Chemical products suited for use as co- catalysts, method for the preparation thereof and their use

专利摘要:
The present invention relates to chemical products obtainable by reacting a compound of formula (I) with a compound of formula (II) and suitable as cocatalysts. [Formula I] M 1 R 1 R 2 (R 3 ) m Wherein R 1 , R 2 , R 3 are the same or different and each is hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 6 -C 20 -aryl, C 6 -C 20- Haloaryl, C 7 -C 40 -arylalkyl, C 7 -C 40 -haloallylalkyl, C 7 -C 40 -alkylaryl or C 7 -C 40 -haloalkylaryl, M 1 is the main Group II or III element of the Periodic Table of the Elements, m is 0 or 1, m is 1 when M 1 is a main group III element, and 0 when M 1 is a main group II element. [Formula II] (R 4 X) q- (G) * (M 2 R 5 R 6 ) g Wherein the substituent R 4 X containing the heteroatom is located on the parent nucleus part G, R 4 is the same or different and is hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 7 -C 40 -Arylalkyl, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl or C 7 -C 40 -haloalkylaryl, X is an element of the main group IV, V or VI of the periodic table of elements, G is at least divalent C 1 -C 20 - alkylene, C 1 -C 20 - haloalkyl-alkylene, C 1 -C 10 - alkylene, C 6 -C 40 - arylene, C 6 -C 40 - haloalkyl Arylene, C 6 -C 40 -aryleneoxy, C 7 -C 40 -arylalkylene, C 7 -C 40 -haloarylalkylene, C 7 -C 40 -alkylarylene, C 7 -C 40- Haloalkylarylene, M 2 is an element of the main Group IV, V or VI of the Periodic Table of the Elements, R 5 and R 6 are the same or different and each is hydrogen, C 1 -C 20 -alkyl, CC 10 -alkoxy, C 2 -C 10 -alkenyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -Alkylaryl, C 6 -C 10 -aryloxy, C 1 -C 10 -haloalkyl, q is an integer from 2 to 100, g is an integer from 1 to 100. The invention also relates to a process for the preparation of said chemical product and to the use thereof in catalyst systems for producing polyolefins.
公开号:KR20030014241A
申请号:KR1020027015873
申请日:2001-05-19
公开日:2003-02-15
发明作者:스코테크요르그
申请人:바젤 폴리올레핀 게엠베하；
IPC主号:

专利说明:

TECHNICAL PRODUCTS SUITED FOR USE AS CO-CATALYSTS, METHOD FOR THE PREPARATION THEREOF AND THEIR USE IN CATALYST SYSTEMS FOR PRODUCING POLYOLEFINS}
[2] The role of cationic complexes in Ziegler-Natta polymerization with metallocenes is generally known (HH Brintzinger, D. Fischer, R. Mulhaupt, R. Rieger, R. Waymouth, Angew. Chem. 1995, 107, 1255 -1283).
[3] As an effective promoter, MAO has the disadvantage of being used in excess. Modified MAO catalysts are described, for example, in the documents WO99 / 30819, WO99 / 30820, WO99 / 30821 and JP-09-278817 A1, but these systems exhibit insufficient polymerization activity and must be used in excess.
[4] The preparation of cationic transition metal alkyl complexes has opened the door to catalysts without MAO, with comparable activity, in which cocatalysts can be used in near stoichiometric amounts.
[5] For synthesis of "cationic" metallocene polymerization catalysts, see J. Am. Chem. Soc. 1991, 113, 3623. A process for the preparation of salts represented by the formula LMX ⁺ XA ^- according to the above principles is disclosed in EP-A-0 520 732.
[6] EP-A-0 558 158 discloses Zwitter ionic catalyst systems prepared from dialkyl-metallocene compounds and salts of the formula [R ₃ NH] ⁺ [B (C ₆ H ₅ ) ₄ ] ^- . . As a result of the reaction of this salt with, for example, Cp ₂ ZrMe ₂ , the proton transfer reaction takes place with the removal of methane, yielding a methyl-zirconocene cation as an intermediate. This is reacted with the activated CH zwitterionic Cp ₂ Zr ⁺ - form a ^{_{- (mC 6 H 4) -BPh}} 3. In this Zwitter ion, the Zr atom is covalently bonded to the carbon atom of the phenyl ring and stabilized by an agostic hydrogen bond.
[7] US-A-5,348,299 has the formula ^{_{[R 3 NH] + [B}} (C 6 F 5) 4] by the proton before reaction ^- with respect to the zwitterionic property catalyst system prepared from the metallocene compound-salt and di-alkyl It is starting. CH-activation does not occur as a subsequent reaction. In EP-A-0 426 637, a Lewis acid CPh ₃ ⁺ cations are used to extract the methyl group from the metal center. B (C ₆ F ₅ ) ₄ ⁻ acts as a weak coordinating anion.
[8] In order for the metallocene compound to be industrially available, the catalyst system must be made heterogeneously to ensure the proper morphology of the resulting polymer. The application of the aforementioned borate anionic cationic metallocene catalyst to the support is disclosed in WO 91/09882. Here, the catalyst system is prepared by applying to the inorganic support a quaternary ammonium compound having a non-coordinated anion, for example tetrakispentafluorophenyl borate, which is a dialkyl-metallocene compound and Bronsted acid. The support material is modified in advance using trialkylaluminum compounds.
[9] The disadvantage of this method of application to the support is that only a portion of the metallocene used is fixed to the support material by physical adsorption. When introducing the catalyst system into the reactor, the metallocene can be readily leached from the support surface. The result is a partially homogeneous polymerization reaction, resulting in an unsatisfactory form of the polymer. WO 96/04319 discloses a catalyst system in which a promoter is covalently bonded to a support material. However, this catalyst system has low polymerization activity, and furthermore, problems may arise during introduction into the polymerization system due to the high sensitivity of the supported cationic metallocene catalyst.
[1] The present invention relates to chemical products suitable as promoters, methods for their preparation and their use in catalyst systems for preparing polyolefins. Specifically, the present invention can form a catalyst system that is electrically neutral and can be usefully used for the polymerization of olefins with organic transition metal compounds. Here, even without using aluminoxanes such as methylaluminoxane (MAO) as cocatalysts, high catalytic activity and good polymer morphology can be obtained.
[10] It is an object of the present invention to provide a chemical product which can be used as a promoter in a catalyst system and exhibits the desirable properties of MAO and which can be covalently bonded or physisorbed to the support material. The catalyst system prepared therefrom must be able to be activated prior to introduction into the reactor or only in the polymerization autoclave.
[11] The inventors have noted that this object can be obtained by reacting a compound of formula (I) with a compound of formula (II) and is achieved by a chemical product suitable as a promoter.
[12] M ¹ R ¹ R ² (R ³ ) _m
[13] Wherein R ¹ , R ² , R ³ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C _20- Haloaryl, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloallylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
[14] M ¹ is the main Group II or III element of the Periodic Table of the Elements,
[15] m is 0 or 1, m is ¹ when M ¹ is a main group III element, and 0 when M ¹ is a main group II element.
[16] (R ⁴ X) _q- (G) * (M ² R ⁵ R ⁶ ) _g
[17] Wherein the substituent R ⁴ X containing the heteroatom is located on the parent nucleus part G,
[18] R ⁴ is the same or different and is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -haloaryl, C ₇ -C ₄₀ -Arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
[19] X is an element of the main group IV, V or VI of the periodic table of elements,
[20] G is at least divalent C ₁ -C ₂₀ - alkylene, C ₁ -C ₂₀ - haloalkyl-alkylene, C ₁ -C ₁₀ - alkylene, C ₆ -C ₄₀ - arylene, C ₆ -C ₄₀ - haloalkyl Arylene, C ₆ -C ₄₀ -aryleneoxy, C ₇ -C ₄₀ -arylalkylene, C ₇ -C ₄₀ -haloarylalkylene, C ₇ -C ₄₀ -alkylarylene, C ₇ -C _40- Haloalkylarylene,
[21] M ² is an element of the main Group IV, V or VI of the Periodic Table of the Elements,
[22] R ⁵ and R ⁶ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, CC ₁₀ -alkoxy, C ₂ -C ₁₀ -alkenyl, C ₇ -C ₂₀ -arylalkyl, C ₇ -C ₂₀ -Alkylaryl, C ₆ -C ₁₀ -aryloxy, C ₁ -C ₁₀ -haloalkyl,
[23] q is an integer from 2 to 100,
[24] g is an integer from 1 to 100.
[25] The present invention provides a process for preparing this chemical product by reacting a compound of formula (I) with a compound of formula (II).
[26] [Formula I]
[27] M ¹ R ¹ R ² (R ³ ) _m
[28] Wherein R ¹ , R ² , R ³ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C _20- Haloaryl, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloallylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
[29] M ¹ is the main Group II or III element of the Periodic Table of the Elements,
[30] m is 0 or 1, m is ¹ when M ¹ is a main group III element, and 0 when M ¹ is a main group II element.
[31] [Formula II]
[32] (R ⁴ X) _q- (G) * (M ² R ⁵ R ⁶ ) _g
[33] Wherein the substituent R ⁴ X containing the heteroatom is located on the parent nucleus part G,
[34] R ⁴ is the same or different and is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -haloaryl, C ₇ -C ₄₀ -Arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
[35] X is an element of the main group IV, V or VI of the periodic table of elements,
[36] G is at least divalent C ₁ -C ₂₀ - alkylene, C ₁ -C ₂₀ - haloalkyl-alkylene, C ₁ -C ₁₀ - alkylene, C ₆ -C ₄₀ - arylene, C ₆ -C ₄₀ - haloalkyl Arylene, C ₆ -C ₄₀ -aryleneoxy, C ₇ -C ₄₀ -arylalkylene, C ₇ -C ₄₀ -haloarylalkylene, C ₇ -C ₄₀ -alkylarylene, C ₇ -C _40- Haloalkylarylene,
[37] M ² is an element of the main Group IV, V or VI of the Periodic Table of the Elements,
[38] R ⁵ and R ⁶ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, CC ₁₀ -alkoxy, C ₂ -C ₁₀ -alkenyl, C ₇ -C ₂₀ -arylalkyl, C ₇ -C ₂₀ -Alkylaryl, C ₆ -C ₁₀ -aryloxy, C ₁ -C ₁₀ -haloalkyl,
[39] q is an integer from 2 to 100,
[40] g is an integer from 1 to 100.
[41] The chemical product of the invention preferably comprises a group of formula III.
[42] [-(R ⁷ )-[XM ³ (R ⁸ )] _p -Y- (R ⁹ )-]
[43] Wherein R ⁷ and R ⁸ are the same or different and each is a hydrogen atom, a halogen atom, a boron-free C ₁ -C ₄₀ group (eg C ₁ -C ₂₀ -alkyl, C ₁ -C ₄₀ -haloalkyl , C ₁ -C ₁₀ -alkoxy, C ₆ -C ₄₀ -aryl, C ₆ -C ₄₀ -haloaryl, C ₆ -C ₂₀ -aryloxy, C ₇ -C ₄₀ -arylalkyl, C ₇ -C _40- Haloarylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₇ -C ₄₀ -haloalkylaryl) or Si (R ¹³ ) ₃ group,
[44] R ⁹ is the same as or different from R ⁷ and R ⁸ and each represents a hydrogen atom or a C ₁ -C ₄₀ group (eg, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₁ -C ₁₀ -alkoxy, C ₆ -C ₄₀ -aryl, C ₆ -C ₄₀ -haloaryl, C ₆ -C ₄₀ -aryloxy, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₇ -C ₄₀ -haloalkylaryl (preferably C ₁ -C ₂₀ -haloalkyl or C ₆ -C ₄₀ -partially halogenated or fully halogenated by chlorine or fluorine) Haloaryl, more preferably C ₆ -C ₄₀ -haloaryl) halogenated by fluorine;
[45] X is the same or different and each is an element of Group IV, V or VI of the Periodic Table of the Elements or an NH group,
[46] Y is the same or different and each is an element of Group IV, V or VI of the Periodic Table of the Elements or an NH group,
[47] M ³ is an element of group IIIa of the periodic table of elements.
[48] Compounds of formula III can form higher oligomers having dimeric, trimer or linear or cage structures with one another. Generally, k compounds of formula III are bound as a result of Lewis acid-base interactions, k being a natural number from 1 to 100.
[49] For new compounds of formula III
[50] R ⁷ , R ⁸ are the same or different and are each C ₁ -C ₂₀ -alkyl, C ₁ -C ₄₀ -haloalkyl, C ₆ -C ₄₀ -aryl, C ₆ -C ₄₀ -haloaryl, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₇ -C ₄₀ -haloalkylaryl,
[51] R ⁹ is the same as or different from R ⁷ and R ⁸ , C ₆ -C ₄₀ -aryl, C ₆ -C ₄₀ -haloaryl, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₇ -C ₄₀ -haloalkylaryl, preferably C ₁ -C ₂₀ -haloalkyl or C ₆ -C ₄₀ partially halogenated or fully halogenated by chlorine or fluorine Haloaryl, particularly preferably C ₆ -C ₄₀ -haloaryl, halogenated by fluorine,
[52] X is the same or different and each is a major Group V or VI element (preferably an oxygen or sulfur atom) of the Periodic Table of the Elements, or an NH group,
[53] Y is the same or different and is each a major group V or VIa element (preferably an oxygen or sulfur atom) of the Periodic Table of the Elements, or an NH group,
[54] M ³ is boron or aluminum, preferably aluminum,
[55] It is preferable that k is a natural number of 1-100.
[56] More preferred for the novel compounds of formula III
[57] R ⁷ , R ⁸ are the same or different and are each a C ₁ -C ₂₀ -alkyl or C ₁ -C ₂₀ -haloalkyl group (eg methyl, ethyl, isopropyl, isobutyl),
[58] R ⁹ is different from R ⁷ and R ⁸ and is partially halogenated or fully halogenated C ₆ -C ₄₀ -haloaryl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -haloalkylaryl (preferably Preferably fluorinated groups such as pentafluorophenoxy, pentachlorophenoxy, halogenated or partially halogenated biphenyloxy groups),
[59] X is an oxygen atom,
[60] Y is an oxygen atom,
[61] M ³ is aluminum,
[62] k is a natural number from 1 to 100.
[63] R ⁷ and R ⁸ are particularly preferably phenyl, methyl, ethyl, isopropyl, butyl, tolyl, biphenyl, or 2,3-dimethylphenyl.
[64] R ⁹ is in particular a halogenated or perhalogenated C ₆ -C ₃₀ -aryl group, for example a halogenated or partially halogenated biphenyl (eg octafluorobiphenyl, heptafluorobiphenyl, hexafluorobiphenyl) .
