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  Monocyclopentadienyl complexesUSPTO Application #: 20060089253Title: Monocyclopentadienyl complexes Abstract: Monocyclopentadienyl complexes in which the cyclopentadienyl system bears at least one unsubstantiated, substituted or fused, hetero aromatic ring system bound via a specific bridge, a catalyst system, comprising at least one of these monocyclopentadienyl complexes, the use of the catalyst system for the polymerization or copolymerization of olefins and a process for preparing polyolefins by polymerization or copolymerization of olefins in the presence of the catalyst system and polymers obtainable therewith. (end of abstract) Agent: Novak Druce Deluca & Quigg, LLP - Washington, DC, US Inventors: Shahram Mihan, Ilya Nifant'ev USPTO Applicaton #: 20060089253 - Class: 502152000 (USPTO) Related Patent Categories: Catalyst, Solid Sorbent, Or Support Therefor: Product Or Process Of Making, Catalyst Or Precursor Therefor, Organic Compound Containing, Organic Compound Including Carbon-metal Bond The Patent Description & Claims data below is from USPTO Patent Application 20060089253. Brief Patent Description - Full Patent Description - Patent Application Claims
[0001] The present invention relates to monocyclopentadienyl complexes in which the cyclopentadienyl system bears at least one unsubstituted, substituted or fused, heteroaromatic ring system bound via a specific bridge and to a catalyst system comprising at least one of these monocyclopentadienyl complexes, and also to a process for preparing them. [0002] In addition, the invention relates to the use of the catalyst system for the polymerization of copolymerization of olefins and to a process for preparing polyolefins by polymerization or copolymerization of olefins in the presence of the catalyst system and to polymers obtainable therewith. [0003] Many of the catalysts which are used for the polymerization of a-olefins are based on immobilized chromium oxides (cf., for example, Kirk-Othmer, "Encyclopedia of Chemical Technology", 1981, vol. 16, p. 402). These generally give ethylene homopolymers and copolymers having high molecular weights, but are relatively insensitive to hydrogen and thus do not allow the molecular weight to be controlled in a simple manner. In contrast, the use of bis(cyclopentadienyl)chromium (U.S. Pat. No. 3,709,853), bis(indenyl)chromium or bis(fluorenyl)chromium (U.S. Pat. No. 4,015,059) applied to an inorganic, oxidic support allows the molecular weight of polyethylene to be controlled in a simple manner by addition of hydrogen. [0004] As in the case of Ziegler-Natta systems, catalyst systems having a uniquely defined, active center, known as single-site catalysts, have recently been sought in the case of the chromium compounds, too. Targeted variation of the ligand framework should enable activity, copolymerization behavior of the catalyst and the properties of polymers obtained in this way to be altered in a simple manner. [0005] Thus, EP 0 742 046 claims constrained geometry complexes of transition group 6, a specific process for preparing them (via metal tetraamides) and a process for preparing a polyolefin in the presence of such catalysts. Polymerization examples are not given. The ligand framework comprises an anionic donor which is bound to a cyclopentadienyl radical. [0006] In Organomet. 1996, 15, 5284-5286, K. H. Theopold et al. describe an analogous {[(tert-butylamido)dimethylsilyl](tetramethylcyclopentadienyl)}chromium chloride complex for the polymerization of olefins. This complex selectively polymerizes ethylene. Comonomers such as hexene are not incorporated, nor can propene be polymerized. [0007] This disadvantage can be overcome by the use of structurally very similar systems. Thus, DE 197 10615 describes monocyclopentadienylchromium compounds substituted by donor ligands by means of which, for example, propene can also be polymerized. Here, the donor is from group 15 and is uncharged. The donor is bound to the cyclopentadienyl ring via a (ZR.sub.2).sub.n fragment, where R is hydrogen, alkyl or aryl, Z is an atom of group 14 and n is .gtoreq.1. DE 196 30 580 specifically claims Z=carbon in combination with an amine donor. [0008] WO 96/13529 describes reduced transition metal complexes of groups 4 to 6 of the Periodic Table with polydentate monoanionic ligands. These include cyclopentadienyl ligands containing a donor function. The examples are restricted to titanium compounds. [0009] There are also ligand systems in which the donor group is rigidly joined to the cyclopentadienyl radical. Such ligand systems and their metal complexes are summarized by, for example, P. Jutzi and U. Siemeling in J. Orgamet. Chem. (1995), 500, 175-185, section 3. In Chem. Ber. (1996), 129, 459-463, M. Enders et al. describe 8-quinolyl-substituted cyclopentadienyl ligands and their titanium trichloride and zirconium trichloride complexes. 