorozirconium, 9-N-pyrrolidino-trans-6,9-bis (indenyl) butadienyldichlorozirconium, 9-N, N-diethylamino-trans-6,9- Bis (indenyl) butadienyldichlorozirconium, 9-N, N-ethylpropylamino-trans-6,9-bis (a Ndenyl) butadienyldichlorozirconium, 9-N, N-methyl-tert-butylamino-trans-6,9-bis (indenyl) butadienyldichlorozirconium, 9-N, N-dimethylamino-trans-6 9-bis (2-methylindenyl)
Butadienyldichlorozirconium,

9-N-morpholino-trans-6,9-bis (2-methylindenyl) butadienyldichlorozirconium, 9-N-pyrrolidino-trans-6,9-bis (2-methylindenyl) buta Dienyldichlorozirconium, 9-N, N-diethylamino-trans-6,9-bis (2-methylindenyl)
Butadienyldichlorozirconium, 9-N, N-ethylpropylamino-trans-6,9-bis (2-methylindenyl) butadienyldichlorozirconium, 9-N, N-methyl-t-butylamino-trans -6,9-bis (2-methylindenyl) butadienyldichlorozirconium, 9-N, N-dimethylamino-trans-6,9-bis (2-methyl-4-phenylindenyl) butadienyldichloro Zirconium, 9-N-morpholino-trans-6,9-bis (2-methyl-4-phenylindenyl) butadienyldichlorozirconium, 9-N-pyrrolidino-trans-6,9-bis (2-methyl- 4-phenylindenyl) butadienyldichlorozirconium, 9-N, N-diethylamino-trans-6,9-bis (2-methyl-4-phenyl Indenyl) butadienyldichlorozirconium, 9-N, N-ethylpropylamino-trans-6,9-bis (2-methyl-4-
Phenylindenyl) butadienyldichlorozirconium, 9-N, N-methyl-t-butylamino-trans-6,9-bis (2-methyl-4
-Phenylindenyl) butadienyldichlorozirconium, 9-N, N-dimethylamino-trans-6,9-bis (2-ethyl-4- (4'-
t-butylphenyl) indenyl) butadienyldichlorozirconium, 9-N-morpholino-trans-6,9-bis (2-ethyl-4- (4′-t-butylphenyl) indenyl) butadienyldichlorozirconium, 9-N-pyrrolidino-trans-6,9-bis (2-ethyl-4- (4'-t-butylphenyl) indenyl) butadienyldichlorozirconium;

9-N, N-diethylamino-trans-6,9-bis (2-ethyl-4- (4′-
t-butylphenyl) indenyl) butadienyldichlorozirconium, 9-N, N-ethylpropylamino-trans-6,9-bis (2-ethyl-4-
(4′-t-butylphenyl) indenyl) butadienyldichlorozirconium,
9-N, N-methyl-t-butylamino-trans-6,9-bis (2-ethyl-4
-(4'-t-butylphenyl) indenyl) butadienyldichlorozirconium, 9-N, N-dimethylamino-trans-6,9-bis (2-methylbenzoindenyl) butadienyldichlorozirconium, 9- N-morpholino-trans-6,9-bis (2-methylbenzoindenyl) butadienyldichlorozirconium, 9-N-pyrrolidino-trans-6,9-bis (2-methylbenzoindenyl) butadienyldichloro Zirconium, 9-N, N-diethylamino-trans-6,9-bis (2-methylbenzoindenyl) butadienyldichlorozirconium, 9-N, N-ethylpropylamino-trans-6,9-bis (2 -Methylbenzoindenyl) butadienyldichlorozirconium, 9-N, N-methyl-t-butylamino-trans-6,9-bi (2-methylbenzoindenyl) butadienyl dichloro zirconium.

The preparation of the novel compounds of the formula I has been described by way of example according to the following reaction scheme.

[0016]

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In this scheme, M ¹ = M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, m, p
, And n are as defined in Formula I above, and m + p can represent 0, 1, 2, 3, or 4.

[0018] Suitable bases are strong bases such as lithium diisopropylamide, lithium hexamethyldisilazide, methyllithium, butyllithium, potassium tert-butoxide or potassium hydride. The reaction is carried out at -50 ° C to + 150 ° C, preferably at 0 ° C to 100 ° C. Suitable solvents for carrying out the reactions described are aliphatic or aromatic hydrocarbons, which may be halogenated, such as pentane, hexane, cyclohexane, methylene chloride, dichloroethane, benzene,
Toluene, xylene, chlorobenzene, dichlorobenzene, diethyl ether,
Ethers such as dibutyl ether, tetrahydrofuran, anisole, dioxane, 1,2-dimethoxyethane (but other solvents are also possible).
). It is also possible to use mixtures of two or more solvents. The reaction takes 1 minute to 2
It takes 0 days. The novel compounds of the formula I are used in isolation or directly.
The compound of formula (II) in the above scheme can be isolated or used directly in the next reaction. The new compounds of the formula I can also be prepared in a single vessel without isolation of intermediates and end products.