[65] According to the invention, preference is given to using compounds of the formula (I) in which R ¹ , R ² and R ³ are C ₁ -C ₆ -alkyl groups. R ¹ , R ² and R ³ are particularly preferably C ₁ -C ₄ -alkyl groups. In the general formula (I), M ¹ is preferably an element of the main group III of the periodic table of the elements, particularly preferably boron or aluminum. Particularly preferred is aluminum.
[66] Particularly preferred aluminum compounds of formula (I) are trimethylaluminum, triethylaluminum, triisopropylaluminum, trihexylaluminum, trioctylaluminum, tri-n-butylaluminum, tri-n-propylaluminum and triisoprenylaluminum. Among these, trimethyl aluminum, triethyl aluminum and triisopropyl aluminum are particularly preferable.
[67] Particularly preferred boron compounds of formula I are boranes with triethylborane and branched alkyl radicals.
[68] In a preferred compound of formula (II), it is preferred that the parental nucleus portion G is C ₁ -C ₂₀ -haloalkylene or C ₆ -C ₄₀ -haloarylene partially or fully halogenated, wherein chlorine and / or fluorine is halogen Used. It is particularly preferred that G is partially or fully fluorinated C ₆ -C ₄₀ -arylene.
[69] In formula (II), X is preferably oxygen, nitrogen or sulfur, particularly preferably oxygen or sulfur, particularly preferably oxygen. In addition, R ⁴ in formula (II) is preferably hydrogen or C ₁ -C ₂₀ -alkyl, particularly preferably oxygen.
[70] In the formula (II), the integer q is preferably assumed to be a value of 1 to 40, particularly preferably to a value of 1 to 10. In a particularly preferred embodiment of the invention, q is 2.
[71] In the compound of formula (II), M ² is preferably silicon, oxygen, nitrogen or sulfur, in particular oxygen. R ^5, R ⁶ is hydrogen or C ₁ -C ₂₀ - preferably an alkyl, and particularly more preferably a hydrogen. The integer g is preferably assumed to be a value of 0 to 10, particularly preferably to be a value of 1 to 5, and even more preferably to 1 or 2. In a particularly preferred embodiment of the invention, g is 1.
[72] In the compound of formula II, (M ² R ⁵ R ⁶ ) _g is preferably water or alcohol. Especially preferred are water, methanol, ethanol and branched alcohols. Especially more preferable is the case of using water.
[73] Particularly preferred compounds of formula (II) wherein G is partially or fully fluorinated C ₆ -C ₄₀ -arylene are 2 to 40, preferably 2 to 20, particularly more preferably 2 to 2, as substituent R ⁴ X It contains eight hydroxyl groups.
[74] Non-limiting examples of compounds of Formula II are as follows:
[75] 4,4'-dihydroxyoctafluorobiphenyl * (s * H ₂ O),
[76] 4,3'-dihydroxyoctafluorobiphenyl * (s * H ₂ O),
[77] 4,5'-dihydroxyoctafluorobiphenyl * (s * H ₂ O),
[78] 4,6'-dihydroxyoctafluorobiphenyl * (s * H ₂ O),
[79] 4,7'-dihydroxyoctafluorobiphenyl * (s * H ₂ O),
[80] 4,8'-dihydroxyoctafluorobiphenyl * (s * H ₂ O),
[81] 1,2-dihydroxyoctafluorobiphenyl * (s * H ₂ O),
[82] 1,3-dihydroxyoctafluorobiphenyl * (s * H ₂ O),
[83] 4,4'-dihydroxyheptafluorobiphenyl * (s * H ₂ O),
[84] 4,3'-dihydroxyheptafluorobiphenyl * (s * H ₂ O),
[85] 4,5'-dihydroxyheptafluorobiphenyl * (s * H ₂ O),
[86] 4,6'-dihydroxyheptafluorobiphenyl * (s * H ₂ O),
[87] 4,7'-dihydroxyheptafluorobiphenyl * (s * H ₂ O),
[88] 4,8'-dihydroxyheptafluorobiphenyl * (s * H ₂ O),
[89] 1,2-dihydroxyheptafluorobiphenyl * (s * H ₂ O),
[90] 1,3-dihydroxyheptafluorobiphenyl * (s * H ₂ O),
[91] 4,4'-dihydroxyhexafluorobiphenyl * (s * H ₂ O),
[92] 4,3'-dihydroxyhexafluorobiphenyl * (s * H ₂ O),
[93] 4,5'-dihydroxyhexafluorobiphenyl * (s * H ₂ O),
[94] 4,6'-dihydroxyhexafluorobiphenyl * (s * H ₂ O),
[95] 4,7'-dihydroxyhexafluorobiphenyl * (s * H ₂ O),
[96] 4,8'-dihydroxyhexafluorobiphenyl * (s * H ₂ O),
[97] 1,2-dihydroxyhexafluorobiphenyl * (s * H ₂ O),
[98] 1,3-dihydroxyhexafluorobiphenyl * (s * H ₂ O),
[99] 4,4'-dihydroxypentafluorobiphenyl * (s * H ₂ O),
[100] 4,3'-dihydroxypentafluorobiphenyl * (s * H ₂ O),
[101] 4,5'-dihydroxypentafluorobiphenyl * (s * H ₂ O),
[102] 4,6'-dihydroxypentafluorobiphenyl * (s * H ₂ O),
[103] 4,7'-dihydroxypentafluorobiphenyl * (s * H ₂ O),
[104] 4,8'-dihydroxypentafluorobiphenyl * (s * H ₂ O),
[105] 1,2-dihydroxypentafluorobiphenyl * (s * H ₂ O),
[106] 1,3-dihydroxypentafluorobiphenyl * (s * H ₂ O),
[107] 4,4'-dihydroxyoctachlorobiphenyl * (s * H ₂ O),
[108] 4,3'-dihydroxyoctachlorobiphenyl * (s * H ₂ O),
[109] 4,5'-dihydroxyoctachlorobiphenyl * (s * H ₂ O),
[110] 4,6'-dihydroxyoctachlorobibiphenyl * (s * H ₂ O),
[111] 4,7'-dihydroxyoctachlorobiphenyl * (s * H ₂ O),
[112] 4,8'-dihydroxyoctachlorobiphenyl * (s * H ₂ O),
[113] 1,2-dihydroxyoctachlorobiphenyl * (s * H ₂ O),
[114] 1,3-dihydroxyoctachlorobiphenyl * (s * H ₂ O),
[115] 4,4'-dihydroxyheptachlorobiphenyl * (s * H ₂ O),
[116] 4,3'-dihydroxyheptachlorobiphenyl * (s * H ₂ O),
[117] 4,5'-dihydroxyheptachlorobiphenyl * (s * H ₂ O),
[118] 4,6'-dihydroxyheptachlorobiphenyl * (s * H ₂ O),
[119] 4,7'-dihydroxyheptachlorobiphenyl * (s * H ₂ O),
[120] 4,8'-dihydroxyheptachlorobiphenyl * (s * H ₂ O),
[121] 1,2-dihydroxyheptachlorobiphenyl * (s * H ₂ O),
[122] 1,3-dihydroxyheptachlorobiphenyl * (s * H ₂ O),
[123] 4,4'-dihydroxyhexachlorobiphenyl * (s * H ₂ O),
[124] 4,3'-dihydroxyhexachlorobiphenyl * (s * H ₂ O),
[125] 4,5'-dihydroxyhexachlorobiphenyl * (s * H ₂ O),
[126] 4,6'-dihydroxyhexachlorobiphenyl * (s * H ₂ O),
[127] 4,7'-dihydroxyhexachlorobiphenyl * (s * H ₂ O),
[128] 4,8'-dihydroxyhexachlorobiphenyl * (s * H ₂ O),
[129] 1,2-dihydroxyhexachlorobiphenyl * (s * H ₂ O),
[130] 1,3-dihydroxyhexachlorobiphenyl * (s * H ₂ O),
[131] 4,4'-dihydroxypentachlorobiphenyl * (s * H ₂ O),
[132] 4,3'-dihydroxypentachlorobiphenyl * (s * H ₂ O),
[133] 4,5'-dihydroxypentachlorobiphenyl * (s * H ₂ O),
[134] 4,6'-dihydroxypentachlorobiphenyl * (s * H ₂ O),
[135] 4,7'-dihydroxypentachlorobiphenyl * (s * H ₂ O),
[136] 4,8'-dihydroxypentachlorobiphenyl * (s * H ₂ O),
[137] 1,2-dihydroxypentachlorobiphenyl * (s * H ₂ O),
[138] 1,3-dihydroxypentachlorolobiphenyl * (s * H ₂ O),
[139] 1,8-dihydroxyhexafluoronaphthalene * (s * H ₂ O),
[140] 1,7-dihydroxyhexafluoronaphthalene * (s * H ₂ O),
[141] 1,6-dihydroxyhexafluoronaphthalene * (s * H ₂ O),
[142] 1,7-dihydroxyhexafluoronaphthalene * (s * H ₂ O),
[143] 1,5-dihydroxyhexafluoronaphthalene * (s * H ₂ O),
[144] 1,4-dihydroxyhexafluoronaphthalene * (s * H ₂ O),
[145] 1,3-dihydroxyhexafluoronaphthalene * (s * H ₂ O),
[146] 1,2-dihydroxyhexafluoronaphthalene * (s * H ₂ O),
[147] 1,8-dihydroxyhexachloronaphthalene * (s * H ₂ O),
[148] 1,7-dihydroxyhexachloronaphthalene * (s * H ₂ O),
[149] 1,6-dihydroxyhexachloronaphthalene * (s * H ₂ O),
[150] 1,7-dihydroxyhexachloronaphthalene * (s * H ₂ O),
[151] 1,5-dihydroxyhexachloronaphthalene * (s * H ₂ O),
[152] 1,4-dihydroxyhexachloronaphthalene * (s * H ₂ O),
[153] 1,3-dihydroxyhexachloronaphthalene * (s * H ₂ O),
[154] 1,2-dihydroxyhexachloronaphthalene * (s * H ₂ O),
[155] 1,8-dihydroxypentafluoronaphthalene * (s * H ₂ O),
[156] 1,7-dihydroxypentafluoronaphthalene * (s * H ₂ O),
[157] 1,6-dihydroxypentafluoronaphthalene * (s * H ₂ O),
[158] 1,7-dihydroxypentafluoronaphthalene * (s * H ₂ O),
[159] 1,5-dihydroxypentafluoronaphthalene * (s * H ₂ O),
[160] 1,4-dihydroxypentafluoronaphthalene * (s * H ₂ O),
[161] 1,3-dihydroxypentafluoronaphthalene * (s * H ₂ O),
[162] 1,2-dihydroxypentafluoronaphthalene * (s * H ₂ O),
[163] 1,8-dihydroxytetrakisfluoronaphthalene * (s * H ₂ O),
[164] 1,7-dihydroxytetrakisfluoronaphthalene * (s * H ₂ O),
[165] 1,6-dihydroxytetrakisfluoronaphthalene * (s * H ₂ O),
[166] 1,7-dihydroxytetrakisfluoronaphthalene * (s * H ₂ O),
[167] 1,5-dihydroxytetrakisfluoronaphthalene * (s * H ₂ O),
[168] 1,4-dihydroxytetrakisfluoronaphthalene * (s * H ₂ O),
[169] 1,3-dihydroxytetrakisfluoronaphthalene * (s * H ₂ O),
[170] 1,2-dihydroxytetrakisfluoronaphthalene * (s * H ₂ O),
[171] 1,2-dihydroxy-3,4,5,6,7,8,9,10,11,12-decafluoroterphenyl * (s * H ₂ O),
[172] 1,3-dihydroxy-2,4,5,6,7,8,9,10,11,12-decafluoroterphenyl * (s * H ₂ O),
[173] 1,4-dihydroxy-2,3,5,6,7,8,9,10,11,12-decafluoroterphenyl * (s * H ₂ O),
[174] 1,5-dihydroxy-2,3,4,6,7,8,9,10,11,12-decafluoroterphenyl * (s * H ₂ O),
[175] 1,6-dihydroxy-2,3,4,5,7,8,9,10,11,12-decafluoroterphenyl * (s * H ₂ O),
[176] 1,7-dihydroxy-2,3,4,5,6,8,9,10,11,12-decafluoroterphenyl * (s * H ₂ O),
[177] 1,8-dihydroxy-2,3,4,5,6,7,9,10,11,12-decafluoroterphenyl * (s * H ₂ O),
[178] 1,9-dihydroxy-2,3,4,5,6,7,8,10,11,12-decafluoroterphenyl * (s * H ₂ O),
[179] 1,10-dihydroxy-2,3,4,5,6,7,8,9,11,12-decafluoroterphenyl * (s * H ₂ O),
[180] 1,11-dihydroxy-2,3,4,5,6,7,8,9,10,12-decafluoroterphenyl * (s * H ₂ O),
[181] 1,12-dihydroxy-2,3,4,5,6,7,8,9,10,11-decafluoroterphenyl * (s * H ₂ O),
[182] 1,9-dihydroxynonafluoroanthracene * (s * H ₂ O),
[183] 1,2-dihydroxynonafluoroanthracene * (s * H ₂ O),
[184] 1,3-dihydroxynonafluoroanthracene * (s * H ₂ O),
[185] 1,4-dihydroxynonafluoroanthracene * (s * H ₂ O),
[186] 1,5-dihydroxynonafluoroanthracene * (s * H ₂ O),
[187] 1,6-dihydroxynonafluoroanthracene * (s * H ₂ O),
[188] 1,7-dihydroxynonafluoroanthracene * (s * H ₂ O),
[189] 1,8-dihydroxynonafluoroanthracene * (s * H ₂ O),
[190] 1,9-dihydroxynonachloroanthracene * (s * H ₂ O),
[191] 1,3-dihydroxynonachloroanthracene * (s * H ₂ O),
[192] 1,4-dihydroxynonachloroanthracene * (s * H ₂ O),
[193] 1,5-dihydroxynonachloroanthracene * (s * H ₂ O),
[194] 1,6-dihydroxynonachloroanthracene * (s * H ₂ O),
[195] 1,7-dihydroxynonachloroanthracene * (s * H ₂ O),
[196] 1,8-dihydroxynonachloroanthracene * (s * H ₂ O),
[197] 1,9-dihydroxyoctaruoroanthracene * (s * H ₂ O),
[198] 1,2-dihydroxyoctafluoroanthracene * (s * H ₂ O),
[199] 1,3-dihydroxyoctafluoroanthracene * (s * H ₂ O),
[200] 1,4-dihydroxyoctafluoroanthracene * (s * H ₂ O),
[201] 1,5-dihydroxyoctafluoroanthracene * (s * H ₂ O),
[202] 1,6-dihydroxyoctafluoroanthracene * (s * H ₂ O),
[203] 1,7-dihydroxyoctafluoroanthracene * (s * H ₂ O),
[204] 1,8-dihydroxyoctafluoroanthracene * (s * H ₂ O),
[205] 1,9-dihydroxyheptafluoroanthracene * (s * H ₂ O),
[206] 1,2-dihydroxyheptafluoroanthracene * (s * H ₂ O),
[207] 1,3-dihydroxyheptafluoroanthracene * (s * H ₂ O),
[208] 1,4-dihydroxyheptafluoroanthracene * (s * H ₂ O),
[209] 1,5-dihydroxyheptafluoroanthracene * (s * H ₂ O),
[210] 1,6-dihydroxyheptafluoroanthracene * (s * H ₂ O),
[211] 1,7-dihydroxyheptafluoroanthracene * (s * H ₂ O),
[212] 1,8-dihydroxyheptafluoroanthracene * (s * H ₂ O),
[213] 1,9-dihydroxyhexafluoroanthracene * (s * H ₂ O),
[214] 1,2-dihydroxyhexafluoroanthracene * (s * H ₂ O),
[215] 1,3-dihydroxyhexafluoroanthracene * (s * H ₂ O),
[216] 1,4-dihydroxyhexafluoroanthracene * (s * H ₂ O),
[217] 1,5-dihydroxyhexafluoroanthracene * (s * H ₂ O),
[218] 1,6-dihydroxyhexafluoroanthracene * (s * H ₂ O),
[219] 1,7-dihydroxyhexafluoroanthracene * (s * H ₂ O),
