Borate activated metallocene catalysts

Abstract

A catalyst system comprising: (i) at least one metallocene complex of formula (I) in which Mt1 is Hf, X is a sigma-donor ligand, R1, R2, R3, equal to or different from each other, may be hydrogen or a saturated linear or branched C1-C10 alkyl group, where the alkyl group may optionally contain a maximum of 2 heteroatoms belonging to groups 14-16 of the Periodic Table of Elements, and where R1, R2, R3, equal to or different from each other, may be hydrogen or a saturated linear or branched C1-C10 alkyl group, where R1, R2, R3 may optionally contain a maximum of 2 heteroatoms belonging to groups 14-16 of the Periodic Table of Elements; or R1 and R2 or R2 and R3 may form a ring having 4 to 6 C atoms and 1 to 3 double bonds, R4 and R5, equal to or different from each other, may be a saturated linear or branched C1-C10 alkyl group, C5-C10 aryl group, C6-C20 alkaryl group or C6-C20 aralkyl group, which may optionally contain a maximum of 2 heteroatoms belonging to groups 14 to 16 of the periodic table of elements, n may be 1 to 5, Ar is C6-C20-aryl group or C6-C20-heteroaryl group, and n may be 1 to 5. And (ii) a boron-containing co-catalyst (I), which may be unsubstituted or substituted by 1 to 5 linear or branched C1-C10 alkyl groups, and (ii) a boron-containing co-catalyst (I).

Description

Technical Field

[0001] This invention relates to a novel catalyst system, particularly capable of producing polyethylene copolymers during high-temperature solution polymerization. The novel catalyst system comprises a specifically substituted bridging hafnium catalyst complex containing a cyclopentadienyl (Cp) ligand, a fluorenyl (Flu) ligand, and a covalent bridge connecting the two ligands, as well as a boron-based cocatalyst. This combination significantly improves the balance between comonomer binding capacity and molecular weight properties of the catalyst system. Background Technology

[0002] Metallocene catalysts have been used in the production of polyolefins for many years. Numerous academic and patent publications describe the applications of these catalysts in olefin polymerization. Metallocene catalysts are now used industrially, and are commonly used in the production of polypropylene and polyethylene using cyclopentadienyl catalyst systems with different substitution modes.

[0003] Several such metallocene catalysts have been described for solution polymerization to produce polyethylene homopolymers or copolymers.

[0004] For example, WO 2000024792 describes a catalyst system comprising a hafnium catalyst complex derived from A) a dicyclopentadienyl hafnium organometallic compound, having i) at least one unsubstituted cyclopentadienyl ligand or an aromatic fused-ring substituted cyclopentadienyl ligand without additional substituents on said ligand, ii) a substituted or unsubstituted aromatic fused-ring substituted cyclopentadienyl ligand, and iii) a covalent bridge connecting the two cyclopentadienyl ligands.

[0005] The bridge could be a single carbon substituted with two aryl groups, each of which is C1-C2. 20 Hydrocarbon or hydroxymethylsilyl substitution, wherein at least one of these substituents is a linear C3 or larger substituent.

[0006] In addition, the catalyst system includes an activated co-catalyst, which is preferably a precursor ionic compound containing a group 13 anion substituted with a tetraaryl halothion.

[0007] US 20060161013 also relates to bridged Cp-Flu metallocene complexes. The C-bridges shown in the examples are substituted methylene bridges, wherein the substituents are the same (e.g., dimethyl, diphenyl, dibenzyl, dicyclohexyl, etc.) or linked together to form a ring (e.g., cyclohexylene).

[0008] EP 1768990 describes the synthesis of Cp-Flu metallocene complexes of Zr or Hf, wherein the Flu- ligand is substituted at positions 2 and 7. Both substituents on the bridge are aliphatic groups, one of which can be alkenyl.

[0009] US 2003092925 describes a bridged Cp-Flu metallocene complex in which the C-bridge is substituted by an unsaturated hydrocarbon substituent at the end and by an aryl substituent, and the Flu ligand is preferably unsubstituted. In relatively low-temperature bulk or slurry polymerization, this complex is used with an aluminoxane cocatalyst or an alkylaluminum compound as a cocatalyst.

[0010] Some researchers (references 1 to 5) have investigated the effect of ligand structure on the copolymerization of ethylene with various Cp-Flu metallocene complexes.

[0011] 1. A. Yano, M. Sone, S. Hasegawa, M. Sato, A. Akimoto, Macromol. Chem. Phys. 1999, 200, 933. 2. A. Yano, S. Hasegawa, T. Kaneko, M. Sone, M. Sato, A. Akimoto, Macromol. Chem. Phys. 1999, 200, 1542. 3. A. Yano, M. Sone, S. Yamada, S. Hasegawa, M. Sato, A. Akimoto, Journal of Molecular Catalysis A: Chemical 2000, 156, 133. 4. S. Hasegawa, M. Sone, M. Tanabiki, M. Sato, A. Yano, Journal of Polymer Science: Part A: Polymer Chemistry 2000, 38, 4641. 5. Q. Yang, MD Jensen, and MP McDaniel Macromolecules 2010, 43,8836. None of the aforementioned documents and patents mention simultaneously improving the molecular weight performance and comonomer binding capacity of the catalyst system.

[0012] Furthermore, the aforementioned literature and patents do not address the potential impact of higher polymerization temperatures on the catalyst performance of hafnium complexes with alkenyl groups on the bridge combined with boron-based activators.

[0013] However, for the effectiveness of the ethylene copolymer production process, it is crucial that the catalyst system used meets a series of very stringent requirements. These include the high comonomer binding capacity (comonomer reactivity), catalyst molecular weight properties (the lowest melt index achievable given polymer density, monomer concentration, and polymerization temperature), and catalyst thermal stability. These must ensure that, at high productivity (to produce the maximum amount of polyethylene with the least amount of catalyst), the copolymer density produced is as low as ~0.850 g / cm³. 3 The melt index MI2 (190℃, 2.16kg) is as low as ~0.3g / 10min. This requires a reaction rate C0. AO / C2 is at least 0.1 (AO = α-olefin).

[0014] Despite extensive work in the field of metallocene catalysts, there is still a need to find new catalyst systems suitable for ethylene copolymerization that can produce polymers with the desired properties and offer an improved balance between comonomer binding capacity and molecular weight properties.

[0015] Therefore, the inventors set out to develop a new catalyst system that has superior polymerization performance in terms of comonomer binding capacity and molecular weight properties compared to the above-mentioned polymerization catalyst systems.

[0016] The inventors have now discovered a new class of olefin polymerization catalyst systems that can solve the above-mentioned problems. In particular, the present invention combines the use of special metallocene complexes with boron-based cocatalysts. Summary of the Invention

[0017] Therefore, in one respect, the present invention relates to catalyst systems, wherein the catalyst system comprises (i) at least one metallocene complex of formula (I) (I) in, Mt 1 is Hf, X is a sigma-donor ligand. R 1 R 2 R 3 They may be the same or different, and can be hydrogen or saturated straight-chain or branched C1-C. 10 Alkyl group, wherein the alkyl group may optionally contain up to two heteroatoms belonging to groups 14-16 of the periodic table, or R 1 With R 2 or R 2 With R 3 It can form rings with 4 to 6 carbon atoms and 1 to 3 double bonds. R 4 and R5 They may be the same or different from each other, and can be saturated straight-chain or branched C1-C. 10 Alkyl, C5-C 10 Aryl, C6-C 20 Alkyl or C6-C 20 Aryl groups, which may optionally contain up to two heteroatoms belonging to groups 14-16 of the periodic table, n can be from 1 to 5. Ar is C6-C 20 -Aryl or C6-C 20 - Heteroaryl groups, which may be unsubstituted or composed of 1-5 straight or branched C1-C1 groups. 10 Alkyl-substituted, and (ii) Boron-containing cocatalysts.

[0018] On the other hand, the present invention provides the use of this catalyst system in the production of ethylene copolymers in a high-temperature solution process.

[0019] In another aspect, the present invention provides a method for preparing an ethylene copolymer, the method comprising reacting ethylene and C in the presence of a catalyst at a temperature above 100°C via a high-temperature solution method. 4-10 α-olefin comonomer polymerization, wherein the catalyst comprises: (i) at least a metallocene complex of formula (I) as defined above, and (ii) Boron-containing cocatalysts.

[0020] In another respect, the present invention provides ethylene copolymers prepared by the methods defined above. Detailed Implementation

[0021] Metallocene complexes Monocentric metallocene complexes, especially those defined by formula (I) specified in this invention, are asymmetric, meaning that the two ligands forming the metallocene complex are different.

[0022] This invention can be achieved using metallocene complexes of formula (I). (I) in, Mt 1 is Hf, X is a sigma-donor ligand. R 1 R 2 R 3 They may be the same or different, and can be hydrogen or saturated straight-chain or branched C1-C. 10 Alkyl group, wherein the alkyl group may optionally contain up to two heteroatoms belonging to groups 14-16 of the periodic table, or R 1With R 2 or R 2 With R 3 It can form rings with 4 to 6 carbon atoms and 1 to 3 double bonds. R 4 and R 5 They may be the same or different from each other, and can be saturated straight-chain or branched C1-C. 10 Alkyl, C5-C 10 Aryl, C6-C 20 Alkyl or C6-C 20 Aryl groups, which may optionally contain up to two heteroatoms belonging to groups 14-16 of the periodic table, n can be from 1 to 5. Ar represents unsubstituted or substituted by 1-5 straight or branched C1-C1 chains. 10 Alkyl-substituted C6-C 20 -Aryl or C6-C 20 - Mixed aromatic compounds.

[0023] This invention can also be achieved using a mixture of metallocene complexes of formula (I) and metallocene complexes of formula (I') as defined above. (I') Where Mt 2 is Zr, R 1 To R 5 As defined in Ar as a complex of formula (I), the mixture contains more than 50 mol% of a complex of formula I and wherein Mt 1 is Hf.

[0024] In equations (I and I'), each X can be the same or different, and is a sigma-donor ligand, preferably a hydrogen atom, a halogen atom, or R. 6 OR 6 OSO2CF3, OCOR 6 SR 6 NR 6 2 or PR 6 2. R in this context 6 It is a linear or branched, cyclic or acyclic C1-C 20 -alkyl, C2-C 20 -Alkenyl, C2-C 20 -Alynyl group, C6-C 20 -Aryl, C7-C 20 -Alkaryl or C7-C 20 -Arylalkyl, optionally containing up to two heteroatoms belonging to Groups 14-16 of the periodic table, or SiR 6 3. SiHR 6 2 or SiH2R 6 R 6C is preferred 1-6 -alkyl, phenyl, or benzyl.

[0025] The term halogen includes fluorine groups, chlorine groups, bromine groups, and iodine groups, with chlorine groups being preferred.

[0026] Heteratoms in Groups 14-16 of the periodic table include, for example, Si, N, O, or S.

[0027] More preferably, each X is independently a halogen atom or R 6 Group or OR 6 Group, wherein R 6 C 1-6 -alkyl, phenyl or benzyl.

[0028] Even more preferred is X as C 1-4 -alkyl or benzyl, with X preferably being methyl. Preferably, both X groups are the same.