The transition metal compound of the present invention is a highly active catalyst component for olefin polymerization.
Depending on the mode of ligand substitution, the transition metal compound can be formed as a mixture of isomers. Preferably, the transition metal compound is used as a pure isomer, but can also be used as a mixture of isomers.

The present invention further provides a process for producing a polyolefin by polymerizing one or more olefins in the presence of a catalyst composition comprising at least one transition metal compound according to the invention and at least one cocatalyst. provide. In the present invention, the term polymerization includes both homopolymerization and copolymerization.

In the method of the present invention, the formula R ^a —CH ＝ CH—R ^b (where R ^a and R ^b may be the same or different and are each a hydrogen atom, or 1 to 20 carbon atoms, In particular, it represents a hydrocarbon radical having 1 to 10 carbon atoms or R ^a and R ^b combine with the atoms to which they are attached to form one or more rings.
It is preferred to polymerize at least one olefin. Examples of such olefins are
1-olefins having 1 to 20 carbon atoms, such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, or acyclic dienes; Examples include 1,3-butadiene, isoprene, 1,4-hexadiene, cyclic olefins, such as norbornene. In the process of the present invention, homopolymerization of propylene or copolymerization of propylene with one or more acyclic 1-olefins having 4 to 20 carbon atoms is preferred.

The polymerization is preferably from -78 ° C. to 250 ° C., particularly preferably from 50 to 200 ° C.
It is done in. The pressure is preferably from 0.5 × 10 ⁵ to 2000 × 10 ⁵ Pa, particularly preferably from 5 × 10 ⁵ to 64 × 10 ⁵ Pa.

The polymerization is carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise,
It can be performed in one stage or in multiple stages.

The catalyst used in the process of the present invention preferably contains one transition metal compound. For example, it is also possible to use mixtures of two or more transition metal compounds for the production of polyolefins having a broad or multimodal molecular weight distribution.

As a cocatalyst in the process according to the invention, in principle any compound is used which converts an uncharged transition metal compound into a cation and stabilizes it (reactive coordination) due to its Lewis acidity. be able to. Furthermore, it is more likely that the cocatalysts or the anions formed therefrom no longer react with the cations formed (EP 427697). As co-catalysts WO 9711775 and German Patent Applications P196325577.9, P1973317.7 or P19744
It is preferred to use aluminum compounds and / or boron compounds as described in 102.5, which are incorporated herein by reference.

The boron compound is preferably of the formula R¹² _xNH_4-xBR¹³ ₄, R¹² _xPH _4-x BR¹³ ₄, R¹² ₃CBR¹³ ₄Or BR¹³ ₃It is represented by However,
x represents 1 to 4, preferably 3, and the radical R¹²May be the same or different
, Preferably identical, each with C₁~ C₁₀Alkyl or C₆~ C₁₈Ally
Or two groups R¹²Combines with the atoms to which they are attached to form a ring, and the group R ¹³ May be the same or different, are preferably the same, and each is an alkyl,
C optionally substituted by haloalkyl or fluorine₆~ C₁₈Aryl
Represent. Especially R¹²Is ethyl, propyl, butyl or phenyl, and R¹³ Is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl
Or mesityl, xylyl or tolyl (EP-A-0277003, EP
-A-0277004, EP-A-0426638).

It is preferable to use aluminoxanes and / or alkylaluminums as cocatalysts.

Particularly preferred as co-catalyst is aluminoxane (R ¹⁴ AlO) _z , which is cyclic and / or linear, wherein R ¹⁴ may be the same or different and are each hydrogen or C ₁ -C _20. hydrocarbon groups such as _C 1 _{-C 18} alkyl _{group, C} 6 ~
Represents a C ₁₈ aryl group or a benzyl group, and z represents an integer of 2 to 50, preferably an integer of 10 to 35.

The radicals R ¹⁴ are preferably identical and represent hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.

[0030] Methods for producing aluminoxanes are known. The exact spatial structure of the aluminoxane is not known (J. Am. Chem. Soc. (1993) 115,4971). For example, it can be imagined that the chain has a huge two-dimensional or three-dimensional structure by being chain-like or connected to form a ring.

Regardless of the method of preparation, all aluminoxane solutions contain varying amounts of unreacted aluminum starting compound present in a single form or in the form of an adduct.

The transition metal compound can be preactivated with a cocatalyst, especially an aluminoxane, before using it in the polymerization reaction. This clearly increases the polymerization activity. The preactivation of the transition metal compound is preferably performed in a solution. Preferably, the transition metal compound is dissolved in an aluminoxane solution in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Preference is given to using toluene.

The concentration of the aluminoxane in the solution ranges from about 1% by weight to the limit of saturation, preferably from 5 to 30% by weight, based on the total amount of the solution. The transition metal compound can be used in the same concentration, but it is preferable to use an amount of 10 ^-4 to 1 mol per 1 mol of aluminoxane. The pre-activation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. Preactivation is performed at -78 to 150 ° C,
To 80 ° C.