[220] 1,8-dihydroxyhexafluoroanthracene * (s * H ₂ O),
[221] 1,9-dihydroxynonafluorophenanthrene * (s * H ₂ O),
[222] 1,2-dihydroxynonafluorophenanthrene * (s * H ₂ O),
[223] 1,3-dihydroxynonafluorophenanthrene * (s * H ₂ O),
[224] 1,4-dihydroxynonafluorophenanthrene * (s * H ₂ O),
[225] 1,5-dihydroxynonafluorophenanthrene * (s * H ₂ O),
[226] 1,6-dihydroxynonafluorophenanthrene * (s * H ₂ O),
[227] 1,7-dihydroxynonafluorophenanthrene * (s * H ₂ O),
[228] 1,8-dihydroxynonafluorophenanthrene * (s * H ₂ O),
[229] 1,9-dihydroxynonachlorophenanthrene * (s * H ₂ O),
[230] 1,3-dihydroxynonachlorophenanthrene * (s * H ₂ O),
[231] 1,4-dihydroxynonachlorophenanthrene * (s * H ₂ O),
[232] 1,5-dihydroxynonachlorophenanthrene * (s * H ₂ O),
[233] 1,6-dihydroxynonachlorophenanthrene * (s * H ₂ O),
[234] 1,7-dihydroxynonachlorophenanthrene * (s * H ₂ O),
[235] 1,8-dihydroxynonachlorophenanthrene * (s * H ₂ O),
[236] 1,9-dihydroxyoctafluorophenanthrene * (s * H ₂ O),
[237] 1,2-dihydroxyoctafluorophenanthrene * (s * H ₂ O),
[238] 1,3-dihydroxyoctafluorophenanthrene * (s * H ₂ O),
[239] 1,4-dihydroxyoctafluorophenanthrene * (s * H ₂ O),
[240] 1,5-dihydroxyoctafluorophenanthrene * (s * H ₂ O),
[241] 1,6-dihydroxyoctafluorophenanthrene * (s * H ₂ O),
[242] 1,7-dihydroxyoctafluorophenanthrene * (s * H ₂ O),
[243] 1,8-dihydroxyoctafluorophenanthrene * (s * H ₂ O),
[244] 1,9-dihydroxyheptafluorophenanthrene * (s * H ₂ O),
[245] 1,2-dihydroxyheptafluorophenanthrene * (s * H ₂ O),
[246] 1,3-dihydroxyheptafluorophenanthrene * (s * H ₂ O),
[247] 1,4-dihydroxyheptafluorophenanthrene * (s * H ₂ O),
[248] 1,5-dihydroxyheptafluorophenanthrene * (s * H ₂ O),
[249] 1,6-dihydroxyheptafluorophenanthrene * (s * H ₂ O),
[250] 1,7-dihydroxyheptafluorophenanthrene * (s * H ₂ O),
[251] 1,8-dihydroxyheptafluorophenanthrene * (s * H ₂ O),
[252] 1,9-dihydroxyhexafluorophenanthrene * (s * H ₂ O),
[253] 1,2-dihydroxyhexafluorophenanthrene * (s * H ₂ O),
[254] 1,3-dihydroxyhexafluorophenanthrene * (s * H ₂ O),
[255] 1,4-dihydroxyhexafluorophenanthrene * (s * H ₂ O),
[256] 1,5-dihydroxyhexafluorophenanthrene * (s * H ₂ O),
[257] 1,6-dihydroxyhexafluorophenanthrene * (s * H ₂ O),
[258] 1,7-dihydroxyhexafluorophenanthrene * (s * H ₂ O),
[259] 1,8-dihydroxyhexafluorophenanthrene * (s * H ₂ O),
[260] 4,5,4'-trihydroxyheptafluorobiphenyl * (s * H ₂ O),
[261] 4,5,3'-trihydroxyheptafluorobiphenyl * (s * H ₂ O),
[262] 4,5,5'-trihydroxyheptafluorobiphenyl * (s * H ₂ O),
[263] 4,5,6'-trihydroxyheptafluorobiphenyl * (s * H ₂ O),
[264] 3,4,5 ', 7'-tetrahydroxyhexafluorobiphenyl * (s * H ₂ O),
[265] 3,4,6 ', 8'-tetrahydroxyhexafluorobiphenyl * (s * H ₂ O),
[266] 3,5,5 ', 7'-tetrahydroxyhepsafluorobiphenyl * (s * H ₂ O),
[267] 3,5,3 ', 5'-tetrahydroxyhepsafluorobiphenyl * (s * H ₂ O),
[268] Here, s is preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.
[269] The present invention also provides a supported catalyst system in which a chemical product obtained by reacting a compound of formula (I) with a compound of formula (II) is used as a promoter, and provides a process for preparing the catalyst system. The present invention also provides a process for producing polyolefins by polymerization in the presence of the catalyst system of the present invention.
[270] According to the present invention, the reaction of a compound of formula (I) with a compound of formula (II) to obtain a chemical product of the invention is generally carried out using the following process.
[271] First, one or more compounds of formula (I) may be placed in the reaction vessel. The compound may be dissolved or suspended in the solvent or present as such. Suitable solvents are aliphatic or aromatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, petroleum ether, toluene, Benzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene,, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene , Ethylbenzene, propylbenzene and the like, and also ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, diisopropyl ether, di-n-butyl ether, anisole or mixtures thereof. Of these, particularly preferred are aromatic hydrocarbons, in particular toluene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene And 1,3,5-trimethylbenzene. The compound of formula (I) and any solvent used are generally placed in a reaction vessel at -100 ° C to 300 ° C, preferably at -80 ° C to 200 ° C, particularly preferably at 20 ° C to 150 ° C. The compound of formula (I) is preferably present in the liquid phase.
[272] Subsequently, one or more compounds of the formula (II) may be added. The compound of formula II can likewise be dissolved or suspended in a solvent or added as such. Suitable solvents are as described above. Preferred solvents are also as described above. The addition can be carried out over 1 minute to 96 hours. The addition is preferably carried out for 10 minutes to 8 hours. The initial charging temperature at the time of addition is -100 degreeC-200 degreeC, It is preferable that it is -80 degreeC-150 degreeC, It is especially preferable that it is 20 degreeC-150 degreeC. The temperature is generally selected such that one or more reactants are in the liquid phase. The temperature of the reaction which follows is generally 20 to 150 degreeC. The reaction can be carried out at atmospheric or superatmospheric pressure, the latter requiring an appropriate reactor. The molar ratio in which the compound of formula I and the compound of formula II are mixed is generally 1: 1000 to 1: 0.01 based on the amount of M ¹ in the compound of formula (I).
[273] The molar ratio of the compound of formula (I) to the compound of formula (II) is preferably 1: 100 to 1: 0.1 based on the amount of M ¹ in the compound of formula (I). Particular preference is given to stoichiometric reactions of the compounds of formulas (I) and (II). The molar ratio here depends on the number g of (M ² R ⁵ R ⁶ ) groups. The figures given here assume a value of 1 for g. If g has a higher value, correspondingly lesser amounts of compound II can be used.
[274] The invention also provides a process for the preparation of products suitable as promoters, in which the compound of formula I is reacted with the compound of formula II.
[275] The present invention also provides a catalyst system which preferably comprises the following components:
[276] A) at least one organic transition metal compound,
[277] B) at least one of the main group alkyls as required,
[278] C) at least one support component as needed, and
[279] D) at least one chemical product obtained by reacting a compound of formula I with a compound of formula II, preferably comprising a compound of formula III.
[280] It is preferable to use a metallocene compound as the organic transition metal compound A). These are for example crosslinked or uncrosslinked biscyclopentadienyl complexes as described in EP-A-0 129 368, EP-A-0 561 479, EP-A-0 543 304 and EP-A-0 576 970 Monocyclopentadienyl complexes such as, for example, crosslinked amidocyclopentadienyl complexes as described in EP-A-0 416 815, for example multinuclear cyclopenta as described in EP-A-0 632 063. Dienyl complexes, for example tetrahydropentalene substituted with π-ligand as described in EP-A-0 659 758, for example tetrahydropental substituted with π-ligand as described in EP-A-0 661 300 Hydroindene. It is also possible to use organometallic compounds in which the complexing ligand does not contain cyclopentadienyl units. See, eg, DH McConville, et al., Macromolecules, 1996, 29, 5241 and DH McConville, et al., J. Am. Chem. Soc., 1996, 118, 10008, diamine complexes of transition group III and IV elements of the periodic table of elements. Brookhart et al., J. Am. Chem. Soc. 1995, 117, 6414 and Brookhart et al., J. Am. Chem. Soc., 1996, 118, 267 can be used diamine complexes (eg, Ni ²⁺ or Pd ²⁺ complexes) of transition group VIII elements of the Periodic Table of the Elements. See also Brookhart et al., J. Am. Chem. Soc. 1998, 120, 4049 and Gibson et al., Chem. Commun. 1998, 849] 2,6-bis (imino) pyridyl complexes (eg, Co ²⁺ or Fe ²⁺ complexes) of transition group VIII metals of the Periodic Table of the Elements can be used. It is also possible to use metallocene compounds in which the complexing ligand contains a heterocycle. Examples of such compounds are described in WO 98/22486.
[281] Preferred metallocene compounds are uncrosslinked or crosslinked compounds of formula IV.
[282]
[283] Where M ⁴ is a metal of transition groups III, IV, V or VI of the Periodic Table of the Elements, in particular Ti, Zr or Hf,
[284] R ¹⁵ are the same or different and each is a hydrogen atom or Si (R ¹⁷ ) ₃ , where R ¹⁷ is the same or different and each is a hydrogen atom or a C ₁ -C ₄₀ group, preferably 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- C ₁₀ - alkenyl, C ₇ -C ₄₀ - aryl, C ₇ -C ₄₀ - alkyl, aryl, or C ₈ -C ₄₀ - aryl, or alkenyl, or R ¹⁵ is C ₁ -C ₃₀ group, preferably a C ₁ -C ₂₅ -alkyl, for example 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 - aryl, fluorinated C ₇ -C ₃₀ - alkyl, aryl or C ₁ -C ₁₂ - alkoxy, two or more radicals R ¹⁵ which is of the cyclopentadienyl ring Character (which connects the radical R ¹⁵⁾ C ₄ -C ₂₄ - may be combined to form a ring system (which may further be substituted),
[285] R ¹⁶ are the same or different and each is a hydrogen atom or Si (R ¹⁸ ) ₃ , wherein R ¹⁸ is the same or different and each is a hydrogen atom or a C ₁ -C ₄₀ group, preferably C ₁ -C ₂₀ -alkyl, C ₁ -C ₁₀ -fluoroalkyl, C ₁ -C ₁₀ -alkoxy, C ₆ -C ₁₄ -aryl, C ₆ -C ₁₀ -fluoroaryl, C ₆ -C ₁₀ -aryloxy, C ₂ -C ₁₀ -alkenyl, C ₇ -C ₄₀ - aryl, C ₇ -C ₄₀ - alkyl, aryl or C ₈ -C ₄₀ - alkenyl or aryl, or R ¹⁶ is C ₁ -C ₃₀ group, preferably C ₁ -C ₂₅ -alkyl, for example 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 ₅ -C ₂₄ -alkylheteroaryl, 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, fluorinated C ₇ -C ₃₀ -alkylaryl or C ₁ -C ₁₂ -alkoxy or at least two radicals R ¹⁶ The elements of the clopentadienyl ring (which link the radicals R ¹⁶ ) can be joined to form a C ₄ -C ₂₄ -ring system (which may be substituted later),
[286] l is 5 when v is 0, l is 4 when v is 1,
[287] m is 5 when v is 0, m is 4 when v is 1,
[288] L ¹ is the same or different and each is a hydrogen atom, a C ₁ -C ₁₀ -hydrocarbon group, for example C ₁ -C ₁₀ -alkyl or C ₆ -C ₁₀ -aryl, a halogen atom or OR ¹⁹ , SR ¹⁹ , OSi (R ¹⁹ ) ₃ , Si (R ¹⁹ ) ₃ , P (R ¹⁹ ) ₂ or N (R ¹⁹ ) ₂ , wherein R ¹⁹ is a halogen atom, a C ₁ -C ₁₀ -alkyl group, halogenated C ₁ -C _10- Alkyl group, C ₆ -C ₂₀ -aryl group or halogenated C ₆ -C ₂₀ -aryl group, or L ¹ is toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluor Robutanesulfonyl or 2,2,2-trifluoroethanesulfonyl group,
[289] o is an integer from 1 to 4, preferably 2,
[290] Z is a crosslinking constituent element between two cyclopentadienyl rings and v is 0 or 1.