[0029] R 1 R 2 R 3 They may be the same or different, and can be hydrogen or saturated straight-chain or branched C1-C. 10 Alkyl group, wherein the alkyl group may optionally contain up to two heteroatoms belonging to groups 14-16 of the periodic table, or R 1 With R 2 or R 2 With R 3 It can form rings with 3 to 8 carbon atoms and 1 to 3 double bonds.

[0030] Such rings include, for example, cyclopentenyl or phenyl.

[0031] Heteratoms in Groups 14-16 of the periodic table include, for example, Si, N, O, or S.

[0032] Preferably, R 1 R 2 R 3 They may be the same as or different from each other, and may be hydrogen-rich, saturated straight-chain or branched C1-C6 alkyl groups, wherein the alkyl group does not contain any heteroatoms belonging to groups 14-16, or R 1 It is hydrogen and R 2 With R 3 It forms a ring with 5 to 6 carbon atoms and 1 to 3 double bonds.

[0033] More preferably, R 1 R 2 R 3 They may be the same as or different from each other, and may be hydrogen-containing, saturated straight-chain or branched C1-C4 alkyl groups, wherein the alkyl group does not contain any heteroatoms belonging to groups 14-16, or R 1It is hydrogen and R 2 With R 3 This forms a ring with 6 carbon atoms and 3 double bonds. In this case, the ring is a benzene ring.

[0034] Most preferably, R 1 R 2 R 3 They are the same and all are hydrogen, or R 1 It is hydrogen and R 2 With R 3 This forms a ring with 6 carbon atoms and 3 double bonds, namely a benzene ring.

[0035] R 4 and R 5 They can be the same or different, and can be saturated straight-chain or branched C1-C 10 Alkyl, C5-C 10 Aryl, C6-C 20 Alkyl or C6-C 20 Araneyl groups, which may optionally contain up to two heteroatoms belonging to groups 14-16 of the periodic table, such as Si, N, O, or S.

[0036] C6-C 20 Alkyl groups refer to C6-C atoms that are substituted with one or more alkyl groups, which may be the same or different. 10 In aryl groups, the number of carbon atoms in the alkyl substituents is counted as C6-C. 20 Within the range of alkylaryl groups.

[0037] Preferably, R 4 and R 5 They may be the same or different from each other, and can be saturated straight-chain or branched C1-C. 10 Alkyl or C6-C 10 Aryl group, wherein the group does not contain any heteroatoms belonging to groups 14-16 of the periodic table.

[0038] More preferably, R 4 and R 5 They may be the same as or different from each other, and may be saturated straight-chain or branched C1-C6 alkyl or phenyl groups, wherein the groups do not contain any heteroatoms belonging to groups 14-16 of the periodic table.

[0039] Most preferably, R 4 and R 5 Identical and saturated straight-chain or branched C2-C6 alkyl groups.

[0040] n can be 1 to 5, preferably 2 to 4.

[0041] Ar represents unsubstituted or substituted by 1-5 straight or branched C1-C1 chains. 10 Alkyl-substituted C6-C20 -Aryl or C6-C 20 - Mixed aromatic compounds.

[0042] Preferably, Ar is unsubstituted or substituted with a straight-chain or branched C1-C6 alkyl group. 10 -Aryl or C6-C 10 - Mixed aromatic compounds.

[0043] More preferably, Ar is unsubstituted C6-C 10 Aryl group, with phenyl group being the most preferred.

[0044] If a mixture of complexes of formula (I) and formula (I') is used, it is preferable that the substituent R in both complexes is used. 1 To R 6 And the same as Ar.

[0045] Specific examples of coordination compounds of formula (I) are as follows: (phenyl)(but-3-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium (phenyl)(but-3-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dibenzylhafnium (phenyl)(but-3-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride (phenyl)(4-penten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)dimethylhafnium (phenyl)(4-penten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)dibenzylhafnium (phenyl)(4-penten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dibenzylhafnium (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride (phenyl)(3-phenylpropyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride (phenyl)(3-phenylpropyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylhafnium (phenyl)(3-phenylpropyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dibenzylhafnium And zirconium analogues of the corresponding formula (I').

[0046] Even more preferred are the dimethyl complexes of formulas (I) and (I').

[0047] The optimal choice is to use only the complex of formula (I).

[0048] co-catalyst To form an active catalytic material, a co-catalyst well known in the art is typically required. This invention requires the use of a boron-containing co-catalyst.

[0049] The boron-based cocatalysts of interest include those containing borate 3 + Boron compounds with ions, namely borate compounds. These compounds typically contain anions of the following formula: (Z)4B - (II) Where Z is an optionally substituted phenyl derivative, and the substituent is a halogenated -C 1-6 -Alkyl or halogen group. Preferably selected from fluorine or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0050] This ionic cocatalyst preferably contains a noncoordinate anion, such as tetra(pentafluorophenyl)borate.

[0051] Suitable counterions are protonated amines or aniline derivatives, carbenium ions, or phosphonium ions. They have the general formula (III), (IV), or (V): NQ4 + (III) or CQ3 + (IV) or PQ4 + (V) Where Q is independently H and C 1-6 -alkyl, C 3-8 -cycloalkyl, phenyl-C 1-6 -alkylene- or optionally substituted phenyl (Ph). Optional substituents may be C 1-6 -alkyl, halogen, or nitro. One or more such substituents may be present. Therefore, preferred substituted Ph groups include para-substituted phenyl groups, more preferably tolyl or dimethylphenyl.

[0052] If at least one Q group in (III) and (V) must be H, then the preferred compound is the compound of the following formula: NHQ3 + (VI) or PHQ3+ (VII) Preferred phenyl-C 1-6 -alkyl- groups include benzyl groups.

[0053] Therefore, suitable counterions include: methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylphenylammonium, diphenylammonium, N,N-dimethylphenylammonium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, p-bromo-N,N-dimethylphenylammonium, or p-nitro-N,N-dimethylphenylammonium, especially dimethylammonium or N,N-dimethylphenylammonium. Using pyridine as the ion is a further option.

[0054] As a carbocation, triphenylmethyl carbon (triphenylmethyl) or trimethylnaphthalene can be used.

[0055] Phosphorus ions of interest include triphenylphosphorus, triethylphosphorus, diphenylphosphorus, tri(methylphenyl)phosphorus, and tri(dimethylphenyl)phosphorus.

[0056] A more preferred counterion is triphenylmethyl (CPh3) + (or its analogues) wherein the Ph group is functionalized to include one or more alkyl groups. Therefore, the most preferred borates in this invention include tetra(pentafluorophenyl)borate ions.

[0057] According to the present invention, preferred ionic compounds that can be used include: Tributylammonium tetra(pentafluorophenyl)borate, Tributylammonium tetra(trifluoromethylphenyl)borate, Tributylammonium tetra-(4-fluorophenyl)borate, N,N-Dimethylcyclohexylammonium tetra(pentafluorophenyl)borate, N,N-Dimethylbenzylammonium tetra(pentafluorophenyl)borate, N,N-Dimethylphenylamine tetra(pentafluorophenyl)borate, N,N-Di(propyl)ammonium tetra(pentafluorophenyl)borate, Di(cyclohexyl)ammonium tetra(pentafluorophenyl)borate, Triphenylcarbium tetra(pentafluorophenyl)borate; A more preferred borate is: Triphenylcarbium tetra(pentafluorophenyl)borate, N,N-Dimethylcyclohexylammonium tetra(pentafluorophenyl)borate, N,N-Dimethylbenzylammonium tetra(pentafluorophenyl)borate, or N,N-Dimethylphenylammonium tetra(pentafluorophenyl)borate.

[0058] Even more preferred borates are: Triphenylcarbamonite tetra(pentafluorophenyl)borate and N,N-dimethylphenylamine tetra(pentafluorophenyl)borate.

[0059] The preferred option is N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate.

[0060] The appropriate amount of co-catalyst is well known to those skilled in the art.

[0061] Alkyl aluminum compounds may also be added. Suitable alkyl aluminum compounds are compounds of formula (IX)AlR3, where R is a straight-chain or branched C2-C8-alkyl group.

[0062] Preferred alkylaluminum compounds are triethylaluminum, triisobutylaluminum, triisohexylaluminum, tri-n-octylaluminum, and triisooctylaluminum.

[0063] As any person skilled in the art will know, Cp-Flu complexes must be alkylated derivatives (e.g., X2 is dimethyl) in order to react with boron-containing cocatalysts. Therefore, if the complexes are initially dihalogenated derivatives or other non-alkylated derivatives, they require pre-alkylation by reacting with alkylated organometallic compounds, such as Li-alkyl, Mg-alkyl, or Al-alkyl compounds. Pre-alkylation methods are well known in the art.

[0064] The molar ratio of boron to metallocene ions can be from 0.5:1 to 10:1 mol / mol, preferably from 1:1 to 10:1, and especially from 1:1 to 5:1 mol / mol.

[0065] Even more preferred is a molar ratio of boron to metallocene ions of 1:1 to less than 2:1 mol / mol, for example, from 1:1 to 1.8:1 or from 1:1 to 1.5:1.

[0066] The metallocene complexes of the present invention are preferably used in combination with a co-catalyst as a catalyst for the polymerization of ethylene and C in a high-temperature solution polymerization process. 4-10 Catalyst system for the polymerization of α-olefin comonomers.

[0067] The catalyst system of the present invention can be used as a homogeneous catalyst or a heterogeneous catalyst, preferably as a homogeneous catalyst system.

[0068] The homogeneous or unsupported catalyst system suitable for the present invention can be prepared in solution, for example in a hydrocarbon solvent such as hexane, cyclohexane, heptane, naphthalene or toluene, by contacting a metallocene of formula (I) or a mixture of metallocenes of formulas (I) and (I') (as a solid or as a solution) with a boron-containing co-catalyst (e.g., borane or borate in a hydrocarbon diluent or pre-dissolved in an aromatic solvent as a slurry), or preferably by directly and sequentially adding the catalyst components into a polymerization reactor.

[0069] polymer The polymer prepared using the catalyst system of this invention is ethylene and C 4-10 A copolymer of α-olefin comonomers (e.g., 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc.). Preferably, 1-butene, 1-hexene, or 1-octene is used as the comonomer, more preferably 1-octene.

[0070] The comonomer content in this polymer can be as high as 45 wt%, preferably 1-40 wt%, more preferably 1.5-35 wt%, and even more preferably 2-25 wt%.

[0071] The polymer density (measured according to ISO 1183-187) is 0.850 g / cm³. 3 To below 0.920 g / cm 3 The preferred value is 0.850 g / cm³. 3 Up to 0.915 g / cm 3 More preferably, it is 0.850 g / cm³. 3 Up to 0.910 g / cm 3 .

[0072] The Mw / Mn value of the polymer of the present invention is less than 5, for example, from 2.0 to 4.5.

[0073] The melting point of the polymer to be produced (measured by DSC according to ISO 11357-3:1999) is below 130°C, preferably below 120°C, more preferably below 110°C, and most preferably below 100°C.

[0074] polymerization The catalyst system of the present invention is preferably used in high-temperature solution polymerization methods to prepare the ethylene copolymers defined above at temperatures above 100°C.

[0075] In view of the present invention, this method is essentially based on the polymerization of monomers with suitable comonomers in a hydrocarbon solvent, the solvent being liquid under the polymerization conditions, and the resulting polymer being soluble in the solvent. Polymerization is carried out at a temperature above the polymer's melting point, ultimately yielding a polymer solution. This solution is flash-evaporated to separate the polymer from unreacted monomers and solvent. The solvent is then recovered and recycled in the process.