The transition metal compound is based on the transition metal, from 10 ⁻³ to 10 ⁻⁸ mol, preferably from 10 ⁻⁴ to 10 ⁻⁷ mol, based on 1 dm ³ of the solvent or 1 dm ³ of the volume of the reactor. It is preferable to use at a transition metal concentration of Aluminoxanes for preferably or reactor volume 1 dm ³ relative to solvent 1 dm ^3, 10 ^{- 6} to ^{10 -1} mole, preferably it is used at a concentration of ^{10 -2} mol to ^{10 -5.} The other mentioned cocatalysts use approximately equimolar amounts relative to the transition metal compound. However, it is also possible in principle to use high concentrations.

To remove the catalyst poisons present in the olefin, purification using an aluminum compound, preferably an alkyl aluminum such as trimethylaluminum or triethylaluminum, is advantageous. The purification can be carried out in the polymerization system itself or by contacting the olefin with an aluminum compound and then separating it again before introducing it into the polymerization system.

As additives, a small amount of an α-olefin such as styrene as an activity promoting component or a small amount of an antistatic agent described in US Application No. 08/365280, during the preparation of the metallocene / cocatalyst mixture, or Can be added after manufacture.

Hydrogen can be added in the process according to the invention as molar mass regulator and / or for increasing the catalytic activity. Thereby, a low molecular weight polyolefin such as wax can be obtained.

In the method of the present invention, prepolymerization with a transition metal compound is performed.
zation) can be performed. The prepolymerization is preferably carried out using one of the olefins or olefins used for the polymerization.

[0039] A carrier can be used for the catalyst used in the method of the present invention. The application of the carrier makes it possible, for example, to control the morphology of the polyolefin particles produced. The transition metal compound is first reacted with the support and then with the cocatalyst. The co-catalyst can be loaded first and then reacted with the transition metal compound.
It is also possible to apply the reaction product of the transition metal compound and the cocatalyst to the support. Suitable carrier materials include, for example, other inorganic carrier materials such as silica gel, aluminum oxide, solid aluminoxane or magnesium chloride. Other suitable carrier materials are polyolefin fine form powders. The production of supported cocatalysts is described, for example, in WO 97/117775, EP-A-0567952, EP-A-0578.
838, P1963255.58.7, P1963434703.3, P19664707
0.6, 19757540.4 or P19804970.6.

Preferably, a cocatalyst such as, for example, an aluminoxane is applied to a carrier, such as silica gel, aluminum oxide, solid aluminoxane, another inorganic carrier material or a powder in finely divided form of a polyolefin, and then reacted with the transition metal compound. Is preferred.

As the inorganic carrier, it is possible to use an oxide which is produced by pyrolysis by burning a halogen element in a hydrogen / oxygen flame. The oxide can also be manufactured as silica gel with a particular particle size distribution and particle shape.

Further possible processes for the preparation of the supported cocatalyst are described in EP-A-0578838. The transition metal compound of the present invention can be applied to a supported cocatalyst by stirring a dissolved transition metal compound with a supported cocatalyst. The solvent is removed and replaced with a hydrocarbon in which both the cocatalyst and the transition metal compound are insoluble.

The reaction for forming the supported catalyst composition is carried out at a temperature of -20 to + 120 ° C., preferably 0 to 10 ° C.
It is carried out at 0 ° C., particularly preferably at 15 to 40 ° C. The transition metal compound is reacted with the cocatalyst by combining the cocatalyst at a concentration of 1 to 40% by weight, preferably 5 to 20% by weight. A suspension of the cocatalyst in an aliphatic inert suspending medium such as, for example, n-decane, hexane, heptane, diesel oil, toluene, hexane,
It is reacted with a solution of the transition metal in an inert solvent such as heptane, dichloromethane or with a finely ground solid of the transition metal compound. Conversely, a solution of the transition metal can be reacted with a solid cocatalyst.

The reaction is carried out by vigorous stirring, for example, by removing Al / catalyst from 100/1 to 1
Together in a molar ratio of 0000/1, preferably 100/1 to 3000/1,
5 to 120 minutes, preferably 10 to 60 minutes, particularly preferably 10 to 3 minutes
It is carried out by stirring for 0 minutes under inert conditions.

In the course of the reaction for the production of the supported catalyst composition, a change in the color of the reaction mixture occurs, especially when the transition metal compound of the present invention is used, which has an absorption maximum in the visible region. It allows to follow the progress of the reaction.

After the reaction time has elapsed, the supernatant is removed by filtration or decantation. The remaining solid is removed 1 to 5 times to remove soluble components in the formed catalyst.
Washing with an inert suspending medium such as toluene, n-decane, hexane, diesel oil, dichloromethane, etc., in order to remove the transition metal compound which is soluble in particular due to unreacted components.

The supported catalyst composition thus prepared is dried under reduced pressure or resuspended while still moist with solvent and polymerized as a suspension of one of the abovementioned inert suspension media. It can be introduced into the system.