[291] Examples of Z include M ⁵ R ²⁰ R ²¹ groups, where M ⁵ is carbon, silicon, germanium, boron or tin, and R ²⁰ and R ²¹ are the same or different and each is a C ₁ -C ₂₀ -hydrocarbon containing group, eg For example C ₁ -C ₁₀ -alkyl, C ₆ -C ₁₄ -aryl or trimethylsilyl. Z is CH ₂ , CH ₂ CH ₂ , CH (CH ₃ ) CH ₂ , CH (C ₄ H ₉ ) C (CH ₃ ) ₂ , C (CH ₃ ) ₂ , (CH ₃ ) ₂ Si, (CH ₃ ) ₂ Ge, (CH ₃ ) ₂ Sn, (C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (CH ₃ ) ₃ Si-Si (CH ₃ ) (C ₆ H ₅ ) ₂ Sn, (CH ₂ ) ₄ Si, CH ₂ Si (CH ₃ ) ₂ , MeSi-Si (Me) ₃ , oC ₆ H ₄ or 2,2 '-(C ₆ H _{4 2} ) or 1,2- (1-methylethanediyl), 1,2- (1,1-dimethylethanediyl) or 1,2 (1,2-dimethylethanediyl) crosslinking. Z may also form a monocyclic or polycyclic ring system with one or more radicals R ¹⁵ and / or R ¹⁶ .
[292] Preferred are chiral crosslinked metallocene compounds of the formula (IV), in particular those in which v is 1 and one or both cyclopentadienyl rings are preferably substituted so that they form an indenyl ring. The indenyl ring is preferably substituted, in particular in 2, 4, 2,4,5-position, 2,4,6-position, 2,4,7-position or 2,4,5,6-position In which is substituted by a C ₁ -C ₂₀ group, for example C ₁ -C ₁₀ -alkyl or C ₆ -C ₂₀ -aryl, wherein at least two substituents of the indenyl ring together form a ring system It may be.
[293] Chiral crosslinked metallocene compounds of formula IV can be used as pure racemic or pure meso compounds. However, it is also possible to use mixtures of racemic compounds and meso compounds.
[294] Examples of metallocene compounds are as follows:
[295] Dimethylsilanediylbis (indenyl) zirconium dichloride
[296] Dimethylsilanediylbis (4-naphthylindenyl) zirconium diclyde
[297] Dimethylsilanediylbis (2-methylbenzoindenyl) zirconium dichloride
[298] Dimethylsilanediylbis (2-methylindenyl) zirconium dichloride
[299] Dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride
[300] Dimethylsilanediylbis (2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride
[301] Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride
[302] Dimethylsilanediylbis (2-methyl-4-tert-butylindenyl) zirconium dichloride
[303] Dimethylsilanediylbis (2-methyl-4-isopropylindenyl) zirconium dichloride
[304] Dimethylsilanediylbis (2-methyl-4-ethylindenyl) zirconium dichloride
[305] Dimethylsilanediylbis (2-methyl-4-α-acenaft indenyl) zirconium dichloride
[306] Dimethylsilanediylbis (2,4-dimethylindenyl) zirconium dichloride
[307] Dimethylsilanediylbis (2-ethylindenyl) zirconium dichloride
[308] Dimethylsilanediylbis (2-ethyl-4-ethylindenyl) zirconium dichloride
[309] Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dichloride
[310] Dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride
[311] Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride
[312] Dimethylsilanediylbis (2-methyl-4,5-diisopropylindenyl) zirconium dichloride
[313] Dimethylsilanediylbis (2,4,6-trimethylindenyl) zirconium dichloride
[314] Dimethylsilanediylbis (2,5,6-trimethylindenyl) zirconium dichloride
[315] Dimethylsilanediylbis (2,4,7-trimethylindenyl) zirconium dichloride
[316] Dimethylsilanediylbis (2-methyl-5-isobutylindenyl) zirconium dichloride
[317] Dimethylsilanediylbis (2-methyl-5-t-butylindenyl) zirconium dichloride
[318] Methyl (phenyl) silanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride
[319] Methyl (phenyl) silanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride
[320] Methyl (phenyl) silanediylbis (2-methyl-4-isopropylindenyl) zirconium dichloride
[321] Methyl (phenyl) silanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride
[322] Methyl (phenyl) silanediylbis (2-methyl-4,5- (methylbenzo) indenyl) zirconium dichloride
[323] Methyl (phenyl) silanediylbis (2-methyl-4,5- (tetramethylbenzo) indenyl) zirconium dichloride
[324] Methyl (phenyl) silanediylbis (2-methyl-4-α-acenaft indenyl) zirconium dichloride
[325] Methyl (phenyl) silanediylbis (2-methylindenyl) zirconium dichloride
[326] Methyl (phenyl) silanediylbis (2-methyl-5-isobutylindenyl) zirconium dichloride
[327] 1,2-ethanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride
[328] 1,4-butanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride
[329] 1,2-ethanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride
[330] 1,4-butanediylbis (2-methyl-4-isopropylindenyl) zirconium dichloride
[331] 1,4-butanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride
[332] 1,2-ethanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride
[333] 1,2-ethanediylbis (2,4,7-trimethylindenyl) zirconium dichloride
[334] 1,2-ethanediylbis (2-methylindenyl) zirconium dichloride
[335] 1,4-butanediylbis (2-methylindenyl) zirconium dichloride
[336] [4- (η ⁵ -cyclopentadienyl) -4,6,6-trimethyl- (η ⁵ -4,5-tetrahydropentalene)] dichlorozirconium
[337] [4- (η ⁵ -3'-trimethylsilylcyclopentadienyl) -4,6,6-trimethyl- (η ⁵ -4,5-tetrahydropentalene)] dichlorozirconium
[338] [4- (η ⁵ -3'-isopropylcyclopentadienyl) -4,6,6-trimethyl- (η ⁵ -4,5-tetrahydropentalene)] dichlorozirconium
[339] [4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorotitanium
[340] [4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorozirconium
[341] [4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl] dichlorohafnium
[342] [4- (η ⁵ -3'-tert-butylcyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorotitanium
[343] 4- (η ⁵ -3'-isopropylcyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydropentalene)] dichlorotitanium
[344] 4- (η ⁵ -3'-methylcyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorotitanium
[345] 4- (η ⁵ -3'-trimethylsilylcyclopentadienyl) -2-trimethylsilyl-4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorotitanium
[346] 4- (η ⁵ -3'-tert-butylcyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorozirconium
[347] (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilyl-dichlorotitanium
[348] (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl-dichlorotitanium
[349] (Methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilyl-dichlorotitanium
[350] (Methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl-dichlorotitanium
[351] (tert-butylamido) (2,4-dimethyl-2,4-pentadien-1-yl) -dimethylsilyldichlorotitanium
[352] Bis- (cyclopentadienyl) zirconium dichloride
[353] Bis- (n-butylcyclopentadienyl) zirconium dichloride
[354] Bis- (1,3-dimethylcyclopentadienyl) zirconium dichloride
[355] Tetrachloro- [1- [bis (η ⁵ -1H-indene-1-ylidene) methylsilyl] -3-η ⁵ -cyclopenta-2,4-diene-1-ylidene) -3-η ^5- 9H-fluorene-9-ylidene) butane] -dizirconium
[356] Tetrachloro- [2- [bis (η ⁵ -2- methyl -1H- inden-1-ylidene) methoxy silyl] -5- (η ⁵ -2,3,4,5- tetramethylcyclopentadienyl -2 , 4-diene-1-ylidene) -5- (η ⁵ -9H-fluorene-9-ylidene) hexane] dizirconium
[357] Tetrachloro- [1- [bis (η ⁵ -1H-indene-1-ylidene) methylsilyl] -6- (η ⁵ -cyclopenta-2,4-diene-1-ylidene) -3- (η ⁵ -9H-fluorene-9-ylidene) -3-oxaheptane] dizirconium
[358] Dimethylsilanediylbis (2-methyl-4- (tert-butylphenylindenyl) zirconium dichloride
[359] Dimethylsilanediylbis (2-methyl-4- (4-methylphenylindenyl) zirconium dichloride
[360] Dimethylsilanediylbis (2-methyl-4- (4-ethylphenylindenyl) zirconium dichloride
[361] Dimethylsilanediylbis (2-methyl-4- (4-trifluoromethylphenylindenyl) zirconium dichloride
[362] Dimethylsilanediylbis (2-methyl-4- (4-methoxyphenylindenyl) zirconium dichloride
[363] Dimethylsilanediylbis (2-ethyl-4- (4-tert-butylphenylindenyl) zirconium dichloride
[364] Dimethylsilanediylbis (2-methyl-4- (4-methylphenylindenyl) zirconium dichloride
[365] Dimethylsilanediylbis (2-ethyl-4- (4-ethylphenylindenyl) zirconium dichloride
[366] Dimethylsilanediylbis (2-ethyl-4- (4-trifluoromethyl-phenylindenyl) zirconium dichloride
[367] Dimethylsilanediylbis (2-ethyl-4- (4-methoxyphenylindenyl) zirconium dichloride
[368] Dimethylsilanediylbis (2-methyl-4- (4-tert-butylphenylindenyl) dimethylzirconium
[369] Dimethylsilanediylbis (2-methyl-4- (4-methylphenylindenyl) dimethylzirconium
[370] Dimethylsilanediylbis (2-methyl-4- (4-ethylphenylindenyl) dimethylzirconium
[371] Dimethylsilanediylbis (2-methyl-4- (4-trifluoromethylphenylindenyl) dimethylzirconium
[372] Dimethylsilanediylbis (2-methyl-4- (4-methoxyphenylindenyl) dimethylzirconium
[373] Dimethylsilanediylbis (2-ethyl-4- (4-tert-butylphenylindenyl) dimethylzirconium
[374] Dimethylsilanediylbis (2-ethyl-4- (4-methylphenylindenyl) dimethylzirconium
[375] Dimethylsilanediylbis (2-ethyl-4- (4-ethylphenylindenyl) diethylzirconium
[376] Dimethylsilanediylbis (2-ethyl-4- (4-trifluoromethylphenylindenyl) dimethylzirconium
[377] Dimethylsilanediylbis (2-ethyl-4- (4-methoxyphenylindenyl) dimethylzirconium
[378] Dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[379] Dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) hafnium dichloride
[380] Dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) titanium dichloride
[381] Dimethylsilanediylbis (2-methyl-4- (4'-methylphenyl) indenyl) zirconium dichloride
[382] Dimethylsilanediylbis (2-methyl-4- (4'-n-propylphenyl) indenyl) zirconium dichloride
[383] Dimethylsilanediylbis (2-methyl-4- (4'-n-butylphenyl) indenyl) zirconium dichloride
[384] Dimethylsilanediylbis (2-methyl-4- (4'-hexylphenyl) indenyl) zirconium dichloride
[385] Dimethylsilanediylbis (2-methyl-4- (4'-sec-butylphenyl) indenyl) zirconium dichloride
[386] Dimethylsilanediylbis (2-ethyl-4-phenyl) indenyl) zirconium dichloride
[387] Dimethylsilanediylbis (2-ethyl-4- (4'-methylphenyl) indenyl) zirconium dichloride
[388] Dimethylsilanediylbis (2-ethyl-4- (4'-ethylphenyl) indenyl) zirconium dichloride
[389] Dimethylsilanediylbis (2-ethyl-4- (4'-n-propylphenyl) indenyl) zirconium dichloride
[390] Dimethylsilanediylbis (2-ethyl-4- (4'-n-butylphenyl) indenyl) zirconium dichloride
[391] Dimethylsilanediylbis (2-ethyl-4- (4'-hexylphenyl) indenyl) zirconium dichloride
[392] Dimethylsilanediylbis (2-ethyl-4- (4'-pentylphenyl) indenyl) zirconium dichloride
[393] Dimethylsilanediylbis (2-ethyl-4- (4'-cyclohexylphenyl) indenyl) zirconium dichloride
[394] Dimethylsilanediylbis (2-ethyl-4- (4'-sec-butylphenyl) indenyl) zirconium dichloride
[395] Dimethylsilanediylbis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[396] Dimethylsilanediylbis (2-n-propyl-4-phenyl) indenyl) zirconium dichloride
[397] Dimethylsilanediylbis (2-n-propyl-4- (4'-methylphenyl) indenyl) zirconium dichloride
[398] Dimethylsilanediylbis (2-n-propyl-4- (4'-ethylphenyl) indenyl) zirconium dichloride
[399] Dimethylsilanediylbis (2-n-propyl-4- (4'-isopropylphenyl) indenyl) zirconium dichloride
[400] Dimethylsilanediylbis (2-n-propyl-4- (4'-n-butylphenyl) indenyl) zirconium dichloride
[401] Dimethylsilanediylbis (2-n-propyl-4- (4'-hexylphenyl) indenyl) zirconium dichloride
[402] Dimethylsilanediylbis (2-n-propyl-4- (4'-cyclohexylphenyl) indenyl) zirconium dichloride
[403] Dimethylsilanediylbis (2-n-propyl-4- (4'-sec-butylphenyl) indenyl) zirconium dichloride
[404] Dimethylsilanediylbis (2-n-propyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[405] Dimethylsilanediylbis (2-n-butyl-4-phenyl) indenyl) zirconium dichloride
[406] Dimethylsilanediylbis (2-n-butyl-4- (4'-methylphenyl) indenyl) zirconium dichloride
[407] Dimethylsilanediylbis (2-n-butyl-4- (4'-ethylphenyl) indenyl) zirconium dichloride
[408] Dimethylsilanediylbis (2-n-butyl-4- (4'-n-propylphenyl) indenyl) zirconium dichloride
[409] Dimethylsilanediylbis (2-n-butyl-4- (4'-isopropylphenyl) indenyl) zirconium dichloride
[410] Dimethylsilanediylbis (2-n-butyl-4- (4'-n-butylphenyl) indenyl) zirconium dichloride
[411] Dimethylsilanediylbis (2-n-butyl-4- (4'-hexylphenyl) indenyl) zirconium dichloride
[412] Dimethylsilanediylbis (2-n-butyl-4- (4'-cyclohexylphenyl) indenyl) zirconium dichloride
[413] Dimethylsilanediylbis (2-n-butyl-4- (4'-sec-butylphenyl) indenyl) zirconium dichloride
[414] Dimethylsilanediylbis (2-n-butyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[415] Dimethylsilanediylbis (2-hexyl-4-phenyl) indenyl) zirconium dichloride
[416] Dimethylsilanediylbis (2-hexyl-4- (4'-methylphenyl) indenyl) zirconium dichloride
[417] Dimethylsilanediylbis (2-hexyl-4- (4'-ethylphenyl) indenyl) zirconium dichloride
[418] Dimethylsilanediylbis (2-hexyl-4- (4'-n-propylphenyl) indenyl) zirconium dichloride
[419] Dimethylsilanediylbis (2-hexyl-4- (4'-isopropylphenyl) indenyl) zirconium dichloride
[420] Dimethylsilanediylbis (2-hexyl-4- (4'-n-butylphenyl) indenyl) zirconium dichloride
[421] Dimethylsilanediylbis (2-hexyl-4- (4'-hexylphenyl) indenyl) zirconium dichloride
[422] Dimethylsilanediylbis (2-hexyl-4- (4'-cyclohexylphenyl) indenyl) zirconium dichloride
[423] Dimethylsilanediylbis (2-hexyl-4- (4'-sec-butylphenyl) indenyl) zirconium dichloride
[424] Dimethylsilanediylbis (2-hexyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[425] Dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium bis (dimethylamide)
[426] Dimethylsilandiylbis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) dibenzylzirconium
[427] Dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) dimethylzirconium
[428] Dimethylgermandiylbis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[429] Dimethylgermandiylbis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) hafnium dichloride
[430] Dimethylgermandiylbis (2-propyl-4- (4'-tert-butylphenyl) indenyl) titanium dichloride
[431] Dimethylgermandiylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[432] Ethylidenebis (2-ethyl-4-phenyl) indenyl) zirconium dichloride
[433] Ethylidenebis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[434] Ethylidenebis (2-n-propyl- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[435] Ethylidenebis (2-n-butyl-4- (4'-tert-butylphenyl) indenyl) titanium dichloride
[436] Ethylidenebis (2-hexyl-4- (4'-tert-butylphenyl) indenyl) dibenzyl zirconium
[437] Ethylidenebis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) dibenzyl hafnium
[438] Ethylidenebis (2-methyl-4- (4'-tert-butylphenyl) indenyl) dibenzyl titanium
[439] Ethylidenebis (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[440] Ethylidenebis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) dimethyl hafnium
[441] Ethylidenebis (2-n-propyl-4-α-phenyl) indenyl) dimethyl titanium
[442] Ethylidenebis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium bis (dimethylamide)
[443] Ethylidenebis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) hafnium bis (dimethylamide)
[444] Ethylidenebis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) titanium bis (dimethylamide)
[445] Methylethylidenebis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[446] Methylethylidenebis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) hafnium dichloride
[447] Phenylphosphinediyl (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[448] Phenylphosphinediyl (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[449] Phenylphosphinediyl (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
[450] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[451] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[452] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[453] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[454] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[455] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[456] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[457] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[458] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[459] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[460] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[461] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[462] Dimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[463] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[464] Dimethylsilandiyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[465] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[466] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[467] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[468] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-methylphenylindenyl) zirconium dichloride
[469] Dimethylsilanediyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[470] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[471] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[472] Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[473] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[474] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[475] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[476] Dimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[477] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[478] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[479] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[480] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[481] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[482] Dimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[483] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[484] Dimethylsilanediyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[485] Dimethylsilanediyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[486] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[487] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[488] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-ethylphenylindenyl) zirconium dichloride
[489] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[490] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[491] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[492] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[493] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[494] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[495] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[496] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[497] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[498] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[499] Dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[500] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[501] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[502] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[503] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[504] Dimethylsilandiyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[505] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[506] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[507] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[508] Dimethylsilanediyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-n-propylphenylindenyl) zirconium dichloride
[509] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[510] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[511] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[512] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[513] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[514] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[515] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[516] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[517] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[518] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[519] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'isopropylphenylindenyl) zirconium dichloride
[520] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[521] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[522] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[523] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[524] Dimethylsilandiyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[525] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[526] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[527] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[528] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-isopropylphenylindenyl) zirconium dichloride
[529] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[530] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[531] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[532] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[533] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[534] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[535] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[536] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[537] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[538] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[539] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[540] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[541] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[542] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[543] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[544] Dimethylsilandiyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[545] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[546] Dimethylsilanediyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[547] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[548] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-n-butylphenylindenyl) zirconium dichloride
[549] Dimethylsilanediyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[550] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[551] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[552] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[553] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[554] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[555] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[556] Dimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[557] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[558] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[559] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4's-butylphenylindenyl) zirconium dichloride
[560] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[561] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[562] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[563] Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[564] Dimethylsilanediyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[565] Dimethylsilanediyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[566] Dimethylsilanediyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[567] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[568] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-sec-butylphenylindenyl) zirconium dichloride