2-Picolylcyclopentadienyltitanium trichloride in combination with MAO has been used by M. Blais, J. Chien and M. Rausch in Organomet. (1998), 17 (17) 3775-3783, for the polymerization of olefins. [0010] WO 01/12641 describes monocyclopentadienyl complexes of chromium, molybdenum and tungsten which bear, in particular, quinolyl or pyridyl donors which are bound either directly or via a Cl or Si bridge to the cyclopentadienyl system. It is an object of the present invention to find further transition metal complexes based on cyclopentadienyl ligands having a bridged donor which are suitable for the polymerization of olefins. A further object of the invention is to find an advantageous process for preparing such complexes. [0011] We have found that the first of these objects is achieved by monocyclopentadienyl complexes which contain the structural feature of the formula (Cp)(-Z-A).sub.mM (I), where the variables have the following meanings: [0012] Cp is a cyclopentadienyl system, [0013] Z is a bridge between A and Cp and is selected from the group consisting of [0014] where [0015] L.sup.1B-L.sup.3B are each, independently of one another, carbon or silicon, [0016] R.sup.1B-R.sup.6B are each, independently of one another, hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.6-C.sub.20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part or SiR.sup.7B.sub.3, where the organic radicals R.sup.1B-R.sup.6B may also be substituted by halogens and two geminal or vicinal radicals R.sup.1B-R.sup.6B or a radical R.sup.1B-R.sup.6B and A may also be joined to form a five- or six-membered ring and [0017] R.sup.7B are each, independently of one another, hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.6-C.sub.20-aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part and two radicals R.sup.7B may also be joined to form a five- or six-membered ring, [0018] A is an unsubstituted, substituted or fused, heteroaromatic ring system, [0019] M is a metal selected from the group consisting of titanium in the oxidation state 3, vanadium, chromium, molybdenum and tungsten and [0020] m is 1, 2 or 3. [0021] Furthermore, we have found a catalyst system comprising the monocyclopentadiehyl complexes of the invention, the use of the monocyclopentadienyl complexes or of the catalyst system for the polymerization or copolymerization of olefins and a process for preparing polyolefins by polymerization of copolymerization of olefins in the presence of the monocyclopentadienyl complex or the catalyst system and polymers obtainable therefrom. [0022] The monocyclopentadienyl complexes of the present invention contain the structural element of the formula (Cp)(-Z-A).sub.mM (I), where the variables are as defined above. Further ligands can therefore be bound to the metal atom M. The number of further ligands depends, for example, on the oxidation state of the metal atom. Possible further ligands do not include further cyclopentadienyl systems. Suitable further ligands are monoanionic and dianionic ligands as are described, for example, for X. In addition, Lewis bases such as amines, ethers, ketones, aldehydes, esters, sulfides or phosphines can also be bound to the metal center M. [0023] Cp is a cyclopentadienyl system which may be substituted as desired and/or fused with one or more aromatic, aliphatic, heterocyclic or heteroaromatic rings, wherein 1, 2 or 3 substituents, preferably 1 substituent, is the group -Z-A. The cyclopentadienyl skeleton itself is a C.sub.5-ring system having 6 .pi. electrons, in which one of the carbon atoms can also be replaced by nitrogen or phosporus, preferably phosphorus. Preference is given to using C.sub.5-ring systems without replacement by a heteroatom. A heteroaromatic ring containing at least one atom from the group consisting of N, P, O and S or an aromatic ring can, for example, be fused onto this cyclopentadienyl skeleton. In the present context, fused-on means that the heterocycle and the cyclopentadienyl skeleton have two atoms, preferably carbon atoms, in common. Preference is given to cyclopentadienyl systems Cp of the formula (II) [0024] where the variables have the following meanings: [0025] E.sup.1A-E.sup.5A are each carbon or not more than one E.sup.1A to E.sup.5A is phosphorus, R.sup.1A-R.sup.5A are each, independently of one another, hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.6-C.sub.20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR.sup.6A.sub.2, N(SiR.sup.6A.sub.3).sub.2, OR.sup.6A, OSiR.sup.6A.sub.3, SiR.sup.6A.sub.3, BR.sup.6A.sub.2, where