If the polymerization is carried out as a suspension or solution polymerization, the inert solvents customary in the Ziegler low-pressure process are used. For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon such as, for example, propane, butane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane. Petroleum fractions or hydrogenated diesel fractions can also be used. Toluene can also be used. It is preferred to carry out the polymerization in a liquid monomer.

Before adding the catalyst, the supported catalyst composition (including the transition metal compound of the present invention and the supported cocatalyst, or the transition metal compound of the present invention and the organoaluminum on finely divided polyolefin powder) is preferably added. Prior to addition, another alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, triisooctylaluminum or isoprenylaluminum is additionally introduced into the reactor to render the polymerization system inert (for example, in olefins). To remove existing catalyst poisons). This means that Al is added to the polymerization system at a concentration of 100 to 0.01 mmol per 1 kg of the contents of the reactor. Triisobutylaluminum and triethylaluminum are added in an amount of from 10 to 0.1
It is preferred to add a millimolar concentration of aluminum. This allows a small molar ratio of Al / catalyst to be selected in the synthesis of the supported catalyst composition.

If an inert solvent is used, the monomers are introduced in gaseous or liquid form.

The polymerization time is freely selected, since the catalyst composition used in the process of the invention shows only a slight decrease in polymerization activity over time.

[0052]

【Example】

General procedure: The preparation and handling of organometallic compounds was carried out under argon and air-free conditions (Schlenk method). All necessary solvents were dried by boiling over a suitable desiccant for several hours before use, followed by distillation under argon.

Compounds were identified by DSC, ¹ H-NMR, ¹³ C-NMR or IR spectroscopy.

Example 1 Preparation of 6-Methyl-6′-dimethylaminofulvene 126 g of dimethyl sulfate are slowly added dropwise at 87 ° C. to 87.12 g of N, N-dimethylacetamide. The mixture is stirred at 70-80 ° C. for a further 2 hours. The resulting oil is added at −10 ° C. to 80.1 g of a solution of sodium cyclopentadienide in tetrahydrofuran, keeping the internal temperature below −5 ° C. After the addition is complete, the mixture is stirred at room temperature for 2 hours. The resulting sodium methyl sulfate is filtered off and the solvent is removed using a vacuum oil pump. A brown oil is obtained, to which 6 g of activated carbon and 400 ml of cyclohexane are added, the mixture is heated and filtered hot. The product precipitates out, is filtered off and the residual solvent is eliminated with a vacuum oil pump. Yield: 69 g of 6-methyl-6'-N, N-dimethylaminofulvene Melting point: 87.5 ° C (DSC)

Example 2 Preparation of 6-methyl-6′-N, N-pyrrolidinoaminofulvene 10.52 g of 6-methyl-6′-N, N-dimethylaminofulvene was taken up in 150 m
Reflux with 1 l of pyrrolidine for 5 days. The solvent is then removed by a rotary evaporator. Yield: 12.3 g of 6-methyl-6'-N, N-pyrrolidinoaminofulvene Melting point: 142.1 ° C (DSC)

Example 3 Preparation of 6-Methyl-6′-N, N-morpholinoaminofulvene 10 g of 6-methyl-6′-N, N-dimethylaminofulvene are refluxed with 150 ml of morpholine for 5 days. The solvent is then removed on a rotary evaporator. Yield: 13 g of 6-methyl-6'-N, N-morpholinoaminofulvene

[0057]

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¹ H-NMR (200.1 MHz, d ₁ -chloroform): δ = 6.60-6.
27 (m, 4H, Cp-H), 3.85-3.64 (m, 8H, 8 / 8'-H and 9 / 9'-H), 2.42 (s, 3H, 7-H). ppm

Example 4: (6-Dimethylamino-5-vinyl) cyclopentadienyllithium At -78 ° C., a suspension of 6 g of 6-methyl-6′-dimethylaminofulvene in 80 ml of tetrahydrofuran was treated with methyl Mix with 27.7 ml of a 1.6 M solution of lithium diethyl ether. The mixture dissolves slowly and is stirred for 12 hours at room temperature. The resulting solution was evaporated using a vacuum oil pump and two additional portions with pentane.
Stir for hours. The mixture is allowed to stand and the pentane layer is decanted off. The precipitate is dried with a vacuum oil pump. Yield: 7 g of (6-dimethylamino-5-vinyl) cyclopentadienyl lithium (89%)

[0060]

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¹ H-NMR (200.1 MHz, d ₆ -benzene / d ₈ -tetrahydrofuran 8: 1): δ = 6.28-6.25 (m, 2H, Cp-H), 6.07-6 .
^{04 (m, 2H, Cp-} H), 4.33 (d, 2 J = 1Hz, 1H, 7-H),
3.91 (d, ² J = 1 Hz, 1H, 7′-H), 2.77 (s, 6H, 8-H)
/ 8'-H) ppm