[0076] Solution polymerization is known to have short reactor residence times (compared to gas-phase or slurry polymerization), thus allowing for very rapid grade changes and significant flexibility in producing a wide range of products in short production cycles.

[0077] According to the present invention, the solution polymerization method used is a high-temperature solution polymerization method with a polymerization temperature higher than 100°C. The polymerization temperature is preferably at least 110°C, more preferably at least 150°C. The polymerization temperature can be as high as 250°C.

[0078] The pressure in the reactor depends on both the temperature and the type and amount of comonomer used. A suitable pressure is 50 to 300 bar, preferably 60 to 250 bar, and more preferably 70 to 200 bar.

[0079] The preferred hydrocarbon solvent used is C 5-12 Hydrocarbons, which may be unsubstituted or C-substituted. 1-4 Alkyl-substituted, for example, pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, and hydrogenated naphtha. More preferably, unsubstituted C4 is used. 6-10 Hydrocarbon solvent.

[0080] advantage A novel catalyst system comprising components (i) and (ii) is advantageously suited for ethylene copolymerization in high-temperature solution polymerization methods.

[0081] The catalyst system of the present invention is used for the copolymerization reaction of ethylene in a high-temperature solution polymerization method, and can show an improved balance in terms of the binding capacity and molecular weight properties of the comonomer.

[0082] The catalyst system of the present invention exhibits at least 0.1 (AO=C) in high-temperature solution polymerization methods. 4-10 The reactivity ratio C of α-olefin comonomers AO / C2.

[0083] application Polymers prepared from the catalyst system of the present invention can be used in all types of final products, such as pipes, films (cast or blown films), fibers, molded products (e.g., injection molded, blow molded, rotational molded products), extruded coatings, etc.

[0084] The invention will now be described with reference to the following non-limiting embodiments.

[0085] method DSC Temperature-regulated DSC experiments were performed on a TA instrument Q2000 DSC, operated in modulation mode and calibrated with indium, tin, and zinc according to ISO 11357-1. Approximately 5 mg of sample was placed in an aluminum dish. The temperature was initially raised to 180 °C and then lowered to -88 °C at a rate of 10 °C / min, as in standard DSC. The temperature was then increased by a temperature-regulated scan at a heating rate of 2 °C / min, adjusting by 0.32 °C every 60 s. The glass transition temperature was measured from the reversible heat flow pyrometry plot as the transition point at the time of transition.

[0086] When estimating polymer composition using Tg (DSC), the following relationship is used: C8 (wt%) = (Tg (°C) + 19.16) / - 1.059.

[0087] Zr and Hf determination (ICP method) Elemental analysis of the catalyst was performed by taking a solid sample of mass M and cooling it on dry ice. The sample was diluted to a known volume V by dissolving it in nitric acid (HNO3, 65%, 5% V) and fresh deionized (DI) water (5% V). The solution was then added to hydrofluoric acid (HF, 40%, 3% V), diluted with deionized water to a final volume V, and allowed to stabilize for 2 hours.

[0088] Analysis was performed at room temperature using a thermoelectric iCAP 6300 inductively coupled plasma optical emission spectrometer (ICP-OES). The spectrometer was calibrated using a blank sample (a deionized aqueous solution containing 5% HNO3 and 3% HF) and six standard samples containing 0.5%, 1 ppm, 10 ppm, 50 ppm, 100 ppm, and 300 ppm Al. Hf and Zr were added to the 5% HNO3 and 3% HF deionized aqueous solution at concentrations of 0.5 ppm, 1 ppm, 5 ppm, 20 ppm, 50 ppm, and 100 ppm.

[0089] Prior to analysis, calibration was immediately “calibrated” using a blank sample and standards containing 100 ppm Al, 50 ppm Hf, and Zr. Quality control samples (containing 20 ppm Al, 5 ppm Hf, and Zr in a deionized aqueous solution of 5% HNO3 and 3% HF) were used to confirm the calibration. Quality control samples were also run after every fifth sample and at the end of the planned analysis set.

[0090] Hafnium content was determined using the 282.022 nm and 339.980 nm lines, and zirconium content was determined using the 339.198 nm line. Aluminum content was monitored using the 167.079 nm line when the Al concentration in the ICP sample was between 0 and 10 ppm (calibrated only to 100 ppm) and when the Al concentration passing through the 396.152 nm line was higher than 10 ppm.

[0091] The recorded values ​​are the average of three consecutive aliquots of the same sample, and the recorded values ​​are correlated with the original catalyst by inputting the original sample mass and dilution volume into the software.

[0092] Quantitative analysis of comonomer content using NMR spectroscopy Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the comonomer content in polymers.

[0093] Quantitative 13 C { 1 The ¹H NMR spectra were recorded in the molten state using a Bruker Advance III 500 NMR spectrometer at 500.13 and 125.76 MHz, respectively. 1 H and 13 C work. Using 13 A C-optimized 7mm magic-angle rotating (MAS) probe tip was used for all pneumatic operations at 150°C with nitrogen gas to record spectra. Approximately 200 mg of material was packed into a 7mm outer diameter zirconia MAS rotor and rotated at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification. [1]，[2]，[3]，[4] A transient NOE is used with a short cycle delay of 3 seconds. [5]，[1] Standard single-pulse excitation of RS-HEPT decoupling scheme [6]，[7] A total of 1024 (1k) transients were obtained for each spectrum. This setting was chosen because of its high sensitivity to low comonomer content.

[0094] Quantitative analysis was performed using a custom-defined automated spectral analysis program. 13 C{ 1 The ¹H NMR spectra were processed, integrated, and quantitatively characterized. All chemical shifts were intrinsically referenced to a large number of methylene groups at 30.00 ppm (δ+) signals. [8] .

[0095] Characteristic signals corresponding to the introduction of 1-octene were observed. [8]，[9]，

[10] ，

[11] ，

[12] And the content of all comonomers calculated considering all other monomers present in the polymer.

[0096] A characteristic signal was observed generated by the introduction of a single 1-octene, i.e., the EEOEE comonomer sequence. The introduction of a single 1-octene was quantified by integrating the signal at 38.32 ppm. This integral was assigned to the signals corresponding to the single (EEOEE) and single bis-discontinuous (EEOEOEE) 1-octene sequences, respectively. * B6 and * Unresolved signal at the βB6B6 site. To compensate for the two... * The effect of the βB6B6 site was determined using the integral of the βB6B6 site at 24.7 ppm: O = I *B6+*βB6B6 - 2*I ββB6B6 A characteristic signal was also observed resulting from the introduction of consecutive 1-octene, namely the EEOOEE comonomer sequence. This quantification of the consecutive 1-octene introduction was performed by integrating the signal at 40.48 ppm using the ααB6B6 sites assigned to the number of reporter sites per comonomer. OO = 2 * I ααB6B6 A characteristic signal was also observed from the introduction of a single discontinuous 1-octene, namely the EEOEOEE comonomer sequence. This isolated discontinuous 1-octene incorporation was quantified by integrating the signal at 24.7 ppm from the ββB6B6 site, which is assigned to the number of reporter sites per comonomer. OEO = 2 * I ββB6B6 A characteristic signal was also observed generated by the introduction of a single tri-continuous 1-octene, namely the EEEOOOEE comonomer sequence. This single tri-continuous 1-octene introduction was quantified by integrating the signal at 41.2 ppm using the ααγB6B6B6 site assigned to the number of reporter sites per comonomer, to illustrate the number of recording sites per comonomer. OOO = 3 / 2 * I ααγB6B6B6 Since no other signals indicating other comonomer sequences were observed, the total amount of 1-octene comonomers was calculated only based on the following quantities: single (EEOEE), single bicontinuous (EEOOEE), single discontinuous (EEOEOEE), and single tricontinuous (EEOOOEE) 1-octene comonomer sequences: O 总 = O + OO + OEO + OOO Characteristic signals generated by saturated end groups were observed. These saturated end groups were quantified by averaging the two resolved signals at 22.84 and 32.23 ppm. The integral at 22.84 ppm was assigned to the unresolved signals corresponding to the 2B6 and 2S sites and the saturated end group of 1-octene, respectively. The integral at 32.23 ppm was assigned to the unresolved signals corresponding to the 3B6 and 3S sites and the saturated end group of 1-octene, respectively. To compensate for the influence of 1-octene at the 2B6 and 3B6 sites, the total 1-octene content was used. S = (1 / 2)*( I 2S+2B6 + I 3S+3B6 - 2*O 总 ) The ethylene comonomer content was quantified by integrating the bulk methylene signal at 30.00 ppm. This integration included the γ and 4B6 sites from 1-octene and the δ+ Site. Total ethylene comonomer content was calculated based on extensive methylene integrals and compensation for observed 1-octene sequences and end groups: E 总 = (1 / 2)*[ I bulk + 2*O + 1*OO + 3*OEO + 0*OOO + 3*S ] It should be noted that there is no need to perform extensive integration on the individual tri-continuous (EEOOOEE) 1-octene comonomer sequence to compensate, since the number of under-counted and over-counted ethylene units is equal.

[0097] The total mole fraction of 1-octene in the polymer was then calculated as follows: fO = (O 总 / (E 总 + O 总 ) The total weight percentage of 1-octene introduced by the total monomers is calculated in the standard manner by mole fraction: O [wt%] = 100 * ( fO * 112.21) / ( (fO * 112.21) + ((1-fO) * 28.05) ) [1] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW,Wilhelm, M., Macromol. Chem. Phys. 2006;207:382. [2] Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007;208:2128. [3] Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373. [4] NMR Spectroscopy of Polymers: Innovative Strategies for ComplexMacromolecules, Chapter 24, 401 (2011). [5] Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M.,Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004;37:813. [6] Philip, X., Tripon, C., Philip, C., J. Mag. Resn. 2005 , 176 , [7] Griffin , JM , Tripon , C. , Samoson , A. , Philip , C. , and Brown , SP , Mag. Res. in Chem. 2007 45, S1, S198. [8] J. Randall, Macromol. Sci., Rev. Sci. Macromol. Chem. Phys. 1989, C29,201. [9] Liu , W. , Rinaldi , P. , McIntosh , L. , Quirk , P. , Macromolecules2001 , 34 , 4757 .

[10] Qiu , X. , Redwine , D. , Gobbi , G. , Nuamthanom , A. , Rinaldi , P. ,Macromolecules 2007 , 40 , 6879 .

[11] Busico , V. , Carbonniere , P. , Cipullo , R. , Pellecchia , R. ,Severn , J. , Talarico , G. , Macromol. Rapid Commun. 2007 , 28 ,

[12] Zhou , Z. , R. Kuemmerle , X. Qiu , D. Redwine , R. Cong , A. Taha , B. Baugh , D. Winniford , J. Mag. Reason. 187 (2007) HT-SEC:Synthetic silver, silver silver, silver solute(Mn,Mw,Mw / Mn) The average molecular weight (Mw, Mn), molecular weight distribution (MWD), and its width were obtained by high-temperature size exclusion chromatography (HT-SEC) at 160 °C using a PolymerLaboratories PLXT-20 rapid GPC polymer analysis system (including pump, refractive index detector, and viscosity detector) with a series of columns in a 3 PLgel Olexis column (300 × 7.5 mm, Polymer Laboratories). 1,2,4-trichlorobenzene containing butylated hydroxytoluene (0.5 g / L) and Irganox 1010 (20 mg / L) was used as the eluent at a flow rate of 1.0 mL / min. Molecular weights were calculated relative to polyethylene standards (Polymer Laboratories, Mp = 5.310 to Mp = 1.510.000 g / mol). A Polymer Laboratories PL XT-220 automated sample handling system was used as the autosampler. The sample concentration was 2 to 4 mg polymer / mL TCB.