the organic radicals R.sup.1A-R.sup.5A may also be substituted by halogens and two vicinal radicals R.sup.1A-R.sup.5A may also be joined to form a five- or six-membered ring, and/or two vicinal radicals R.sup.1A-R.sup.5A are joined to form a heterocycle which contains at least one atom from the group consisting of N, P, O and S, where 1, 2 or 3 substituents, preferably 1 substituent, R.sup.1A-R.sup.5A is a group -Z-A and [0026] R.sup.6A are each, independently of one another, hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.6-C.sub.20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two geminal radicals R.sup.6A may also be joined to form a five- or six-membered ring. [0027] In preferred cyclopentadienyl systems Cp, all E.sup.1A to E.sup.5A are carbon. [0028] Two vicinal radicals R.sup.1A-R.sup.5A can, in each case together with the E.sup.1A-E.sup.5A to which they are bound, form a heterocycle, preferably a heteroaromatic, which contains at least one atom from the group consisting of nitrogen, phosphorus, oxygen and sulfur, particularly preferably nitrogen and/or sulfur, with the E.sup.1A-E.sup.5A present in the heterocycle or heteroaromatic are preferably carbon atoms. Preference is given to heterocycles and heteroaromatics having a ring size of 5 or 6 ring atoms. Examples of 5-membered heterocycles, which may contain from 1 to 4 nitrogen atoms and/or a sulfur or oxygen atom as ring atoms in addition to carbon atoms, are 1,2-dihydrofuran, furan, thiophene, pyrrole, isoxazole, 3-isothiazole, pyrazole, oxazole, thiazole, imidazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-triazole and 1,2,4-triazole. Examples of 6-membered heteroaryl groups, which may contain from 1 to 4 nitrogen atoms and/or a phosphorus atom, are pyridine, phosphabenzene, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine and 1,2,3-triazine. The 5- and 6-membered heterocycles may also be substituted by C.sub.1-C.sub.10-alkyl, C.sub.6-C.sub.10-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-10 carbon atoms in the aryl part, trialkylsilyl or halogens such as fluorine, chlorine or bromine, dialkylamide, alkylarylamide, diarylamide, alkoxy or aryloxy or be fused with one or more aromatics or heteroaromatics. Examples of the benzo-fused 5-membered heteroaryl groups are indole, indazole, benzofuran, benzothiophene, benzothiazole, benzoxazole and benzimidazole. Examples of benzo-fused 6-membered heteroaryl groups are chroman, benzopyran, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quioxaline, 1,10-phenanthroline and quinolizine. Naming and numbering of the heterocycles has been taken from Lettau, Chemie der Heterocyclen, 1st edition, VEB, Weinheim 1979. The heterocycles/heteroaromatics are preferably fused with the cyclopentadienyl skeleton via a C--C double bond of the heterocycle/heteroaromatic. Heterocycles/heteroaromatics containing a heteroatom are preferably 2,3-fused or b-fused. [0029] Examples of cyclopentadienyl systems Cp having a fused heterocycle are thiapentalene, 2-methylthiapentalene, 2-ethylthiapentalene, 2-isopropylthiapentalene, 2-n-butylthiapentalene, 2-tert-butylthiapentalene, 2-trimethylsilylthiapentalene, 2-phenylthiapentalene, 2-naphthylthiapentalene, 3-methylthiopentalene, 4-phenyl-2,6-dimethyl-1-thiapentalene, 4-phenyl-2,6-diethyl-1-thiapentalene, 4-phenyl-2,6-diisopropyl-1-thiapentalene, 4-phenyl-2,6-di-n-butyl-1-thiapentalene, 4-phenyl-2,6-di(trimethylsilyl)-1-thiapentalene, azapentalene, 2-methylazapentalene, 2-ethylazapentalene, 2-isopropylazapentalene, 2-n-butylazapentalene, 2-trimethylsilylazapentalene, 2-phenylazapentalene, 2-naphthylazapentalene, 1-phenyl-2,5-dimethyl-1-azapentalene, 1-phenyl-2,5-diethyl-1-azapentalene, 1-phenyl-2,5-di-n-butyl-1-azapentalene, 1-phenyl-2,5-di-tert-butyl-1-azapentalene, 1-phenyl-2,5-di(trimethysilyl)-1-azapentalene, 1-tert-butyl-2,5-dimethyl-1-azapentalene, oxapentalene, phosphapentalene, 1-phenyl-2,5-dimethyl-1-phosphapentalene, 1-phenyl-2,5-diethyl-1-phqsphapentalene, 1-phenyl-2,5-di-n-butyl-1-phosphapentalene, 1-phenyl-2,5-di-tert-butyl-1-phosphapentalene, 1-phenyl-2,5-di(trimethylsilyl)-1-phosphapentalene, 1-methyl-2,5-dimethyl-1-phosphapentalene, 1-tert-butyl-2,5-dimethyl-1-phosphapentalene, 7-cyclopenta-[1,2]thieno[3,4]cyclopentadiene or 7-cyclopenta[1,2]pyrrolo[3,4]cyclopentadiene. [0030] In further preferred cyclopentadienyl systems Cp, four of the radicals R.sup.1A-R.sup.5A i.e. two pairs of vicinal radicals, form two heterocycles, in particular heteroaromatics. The heterocyclic systems are the same as those described in more detail above. Examples of cyclopentadienyl