Example 5 Preparation of (6-Pyrrolidino-5-vinyl) cyclopentadienyl Lithium At −78 ° C., 5 g of 6-methyl-6′-N in 80 ml of tetrahydrofuran
, N-pyrrolidinoaminofulvene are mixed with 19.5 ml of a 1.6 M solution of methyllithium in diethyl ether. The mixture dissolves slowly and is stirred for 12 hours at room temperature. The solution obtained is evaporated using a vacuum oil pump and stirred with pentane for a further 2 hours. The mixture is allowed to stand and the pentane layer is decanted off. The precipitate is dried with a vacuum oil pump. Yield: 5.14 g of (6-pyrrolidino-5-vinyl) cyclopentadienyl lithium (98%)

[0063]

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¹ H-NMR (200.1 MHz, d ₆ -benzene / d ₈ -tetrahydrofuran 8: 1): δ = 6.23-6.20 (m, 2H, Cp-H), 6.02-5 .
^{99 (m, 2H, Cp-} H), 4.04 (d, 2 J = 1Hz, 1H, 7-H),
3.73 (d, ² J = 1 Hz, 1H, 7'-H), 3.53-3.47 (m, 4
H, 8-H / 8'-H), 1.68-1.58 (m, 4H, 9-H / 9'-H) p
pm

Example 6 Preparation of (6-morpholino-5-vinyl) cyclopentadienyllithium At −78 ° C., 6-methyl-6′-N, N- in 80 ml of tetrahydrofuran
A suspension of 6.94 g of morpholinoaminofulvene is mixed with 24 ml of a 1.75 M solution of methyllithium in diethyl ether. The mixture dissolves slowly and is stirred for 12 hours at room temperature. The solution obtained is evaporated using a vacuum oil pump and stirred with pentane for a further 2 hours. The mixture is allowed to stand and the pentane layer is decanted off. The precipitate is dried with a vacuum oil pump. Yield: 7.07 g of (6-morpholino-5-vinyl) cyclopentadienyl lithium (92%)

[0066]

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¹ H-NMR (200.1 MHz, d ₆ -benzene / d ₈ -tetrahydrofuran 8: 1): δ = 6.14-6.12 (m, 2H, Cp-H), 5.96-9 .
^{92 (m, 2H, Cp-} H), 4.23 (d, 2 J = 1Hz, 1H, 7-H),
^{3.79 (d, 2 J = 1Hz} , 1H, 7'-H), 3.64-3.60 (m, 4
H, 9-H / 9'-H), 3.0-2.96 (m, 4H, 8-H / 8'-H) pp
m

Example 7 9-N, N-Dimethylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium At -78 ° C., 5.29 g of (29 g in 60 ml of diethyl ether 6-N, N-dimethylamino-5-vinyl) cyclopentadienyllithium is mixed with 4.37 g of zirconium tetrachloride. The mixture dissolves slowly and is stirred at room temperature for 12 hours. The precipitate obtained is filtered off and washed with a little diethyl ether and then a little dichloromethane. The filtrate is evaporated to dryness in a vacuum oil pump. Recrystallization from diethyl ether gives 2.32 g (32%) of 9-N, N-dimethylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium.

[0069]

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¹ H-NMR (200.1 MHz, d ₁ -chloroform): δ = 6.74-6.
69 (m, 4H, Cp-H), 6.13-6.10 (m, 2H, Cp-H), 6
. 08-6.05 (m, 2H, Cp-H), 5.6 (ps, 1H, 8-H), 4
. 80 (m, 1H, 7-H), 4.74 (m, 1H, 7'-H), 2.07 (s
, 6H, 11-H / 11'-H) ppm

Example 8 Preparation of 9-N-Pyrrolidino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium At −78 ° C., 3 g of (6- Pyrrolidino-5
-Vinyl) cyclopentadienyllithium is mixed with 2.1 g of zirconium tetrachloride. The mixture dissolves slowly and is stirred at room temperature for 12 hours. The precipitate obtained is filtered off and washed with a little diethyl ether and then a little dichloromethane. The filtrate is evaporated to dryness in a vacuum oil pump. Recrystallize from toluene;
55 g (69%) of 9-N-pyrrolidino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium are obtained.

[0072]

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¹ H-NMR (200.1 MHz, d ₁ -chloroform): δ = 6.74-6.
71 (m, 2H, Cp-H), 6.69-6.66 (m, 2H. Cp-H), 6
. 18-6.66 (m, 2H, Cp-H), 6.18-6.16 (m, 2H, C
p-H), 6.09-6.06 (m, 2H, Cp-H), 5.44 (ps, 1H)
, 8-H), 4.92 (m, 1H, 7-H), 4.84 (ps, 1H, 7'-H).
), 3.03-2.97 (m, 4H, 11-H / 11'-H), 1.90-1.
83 (12-H / 12'-H) ppm

Example 9 Preparation of 9-N-morpholino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium At −78 ° C., 3.5 g of ( 6-morpholino-5-vinyl) cyclopentadienyl lithium is mixed with 2.23 g of zirconium tetrachloride. The mixture dissolves slowly and is stirred at room temperature for 12 hours. The precipitate obtained is filtered off and washed with a little diethyl ether and then a little dichloromethane. The filtrate is evaporated to dryness in a vacuum oil pump. Recrystallisation from toluene gives 897 mg (22%) of 9-N-morpholino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium.