[569] Dimethylsilanediyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[570] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[571] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[572] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[573] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[574] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[575] Dimethylsilandiyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[576] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[577] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[578] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[579] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[580] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[581] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[582] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[583] Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[584] Dimethylsilanediyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[585] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[586] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[587] Dimethylsilandiyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[588] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[589] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[590] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[591] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[592] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[593] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[594] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[595] Dimethylsilandiyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[596] Dimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[597] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[598] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[599] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[600] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[601] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[602] Dimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[603] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[604] Dimethylsilanediyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[605] Dimethylsilanediyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[606] Dimethylsilanediyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[607] Dimethylsilandiyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[608] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-n-pentylphenylindenyl) zirconium dichloride
[609] Dimethylsilanediyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[610] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[611] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[612] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[613] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[614] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[615] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[616] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[617] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[618] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[619] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[620] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[621] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[622] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[623] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[624] Dimethylsilanediyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[625] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[626] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[627] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[628] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-n-hexylphenylindenyl) zirconium dichloride
[629] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[630] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[631] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[632] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[633] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[634] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[635] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[636] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[637] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[638] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[639] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'cyclohexylphenylindenyl) zirconium dichloride
[640] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[641] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[642] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[643] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[644] Dimethylsilandiyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[645] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[646] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[647] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[648] Dimethylsilanediyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-cyclohexylphenylindenyl) zirconium dichloride
[649] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[650] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[651] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[652] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[653] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[654] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[655] Dimethylsilandiyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[656] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[657] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[658] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[659] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'trimethylsilylphenylindenyl) zirconium dichloride
[660] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[661] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[662] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[663] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[664] Dimethylsilanediyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[665] Dimethylsilanediyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[666] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[667] Dimethylsilandiyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[668] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-trimethylsilylphenylindenyl) zirconium dichloride
[669] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[670] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[671] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[672] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[673] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[674] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[675] Dimethylsilandiyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[676] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[677] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[678] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[679] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'adamantylphenylindenyl) zirconium dichloride
[680] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[681] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[682] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[683] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[684] Dimethylsilandiyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[685] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[686] Dimethylsilanediyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[687] Dimethylsilandiyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[688] Dimethylsilanediyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-adamantylphenylindenyl) zirconium dichloride
[689] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[690] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[691] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[692] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[693] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[694] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[695] Dimethylsilandiyl (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[696] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[697] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[698] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[699] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4'tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[700] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[701] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[702] Dimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[703] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[704] Dimethylsilanediyl (2-methyl-4-oxapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[705] Dimethylsilanediyl (2-methyl-5-oxapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[706] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[707] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[708] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenylindenyl) zirconium dichloride
[709] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-ethyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[710] Dimethylsilanediyl (2-methyl-5,6-dihydro-4-azapentalene) (2-ethyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[711] Dimethylsilanediyl (2-methyl-4-azapentalene) (2-ethyl-4- (4'-tert-butylphenylindenylphenylindenyl) zirconium dichloride
[712] Dimethylsilanediyl (2-methyl-5,6-dihydro-4-azapentalene) (2-ethyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[713] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-ethyl-4- (4'-tert-butylphenyltetrahydroindenyl) zirconium dichloride
[714] Dimethylsilanediyl (2-methyl-5-azapentalene) (2-n-butyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[715] Ethylidene (2-methyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[716] Dimethylsilandiyl (2-methyl-N-trimethylsilyl-4-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[717] Dimethylsilandiyl (2-methyl-N-tolyl-5-azapentalene) (2-n-propyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[718] Dimethylgermandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[719] Methylethylidene (2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[720] Dimethylsilanediyl (2,5-diisopropyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[721] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2,6-dimethyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[722] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (6'-tert-butylnaphthylindenyl) zirconium dichloride
[723] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4- (6'-tert-butylanthracenylindenyl) zirconium dichloride
[724] Dimethylsilandiyl (2-methyl-4-phosphapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[725] Diphenylsilanediyl (2-methyl-5-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[726] Methylphenylsilanediyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[727] Methylidene (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[728] Dimethylmethylidene (2,5, -dimethyl-6-thiapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[729] Diphenylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[730] Diphenylsilanediyl (2-methyl-6-oxapentalene) (2-methyl-4- (4'-tert-butylphenylindenyl) zirconium dichloride
[731] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methylindenyl) zirconium dichloride
[732] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methylindenyl) zirconium dichloride
[733] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methylindenyl) zirconium dichloride
[734] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methylindenyl) zirconium dichloride
[735] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methylindenyl) zirconium dichloride
[736] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methylindenyl) zirconium dichloride
[737] Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methylindenyl) zirconium dichloride
[738] Dimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methylindenyl) zirconium dichloride
[739] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methylindenyl) zirconium dichloride
[740] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methylindenyl) zirconium dichloride
[741] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methylindenyl) zirconium dichloride
[742] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methylindenyl) zirconium dichloride
[743] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methylindenyl) zirconium dichloride
[744] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methylindenyl) zirconium dichloride
[745] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methylindenyl) zirconium dichloride
[746] Dimethylsilandiyl (2-methyl-4-oxapentalene) (2-methylindenyl) zirconium dichloride
[747] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methylindenyl) zirconium dichloride
[748] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methylindenyl) zirconium dichloride
[749] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methylindenyl) zirconium dichloride
[750] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methylindenyl) zirconium dichloride
[751] Dimethylsilandiyl (2-methyl-4-azapentalene) (indenyl) zirconium dichloride
[752] Dimethylsilandiyl (2-methyl-5-azapentalene) (indenyl) zirconium dichloride
[753] Dimethylsilandiyl (2-methyl-6-azapentalene) (indenyl) zirconium dichloride
[754] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (indenyl) zirconium dichloride
[755] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (indenyl) zirconium dichloride
[756] Dimethylsilandiyl (2,5-dimethyl-4-azapentalene) (indenyl) zirconium dichloride
[757] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (indenyl) zirconium dichloride
[758] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (indenyl) zirconium dichloride
[759] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (indenyl) zirconium dichloride
[760] Dimethylsilandiyl (2-methyl-4-thiapentalene) (indenyl) zirconium dichloride
[761] Dimethylsilandiyl (2-methyl-5-thiapentalene) (indenyl) zirconium dichloride
[762] Dimethylsilandiyl (2-methyl-6-thiapentalene) (indenyl) zirconium dichloride
[763] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (indenyl) zirconium dichloride
[764] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (indenyl) zirconium dichloride
[765] Dimethylsilandiyl (2-methyl-4-oxapentalene) (indenyl) zirconium dichloride
[766] Dimethylsilandiyl (2-methyl-5-oxapentalene) (indenyl) zirconium dichloride
[767] Dimethylsilandiyl (2-methyl-6-oxapentalene) (indenyl) zirconium dichloride
[768] Dimethylsilandiyl (2,5-dimethyl-4-oxapentalene) (indenyl) zirconium dichloride
[769] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (indenyl) zirconium dichloride
[770] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[771] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[772] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[773] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[774] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[775] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[776] Dimethylsilandiyl (2,5-dimethyl-4-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[777] Dimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[778] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[779] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[780] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4- (4's-butylphenyl2-methyl-4-phenylindenyl) zirconium dichloride
[781] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[782] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[783] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[784] Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[785] Dimethylsilanediyl (2-methyl-4-oxapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[786] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[787] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[788] Dimethylsilanediyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[789] Dimethylsilandiyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride
[790] Dimethylsilandiyl (2-methyl-4-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[791] Dimethylsilandiyl (2-methyl-5-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[792] Dimethylsilandiyl (2-methyl-6-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[793] Dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[794] Dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[795] Dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[796] Dimethylsilandiyl (2,5-dimethyl-4-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[797] Dimethylsilandiyl (2,5-dimethyl-6-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[798] Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[799] Dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[800] Dimethylsilandiyl (2-methyl-4-thiapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[801] Dimethylsilandiyl (2-methyl-5-thiapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[802] Dimethylsilandiyl (2-methyl-6-thiapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[803] Dimethylsilandiyl (2,5-dimethyl-4-thiapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[804] Dimethylsilandiyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[805] Dimethylsilandiyl (2-methyl-4-oxapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[806] Dimethylsilandiyl (2-methyl-5-oxapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[807] Dimethylsilandiyl (2-methyl-6-oxapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[808] Dimethylsilandiyl (2,5-dimethyl-4-oxapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[809] Dimethylsilanediyl (2,5-dimethyl-6-oxapentalene) (2-methyl-4,5-benzoindenyl) zirconium dichloride
[810] Dimethylsilanediylbis (2-methyl-4-azapentalene) zirconium dichloride
[811] Dimethylsilanediylbis (2-methyl-5-azapentalene) zirconium dichloride
[812] Dimethylsilanediylbis (2-methyl-6-azapentalene) zirconium dichloride
[813] Dimethylsilanediylbis (2-methyl-N-phenyl-4-azapentalene) zirconium dichloride
[814] Dimethylsilanediylbis (2-methyl-N-phenyl-5-azapentalene) zirconium dichloride
[815] Dimethylsilanediylbis (2-methyl-N-phenyl-6-azapentalene) zirconium dichloride
[816] Dimethylsilanediylbis (2,5-dimethyl-4-azapentalene) zirconium dichloride
[817] Dimethylsilanediylbis (2,5-dimethyl-6-azapentalene) zirconium dichloride
[818] Dimethylsilanediylbis (2,5-dimethyl-N-phenyl-4-azapentalene) zirconium dichloride
[819] Dimethylsilanediylbis (2,5-dimethyl-N-phenyl-6-azapentalene) zirconium dichloride
[820] Dimethylsilanediylbis (2-methyl-4-thiapentalene) zirconium dichloride
[821] Dimethylsilanediylbis (2-methyl-5-thiapentalene) zirconium dichloride
[822] Dimethylsilanediylbis (2-methyl-6-thiapentalene) zirconium dichloride
[823] Dimethylsilanediylbis (2,5-dimethyl-4-thiapentalene) zirconium dichloride
[824] Dimethylsilanediylbis (2,5-dimethyl-6-thiapentalene) zirconium dichloride
[825] Dimethylsilanediylbis (2-methyl-4-oxapentalene) zirconium dichloride
[826] Dimethylsilanediylbis (2-methyl-5-oxapentalene) zirconium dichloride
[827] Dimethylsilanediylbis (2-methyl-6-oxapentalene) zirconium dichloride
[828] Dimethylsilanediylbis (2,5-dimethyl-4-oxapentalene) zirconium dichloride
[829] Dimethylsilanediylbis (2,5-dimethyl-6-oxapentalene) zirconium dichloride
[830] Further examples of metallocenes that can be used in the process of the invention are the metallocenes in the list above in which the zirconium moiety “-zirconium dichloride” is substituted with:
[831] Zirconium Monochloride Mono (2,4-di-tert-butylphenoxide)
[832] Zirconium Monochloride Mono (2,6-di-tert-butylphenoxide)
[833] Zirconium Monochloride Mono (3,5-di-tert-butylphenoxide)
[834] Zirconium Monochloride Mono (2,6-di-sec-butylphenoxide)
[835] Zirconium Monochloride Mono (2,4-dimethylphenoxide)
[836] Zirconium Monochloride Mono (2,3-dimethylphenoxide)
[837] Zirconium Monochloride Mono (2,5-dimethylphenoxide)
[838] Zirconium Monochloride Mono (2,6-dimethylphenoxide)
[839] Zirconium Monochloride Mono (3,4-dimethylphenoxide)
[840] Zirconium Monochloride Mono (3,5-dimethylphenoxide)
[841] Zirconium Monochloride Monophenoxide
[842] Zirconium Monochloride Mono (2-Methylphenoxide)
[843] Zirconium Monochloride Mono (3-methylphenoxide)
[844] Zirconium Monochloride Mono (4-methylphenoxide)
[845] Zirconium Monochloride Mono (2-ethylphenoxide)
[846] Zirconium Monochloride Mono (3-ethylphenoxide)
[847] Zirconium Monochloride Mono (4-ethyloxide)
[848] Zirconium Monochloride Mono (2-sec-butylphenoxide)
[849] Zirconium Monochloride Mono (2-tert-Butylphenoxide)
[850] Zirconium Monochloride Mono (3-tert-Butylphenoxide)
[851] Zirconium Monochloride Mono (4-sec-Butylphenoxide)
[852] Zirconium Monochloride Mono (4-tert-Butylphenoxide)
[853] Zirconium Monochloride Mono (2-isopropyl-5-methylphenoxide)
[854] Zirconium Monochloride Mono (4-isopropyl-3-methylphenoxide)
[855] Zirconium Monochloride Mono (5-isopropyl-2-methylphenoxide)
[856] Zirconium Monochloride Mono (5-isopropyl-3-methylphenoxide)
[857] Zirconium Monochloride Mono (2,4-bis (2-methyl-2-butyl) phenoxide)
[858] Zirconium Monochloride Mono (2,6-di-tert-butyl-4-methylphenoxide)
[859] Zirconium Monochloride Mono (4-nonylphenoxide)
[860] Zirconium Monochloride Mono (1-naphthoxide)
[861] Zirconium Monochloride Mono (2-phenylphenoxide)
[862] Zirconium Monochloride Mono (2-naphthoxide)
[863] Zirconium Monochloride Mono (tert-butoxide)
[864] Zirconium Monochloride Mono (N-methylanilide)
[865] Zirconium monochloride mono (2-tert-butylanilide)
[866] Zirconium monochloride mono (tert-butylamide)
[867] Zirconium Monochloride Mono (di-isopropylamide)
[868] Zirconium Monochloride Monomethyl
[869] Zirconium Monochloride Monobenzyl
[870] Zirconium Monochloride Mononeopentyl
[871] Also preferred are the corresponding dimethyl zirconium compounds and the corresponding zirconium-η ⁴ -butadiene compounds.