[0098] Determine the reactivity ratio R of the relative comonomers. The ethylene concentration in the liquid phase can be considered constant because the total pressure is kept constant by adding ethylene during polymerization. AO The C8 / C2 ratio, for example, the C8 / C2 ratio in the solution at the end of polymerization, is calculated by subtracting the amount of comonomer from the measured component of the polymer, for example, subtracting the octene (%wt comonomer, for example, 1-octene) contained in the measured component of the polymer.

[0099] The polymerization reactivity ratio R for each catalyst is calculated as follows: R = [(C8 / C2)] pol ] / [(C8 / C2) 液相平均值 ] Among them (C8 / C2) 液相平均值 The calculation is (C8 / C2). 最终 +(C8 / C2) 进料 ) / 2 chemical Triphenylcarbium tetra(pentafluorophenyl)borate (TB) (alternative name triphenylmethyl-(pentafluorophenyl)borate) (CAS 136040-19-2) was purchased from Acros (tritylBF20).

[0100] N,N-Dimethylphenylammonium tetra(pentafluorophenyl)borate (AB) (CAS 118612-00-3) was purchased from Boulder.

[0101] 1-Octenene (99%, Sigma Aldrich), used as a comonomer, is dried on a molecular sieve and degassed with nitrogen before use.

[0102] Isopar-E (from ExxonMobil, isoalkane C) purchased from Brenntag. 7-10 (CAS No.: 90622-56-3) was then purified by two columns containing (i) BTS-catalyst (Cu) to remove oxygen, and (ii) molecular sieve 3Å and Selexsorb CD (BASF) as a drying agent to remove polar impurities.

[0103] Chemicals used in catalyst complexes: Use HfCl4 as is, <1 (mol)% Zr (Strem Chemicals), 9 H - Acros, 2.5M n BuLi hexane solution (Chemetall), KH (Aldrich), 1-bromobutane (Acros), benzophenone (Acros), 1,2-dibromoethane (Acros), trimethylchlorosilane (Acros), 2-bromo-2-methylpropionyl bromide (Acros), ethyl benzoate (Aldrich), allyl bromide (Acros), 4-bromobut-1-ene (Aldrich), 1,4-diphenylbut-1-one (ABCR), TsOH (Aldrich), triethylamine (Acros), methyl iodide (Merck), THF (Merck), hexane (Merck), ethyl acetate (Merck), diethyl ether (Merck), dichloromethane (Merck), toluene (Merck), methanol (Merck), dimethyl sulfoxide (Merck), silica gel 60, 40-63 μm (Merck), 8 M HCl (Merck), Na2SO4 (Akzo Nobel), K2CO3 (Merck), AlCl3 (Merck), NaBH4 (Aldrich), Na2CO3 (Merck), CuCN (Merck), NaHCO3 (Merck), bromine (Merck) and KOH (Merck).

[0104] Toluene and hexane for organometallic synthesis, and CDCl3 (deuterium-containing GmbH) for NMR measurements of air and moisture-sensitive compounds, were dried on 4A (Acros) molecular sieves.

[0105] THF and ethers used in organometallic synthesis via benzophenone distillation.

[0106] According to the literature [Den Besten, R.; Harderm S.; Brandsma, LJ Organomet. Chem. 1990, 385, 153], cyclopentadienyl lithium is prepared from cyclopentadiene obtained by dicyclopentadiene (Acros) and butyllithium in hexane.

[0107] Magnesium cyclopentadienyl bromide was prepared by cyclopentadiene obtained from dicyclopentadiene (Acros) and methyl magnesium bromide in diethyl ether (Aldrich), as described in [Stille, JR; Grubbs, RHJ Org. Chem 1989, 54, 434].

[0108] According to the literature [Motiwala, HF; Gülgeze, B., Aubé, JJ Org. Chem. 2012,77, 7005], 1-phenylhept-6-en-1-one was prepared from 5-bromo-1-pentene (Aldrich), acetophenone (Merck), N,N-dimethylhydrazine (Aldrich), and lithium diisopropylaminoide (Aldrich).

[0109] 2,7-Di-tert-butylfluorene is obtained from 9H-fluorene and 2,6-di-tert-butyl-p-phenol (Aldrich), as described in [Kajigaeshi, S.; Kadowaki, T.; Nishida, A.; Fujisaki, S.; Noguchi, M. Synthesis 1984, 335].

[0110] Catalyst Preparation Examples Complex 1 (C-1): (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium Step 1: 1-Phenylacetyl-1-(hex-5-en-1-yl)-1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)methane

[0111] 15.2 ml (36.5 mmol) of 2.5 M fluorene was added at once to a solution prepared by 10.59 g (38.04 mmol) of 2,7-di-tert-butylfluorene in 125 ml of THF cooled to -78 °C. nBuLi was dissolved in hexane. The mixture was stirred overnight at room temperature. The resulting pale orange solution was cooled to -30°C, and 9.46 g (40.03 mmol, 1.05 equivalents) of 6-phenyl-6-(hex-5-en-1-yl)fulne in 125 mL of THF was added in one go. After stirring overnight at room temperature, the deep red reaction mixture was cooled in an ice bath and then quenched to a slightly acidic pH with 10% HCl. The resulting orange mixture was diluted with 400 mL of water and extracted with 300 mL of diethyl ether. The organic layer was separated, and the aqueous layer was extracted with 150 mL of dichloromethane. The combined organic extracts were dried over Na2SO4 and filtered through a layer of silica gel 60 (40-63 μm) washed with 2 × 50 mL of dichloromethane. The solvent was removed under vacuum to give an orange oil, which was dissolved in 125 mL of n-hexane. The crystals precipitated overnight from this solution were collected at -30°C and dried under vacuum. The method yielded 14.61 g (75%) of the target product as a pale yellow solid, which was a mixture of isomers.

[0112] C 39 H 46 Analytical values: C, 90.99; H, 9.01. Measured values: C, 91.14; H, 9.07.

[0113] 1 H NMR (CDCl3): δ 7.57-6.95 (m, 11H), 6.34-5.59 (m, 4H), 4.98-4.70 (m,3H), 2.93-2.55 (m, 2H), 2.49-2.15 (m, 2H), 2.04-1.80 (m, 2H), 1.46-0.91 (m,22H). Step 2: (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dichloro Hafnium

[0114] 22.7 ml (56.8 mmol) of 2.5 M ether was added at once to a solution of 14.61 g (28.38 mmol) of 1-phenyl-1-(hex-5-en-1-yl)-1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)methane cooled to -50 °C in 300 ml of diethyl ether. nA hexane solution of BuLi was prepared. The mixture was stirred at room temperature for 5 hours. The resulting slightly reddish solution was cooled to -50°C, and 9.09 g (28.38 mmol) of HfCl4 was added. The resulting mixture was stirred at room temperature for 24 hours, and then evaporated to dryness. The residue was stirred with 200 mL of warm toluene, and the resulting suspension was filtered through a glass frit (G4) filter. The filtrate was evaporated to approximately 30 mL. 70 mL of n-hexane was added. The yellow crystalline solid precipitated overnight at -30°C was collected and dried under vacuum. This method yielded 12.9 g (60%) of the target complex.

[0115] C 39 H 44 C l2 Analytical values ​​of Hf: C, 61.46; H, 5.82. Measured values: C, 61.59; H, 6.00.

[0116] 1 H NMR (CDCl3): δ 8.01 (d, J = 9.1 Hz, 1H),.7.96 (d, J = 8.9 Hz, 1H), 7.83 (dm, J = 7.7 Hz, 1H), 7.69 (m, 1H), 7.66-7.59 (m, 2H), 7.59-7.52 (m, 1H), 7.5(dd, J = 8.9 Hz, J = 1.4 Hz, 1H), 7.45-7.38 (m, 2H), 6.35-6.31 (m, 1H), 6.22-6.18(m, 1H), 6.13 (s, 1H), 5.81-5.69 (m, 2H), 5.55-5.51 (m, 1H), 4.94 (dm, J = 17.2Hz, 1H), 4.89 (dm, J = 10.2 Hz, 1H), 3.13-2.99 (m, 1H), 2.82-2.67 (m, 1H), 2.15-1.95 (m, 2H), 1.66-1.45 (m, 4H), 1.40 (s, 9H), 0.99 (s, 9H). 13 C{ 1 H} NMR (CDCl3): δ152.19, 149.61, 143.26, 138.38, 130.52, 128.51, 128.33, 127.24, 127.08, 124.22, 124.18, 124.02, 123.52, 122.63, 120.25, 119.87, 119.67, 118.84, 117.81, 116.62, 114.65, 114.52, 99.66, 77.77, 53.68, 41.16, 35.44, 34.87, 33.80, 31.13, 30.53, 29.45, 23.64.

[0117] Step 3: (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethyl Hafnium

[0118] 7.1g (9.32mmol) [1-(η] 5 -cyclopentadien-1-yl)-1-(η 5 Hafnium dichloride was dissolved in a mixture of 90 mL toluene and 50 mL diethyl ether to form a solution. 13.0 mL (27.43 mmol) of a 2.11 M MeMgBr solution in diethyl ether was added to this solution. The resulting mixture was refluxed for 30 minutes and then evaporated to approximately 40 mL. The resulting solution was heated to 80–90 °C and filtered hot through a glass frit (G4) filter to remove insoluble magnesium salts. The filter cake was further washed with 2 × 20 mL toluene. The combined filtrates were evaporated to approximately 20 mL. The solution was reheated to 80–90 °C and filtered hot through a glass frit (G4) filter. The mother liquor was evaporated to dryness, and the residue was dissolved in 30 mL of hexane. The yellow powder precipitated from the solution overnight at -30 °C was collected and dried under vacuum. This method yielded 3.20 g of pure (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylhafnium. Using the same method, but with smaller volumes of hexane (approximately 20 ml and 5 ml), two additional portions (1.18 g and 0.57 g) of the desired complex were obtained. Therefore, the total yield of (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylhafnium was 4.95 g (74%).

[0119] C 41 H 50 Analytical values ​​of Hf: C, 68.27; H, 6.99. Measured values: C, 68.44; H, 7.21.