[0075]

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¹ H-NMR (200.1 MHz, d ₁ -chloroform): δ = 6.75-6.
71 (m, 4H, Cp-H), 6.17-6.14 (m, 2H, Cp-H), 6
. 05-6.14 (m, 2H, Cp-H), 6.05-6.02 (m, 2H, C
pH), 5.73 (ps, 1H, 8-H), 5.09-5.07 (m, 1H,
7-H), 5.00-4.98 (m, 1H, 7'-H), 3.77-3.69 (
m, 4H, 12-H / 12'-H), 2.84-2.79 (m, 4H, 11-H
/ 11'-H) ppm

Example 10 Preparation of 9-N, N-Dimethylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorohafnium 1.5 g in 60 ml of diethyl ether at −78 ° C. Of (6-N, N-dimethylamino-5-vinyl) cyclopentadienyl lithium is mixed with 1.7 g of hafnium tetrachloride. The mixture dissolves slowly and is stirred at room temperature for 12 hours. The precipitate obtained is filtered off and washed with a little diethyl ether and then a little dichloromethane. The filtrate is evaporated to dryness in a vacuum oil pump. Recrystallization from diethyl ether gave 1.48 g (59%) of 9-N, N-dimethylamino-trans
-6,9-Bis (cyclopentadienyl) butadienyldichlorohafnium is obtained.

[0078]

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¹ H-NMR (200.1 MHz, d ₁ -chloroform): δ = 6.63-6.
57 (m, 4H, Cp-H), 6.04-6.02 (m, 2H, Cp-H), 5
. 96-5.93 (m, 2H, Cp-H), 5.58 (ps, 1H, 8-H),
4.96 (ps, 1H, 7-H), 4.91 (m, 1H, 7'-H), 2.60
(S, 6H, 11-H / 11'-H) ppm

Example 11 Preparation of 9-N-Pyrrolidino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorohafnium 1.5 g of 6-g in 60 ml of diethyl ether at −78 ° C. Pyrrolidino-5
The vinylcyclopentadienyl lithium is mixed with 1.44 g of hafnium tetrachloride. The mixture dissolves slowly and is stirred at room temperature for 12 hours. The precipitate obtained is filtered off and washed with a little diethyl ether and then a little dichloromethane. The filtrate is evaporated to dryness in a vacuum oil pump. Recrystallization from diethyl ether gives 1.08 g (49%) of 9-N-pyrrolidino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorohafnium.

[0081]

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¹ H-NMR (200.1 MHz, d ₁ -chloroform): δ = 6.62-6.
60 (m, 2H, Cp-H), 6.57-6.54 (m, 2H, Cp-H), 6
. 07-6.04 (m, 2H, Cp-H), 6.00-5.97 (m, 2H, C
pH), 5.44 (ps, 1H, 8-H), 4.87-4.84 (m, 2H,
7-H / 7'-H), 3.03-2.91 (m, 4H, 11-H / 11'-H),
1.89-1.83 (12-H / 12'-H) ppm

Example 12 Preparation of 9-N, N-Dimethylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorotitanium At −78 ° C., 1 g of ((g) in 60 ml of diethyl ether 6-N, N-dimethylamino-5-vinyl) cyclopentadienyllithium is mixed with 1.16 g of tetrachlorobis (diethylether) titanium. The mixture dissolves slowly and is stirred at room temperature for 12 hours. The precipitate obtained is filtered off and washed with a little diethyl ether and then a little dichloromethane. The filtrate is evaporated to dryness in a vacuum oil pump. Recrystallization from diethyl ether gave 203 mg (17%) of 9-N, N-
This gives dimethylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorotitanium.

[0084]

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¹ H-NMR (200.1 MHz, d ₁ -chloroform): δ = 6.96-6.
90 (m, 4H, Cp-H), 6.11-6.05 (m, 4H, Cp-H), 5
. 64 (ps, 1H, 8-H), 5.00 (ps, 1H, 7-H), 4.93 (
m, 1H, 7'-H), 2.63 (s, 6H, 11-H / 11'-H) ppm

Example 13 300 ml of toluene and 20 ml of a 10.5% strength solution of methylaluminoxane toluene are placed in a 1 L autoclave. The polymerization temperature is set at 0 ° C. and the propene pressure at 2 × 10 ⁵ Pa. The polymerization was performed with 18 mg of 9 dissolved in toluene.
Initiated by injection of -N-pyrrolidino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium. After 1 hour, the polymerization is terminated by stripping off the excess monomer and carefully adding methanol acidified with hydrochloric acid. The obtained activity is 5349 g / (mol · Zr · 10 ⁵ Pa · h) in PP.