[872] Preferred catalyst systems of the present invention are those comprising at least one main group alkyl B), wherein B) is particularly preferred for compounds of formula V, which are generally organometallic compounds, which are optional with compounds of formulas III and IV. Can be reacted in a stoichiometric ratio of.
[873]
[874] The radicals R ²⁰ of formula V are the same or different and each is a halogen atom, a hydrogen atom, a C ₁ -C ₄₀ group, preferably C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -haloaryl, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl, or C ₇ -C ₄₀ -haloalkyl Aryl. R ²⁰ is preferably a C ₁ -C ₆ -alkyl group, particularly preferably a C ₁ -C ₄ -alkyl group.
[875] To react the compounds of Formulas III and IV with the compounds of Formula V, the compounds may be suspended or dissolved in a solvent. However, the reaction may also be carried out in the absence of solvents or suspending media. Suitable solvents are as described above. Preferred solvents are also as described above. The reaction is generally carried out for 1 minute to 96 hours, preferably 10 minutes to 8 hours. The initial charging temperature at the time of addition is -100 degreeC-200 degreeC, Preferably it is -80 degreeC-150 degreeC, It is especially preferable that it is 20 degreeC-150 degreeC. The temperature is chosen such that one or more reactants are in the liquid phase. It is preferable that following reaction temperature is 20 degreeC-150 degreeC. The reaction can also be carried out at atmospheric or superatmospheric pressure, but the latter requires an appropriate reactor. The molar ratio in which the compounds of formulas III and IV are mixed with the compounds of formula V is 1000: 1 to 0.01: 1 based on the amounts of M ³ and M ⁴ in the compounds of formulas III and IV used.
[876] The molar ratio of the compounds of Formulas III and IV to the compounds of Formula V is preferably from 100: 1 to 1: 1 based on the amount of M ³ or M ⁴ in the compounds of Formulas III and IV used.
[877] In the preparation of the catalyst system of the present invention, the molar ratio of aluminum in the compound of formula III to M ⁴ in the compound of formula IV is 10,000 to 0.01. Preference is given to using molar ratios of 1000 to 0.1. Particular preference is given to using molar ratios of 100 to 1. For this purpose, the compound of formula V can be added so that the molar ratio of Al: M ⁴ is from 10,000 to 0.01. It is preferable that molar ratio is 1000-0.1, and it is especially preferable that it is 100-1.
[878] The compounds may be contacted with each other in any conceivable combination. One possible method is to dissolve or suspend the organic transition metal compound of formula IV in an aliphatic or aromatic solvent such as toluene, heptane, tetrahydrofuran or diethyl ether. The compound of formula V is then added in suspended or dissolved form. The reaction time is 1 minute to 24 hours, preferably 5 minutes to 120 minutes. Reaction temperature is -10 degreeC-+200 degreeC, Preferably it is 0 degreeC-50 degreeC. The organoaluminum compound of formula III is then added as such or in dissolved or suspended form. The reaction time is 1 minute to 24 hours, preferably 5 minutes to 120 minutes. Reaction temperature is -10 degreeC-+200 degreeC, Preferably it is 0 degreeC-50 degreeC. Each component may be introduced into the polymerization vessel continuously in any order.
[879] If necessary, the catalyst system of the present invention can be used in a supported form. To this end, the catalyst system of the present invention may be reacted with a support component.
[880] Preferred catalysts of the present invention include support component C), which may be an organic or inorganic inert solid. Particular preference is given to porous supports such as talc, inorganic oxides, mixed oxides and finely divided polymer particles (eg polyolefins).
[881] Suitable inorganic oxides are the oxides of the main group II-VI and transition group III-IV elements of the periodic table of elements. Examples of oxides preferred as the support include silicon dioxide, aluminum oxide and mixed oxides of the two elements and the corresponding oxide mixtures. Other inorganic oxides that may be used alone or in combination with the above-described preferred oxide supports are, for example, MgO, ZrO ₂ , TiO ₂ or B ₂ O ₃ .
[882] Supports generally used have a specific surface area of 10 to 1000 m ² / g, pore volume of 0.1 to 5 ml / g, and an average particle size of 1 to 500 μm. Preferred are supports having a specific surface area of 50 to 500 μm, pore volume of 0.5 to 3.5 ml / g and an average particle size of 5 to 350 μm. In particular, a support having a specific surface area of 200 to 400 m ² / g, a void volume of 0.8 to 3.0 ml / g and an average particle size of 10 to 200 μm is preferred.
[883] If the support material used originally had a low water content or residual solvent content, the dehydration or drying process before use can be omitted. If this is not the case, it is preferable to dehydrate or dry, for example when using silica gel as the support material. Thermal dehydration or drying of the support material can be carried out under reduced pressure while shielding with an inert gas (eg nitrogen). The drying temperature is in the range of 100 to 1000 ° C, preferably 200 to 800 ° C. In this case, the parameter pressure is not important. Drying can last for 1 to 24 hours. Shorter or longer drying times are also possible if equilibrium with hydroxyl groups on the support surface can be established under given conditions. It usually takes 4 to 8 hours.
[884] Dehydration or drying of the support material can be carried out by chemical means by reacting the hydroxyl groups and the absorbed water on the surface using a suitable passivating agent. The reaction with the passivating agent may convert the hydroxyl group completely or partially into a form that does not cause any reverse interaction with the catalytically active center. Suitable passivating agents include, for example, silicon halides and silanes, for example silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane, or organometallic compounds of aluminum, boron and magnesium, for example trimethylaluminum, triethylaluminum, Triisobutylaluminum, triethylborane and dibutylmagnesium. Chemical dehydration or passivation of the support material is carried out, for example, by reacting a suspension of the support material in a suitable solvent in the absence of air and moisture, either as a solution in a suitable solvent or with a passivating agent in pure form. Suitable solvents are for example aliphatic or aromatic hydrocarbons, for example pentane, hexane, heptane, toluene or xylene. Passivation is generally carried out at 25 ° C to 120 ° C, preferably at 50 ° C to 70 ° C. The reaction time is 30 minutes to 20 hours, preferably 1 hour to 5 hours. After the end of chemical dehydration, the support material can be separated by filtration under inert conditions as described above, washed one or more times with a suitable inert solvent and then dried under reduced pressure or in an inert gas stream.
[885] Organic support materials, for example finely divided polyolefin powders (e.g., polyethylene, polypropylene, or polystyrene) may be used, and also moisture, solvent residues or other impurities may be removed through appropriate purification or pre-use drying operations. There should be no.
[886] In order to apply the catalyst system of the present invention to the support, the catalyst mixture prepared above is dehydrated or mixed with the immobilized support material, the solvent is removed, and the obtained supported metallocene catalyst system is dried to obtain all or the solvent. Most are reliably removed from the pores of the support material. The supported catalyst is obtained as a free flowing powder.
[887] The present invention also provides a process for the production of polyolefins by the polymerization of one or more olefins in the presence of a catalyst system of the invention, preferably a catalyst system comprising at least one organometallic component of formula (V). For this purpose of the present invention, the term "polymerization reaction" includes homopolymerization and copolymerization.
[888] It is preferred to polymerize olefins of the formula R _m -CH = CH-R _n , wherein R _m and R _n are the same or different and each is a hydrogen atom or an organic radical having 1 to 20, in particular 1 to 10 carbon atoms R _m and R _n may form one or more rings together with the atoms to which they are bonded.
[889] Examples of such olefins are 1-olefins having 2 to 40, preferably 2 to 10 carbon atoms, for example ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- Pentene or 1-octene, styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinylnorbornene, norbornadiene or ethylnorbornadiene and cyclic olefins such as nord Bornenne, tetracyclododecene or methylnorbornene. In the process of the invention, propene or ethene is homopolymerized, or propene is ethene and / or one or more 1-olefins (eg hexene) having 4 to 20 carbon atoms, and / or 4 Preference is given to copolymerizing at least one diene having from 20 to 20 carbon atoms (eg, 1,4-butadiene, norbornadiene, ethylidenenorbornene or ethylnorbornadiene). Examples of corresponding copolymers are ethene-propene copolymers or ethene-propene-1,4-hexadiene terpolymers.
[890] The polymerization reaction is -60 ° C to 300 ° C, preferably 50 ° C to 200 ° C, and particularly preferably 50 ° C to 80 ° C. This pressure is between 0.5 and 2000 bar, preferably between 5 and 64 bar.
[891] The polymerization can be carried out in one or more steps, in solution, in bulk, in suspension or in gas phase, continuously or in batch units.
[892] The catalyst system prepared according to the invention is used as the sole catalyst component for the polymerization of olefins having 2 to 20 carbon atoms, or preferably at least one alkyl compound of the main Group I to III elements of the periodic table of the elements, for example It can be used with alkylaluminum, alkylmagnesium or alkyllithium or aluminoxane. Alkyl compounds are added to the monomer or suspending medium, which serve to purify the monomers of the substance which may impair the catalytic activity. The amount of alkyl compound added depends on the amount of monomer used.
[893] As molar mass regulators and / or to increase activity, hydrogen is added if necessary.
[894] Supported catalyst systems can be used directly for the polymerization. However, after removing the solvent, the catalyst system can be resuspended for use in the polymerization. The advantage of this activation method is that it provides the option of forming a polymerization-active catalyst system only in the reactor. This prevents partial decomposition from occurring when introducing an air sensitive catalyst.
[895] In addition, additives such as antistatic agents can be used according to the invention, for example, to improve the particle shape of the polymer.
[896] It is generally possible to use all antistatic agents suitable for the polymerization reaction. An example is a mixture of calcium salts of medialanic acid and chromium salts of N-stearylantranylic acid as described in DE-A-3,543,360. Other suitable antistatic agents include, for example, C ₁₂ -C ₂₂ fatty acid soaps of alkali or alkaline earth metals, salts of sulfonic acid esters, esters of polyethylene glycols and fatty acids, polyoxyethylene alkyl ethers, and the like. An overview of antistatic agents is given in EP-A-0,107,127.
[897] As disclosed in EP-A-0,636,636, mixtures of metal salts of medialanic acid, metal salts of anthranilic acid and polyamines can be used as antistatic agents.
[898] Toluene, isopropanol, dodecylbenzenesulfonic acid, polyamine, copolymer of 1-decene and SO ₂ , and Stadith 450 (registered trademark) of DuPont, a mixture of 1-decene, or ASA-3 (registered trademark) of Shell Commercially available products such as ARU5R® from ICI may also be used.
[899] The antistatic agent is preferably used as a solution. If Stadis 450 is preferred, this solution is the weight of the supported catalyst used (the compound forming metallocenium and the support covalently bonded with at least one metallocene compound (eg, compound of formula IV)) It is preferable to use 1 to 50% by weight, more preferably 5 to 25% by weight based on the above. However, the required amount of antistatic agent varies widely depending on the type of antistatic agent used.
[900] The polymers produced using the catalyst system of the present invention show a uniform particle shape and do not contain fine particles. Polymerization with the catalyst system of the present invention does not produce any deposits or cake materials.
[901] The polymers produced by the process of the invention are particularly suitable for producing rigid rigid shaped bodies, for example fibers, filaments, injection-molded parts, films, sheets or large hollow bodies (eg pipes) with good tension. Especially useful for
[902] The catalyst system preparation of the present invention, described in the above general terms, can be carried out by two different methods based on covalent bonding or physisorption to the support. The sequence of steps used in the two methods is described below:
[903] Method 1 (Physorption):
[904] In step 1, the inorganic support material (C) is reacted with a metal compound of formula (V). Preference is given to adding the metal compound of the formula V to the suspension of the support as a solution. Solvents or suspensions that can be used are those described in B. The amount of metal compound of formula V can vary widely; The minimum amount depends on the number of hydroxyl groups on the support. Temperature, reaction time and pressure by themselves are not critical. Preference is given if the temperature and reaction temperature are as described in Method 2. After pretreatment of the support, it was found that it is desirable to remove excess metal compound of formula V and dry the support by washing, for example by washing with a hydrocarbon such as pentane, hexane, ethylbenzene or heptane.