[0120] 1 H NMR (CDCl3): δ 8.08 (d, J = 8.9 Hz, 1H), 7.99 (d, J = 8.6 Hz, 1H), 7.81(dm, J = 7.8 Hz, 1H), 7.62-7.57 (m, 2H), 7.51 (dd, J = 8.9 Hz, J = 1.2 Hz, 1H),7.50-7.44 (m, 1H), 7.39-7.30 (m, 3H), 6.28-6.21 (m, 1H), 6.15-6.08 (m, 1H),6.03 (s, 1H), 5.74 (ddt, J = 17.1 Hz, J = 10.3 Hz, J = 6.6 Hz, 1H), 5.64-5.59 (m,1H), 5.35-5.28 (m, 1H), 4.92 (dm, J = 17.2 Hz, 1H), 4.87 (dm, J = 10.0 Hz, 1H),2.94-2.79 (m, 1H), 2.63-2.48 (m, 1H), 2.11-1.92 (m, 2H), 1.60-1.41 (m, 4H),1.38 (s, 9H), 0.97 (s, 9H), -1.76 (s, 3H), -1.90 (s, 3H). 13 C{ 1 H} NMR (CDCl3,): δ 150.29, 147.84, 144.27, 138.66, 130.71, 128.09, 127.97, 127.25, 126.67,124.53, 123.78, 122.91, 122.76, 121.05, 120.67, 119.15, 117.55, 116.38,115.88, 114.43, 112.91, 111.14, 109.56, 100.99, 100.60, 76.51, 53.51, 41.07,38.18, 37.42, 35.36, 34.77, 33.88, 31.38, 30.77, 29.61, 23.79。

[0121] Complex 2 (C-2): (phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium Step 1: 1-Phenylacet-4-en-1-one Method A

[0122] Add 67.27 g (350 mmol) of ethyl benzoyl peroxide to a sodium ethoxide solution obtained from 7.9 g (343.6 mmol) of metallic sodium and 235 mL of anhydrous ethanol. Stir the resulting mixture for 15 minutes, then add 42.37 g (350 mmol) of allyl bromide dropwise at a rate maintained below 40 °C. Reflux the resulting mixture for 3 hours, then cool to room temperature. Add a solution of 37 g KOH in 120 mL of water. Reflux the resulting pale orange homogeneous mixture for 5 hours, eventually forming a biphasic system. After cooling to room temperature, carefully treat the reaction mixture with 4 M HCl to a slightly acidic pH (Caution! Strong gas escape!). Dilute the resulting mixture with 700 mL of water, then extract with 3 × 200 mL of diethyl ether. Wash the combined ether extracts with a solution of 30 g KOH in 300 mL of water, dry with K₂CO₃, pass through a small piece of silica gel 60 (40–63 μm), and then evaporate to dryness. Vacuum distillation of the residue yielded 41.58 g (74%; purity approximately 95%) of 1-phenylpent-4-en-1-one, bp 73-81℃ / 6 mm Hg.

[0123] Method B

[0124] At 0°C, over 30 minutes, add 27.83 g (275.0 mmol) of diisopropylamine to a lithium diisopropylamide solution (at -78°C, 400 ml THF and 110 ml (275.0 mmol) 2.5 M) in 400 ml THF and 110 ml (275.0 mmol) 2.5 M sodium chloride solution. nTo the solution obtained in hexane from BuLi, add 40.56 g (250 mmol) of a solution of (1E)-1-phenylethylone dimethylhydrazine in 60 mL of THF. Stir the mixture at 0 °C for 4 hours, then cool to -78 °C, and add 36.3 g (300 mmol) of a solution of 3-bromoprop-1-ene in 45 mL of THF over 30 minutes. Slowly warm the reaction to room temperature, then stir at that temperature overnight. Evaporate the resulting solution to dryness under vacuum, and dilute the residue with 400 mL of diethyl ether. Treat the solution, cooled to 0 °C (ice bath), with an ice-cold solution of 120 mL of 96% sulfuric acid in 900 mL of water for 30 minutes. After stirring the mixture at room temperature for 30 minutes, separate the organic layer and extract the aqueous solution with 2 × 200 mL of diethyl ether. Wash the combined organic extracts with 2 × 200 mL of water, dry with Na₂SO₄, and concentrate under reduced pressure. The product was separated by rapid chromatography on silica gel 60 (40-63 μm; eluent: hexane-ethyl acetate = 97:3, by volume). This method yielded 40.5 g (approximately 100%) of 1-phenylpent-4-en-1-one as a colorless liquid.

[0125] C 11 H 12 Analytical values ​​for O: C, 82.46; H, 7.55. Measured values: C, 82.70; H, 7.63.

[0126] 1 H NMR (CDCl3): δ 7.99-7.91 (m, 2H), 7.56-7.51 (m, 1H), 7.47-7.40 (m,2H), 5.90 (ddt, J = 17.0 Hz, J = 10.2 Hz, J = 6.5 Hz, 1H), 5.08 (ddt, J = 17.0 Hz, J =1.6 Hz, J = 1.6 Hz, 1H), 5.00 (ddt, J = 10.2 Hz, J = 1.6 Hz, J = 1.6 Hz, 1H), 3.05(t, J = 7.4 Hz, 2H), 2.53-2.45 (m, 2H). 13 C{ 1 H NMR (CDCl3): δ199.15, 137.16, 136.81, 132.83, 128.43, 127.86, 115.12, 37.57, 27.99.

[0127] Step 2: 6-Phenylacetyl-6-(but-3-en-1-yl)fulne

[0128] Method A To a sodium ethoxide solution obtained from 3.42 g (148.8 mmol) metallic sodium and 120 mL anhydrous ethanol, 23.7 g (147.9 mmol) of 1-phenylpent-4-en-1-one obtained according to method A in step 1 was added. The resulting mixture was cooled to 0 °C, and then 25 mL of freshly cleaved cyclopent-1,3-diene was added dropwise over 40 minutes. The resulting mixture was stirred at room temperature for 4 hours. The red reaction mixture was poured into 200 mL of water, and the resulting mixture was extracted with 3 × 100 mL of n-hexane. The combined organic extracts were dried over anhydrous K₂CO₃ and then evaporated to dryness to give a red oily liquid. The crude product was purified by rapid chromatography on silica gel 60 (300 ml, 40-63 μm; eluent: hexane / EtOAc = 30 / 1, volume) to give 29.17 g (93%, approximately 75% purity) of 6-phenyl-6-(but-3-en-1-yl)fulne as a red oily liquid.

[0129] Method B 23.5 g (146.7 mmol) of 1-phenylpent-4-en-1-one, obtained according to method A in step 1, was added to a solution prepared by dissolving 10.2 g (149.9 mmol) of sodium ethoxide in 100 mL of THF and cooled to 0 °C. Then, 25 mL of freshly cleaved cyclopent-1,3-diene was added dropwise over 40 minutes. The resulting mixture was stirred at room temperature for 4 hours. 5 mL of water was added to the dark red reaction mixture, and the resulting mixture was passed through a small piece of silica gel 60 (40–63 μm). The filtrate was dried over anhydrous K₂CO₃ and then evaporated to dryness to give a red oily liquid. The crude product was purified by rapid chromatography on silica gel 60 (300 mL, 40–63 μm; eluent: hexane / ethyl acetate = 30 / 1, v / v) to give 29.78 g (95%, approximately 75% purity) of 6-phenyl-6-(but-3-en-1-yl)fulne as a red oily liquid.

[0130] Method C A solution of 41.0 g (255.9 mmol) of 1-phenylpent-4-en-1-one obtained according to method B in step 1 was prepared in 100 mL of THF and cooled in an ice bath to obtain a solution. A solution of 55.0 g (324.9 mmol, 1.27 equivalent) of cyclopentadienyl magnesium bromide prepared in 300 mL of THF was added dropwise. The resulting mixture was refluxed for 3 hours, then stirred overnight at room temperature, and finally cooled in an ice bath and quenched with 10% HCl to pH ~5-6. The mixture was extracted with 4 × 250 mL of hexane, and the combined organic extract was dried over Na₂SO₄. The solvent was removed under vacuum to give a deep red oil. The product was separated by rapid chromatography on silica gel 60 (40-63 μm; eluent: hexane-ethyl acetate = 100:1, v / v). This method yielded 26.98 g (51%, approximately 95% purity) of 6-phenyl-6-(but-3-en-1-yl)fulne, which was a red oily liquid.

[0131] C 16 H 16 Analytical values: C, 92.26; H, 7.74. Measured values: C, 92.39; H, 7.88.

[0132] 1 H NMR (CDCl3): δ 7.40-7.30 (m, 5H), 6.62 (ddd, J = 5.3 Hz, J = 2.0 Hz, J =1.5 Hz, 1H), 6.56 (ddd, J = 5.3 Hz, J = 2.0 Hz, J = 1.5 Hz, 1H), 6.47 (ddd, J = 5.3Hz, J = 2.0 Hz, J = 1.5 Hz, 1H), 6.10 (ddd, J = 5.3 Hz, J = 2.0 Hz, J = 1.5 Hz, 1H), 5.76 (ddt, J = 17.0 Hz, J = 10.3 Hz, J = 6.6 Hz, 1H), 5.00-4.91 (m, 2H), 2.99 (t, J =7.7 Hz, 2H), 2.20-2.12 (m, 2H).

[0133] Step 3: (phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dichloro Hafnium Method A

[0134] 20.2 ml (50.5 mmol) of 2.5 M fluorene was added in a single batch to a solution prepared by dissolving 14.07 g (50.53 mmol) of 2,7-di-tert-butylfluorene in 200 ml of THF and cooled to -50 °C. n BuLi's hexane solution. The mixture was stirred overnight at room temperature, then cooled to -50°C, and a solution of 11.55 g (55.45 mmol) of 6-phenyl-6-(but-3-en-1-yl)-fullen obtained from method C in step 2 was added in 200 mL of THF. After stirring overnight at room temperature, the resulting deep red reaction mixture was cooled in an ice bath and then quenched to pH ~5-6 with 5 mL of a solution of 12 M HCl in 200 mL of water. The resulting yellow mixture was extracted with 400 mL of dichloromethane. The organic layer was separated, and the aqueous layer was extracted with 150 mL of dichloromethane. The combined organic extracts were dried over Na2SO4 and then filtered through a small piece of silica gel 60 (40-63 μm) that had been separately washed with 2 × 50 mL of dichloromethane. The solvent was removed under vacuum, yielding an orange oily substance, which was then dried under vacuum to give 25.7 g of 1-phenyl-1-(but-3-en-1-yl)-1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)methane, which could be further used without additional purification. 22.7 ml (56.8 mmol) of 2.5 M ether was added at once to a pale yellow solution formed by 13.78 g (28.31 mmol) of 1-phenyl-1-(but-3-en-1-yl)-1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)methane in 170 ml of diethyl ether, cooled to -78 °C. n A hexane solution of BuLi was prepared. The mixture was stirred at room temperature for 5 hours. 9.07 g (28.32 mmol) of HfCl4 was added to the resulting orange suspension, which was cooled to -50 °C. The resulting mixture was stirred at room temperature for 24 hours and then evaporated to dryness. The residue was stirred with 200 mL of warm toluene, and the resulting suspension was filtered through a glass frit filter (G4). The filtrate was evaporated to about 20 mL, and the orange solid precipitated from the solution was filtered off (G3), washed with a mixture of 3 × 10 mL toluene and hexane (1:2, by volume), and then dried under vacuum. This method yielded 8.7 g (42%) of (phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl) hafnium dichloride.