Example 14 300 ml of toluene and 20 ml of a 10.5% strength solution of methylaluminoxane toluene are placed in a 1 L autoclave. The polymerization temperature is set at −5 ° C. and the propene pressure is set at 2 × 10 ⁵ Pa. The polymerization is initiated by injection of 16 mg of 9-N-morpholino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium dissolved in toluene. After 1 hour, the polymerization is terminated by stripping off the excess monomer and carefully adding methanol acidified with hydrochloric acid. The obtained activity is 7905 g / (mol · Zr · 10 ⁵ Pa · h) in PP.
It is.

Example 15 300 ml of toluene and 20 ml of a 10.5% strength methylaluminoxane toluene solution are placed in a 1 L autoclave. The polymerization temperature is set at 20 ° C. and the propene pressure is set at 2 × 10 ⁵ Pa. The polymerization is initiated by injection of 16 mg of 9-N-morpholino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium dissolved in toluene. After 1 hour, the polymerization is terminated by stripping off the excess monomer and carefully adding methanol acidified with hydrochloric acid. The obtained activity is 12571 g / (mol · Zr · 10 ⁵ Pa · h) in PP.
).

Example 16 300 ml of toluene and 20 ml of a 10.5% strength solution of methylaluminoxane toluene are placed in a 1 L autoclave. The polymerization temperature is set at 20 ° C. and the propene pressure is set at 2 × 10 ⁵ Pa. The polymerization was carried out with 21 mg of 9 dissolved in toluene.
Initiated by injection of -N-pyrrolidino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium. After 1 hour, the polymerization is terminated by stripping off the excess monomer and carefully adding methanol acidified with hydrochloric acid. The obtained activity is 12418 g / (mol · Zr · 10 ⁵ Pa · h) in PP.
It is.

Example 17 300 ml of toluene and 20 ml of a 10.5% strength methylaluminoxane toluene solution are placed in a 1 L autoclave. The polymerization temperature is set at 20 ° C. and the propene pressure is set at 2 × 10 ⁵ Pa. The polymerization was performed using 24 mg of 9-N, N-dimethylamino-trans-6,9-bis (cyclopentadienyl) dissolved in toluene.
Initiated by injection of butadienyldichlorozirconium. After 1 hour, the polymerization is terminated by stripping off the excess monomer and carefully adding methanol acidified with hydrochloric acid. The obtained activity is 97715 g / (mol · Zr · 10 ⁵ Pa · h) in PP.

Example 18: 200 ml of toluene, 2.3 g of norbornene in 100 ml of toluene,
And 20 ml of a 10.5% strength methylaluminoxane toluene solution are placed in a 1 L autoclave. The polymerization temperature is 50 ° C. and the ethene pressure is 2 × 10 ⁵ Pa
Set to. The polymerization is initiated by injection of 18 mg of 9-N, N-dimethylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorozirconium dissolved in toluene. After 40 minutes, the polymerization is terminated by stripping off the excess monomer and carefully adding methanol acidified with hydrochloric acid. The obtained activity of the copolymer is 222765 g / (mol · Zr · 10 ⁵ Pa · h).

The ratio of norbornene: ethene in the copolymer = 1: 57

Example 19: 200 ml of toluene, 2.3 g of norbornene in 100 ml of toluene,
And 20 ml of a 10.5% strength methylaluminoxane toluene solution are placed in a 1 L autoclave. The polymerization temperature is 50 ° C. and the ethene pressure is 2 × 10 ⁵ Pa
Set to. The polymerization is initiated by injection of 23 mg of 9-N, N-dimethylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorotitanium dissolved in toluene. After 40 minutes, the polymerization is terminated by stripping off the excess monomer and carefully adding methanol acidified with hydrochloric acid. The obtained activity is 92127 g / (mol · Zr · 10 ⁵ Pa · h) in the copolymer.

The ratio of norbornene: ethene in the copolymer = 1: 70

──────────────────────────────────────────────────の Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), JP, KR, US (72) Inventor Flitze, Cornelia Germany, D-60529, Frankfurt, Am, Main, Geisenheimer, Straße, 97F term (reference) 4H050 AA01 AB40 4J028 AA01A AB01A AC01A AC10A AC28A BA00A BA01B BB00A BB01B BC12B BC15B BC25B EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB13 EB14 EB16 EB18 EB21 FA01 FA02 FA03 FA04 4J128 AA01 AB01 AC01 AC10 AC28 AD00 BA00A BA01B BB00 EB01 EB01 BB00 FA01 FA02 FA03 FA04

Claims (8)