[905] This material is then reacted with the metallocene complex of formula IV and one or more compounds of the invention, preferably comprising a compound of formula III. It is also possible to use mixtures of various metallocene complexes.
[906] The conditions for the reaction of the compound of the present invention with the metallocene complex are not critical by themselves. The reaction is carried out in solution, in particular in hydrocarbons, preferably aromatic hydrocarbons (for example toluene) as solvents.
[907] Particularly useful are amounts of 0.1 to 10% by weight of the metallocene composite, based on the inorganic support material. Conditions are likewise not important in this reaction. Temperatures of 20 to 80 ° C. and reaction times of 0.1 to 20 hours have been found to be particularly useful.
[908] In a third step, the material obtained in the second step is reacted with a metal compound of formula V. This activation can be carried out at any point, ie before, during or after the material obtained in step 2 is introduced into the reactor. The activation is preferably carried out after the material obtained in step 2 has been introduced into the reactor.
[909] The chemical product of the invention, in particular the product comprising the compound of formula III, exhibits high activity, especially when used as a promoter in the polymerization of olefins. In addition, they can be stored for a long time and are also not flammable and can be easily dissolved.
[910] Method 2 (Covalent Bond to Supports)
[911] The catalyst system of the present invention may further comprise a Lewis base of formula VI.
[912] M ⁶ R ²¹ R ²² R ²³
[913] M ⁶ is the main group V element of the periodic table of elements,
[914] R ²¹ , R ²² , R ²³ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₄₀ -aryl, C ₆ -C ₄₀ -haloaryl , C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -arylalkyl group wherein two radicals or all three radicals R ²¹ , R ²² and R ²³ can be bonded to one another via a C ₂ -C ₂₀ unit At least one radical R ²¹ , R ²² , or R ²³ is not a hydrogen atom or a straight chain alkyl,
[915] Preferably, R ²¹ , R ²² and R ²³ are the same or different and each is a hydrogen atom or C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₄₀ -aryl, C ₆ -C _{A 40} -haloaryl, a C ₇ -C ₄₀ -alkylaryl or a C ₇ -C ₄₀ -arylalkyl group, two radicals or all three radicals R ²¹ , R ²² , and R ²³ are via C ₂ -C ₂₀ units At least one radical R ²¹ , R ²² , and R ²³ may be a radical or aromatic group having 2 to 20 carbon atoms, each of which may be substituted and / or consists of P, O, S, N Lewis base d of formula VI which may contain a hetero atom selected from: It is preferred that at least one radical R ²¹ , R ²² and R ²³ is an alkylaryl group, in particular a benzyl group.
[916] It is preferable that M ⁶ is nitrogen.
[917] Non-limiting examples of Lewis bases of Formula VI include
[918] N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylisopropylamine, N, N-diethylbenzylamine, N, N-dimethyl-p-toluidine, N, N -Diethyl-p-toluidine, N, N, -dimethylbenzylamine, N, N-diethylisopropylamine, N, N-diisopropylmethylamine, N, N-diisopropylethylamine, N, N -Dimethylcyclopentylamine, N, N-dimethylcycloheptenylamine, N, N-dimethylcyclooctanylamine, N, N-dimethylnonanoylamine, N, N-diethylcyclopentylamine, N, N- Diethylcycloheptenylamine, N, N-diethylcyclooctanylamine, N, N-diethylnonanoylamine;
[919] N-benzyldimethylamine, N-benzyldiethylamine, N-benzylbutylamine, N-benzyl-t-butylamine, N'-benzyl-N, N-dimethylethylenediamine, N-benzylethylenediamine, N-benzyl Isopropylamine, N-benzylmethylamine, N-benzylethylamine, N-benzyl-1-phenylethylamine, N-benzyl-2-phenylethylamine, or N-benzylpiperazine;
[920] N, N-dimethylisopropylamine, N, N-dimethyl-2-butylamine, N, N-dimethylisobutylamine, N, N-dimethyl-2-pentylamine, N, N-dimethyl-3-pentylamine , N, N-dimethyl-2-methylbutylamine, N, N-dimethyl-3-methylbutylamine, N, N-dimethylcyclopentanylamine, N, N-dimethyl-2-hexylamine, N, N-dimethyl -3-hexylamine, N, N-dimethyl-2-methylpentylamine, N, N-dimethyl-3-methylpentylamine, N, N-dimethyl-4-methylpentylamine, N, N-dimethyl-2- Ethylbutylamine, N, N-dimethylcyclohexylamine, N, N-dimethyl-2-heptylamine, N, N-dimethyl-3-heptylamine, N, N-dimethyl-4-heptylamine, N, N- Dimethyl-2-methylhexylamine, N, N-dimethyl-3-methylhexylamine, N, N-dimethyl-4-methylhexylamine, N, N-dimethyl-5-methylhexylamine, N, N-dimethyl- 2-ethylpentylamine, N, N-dimethyl-3-ethylpentylamine, N, N-dimethyl-2-propylbutylamine, N, N-dimethylcycloheptylamine, N, N-dimethylmethylcyclohexylamine, N , N-dimethylbenzylamine, N, N-dimethyl-2-octylamine, N, N-dimeth Methyl-3-octylamine;
[921] N, N-dimethyl-4-octylamine, N, N-dimethyl-2-methylheptylamine, N, N-dimethyl-3-methylheptylamine, N, N-dimethyl-4-methylheptylamine, N, N -Dimethyl-5-methylheptylamine, N, N-dimethyl-6-methylheptylamine, N, N-dimethyl-2-ethylhexylamine, N, N-dimethyl-3-ethylhexylamine, N, N-dimethyl -4-ethylhexylamine, N, N-dimethyl-2-propylpentylamine, N, N-dimethylcyclooctylamine, N, N-dimethyldimethylcyclohexylamine, N, N-diethylisopropylamine, N, N-diethyl-2-butylamine, N, N-diethylisobutylamine, N, N-diethyl-2-pentylamine, N, N-diethyl-3-pentylamine, N, N-diethyl 2-methylbutylamine, N, N-diethylcyclopentylamine, N, N-diethyl-2-hexylamine, N, N-diethyl-3-hexylamine, N, N-diethyl-2- Methylpentylamine, N, N-diethyl-3-methylpentylamine, N, N-diethyl-4-methylpentylamine, N, -diethyl-2-ethylbutylamine, N, N-diethylcyclohexyl Amine, N, N-diethyl-2-heptylamine, N, N-diethyl-3-heptylamine, N, N-diethyl-4-heptylamine, N, N-diethyl-2-methylhexylamine, N, N-diethyl-3-methylhexylamine, N, N-diethyl-4-methylhexylamine, N, N-diethyl-5-methylhexylamine, N, N-diethyl-2-ethylpentylamine, N, N-diethyl-3-ethylpentylamine, N, N-diethyl-2-propylbutylamine, N, N-diethylcycloheptylamine, N , N-diethylmethylcyclohexylamine, N, N-diethylbenzylamine, N, N-diethyl-2-octylamine, N, N-diethyl-3-octylamine, N, N-diethyl- 4-octylamine, N, N-diethyl-2-methylheptylamine, N, N-diethyl-3-methylheptylamine, N, N-diethyl-4-methylheptylamine, N, N-diethyl -5-methylheptylamine, N, N-diethyl-6-methylheptylamine, N, N-diethyl-2-ethylhexylamine, N, N-diethyl-3-ethylhexylamine, N, N- Diethyl-4-ethylhexylamine, N, N-diethyl-2-propylpentylamine, N, N-diethylcyclooctylamine, N, N-diethyldimethylcyclohexylamine, N-methyl-N-ethyl Isopropylamine, N-methyl-N-ethyl-2-butylamine, N-methyl-N-ethylisobutylamine, N-methyl-N-ethyl-2-pentylamine , N-methyl-N-ethyl-3-pentylamine, N-methyl-N-ethyl-2-methylbutylamine, N-methyl-N-ethyl-3-methylbutylamine, N-methyl-N-ethylcyclo Pentylamine, N-methyl-N-ethyl-2-hexylamine, N-methyl-N-ethyl-3-hexylamine, N-methyl-N-ethyl-2-methylpentylamine, N-methyl-N-ethyl -3-methylpentylamine, N-methyl-N-ethyl-4-methylpentylamine, N-methyl-N-ethyl-2-ethylbutylamine, N-methyl-N-ethyl-ethylcyclohexylamine, N- Methyl-N-ethyl-2-heptylamine, N-methyl-N-ethyl-3-heptylamine;
[922] N-methyl-N-ethyl-4-heptylamine, N-methyl-N-ethyl-2-methylhexylamine;
[923] M-methyl-N-ethyl-3-methylhexylamine, N-methyl-N-ethyl-4-methylhexylamine, N-methyl-N-ethyl-5-methylhexylamine, N-methyl-N-ethyl- 2-ethylpentylamine, N-methyl-N-ethyl-3-ethylpentylamine, N-methyl-N-ethyl-2-propylbutylamine, N-methyl-N-ethylcycloheptylamine, N-methyl-N -Ethylmethylcyclohexylamine, N-methyl-N-ethylbenzylamine, N-methyl-N-ethyl-2-octylamine, N-methyl-N-ethyl-3-octylamine, N-methyl-N-ethyl 4-octylamine, N-methyl-N-ethyl-2-methylheptylamine, N-methyl-N-ethyl-3-methylheptylamine, N-methyl-N-ethyl-4-methylheptylamine, N- Methyl-N-ethyl-5-methylheptylamine, N-methyl-N-ethyl-6-methylheptylamine, N-methyl-N-ethyl-2-ethylhexylamine, N-methyl-N-ethyl-3- Ethylhexylamine, N-methyl-N-ethyl-4-ethylhexylamine, N-methyl-N-ethyl-2-propylpentylamine, N-methyl-N-ethylcyclooctylamine, N-methyl-N-ethyl Dimethylcyclohexylamine, N-methylbis (diisopropyl) amine, N-methylbis (2-butyl) amine, N-methyl ratio (Isobutyl) amine, N-methylbis (2-pentyl) amine, N-methylbis (3-pentyl) amine, N-methylbis (2-methylbutyl) amine, N-methylbis (3-methylbutyl) Amine, N-methyldicyclopentylamine, N-methylbis (2-hexyl) amine, N-methylbis (3-hexyl) amine, N-methylbis (2-methylpentyl) amine, N-methylbis (3 -Methylpentyl) amine, N-methylbis (4-methylpentyl) amine, N-methylbis (2-ethylbutyl) amine, N-methyldicyclohexylamine, N-methylbis (2-heptyl) amine, N -Methylbis (3-heptyl) amine, N-methylbis (2-heptyl) amine, N-methylbis (4-methylhexyl) amine, N-methylbis (3-methylhexyl) amine, N-methylbis ( 4-methylhexyl) amine, N-methylbis (5-methylhexyl) amine, N-methylbis (2-ethylpentyl) amine, N-methylbis (3-ethylpentyl) amine, N-methylbis (2- Propylbutyl) amine, N-methylbis (cycloheptyl) amine, N-methylbis (methylcyclohexyl) amine, N-methyldibenzylamine, N-methylbis (2-octyl) amine, N-methylbis (3 -Octyl) amine, N-methylbis (4-octyl) amine, N-methylbis (2-methylheptyl) amine, N-methylbis (3-methylheptyl) amine, N-methylbis (4-methylheptyl) amine, N-methylbis (5- Methylheptyl) amine, N-methylbis (6-methylheptyl) amine, N-methylbis (2-ethylhexyl) amine, N-methylbis (3-ethylhexyl) amine, N-methylbis (4-ethylhexyl ) Amine, N-methylbis (2-propylpentyl) amine, N-methylbis (cyclooctyl) amine, N-methylbis (dimethylcyclohexyl) amine, N-ethyldiisopropylamine, N-ethylbis (2 -Butyl) amine, N-ethylbis (isobutyl) amine, N-ethylbis (2-pentyl) amine, N-ethylbis (3-pentyl) amine, N-ethylbis (2-methylbutyl) amine, N -Ethylbis (3-methylbutyl) amine, N-ethyldicyclopentylamine, N-ethylbis (2-hexyl) amine, N-ethylbis (3-hexyl) amine, N-ethylbis (2-methylpentyl ) Amine, N-ethylbis (3-methylpentyl) amine, N-ethylbis (4-methylpentyl) amine, N-ethylbis (2-ethylbutyl) amine, N-ethyldicyclohexylamine, N-ethyl Bis (2-heptyl) Min, N-ethylbis (3-heptyl) amine, N-ethylbis (2-heptyl) amine, N-ethylbis (4-methylhexyl) amine, N-ethylbis (3-methylhexyl) amine, N- Ethylbis (4-methylhexyl) amine, N-ethylbis (5-methylhexyl) amine, N-ethylbis (2-ethylpentyl) amine, N-ethylbis (3-ethylpentyl) amine, N-ethylbis (2-propylbutyl) amine, N-ethylbis (cycloheptyl) amine, N-ethylbis (methylcyclohexyl) amine, N-ethylbis (benzyl) amine, N-ethylbis (2-octyl) amine, N -Ethylbis (3-octyl) amine, N-ethylbis (4-octyl) amine, N-ethylbis (2-methylheptyl) amine, N-ethylbis (3-methylheptyl) amine, N-ethylbis ( 4-methylheptyl) amine, N-ethylbis (5-methylheptyl) amine, N-ethylbis (6-methylheptyl) amine, N-ethylbis (2-ethylhexyl) amine, N-ethylbis (3- Ethylhexyl) amine, N-ethylbis (4-ethylhexyl) amine, N-ethylbis (2-propylpentyl) amine, N-ethylbis (cyclooctyl) amine, N-ethylbis (dimethylcyclohexyl) amine.
[924] In step 1 of method 2, the inorganic support material (C) is reacted with a Lewis base of formula VI. The Lewis base of formula VI is preferably added to the support suspension as a solution. Suitable solvents or suspending media are especially hydrocarbons, preferably aromatic hydrocarbons such as toluene. The amount of Lewis bases of formula VI can vary widely: the minimum amount depends on the number of hydroxyl groups on the support. After pretreatment of the support, the support material was found to be useful for use in the wet state in step 2.
[925] This material is then reacted with at least one compound of the invention (preferably comprising a compound of formula III) in step 2. It is useful to remove excess Lewis base of Formula VI and to dry the support by washing after step 2 (eg using a hydrocarbon such as pentane, hexane, ethylbenzene or heptane).