[0135] Method B

[0136] 20.6 ml (50.0 mmol) of 2.43 M fluorene was added at once to a solution prepared by 13.92 g (50.0 mmol) of 2,7-di-tert-butylfluorene in 200 ml of diethyl ether and cooled to -50 °C. n BuLi's hexane solution. The mixture was stirred at room temperature for 4 hours. The resulting orange solution was cooled to ~50°C, and 11.09 g (53.2 mmol) of 6-phenyl-6-(but-3-en-1-yl)fulne obtained according to method C in step 2 was added. After stirring overnight at room temperature, the orange reaction mixture was cooled to ~50°C, and then 20.6 ml (50.0 mmol) of 2.43 M was added in one go. n A hexane solution of BuLi was prepared. The mixture was stirred at room temperature for 6 hours. The resulting deep red solution with a large amount of brick-red precipitate was cooled to -50°C, and 16.02 g (50.02 mmol) of HfCl4 was added. The resulting mixture was stirred at room temperature for 24 hours. The orange precipitate was filtered, heated with 250 mL of toluene, filtered again from LiCl, and the mother liquor was evaporated to near dryness. 50 mL of n-hexane was added to the residue, the precipitated orange powder was filtered off (G3), and dried under vacuum. This method yielded 16.7 g of (phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride. The ethereal mother liquor (from the reaction mixture) was evaporated to near dryness, and the residue was ground together with 25 mL of n-hexane. The orange precipitate (G3) was filtered off, giving 3.5 g of the target complex. Therefore, the total yield of (phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride isolated in this synthesis was 20.2 g (55%).

[0137] C 37 H 40 Analytical values ​​of Cl2Hf: C, 60.54; H, 5.49. Measured values: C, 60.32; H, 5.66.

[0138] 1 H NMR (CDCl3): δ 8.02 (d, J = 8.9 Hz, 1H), 7.96 (d, J = 8.9 Hz, 1H), 7.85 (dm, J= 7.6 Hz, 1H), 7.69 (s, 1H), 7.66-7.61 (m, 2H), 7.61-7.54 (m, 1H), 7.51(dd, J = 8.9 Hz, J = 1.5 Hz, 1H), 7.46-7.38 (m, 2H), 6.36-6.32 (m, 1H), 6.23-6.19(m, 1H), 6.15 (s, 1H), 5.99-5.86 (m, 1H), 5.81-5.77 (m, 1H), 5.55-5.51 (m,1H), 5.11 (dd, J = 17.2 Hz, J = 1.5 Hz, 1H), 5.06 (dd, J = 10.3 Hz, J = 1.5 Hz, 1H),3.29-3.19 (m, 1H), 2.81-2.70 (m, 1H), 2.43-2.26 (m, 2H), 1.38 (s, 9H), 0.99(s, 9H). 13 C{ 1 H} NMR (CDCl3,): δ 152.39, 149.63, 142.90, 137.61, 130.60, 128.68,128.29, 127.40, 127.07, 124.33, 124.16, 124.05, 123.55, 122.49, 120.18,119.86, 119.65, 118.84 (two resonances), 117.77, 116.65, 115.23, 114.34,99.61, 99.57, 77.31, 53.42, 39.89, 35.49, 34.87, 31.14, 30.52, 28.27。

[0139] Step 4: (phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethyl Hafnium

[0140] To a solution formed from 3.67 g (5.0 mmol) of (phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride obtained according to method A in step 3, 7.0 mL of a 2.11 M MeMgBr solution in diethyl ether was added. The resulting mixture was refluxed for 30 minutes and then evaporated to about 25 mL. The resulting solution was heated to 80–90 °C, and the resulting suspension was filtered hot through a glass frit (G3) to remove insoluble magnesium salts. The filter cake was washed with 2 × 20 mL of toluene. The combined filtrates were evaporated to almost dryness, and 20 mL of hexane was added to the residue. The resulting mixture was filtered again through a glass frit (G4). The mother liquor was evaporated to dryness, and the residue was dissolved in 7 mL of hexane. The yellow powder precipitated from the solution overnight at -40 °C was collected and dried under vacuum. This method yielded 3.18 g (92%) of pure (phenyl)(3-buten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium complex.

[0141] C 39 H 46 Analytical values ​​of Hf: C, 67.57; H, 6.69. Measured values: C, 67.82; H, 6.85.

[0142] 1 H NMR (CDCl3): δ 8.08 (d, J = 8.9 Hz, 1H), 8.00 (d, J = 8.9 Hz, 1H), 7.83 (dm, J = 7.9 Hz, 1H), 7.63-7.56 (m, 2H), 7.53-7.45 (m, 2H), 7.39-7.31 (m, 3H), 6.28-6.22 (m, 1H), 6.14-6.10 (m, 1H), 6.05 (s, 1H), 5.95-5.83 (m, 1H), 5.67-5.62 (m, 1H), 5.34-5.29 (m, 1H), 5.07 (dd, J = 17.2 Hz, J = 1.5 Hz, 1H), 5.01(dd, J = 10.2 Hz, J= 1.5 Hz, 1H), 3.12-2.98 (m, 1H), 2.62-2.49 (m, 1H), 2.33-2.15 (m, 2H), 1.37 (s, 9H), 0.98 (s, 9H), -1.76 (s, 3H), -1.90 (s, 3H). 13 C{ 1 HNMR (CDCl3): δ 150.44, 147.83, 143.87, 138.19, 130.77, 128.26, 127.92, 127.20, 126.82, 124.38, 123.76, 122.94, 122.66, 121.16, 120.70, 119.09, 117.45, 116.37, 115.88, 114.73, 112.91, 111.16, 109.34, 100.91, 100.51, 75.97, 53.23, 39.73, 38.29, 37.49, 35.39, 34.76, 31.39, 30.75, 28.39 Complex 3 (C-3): (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium Step 1: 1-Phenylaceto-5-en-1-one

[0143] Add 48.05 g (0.25 mol) of ethyl benzoyl to a sodium ethoxide solution obtained from 5.75 g (0.25 mol) of metallic sodium and 175 mL of anhydrous ethanol. Stir the resulting mixture for 10 minutes, then add 42.5 g (314.8 mmol) of 4-bromobut-1-ene, and reflux the mixture for 5 hours. Then, cool the reaction mixture to room temperature and add a solution obtained from 37 g of KOH in 120 mL of water. Reflux the resulting mixture for 5 hours. After cooling to room temperature, carefully treat the reaction mixture with 4 M HCl to a slightly acidic pH (Caution! Strong gas escape!). Dilute the resulting mixture with 700 mL of water and extract with 3 × 250 mL of diethyl ether. Wash the combined ether extracts with a solution obtained from 20 g of KOH in 200 mL of water, dry with K₂CO₃, pass through a small piece of silica gel 60 (40–63 μm), and then evaporate to dryness. Vacuum distillation of the residue yielded 25.91 g (60%; approximately 95% purity) of 1-phenylhex-5-en-1-one, bp 95-105 °C / 6 mm Hg.

[0144] 1 H NMR (CDCl3): δ 8.00-7.90 (m, 2H), 7.58-7.50 (m, 1H), 7.50-7.39 (m,2H), 5.82 (ddt, J = 17.1 Hz, J = 10.2 Hz, J = 6.7 Hz, 1H), 5.05 (dm, J = 17.1 Hz, 1H), 4.99 (dm, J = 10.2 Hz, 1H), 2.97 (t, J = 7.3 Hz, 2H), 2.16 (td, J = 7.3 Hz, J =6.7 Hz, 2H), 1.85 (quin, J = 7.3 Hz, 2H). 13 C{ 1 H NMR (CDCl3): δ 200.09, 137.98, 137.01, 132.82, 128.47, 127.94, 115.20, 37.61, 33.11, 23.23. Step 2: 6-Phenylacetyl-6-(pent-4-en-1-yl)fulne

[0145] To a solution of 17.4 g (100 mmol) of 1-phenylhex-5-en-1-one in 40 mL of THF, which had been cooled in an ice bath, 20.3 g (120 mmol, 1.2 equivalents) of cyclopentadienyl magnesium bromide in 120 mL of THF was added dropwise. The resulting mixture was refluxed for 3 hours, then stirred overnight at room temperature, and finally cooled in an ice bath and quenched with 10% HCl to pH ~5-6. The mixture was extracted with 3 × 150 mL of hexane, and the combined organic extracts were dried over Na₂SO₄. The solvent was removed under vacuum to give a deep red oil. The product was separated by rapid chromatography on silica gel 60 (40-63 μm; eluent: hexane-ethyl acetate = 100:1, v). This method yielded 10.23 g (46%) of 6-phenyl-6-(pent-4-en-1-yl)fulne as a red oil.

[0146] C 17 H 18Analytical values: C, 91.84; H, 8.16. Measured values: C, 92.11; H, 8.35.

[0147] 1 H NMR (CDCl3): δ 7.41–7.29 (m, 5H), 6.62 (ddd, J = 5.3 Hz, J = 1.9 Hz, J =1.5 Hz, 1H), 6.56 (ddd, J = 5.3 Hz, J = 1.9 Hz, J = 1.5 Hz, 1H), 6.47 (ddd, J = 5.3Hz, J = 1.9 Hz, J = 1.5 Hz, 1H), 6.10 (ddd, J = 5.3 Hz, J = 1.9 Hz, J = 1.5 Hz, 1H), 5.73 (ddt, J = 17.1 Hz, J = 10.3 Hz, J = 6.7 Hz, 1H), 5.01-4.90 (m, 2H), 2.92 (t, J =7.7 Hz, 2H), 2.09-2.00 (m, 2H), 1.52 (quin, J = 7.7 Hz, 2H). 13 C{ 1 H NMR (CDCl3): δ 154.28, 143.47, 140.68, 138.01, 131.83, 131.46, 129.43, 128.05, 127.79, 123.83, 120.93, 115.01, 35.57, 33.37, 28.63. Step 3: (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dichloro Hafnium

[0148] 19 ml (46.17 mmol) of 2.43 M fluorene was added at once to a solution of 12.81 g (46.01 mmol) of 2,7-di-tert-butylfluorene in 250 ml of diethyl ether, cooled to -50 °C.n BuLi's hexane solution. The mixture was stirred overnight at room temperature. The resulting orange solution was cooled to -50°C and a solution of 10.23 g (46.01 mmol) of 6-phenyl-6-(pent-4-en-1-yl)fulne in 150 mL of diethyl ether was added. After stirring overnight at room temperature, the deep red reaction mixture was cooled to -50°C and 19 mL (46.17 mmol) of 2.43 M ether was added in one go. n A hexane solution of BuLi was prepared. The mixture was stirred overnight at room temperature. The resulting deep red solution with a large amount of brick-red precipitate was cooled to -50°C, and 14.74 g (46.02 mmol) of HfCl4 was added. The resulting mixture was stirred at room temperature for 24 hours, then evaporated to dryness, and the residue was treated with 100 ml of hot toluene. The mixture was filtered while hot through a glass frit (G4) filter, and the filtrate was evaporated to dryness. The residue was ground with 100 ml of n-hexane, and the orange powder precipitated by (G3) was filtered off and then dried under vacuum. This method yielded 10.1 g of (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)hafnium dichloride. The mother liquor was evaporated to about 50 ml, the orange solid precipitated was filtered off, and then dried under vacuum. This method yielded an additional 3.82 g of the target complex. Therefore, the total yield of (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride isolated in this synthesis was 13.92 g (40%).

[0149] C 38 H 42 C l2 Analytical calculation values ​​of Hf: C, 61.01; H, 5.66. Measured values: C, 61.14; H, 5.82.