[Claims] 1. A compound of the formula I [M represents a metal of Group 3, 4, 5, or 6 of the periodic table or a lanthanide or actinide, and R ¹ and R ⁵ may be the same or different, and each represents a hydrogen atom or C ₁ -C _{4 0} group or SiR ⁶ group ^{(R 6} may be the same or different, each. represents a hydrogen atom or a _C 1 _{-C 40} group) or represents two or more groups ^{R 1} or ^{R 5,} The groups R ¹ or R ⁵ and the atoms of the cyclopentadienyl ring to which they are attached may be linked to each other in such a way as to form an optionally substituted C ₄ -C ₂₄ ring, wherein m is 0 , 1, 2, 3 or 4; p represents 0, 1, 2, 3 or 4; R ² and R ³ may be the same or different and each represents a hydrogen atom or C _1-
Represents a C ₄₀ group or a SiR ⁶ group (R ⁶ may be the same or different and each represents a hydrogen atom or a C _{1 to} C ₄₀ group), or two or more groups R ¹ or R ⁵ represent a group R ¹ or R ⁵ and the atoms of the cyclopentadienyl ring to which they are attached may be linked to each other in such a way as to form an optionally substituted C ₄ -C ₂₄ ring, wherein R ⁴ is NR ⁷ R ⁸ groups (R ⁷ and R ⁸ may be the same or different and each represent a hydrogen atom or a C ₁ -C ₄₀ group, or a C ₄ -C _{24 wherein the} groups R ⁷ and R ⁸ may be substituted N may represent 0, 1, 2, 3 or 4, X may be the same or different, and each may be a hydrogen atom, C ₁ -C ₁₀ alkyl groups, C ₁ -C ₁₀ alkoxy groups, C ₆ A C ₁₀ -aryl group, a C ₆ -C ₁₀ aryloxy group, a C ₂ -C ₁₀ alkenyl group, a C ₇ -C ₄₀ arylalkyl group, a C ₇ -C ₄₀ alkylaryl group, a C ₈ -C ₄₀ arylalkenyl group, Represents an OH group or a halogen atom. ] The compound represented by this. 2. The method according to claim 1, wherein M represents titanium, zirconium or hafnium.
The compound according to the above. 3. R ¹ and R ⁵ may be the same or different and each is methyl, ethyl, tert-butyl, cyclohexyl or octyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C _6- C _{24 aryl,} C 5 _{-C 24 heteroaryl,} C 7 _{-C 30 arylalkyl,} C 7 _{-C 30} alkylaryl, fluorinated _C 1 _{-C 25} alkyl, fluorinated _C 6 _{-C 24} aryl, fluorinated _{C 7} ~
C _{30 arylalkyl,} C 7 _{-C 40} arylalkenyl, fluoride _C 7 _{-C 3 0} alkyl _aryl, C 1 _{-C 12} alkoxy or _C 1 _{-C 12} amino, or SiR ⁶ group ^{(R 6} are the same or different at best, each _C 1 _{-C 20 alkyl,} C 1 _{-C 10 fluoroalkyl,} C 1 _{-C 10 alkoxy,} C 6 _{-C 20 aryl,} C 6 _{-C 10 fluoroaryl,} C 6 _{-C 10} aryloxy, C _2-
Represents C ₁₀ alkenyl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl or C ₈ -C ₄₀ arylalkenyl. The compound according to claim 1, wherein 4. R ² and R ³ may be the same or different and each is methyl, ethyl, tert-butyl, cyclohexyl or octyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₃ C _{24 aryl,} C 5 _{-C 24 heteroaryl,} C 7 _{-C 30 arylalkyl,} C 7 _{-C 30} alkylaryl, fluorinated _C 1 _{-C 25} alkyl, fluorinated _C 6 _{-C 24} aryl, fluorinated _{C 7} ~
C _{30 arylalkyl,} C 7 _{-C 40} arylalkenyl, fluoride _C 7 _{-C 3 0} alkyl _aryl, C 1 _{-C 12} alkoxy or _C 1 _{-C 12} amino, or SiR ⁶ group ^{(R 6} are the same or different at best, each _C 1 _{-C 20 alkyl,} C 1 _{-C 10 fluoroalkyl,} C 1 _{-C 10 alkoxy,} C 6 _{-C 20 aryl,} C 6 _{-C 10 fluoroaryl,} C 6 _{-C 10} aryloxy, C _2-
Represents C ₁₀ alkenyl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl or C ₈ -C ₄₀ arylalkenyl. 4. The method according to claim 1, wherein
The compound according to any one of the above. 5. R ⁷ and R ⁸ may be the same or different and are each methyl, ethyl, tert-butyl, cyclohexyl or octyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C _6- C _{24 aryl,} C 5 _{-C 24 heteroaryl,} C 7 _{-C 30 arylalkyl,} C 7 _{-C 30} alkylaryl, fluorinated _C 1 _{-C 25} alkyl, fluorinated _C 6 _{-C 24} aryl, fluorinated _{C 7} ~
C ₃₀ arylalkyl, _C 7 _{-C 40} arylalkenyl, fluoride _C 7 _{-C 30 alkylaryl,} represents a C 1 _{-C 12} alkoxy or _C 1 _{-C 12} amino, in any one of claims 1 4 A compound as described. 6. Use of the compounds according to claim 1 for the preparation of polyolefins, in particular of polypropylene, polyethylene and cycloolefin copolymers. 7. A process for producing a polyolefin by polymerizing one or more olefins in the presence of a compound of the formula (I) according to any one of claims 1 to 5. 8. A catalyst composition comprising a compound of formula (I) according to claim 1 and a cocatalyst.