[926] The covalently supported promoter prepared in this manner is contacted in step 3 with a reaction mixture comprising an organometallic compound of formula IV and an alkylaluminum of formula V. This reaction is preferably carried out in solution (especially hydrocarbon as solvent, in particular aromatic hydrocarbon, for example toluene).
[927] Particularly useful are 0.1-10% by weight of the metallocene composite, based on the inorganic support material.
[928] The reaction conditions in steps 1 to 3 are not critical: temperatures of 20 to 150 ° C. and reaction times of 0.1 to 20 hours have been found to be particularly suitable.
[929] The catalyst material prepared in this way is filtered and washed with hydrocarbons, for example pentane, hexane, ethylbenzene or heptane, if necessary and dried to a constant weight.
[930] The following examples are presented for the purpose of illustrating the invention. In the examples, the preparation and handling of the compounds was carried out under argon, in the absence of humidity and air (Schlenktechnique). All solvents used were dried before use by heating on a suitable desiccant for several hours and distilling under argon. For characterization of the invention, samples were taken from individual reaction mixtures and dried under oil pump vacuum.
[931] A) Preparation / explanation of promoters used for the preparation and comparison of novel compounds suitable as promoters
[932] Example 1: Cocatalyst (1)
[933] 5.0 ml of trimethylaluminum (2M in Exol, a commercially available hydrocarbon mixture; 5.4 mmol) and 100 ml of toluene were placed in the reaction vessel. 3.65 g (5.4 mmol) of 4,4'-dihydroxyoctafluorobiphenyl monohydrate was added to this solution. The reaction solution was stirred at 60 ° C. for 1 hour. Compound 1 obtained was then used without purification in application to the support.
[934] Example 2: Cocatalyst (2)
[935] 8.0 ml of triethylaluminum (2M in oxol, 5.4 mmol) and 100 ml of toluene were placed in a reaction vessel. 3.65 g (5.4 mmol) of 4,4'-dihydroxyoctafluorobiphenyl monohydrate was placed in this vessel. The reaction solution was stirred at 60 ° C. for 1 hour. Compound 2 was then used without purification in applying to the support.
[936] Example 3: Cocatalyst (3)
[937] 7.7 ml of triisobutylaluminum (2M in a hydrocarbon mixture Barsol purchased from Exxon, 5.4 mmol) and 100 ml of toluene were placed in a reaction vessel. 3.65 g (5.4 mmol) of 4,4'-dihydroxyoctafluorobiphenyl monohydrate was placed in this vessel. The reaction solution was stirred at 60 ° C. for 1 hour. Compound 3 was then used without purification in applying to the support.
[938] Comparative Example 1: Cocatalyst (4)
[939] 30% strength methylaluminoxane solution (Albemar Corporation, Baton Rouge, Louisiana, USA)
[940] Comparative Example 2: Cocatalyst (5) (no prior art)
[941] 10 ml of a solution of trimethylaluminum (TMA) in toluene (2 mol / l) was added dropwise to a suspension of 20 mmol of dihydroxyoctafluorobiphenyl at room temperature. This mixture was then stirred at rt for 3 h. As a reaction product, a 1: 1 condensate of TMA and dihydroxyoctafluorobiphenyl was obtained.
[942] B) Preparation of Supported Cocatalysts
[943] 14.0 g of SiO ₂ (XPO 2107, purchased from Grace, dried at 600 ° C. in an argon stream) and 20 ml of toluene were placed in a reaction vessel. 2.6 ml of N, N-dimethylaniline (20.80 mmol) was added dropwise and the mixture was stirred at room temperature for 2 hours. Then 20.80 mmol of each promoter 1-3 dissolved in 40 ml of toluene in each case at 0 ° C. was added. The suspension was left to warm to room temperature and stirred at this temperature for 2 hours. Then, 20.80 ml of promoter 1-3 dissolved in 40 ml of toluene at 0 ° C. were added, respectively. The suspension was left to warm to room temperature and stirred at this temperature for 2 hours. The resulting bluish suspension was filtered and the residue was washed with 50 ml of toluene and 3 x 100 ml of n-pentane. The residue was then dried under oil pump vacuum. In each case this produced a supported promoter.
[944] C) Preparation of Catalyst System
[945] Catalyst system according to the present invention
[946] 0.30 ml of trimethylaluminum (20% strength in axole, 700 μmol) was added to a solution of 50 mg (80 μmol) of dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride in 50 ml of toluene, solution Was stirred at RT for 1.5 h. Subsequently, promoters 1-3, 1,920 μmol / g [SiO ₂ ] supported from B were added in small portions at one time. The solution was stirred at room temperature for 60 minutes. The solvent was then removed in an oil pump vacuum to give free reddish flowable powders, respectively.
[947] compare:
[948] Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride / MAO system
[949] 0.30 ml of trimethylaluminum (20% strength in axole, 700 μmol) was added to a solution of 50 mg (80 μmol) of dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride in 50 ml of toluene, The solution was stirred at rt for 1.5 h. Then, 1920 μmol [SiO ₂ ] of a solution of methylaluminoxane in 30% strength in toluene supported as described in B was added as cocatalyst. The solution was stirred at room temperature for 60 minutes. The solvent was then removed in an oil pump vacuum to give free reddish flowable powders, respectively.
[950] compare :
[951] Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride / dihydroxyoctafluorobiphenyl
[952] 0.30 ml of trimethylaluminum (20% strength in axole, 700 μmol) was added to a solution of 50 mg (80 μmol) of dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride in 50 ml of toluene, The solution was stirred at rt for 1.5 h. Then, 1920 μmol / g [SiO ₂ ] of the cocatalyst (5) was added. The solution was stirred at room temperature for 60 minutes. The solvent was then removed in an oil pump vacuum to give free reddish flowable powders, respectively.
[953] (D) polymerization
[954] To enter the polymerization system, an appropriate amount of supported catalyst system (16 μmol metallocene) prepared according to B was resuspended in 30 ml of Axol. Parallel to it, the dry 16 dm ³ reactor was first cleaned in the order of nitrogen, then propylene, and then charged with 10 dm ³ of liquid propene. Subsequently, 0.5 cm ³ of a 20% strength triisobutylaluminum solution in barsol, diluted with Axol 30 cm ³ , was introduced into the reactor and the mixture was stirred at 30 ° C. for 15 minutes. The catalyst suspension was then introduced into the reactor. The reaction mixture was then heated to the polymerization temperature of 60 ° C. (4 ° C./min) and the polymerization system was held at 60 ° C. for 1 hour by cooling. The polymerization was stopped by venting the remaining propylene. The polymer obtained was dried in a vacuum drying oven. The reactor showed no deposits on the inner wall or on the stirrer. The results of the polymerization reaction are summarized as in the table below. This result demonstrates that the polymerization activity is high when the compound of the present invention is used as a promoter.
[955] Supported Cocatalyst Systems Manufactured Using CocatalystsOne2345 Amount of metallocene (mg)5050505050 Metallocene (μmol) promoter801920801920801920801920801920 Weight of obtained catalyst system (mg)10001000100010001000 Weight of catalyst system used in polymerization (mg) [metallocene 16 μmol]200200200200200 Minutes6060606060 PP (kg)0.620.780.580.410.18

权利要求:
Claims (7)
[1" claim-type="Currently amended] A chemical product suitable as a promoter, obtained by reacting a compound of formula I with a compound of formula II.
[Formula I] M ¹ R ¹ R ² (R ³ ) _m
Wherein R ¹ , R ² , R ³ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -Haloaryl, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloallylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
M ¹ is the main Group II or III element of the Periodic Table of the Elements,
m is 0 or 1, m is ¹ when M ¹ is a major group III element, and 0 when M ¹ is a major group II element)
[Formula II] (R ⁴ X) _q- (G) * (M ² R ⁵ R ⁶ ) _g
Wherein the substituent R ⁴ X containing the heteroatom is located on the parent nucleus portion G,
R ⁴ is the same or different and is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -haloaryl, C ₇ -C ₄₀ -Arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
X is an element of the main group IV, V or VI of the periodic table of elements,
G is at least divalent C ₁ -C ₂₀ - alkylene, C ₁ -C ₂₀ - haloalkyl-alkylene, C ₁ -C ₁₀ - alkylene, C ₆ -C ₄₀ - arylene, C ₆ -C ₄₀ - haloalkyl Arylene, C ₆ -C ₄₀ -aryleneoxy, C ₇ -C ₄₀ -arylalkylene, C ₇ -C ₄₀ -haloarylalkylene, C ₇ -C ₄₀ -alkylarylene, C ₇ -C _40- Haloalkylarylene,
M ² is an element of the main Group IV, V or VI of the Periodic Table of the Elements,
R ⁵ and R ⁶ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, CC ₁₀ -alkoxy, C ₂ -C ₁₀ -alkenyl, C ₇ -C ₂₀ -arylalkyl, C ₇ -C ₂₀ -Alkylaryl, C ₆ -C ₁₀ -aryloxy, C ₁ -C ₁₀ -haloalkyl,
q is an integer from 2 to 100,
g is an integer from 1 to 100)
[2" claim-type="Currently amended] The chemical product of claim 1 comprising at least one group of formula III.
[Formula III] [-(R ⁷ )-[XM ³ (R ⁸ )] _p -Y- (R ⁹ )-] Wherein R ⁷ and R ⁸ are the same or different and each is a hydrogen atom, a halogen atom, a boron-free C ₁ -C ₄₀ group (e.g., C ₁ -C ₂₀ -alkyl, C ₁ -C ₄₀ -halo Alkyl, C ₁ -C ₁₀ -alkoxy, C ₆ -C ₄₀ -aryl, C ₆ -C ₄₀ -haloaryl, C ₆ -C ₂₀ -aryloxy, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -Haloarylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₇ -C ₄₀ -haloalkylaryl) or Si (R ¹³ ) ₃ group,
R ⁹ is the same as or different from R ⁷ and R ⁸ and each represents a hydrogen atom or a C ₁ -C ₄₀ group (eg, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₁ -C ₁₀ -alkoxy, C ₆ -C ₄₀ -aryl, C ₆ -C ₄₀ -haloaryl, C ₆ -C ₄₀ -aryloxy, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl, C ₇ -C ₄₀ -haloalkylaryl (preferably C ₁ -C ₂₀ -haloalkyl or C ₆ -C ₄₀ -partially halogenated or fully halogenated by chlorine or fluorine) Haloaryl, more preferably C ₆ -C ₄₀ -haloaryl) halogenated by fluorine;
X is the same or different and each is an element of Group IV, V or VI of the Periodic Table of the Elements or an NH group,
Y is the same or different and each is an element of Group IV, V or VI of the Periodic Table of the Elements or an NH group,
M ³ is an element of Group IIIa of the Periodic Table of Elements)
[3" claim-type="Currently amended] A process for reacting a compound of formula (I) with a compound of formula (II) to produce a chemical product suitable as a promoter.
[Formula I] M ¹ R ¹ R ² (R ³ ) _m
Wherein R ¹ , R ² , R ³ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -Haloaryl, C ₇ -C ₄₀ -arylalkyl, C ₇ -C ₄₀ -haloallylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
M ¹ is the main Group II or III element of the Periodic Table of the Elements,
m is 0 or 1, m is ¹ when M ¹ is a major group III element, and 0 when M ¹ is a major group II element)
[Formula II] (R ⁴ X) _q- (G) * (M ² R ⁵ R ⁶ ) _g
Wherein the substituent R ⁴ X containing the heteroatom is located on the parent nucleus portion G,
R ⁴ is the same or different and is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -haloaryl, C ₇ -C ₄₀ -Arylalkyl, C ₇ -C ₄₀ -haloarylalkyl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -haloalkylaryl,
X is an element of the main group IV, V or VI of the periodic table of elements,
G is at least divalent C ₁ -C ₂₀ - alkylene, C ₁ -C ₂₀ - haloalkyl-alkylene, C ₁ -C ₁₀ - alkylene, C ₆ -C ₄₀ - arylene, C ₆ -C ₄₀ - haloalkyl Arylene, C ₆ -C ₄₀ -aryleneoxy, C ₇ -C ₄₀ -arylalkylene, C ₇ -C ₄₀ -haloarylalkylene, C ₇ -C ₄₀ -alkylarylene, C ₇ -C _40- Haloalkylarylene,
M ² is an element of the main Group IV, V or VI of the Periodic Table of the Elements,
R ⁵ and R ⁶ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, CC ₁₀ -alkoxy, C ₂ -C ₁₀ -alkenyl, C ₇ -C ₂₀ -arylalkyl, C ₇ -C ₂₀ -Alkylaryl, C ₆ -C ₁₀ -aryloxy, C ₁ -C ₁₀ -haloalkyl,
q is an integer from 2 to 100,
g is an integer from 1 to 100)
[4" claim-type="Currently amended] A catalyst system comprising as a cocatalyst a chemical product obtained by reacting a compound of Formula I with a compound of Formula II.
[5" claim-type="Currently amended] The method of claim 4, wherein
A) at least one organic transition metal compound,
B) at least one of the main group alkyls as required,
C) at least one support component as needed, and
D) at least one chemical product obtained by reacting a compound of formula (I) with a compound of formula (II)
Catalyst system comprising a.
[6" claim-type="Currently amended] The method according to claim 4 or 5,
A) at least one metallocene, and
B) at least one Lewis base of formula VI, if desired
Catalyst system comprising a.
[Formula VI] M ⁶ R ²¹ R ²² R ²³
(Wherein M ⁶ is an element of the main group V of the periodic table of elements,
R ²¹ , R ²² , R ²³ are the same or different and each is hydrogen, C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -haloalkyl, C ₆ -C ₄₀ -aryl, C ₆ -C ₄₀ -haloaryl , C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -arylalkyl, wherein two radicals or all three radicals R ²¹ , R ²² and R ²³ can be bonded to one another via a C ₂ -C ₂₀ unit At least one radical R ²¹ , R ²² , or R ²³ is not a hydrogen atom or a straight chain alkyl)
[7" claim-type="Currently amended] A process for producing polyolefins by polymerizing one or more olefins in the presence of a catalyst system according to claim 4.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-05-24|Priority to DE10025412.8

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2000-05-24|Priority to DE2000125412

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2001-05-19|Application filed by 바젤 폴리올레핀 게엠베하

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2003-02-15|Publication of KR20030014241A

优先权:

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申请号 | 申请日 | 专利标题

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DE10025412.8|2000-05-24|

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DE2000125412|DE10025412A1|2000-05-24|2000-05-24|Chemical products suitable as cocatalysts, processes for their preparation and their use in catalyst systems for the production of polyolefins|