[0150] 1 H NMR (CDCl3): δ 8.01 (d, J = 8.9 Hz, 1H), 7.95 (d, J = 8.9 Hz, 1H), 7.83(br.d, J = 7.7 Hz, 1H), 7.73 (s, 1H), 7.67-7.59 (m, 2H), 7.59-7.52 (m, 1H),7.49 (d, J= 8.8 Hz, 1H), 7.45-7.38 (m, 2H), 6.34 (br.s, 1H), 6.21 (br.s, 1H),6.10 (s, 1H), 5.86-5.70 (m, 2H), 5.55 (br.s, 1H), 5.05 (br.d, J = 17.1 Hz, 1H),5.00 (br.d, J = 10.3 Hz, 1H), 3.01-2.87 (m, 2H), 2.34-2.21 (m, 1H), 2.19-2.06(m, 1H), 1.75-1.48 (m, 2H), 1.39 (s, 9H), 0.98 (s, 9H). 13 C{ 1 H} NMR (CDCl3,): δ 152.19, 149.66, 143.23, 138.17, 130.20, 128.67, 128.37, 127.26, 127.15,124.21, 124.05, 123.52, 122.64, 120.26, 119.89, 119.57, 118.89, 118.81,117.98, 116.72, 115.46, 114.15, 99.74, 99.68, 53.64, 40.32, 35.44, 34.86,34.02, 31.13, 30.52, 23.41. Step 4: (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethyl Hafnium

[0151] To a solution formed by 5.24 g (7.0 mmol) of (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride in 50 mL of toluene and 15 mL of diethyl ether, 10 mL (27 mmol) of a 2.7 M MeMgBr solution in diethyl ether was added. The resulting mixture was stirred overnight at room temperature. Most of the diethyl ether was distilled off, and the resulting mixture was filtered through a glass frit (G4) filter to remove insoluble magnesium salts. The filtrate was evaporated to almost dryness, the residue was dissolved in 30 mL of n-hexane, the resulting suspension was filtered through a glass frit (G3), and the mother liquor was evaporated to about 10 mL. The yellow powder precipitated from the solution overnight at -30 °C was collected and dried under vacuum. This method yielded 1.17 g of (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylhafnium. The mother liquor was evaporated to 5 mL. The yellow powder obtained by incubating the solution overnight at -30 °C was collected and dried under vacuum to give an additional 1.03 g of the target complex. Therefore, the total yield of (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylhafnium isolated in this synthesis was 2.21 g (44%). A similar synthesis began with 8.65 g of (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)hafnium dichloride, yielding (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylhafnium in 64% yield.

[0152] C 40 H 50 Analytical values ​​of Hf: C, 67.92; H, 6.84. Measured values: C, 67.84; H, 6.99.

[0153] 1 H NMR (CDCl3): δ 8.08 (d, J = 8.9 Hz, 1H), 7.99 (d, J = 8.8 Hz, 1H), 7.81 (dm, J = 7.7 Hz, 1H), 7.64-7.57 (m, 2H), 7.53-7.44 (m, 2H), 7.39-7.31 (m, 3H), 6.27-6.23 (m, 1H), 6.14-6.10 (m, 1H), 6.00 (br.d, J = 0.8 Hz, 1H), 5.76 (ddt, J =17.1 Hz, J= 10.1 Hz, J = 6.8 Hz, 1H), 5.63-5.57 (m, 1H), 5.36-5.30 (m, 1H), 5.01(dm, J = 17.1 Hz, 1H), 4.96 (dm, J = 10.1 Hz, 1H), 2.82-2.67 (m, 2H), 2.28-2.16(m, 1H), 2.13-2.01 (m, 1H), 1.66-1.40 (m, 2H), 1.38 (s, 9H), 0.97 (s, 9H), -1.77 (s, 3H), -1.91 (s, 3H). 13 C{ 1 H NMR (CDCl3): δ 150.24, 147.84, 144.25, 138.51, 130.42, 128.29, 127.96, 127.31, 126.68, 124.56, 123.76, 122.90, 122.77, 121.04, 120.67, 119.05, 117.69, 116.37, 115.86, 115.08, 112.90, 111.16, 109.23, 101.03, 100.63, 76.68, 53.46, 40.31, 38.15, 37.43, 35.35, 34.76, 34.19, 31.40, 30.76, 23.52. Complex 4 (C-4): (phenyl)(pent-4-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium Step 1: 6-Phenylacetyl-6-(3-Phenylacetyl)fulne

[0154] Add 50 mL of THF to a sodium ethoxide solution obtained from 1.15 g (50 mmol) of metallic sodium and 40 mL of anhydrous ethanol, followed by 11.2 g (49.9 mmol) of 1,4-diphenylbut-1-one (ABCR, 98%). Cool the resulting deep red solution to 0 °C, and then add 8.4 mL of freshly cleaved cyclopentadiene dropwise over 15 minutes. Stir the resulting mixture at room temperature for 4 hours. Pour the reaction mixture into 500 mL of water and extract the mixture with 150 mL of dichloromethane. Separate the organic layer, and extract the aqueous phase with 2 × 75 mL of dichloromethane. Dry the combined organic extracts with anhydrous K₂CO₃ and then evaporate to dryness to give a deep red oily liquid. The crude product was rapidly purified by silica gel 60 (300 ml, 40-63 μm; eluent: hexane / ethyl acetate = 100 / 1, volume) to give 7.89 g (58%) 6-phenyl-6-(3-phenylpropyl)fulne, which was a light orange liquid.

[0155] C 21 H 20 Analytical values: C, 92.60; H, 7.40. Measured values: C, 92.79; H, 7.60.

[0156] 1 H NMR (CDCl3, 400 MHz, 27 o C): δ 7.42-7.29 (m, 5H), 7.27-7.19 (m, 2H), 7.19-7.12 (m, 1H), 7.11-7.04 (m, 2H), 6.58-6.53 (m, 2H), 6.47 (ddd, J = 5.2 Hz, J = 1.5 Hz, J = 1.5 Hz, 1H), 6.11 (ddd, J = 5.2 Hz, J = 1.5 Hz, J = 1.5 Hz, 1H), 2.94(t, J = 7.7 Hz, 2H), 2.60 (t, J = 7.7 Hz, 2H), 1.75 (quin, J = 7.7 Hz, 2H). 13 C{ 1 HNMR (CDCl3): δ154.18, 143.52, 141.71, 140.56, 131.89, 131.53, 129.45, 128.34, 128.26, 128.12, 127.84, 125.80, 123.86, 120.89, 35.69, 35.54, 30.99. Step 2: [1-(η 5 -cyclopentadien-1-yl)-1-(η 5 -2,7-Di-tert-butylfluorenyl)-1-(3-phenylpropyl)-1- [Phenylenylmethane] Hafnium dichloride

[0157] 12 ml (29.16 mmol) of 2.43 M fluorene was added at once to a solution of 8.07 g (28.98 mmol) of 2,7-di-tert-butylfluorene in 200 ml of diethyl ether, cooled to -50 °C. n BuLi's hexane solution. The mixture was stirred overnight at room temperature. The resulting orange solution was cooled to -50°C, and a solution of 7.89 g (28.97 mmol) 6-phenyl-6-(3-phenylpropyl)fulne in 25 mL of diethyl ether was added in one go. After stirring at room temperature for 5 hours, the orange reaction mixture was cooled to -50°C, and 11.9 mL (28.92 mmol) of 2.43 M ether was added in one go. n A hexane solution of BuLi. The mixture was stirred overnight at room temperature. The resulting orange solution with a large amount of orange precipitate was cooled to -50°C, and 9.28 g (28.97 mmol) of HfCl4 was added. The resulting mixture was stirred at room temperature for 24 hours, and then evaporated to about 100 mL. The resulting orange precipitate was filtered off (G3), heated with 70 mL of toluene, filtered again from LiCl, and the mother liquor was evaporated to about 10 mL. The red crystals precipitated overnight at room temperature were filtered off (G3), and then dried under vacuum. This method yielded 7.56 g of [1-(η 5 -cyclopentadien-1-yl)-1-(η 5 -2,7-di-tert-butylfluorenyl)-1-(3-phenylpropyl)-1-phenylmethane]-hafnium dichloride. The mother liquor was combined with the ethereal mother liquor (from the evaporated reaction mixture), and the resulting mixture was evaporated to almost dryness. The residue was ground together with 60 ml of n-hexane. The resulting orange precipitate was filtered off (G3) to give 3.71 g of the target complex. Thus, [1-(η-2-( ... 5 -cyclopentadien-1-yl)-1-(η 5The total yield of hafnium dichloride was 11.27 g (49%).

[0158] C 42 H 44 Analytical values ​​of Cl2Hf: C, 63.20; H, 5.56. Measured values: C, 63.38; H, 5.59.

[0159] 1 H NMR (CDCl3): δ 7.98 (d, J = 8.9 Hz, 1H), 7.93 (d, J = 8.9 Hz, 1H), 7.85 (d, J = 7.3 Hz, 1H), 7.67 (s, 1H), 7.61 (d, J = 8.5 Hz, 2H), 7.59-7.52 (m, 1H),7.48 (d, J = 8.5 Hz, 1H), 7.45-7.36 (m, 2H), 7.30-7.21 (m, 2H), 7.21-7.03 (m,3H), 6.29 (s, 1H), 6.19 (s, 1H), 6.08 (s, 1H), 5.58-5.51 (m, 2H), 3.06-2.80(m, 3H), 2.69-2.36 (m, 1H), 1.99-1.85 (m, 1H), 1.85-1.71 (m, 1H), 1.38 (s,9H), 0.97 (s, 9H). 13 C{ 1 H NMR (CDCl3): δ 152.11, 149.61, 143.18, 141.56, 130.16, 128.74, 128.46, 128.32, 127.26, 127.17, 126.01, 124.15, 124.02, 123.45, 122.56, 120.24, 119.84, 119.53, 118.84, 118.72, 117.84, 116.65, 114.07, 99.69, 99.56, 77.90, 53.61, 40.15, 35.89, 35.39, 34.83, 31.19, 30.51, 25.91. Step 3: [1-(η 5 -cyclopentadien-1-yl)-1-(η 5 -2,7-Di-tert-butylfluorenyl)-1-(3-phenylpropyl)-1- [Phenylmethane]dimethylhafnium

[0160] Towards 3.7g (5.0mmol) [1-(η 5 -cyclopentadien-1-yl)-1-(η 5 [1-(η-2-di-tert-butylfluorenyl)-1-(3-phenylpropyl)-1-phenylmethane] hafnium dichloride was added to a solution formed in a mixture of 40 mL toluene and 30 mL diethyl ether, followed by the addition of 7.0 mL (18.9 mmol) of a 2.7 M MeMgBr solution in diethyl ether. The resulting mixture was refluxed for 30 min and then evaporated to about 30 mL. The resulting solution was heated to 80–90 °C and filtered hot through a glass frit (G3) filter to remove insoluble magnesium salts. The filter cake was washed with 10 mL of warm toluene. The combined filtrates were evaporated to about 15 mL, heated to 80–90 °C, and then filtered through a hot glass frit (G3) filter. The mother liquor was evaporated to about 10 mL, followed by the addition of 10 mL of n-hexane. The yellow powder precipitated from the solution overnight at room temperature was collected and dried under vacuum. This method yielded 2.11 g (60%) pure [1-(η-2-butylfluorenyl)-1-(3-phenylpropyl)-1-phenylmethane] hafnium dichloride. 5 -cyclopentadien-1-yl)-1-(η 5 [-2,7-di-tert-butylfluorenyl)-1-(3-phenylpropyl)-1-phenylmethane]dimethylhafnium.