systems Cp having two fused-on heterocycles are 7-cyclopentadithiophene, 7cyclopentadipyrrole or 7-cyclopentadiphosphole. [0031] The synthesis of such cyclopentadienyl systems having a fused-on heterocycle is described, for example, in the abovementioned WO 98/22486. In "metalorganic catalysts for synthesis and polymerization", Springer Verlag 1999, p. 150 ff, Ewen et al. describe further syntheses of these cyclopentadienyl systems. [0032] The polymerization behavior of the metal complexes can likewise be influenced by variation of the substituents R.sup.1A-R.sup.5A. The number and type of substituents can influence the ability of the olefins to be polymerized to gain access to the metal atom M. This makes it possible to modify the activity and selectivity of the catalyst in respect of various monomers, in particular bulky monomers. Since the substituents can also influence the rate of termination reactions of the growing polymer chain, the molecular weight of the polymers formed can also be altered in this way. The chemical structure of the substituents R.sup.1A to R.sup.5A can therefore be varied within a wide range in order to achieve the desired results and to obtain a tailored catalyst system. [0033] Possible carboorganic substituents R.sup.1A-R.sup.5A are, for example, the following: C.sub.1-C.sub.20-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl which may in turn bear a C.sub.6-C.sub.10-aryl group as substituent, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C.sub.2-C.sub.20-alkenyl which may be linear, cyclic or branched and have an internal or terminal double bond, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C.sub.6-C.sub.20-aryl which may be substituted by further alkyl groups, e.g. phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or arylalkyl which may be substituted by further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl, where two R.sup.1A to R.sup.5A may also be joined to form a 5- or 6-membered ring and the organic radicals R.sup.1A-R.sup.5A may also be substituted by halogens, e.g. fluorine, chlorine or bromine. Furthermore, R.sup.1A-R.sup.5A can also be amino or alkoxyl, for example dimethylamino, n-pyrrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy. In organosilicon substituents SiR.sup.6A.sub.3, R.sup.6A may be the same radicals as described in more detail above for R.sup.1A-R.sup.5A, with two R.sup.6A also being able to be joined to form a 5- or 6-membered ring. Examples of substituents SiR.sup.6A.sub.3 are trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl and dimethylphenylsilyl. These SiR.sup.6A.sub.3 radicals can also be joined to the cyclopentadienyl skeleton via an oxygen or nitrogen atom, for example trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyoxy or tri-tert-butylsilyloxy. Preferred radicals R.sup.1A-R.sup.5A are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho-dialkyl- or ortho-dichloro-substituted phenyls, trialkyl- or trichloro-substituted phenyls, naphthyl, biphenyl and anthranyl. As organosilicon substituents, particular preference is given to trialkylsilyl groups having from 1 to 10 carbon atoms in the alkyl radical, in particular trimethylsilyl groups. [0034] Examples of such cyclopentadienyl systems (without the group -Z-A, which is preferably located in the 1 position) are 3-methylcyclopentadienyl, 3-ethylcyclopentadienyl, 3-isopropylcyclopentadienyl, 3-tert-butylcyclopentadienyl, dialkylcyclopentadienyl such as tetrahydroindenyl, 2,4-dimethylcyclopentadienyl or 3-methyl-5-tert-butylcyclopentadienyl, trialkylcyclopentadienyl such as 2,3,5-trinethylcyclopentadienyl or tetraalkylcyclopentadienyl such as 2,3,4,5-tetramethylcyclopentadienyl. [0035] Preference is also given to compounds in which two vicinal radicals R.sup.1A-R.sup.5A form a cyclic fused ring system, i.e. together with the E.sup.1A-E.sup.5A skeleton, preferably a C.sub.5-cyclopentadienyl skeleton, form, for example, an unsubstituted or substituted indenyl, benzindenyl, phenanthrenyl, fluorenyl or tetrahydroindenyl system, for example indenyl, 2-methylindenyl, 2-ethylindenyl, 2-isopropylindenyl, 3-methylindenyl, benzindenyl or 2-methylbenzindenyl. [0036] The fused ring system may be a further C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20-alkenyl, C.sub.6-C.sub.20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, NR.sup.6A.sub.2, N(SiR.sup.6A.sub.3).sub.2, OR.sup.6A, OSiR.sup.6A.sub.3 or SiR.sup.6A.sub.3 groups, e.g. 4-methylindenyl, 4-ethylindenyl, 4-isopropylindenyl, 5-methylindenyl, 4-phenylindenyl, 5-methyl-4-phenylindenyl, 2-methyl-4-phenylindenyl or 4-naphthylindenyl. Continue reading... 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