[0161] C 44 H 50 Calculated Hf values: C, 69.78; H, 6.65. Measured values: C, 69.86; H, 6.83.

[0162] 1 H NMR (CDCl3): δ 8.07 (d, J = 8.7 Hz, 1H), 7.98 (d, J = 8.7 Hz, 1H), 7.82 (dm, J = 7.7 Hz, 1H), 7.62-7.54 (m, 2H), 7.53-7.44 (m, 2H), 7.39-7.29 (m, 3H), 7.27-7.19 (m, 2H), 7.19-7.08 (m, 3H), 6.24-6.19 (m, 1H), 6.13-6.08 (m, 1H),5.99 (br.d, J= 0.9 Hz, 1H), 5.48-5.41 (m, 1H), 5.34-5.30 (m, 1H), 2.89-2.76(m, 2H), 2.71 (td, J = 13 Hz, J = 4.3 Hz, 1H), 2.58 (dt, J = 14 Hz, J = 8.0 Hz, 1H),1.91-1.76 (m, 1H), 1.76-1.62 (m, 1H), 1.37 (s, 9H), 0.96 (s, 9H), -1.80 (s,3H), -1.92 (s, 3H). 13 C{ 1 H NMR (CDCl3): δ 150.24, 147.86, 144.20, 141.95, 30.42, 128.36, 127.97, 127.34, 126.72, 125.83, 124.50, 123.76, 122.88, 122.77, 121.03, 120.69, 119.06, 117.57, 116.38, 115.86, 112.87, 111.16, 109.13, 101.02, 100.60, 53.47, 40.26, 38.14, 37.45, 36.10, 35.33, 34.76, 31.46, 30.77, 25.96. Comparative example of coordination compound (CC-1) (phenyl)(hex-5-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylzirconium Step 1: 1-Phenylacetyl-1-(hex-5-en-1-yl)-1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)methane

[0163] 20.0 ml (50.0 mmol) of 2.5 M fluorene was added at once to a solution prepared by 13.92 g (50.0 mmol) of 2,7-di-tert-butylfluorene in 170 ml of THF cooled to -78 °C. nBuLi was dissolved in hexane. The mixture was stirred overnight at room temperature. The resulting pale orange solution was cooled to -50°C, and 12.44 g (52.6 mmol, 1.05 equivalent) of 6-phenyl-6-(hex-5-en-1-yl)fulne dissolved in 170 mL of THF was added in one go. After stirring overnight at room temperature, the deep red reaction mixture was cooled in an ice bath and then quenched to a slightly acidic pH with 10% HCl. The resulting orange mixture was diluted with 400 mL of water and extracted with 500 mL of diethyl ether. The organic layer was separated, and the aqueous layer was extracted with 150 mL of dichloromethane. The combined organic extracts were dried over Na2SO4 and filtered through a small piece of silica gel 60 (40-63 μm) that had been separately washed with 2 × 50 mL of dichloromethane. The solvent was removed under vacuum to obtain a semi-crystalline yellow substance, which was ground together with 50 ml of n-hexane, filtered, and dried under vacuum to give 16.62 g of 1-phenyl-1-(hex-5-en-1-yl)-1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)methane as a white solid. The mother liquor was evaporated to dryness, and the residue was dissolved in 100 ml of hot n-hexane. The solid precipitated overnight from this solution at -30 °C was filtered off, washed with 30 ml of cold n-hexane, and dried under vacuum. This method yielded 7.82 g of the target product as a mixture of isomers, a pale yellow solid. Therefore, the total yield of 1-phenyl-1-(hex-5-en-1-yl)-1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)methane isolated in this synthesis was 24.44 g (94.8%).

[0164] C 39 H 46 Analytical values: C, 90.99; H, 9.01. Measured values: C, 91.15; H, 9.20.

[0165] 1 H NMR (CDCl3): δ 7.57-6.95 (m, 11H), 6.34-5.59 (m, 4H), 4.98-4.70 (m,3H), 2.93-2.55 (m, 2H), 2.49-2.15 (m, 2H), 2.04-1.80 (m, 2H), 1.46-0.91 (m,22H). Step 2: (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dichloro Zirconium

[0166] 25.7 ml (64.25 mmol) of 2.5 M ether was added in a single batch to a solution of 16.51 g (32.07 mmol) of 1-phenyl-1-(hex-5-en-1-yl)-1-cyclopentadienyl-1-(2,7-di-tert-butylfluorenyl)methane cooled to -50 °C in 300 ml of diethyl ether. n BuLi was dissolved in hexane. The mixture was stirred overnight at room temperature. The resulting yellow solution with a yellow precipitate was cooled to -50°C and 7.48 g (32.1 mmol) of ZrCl4 was added. The resulting mixture was stirred at room temperature for 24 hours and then evaporated to dryness. The residue was stirred with 150 mL of warm toluene and the resulting suspension was filtered through a glass frit (G4) filter. The filtrate was evaporated to about 40 mL and 70 mL of n-hexane was added. The red solid precipitated overnight at -30°C was collected and dried under vacuum. This method yielded 19.7 g (91%) of (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)zirconium dichloride, solvated with toluene in a 1:1 ratio.

[0167] C 39 H 44 Analytical values ​​of Cl2Zr*C7H8: C, 72.03; H, 6.83. Measured values: C, 72.24; H, 7.09.

[0168] 1 H NMR (CDCl3): δ 8.04 (d, J = 8.7 Hz, 1H), 7.98 (d, J = 8.7 Hz, 1H), 7.82 (dm, J = 7.7 Hz, 1H), 7.67 (s, 1H), 7.66 (dd, J = 9.4 Hz, J= 1.4 Hz, 1H), 7.64-7.60 (m, 1H), 7.59-7.51 (m, 2H), 7.44-7.38 (m, 2H), 6.41-6.37 (m, 1H), 6.28-6.24 (m, 1H), 6.09 (m, 1H), 5.84-5.80 (m, 1H), 5.80-5.68 (m, 1H), 5.59-5.55(m, 1H), 4.97-4.86 (m, 2H), 3.10-2.97 (m, 1H), 2.82-2.69 (m, 1H), 2.15-1.96(m, 2H), 1.64-1.44 (m, 4H), 1.39 (s, 9H), 0.98 (s, 9H). 13 C{ 1 H} NMR (CDCl3,): δ 152.50, 149.95, 143.09, 138.34, 130.47, 128.56, 128.36, 127.26, 127.09,124.58, 124.32, 124.29, 123.84, 123.63, 121.45, 121.38, 120.51, 120.03,119.77, 118.32, 117.64, 114.67, 111.87, 102.14, 77.73, 53.80, 40.88, 35.48,34.90, 33.76, 31.11, 30.50, 29.43, 23.57. Step 3: (phenyl)(hex-5-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethyl Zirconium

[0169] To a solution formed from 3.37 g (4.99 mmol) of (phenyl)(hex-5-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)zirconium dichloride in 50 mL of toluene and 25 mL of diethyl ether, 7.0 mL (14.77 mmol) of 2.11 M MeMgBr in diethyl ether was added. The resulting mixture was refluxed for 30 minutes and then evaporated to about 25 mL. The resulting suspension was heated to 80–90 °C and filtered hot through a glass frit (G3) filter to remove insoluble magnesium salts. The filter cake was washed with 2 × 15 mL of toluene. The combined filtrates were evaporated to about 10 mL, and the resulting solution was reheated to 80–90 °C and filtered hot through a glass frit (G3) filter. The mother liquor was evaporated to dryness, and the residue was dissolved in 12 mL of n-hexane. The yellow powder precipitated from the solution overnight at -40 °C was collected and dried under vacuum. This method yielded 1.68 g (53.1%) of pure (phenyl)(hex-5-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylzirconium.

[0170] C 41 H 50 Analytical values ​​of Zr: C, 77.66; H, 7.95. Measured values: C, 77.62; H, 8.19.

[0171] 1 H NMR (CDCl3): δ 8.10 (d, J = 8.6 Hz, 1H), 8.00 (d, J = 8.9 Hz, 1H), 7.79 (dm, J = 7.9 Hz, 1H), 7.61-7.54 (m, 2H), 7.52 (dd, J = 8.9 Hz, J = 1.2 Hz, 1H),7.50-7.44 (m, 1H), 7.37 (dd, J = 8.9 Hz, J = 1.6 Hz, 1H), 7.35-7.30 (m, 2H), 6.35-6.29 (m, 1H), 6.22-6.15 (m, 1H), 5.97 (s, 1H), 5.80-5.63 (m, 2H), 5.36-5.30 (m, 1H), 4.92 (dm, J = 17.2 Hz, 1H), 4.87 (dm, J= 10.0 Hz, 1H), 2.89-2.74(m, 1H), 2.60-2.45 (m, 1H), 2.11-1.92 (m, 2H), 1.58-1.39 (m, 4H), 1.38 (s,9H), 0.97 (s, 9H), -1.57 (s, 3H), -1.71 (s, 3H). 13 C{ 1 H NMR (CDCl3): δ 150.24, 147.86, 144.21, 138.65, 130.62, 128.09, 127.96, 127.22, 126.63, 125.03, 123.57, 123.27, 122.78, 121.01, 120.57, 119.42, 117.91, 117.31, 117.09, 114.42, 113.10, 111.42, 106.37, 102.02, 101.49, 74.70, 53.59, 40.88, 35.35, 34.77, 33.86, 32.24, 31.55, 31.43, 30.80, 29.60, 23.70. Elemental analysis of coordination compounds (ICP method):

[0172] b) Polymerization process Polymerization experiments were conducted in a 125 mL reactor equipped with a bottom valve at 160 °C and in liquid phases with different C8 / C2 weight ratios. Different catalyst loadings were tested to find the optimal amount that maintained nearly constant temperature and pressure during the 10-minute polymerization. TEA (7 x 10⁻⁶ in Isopar E) -2 (mol / kg) has been used as the scavenger in all experiments.

[0173] • Activation process Two different borate activators were tested: triphenylmethyltetra(pentafluorophenyl)borate (TB) used in Example IE-3 of this invention and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate (AB) used in all other experiments. In all cases, the B / Hf molar ratio used was 1.25. The complex and activator were dissolved separately in 4 mL of toluene. The borate solution was then injected into the reactor feed line, followed by the complex solution, allowing both to contact for a few seconds before being injected into the reactor under nitrogen overpressure.

[0174] • Aggregation process Fill the reactor with the required amount (57-73 mL solvent (isopar E, see Table 1) of scavenger (0.035 mmol TEA) and 1-octene. Select the solvent and monomer amounts to achieve an initial liquid volume of 80 mL under polymerization conditions.

[0175] The reactor was then heated and carefully pressurized with ethylene (25-28 bar-g). Once conditions stabilized, the ethylene pressure was adjusted to 30 bar-g, and the mixture was stirred at 750 rpm for 10 minutes to determine the absorption of the remaining ethylene.

[0176] Subsequently, the catalyst (dissolved in 4 mL toluene) and co-catalyst (also dissolved in 4 mL toluene) were combined in the injection line and immediately injected into the reactor under nitrogen overpressure. The pressure was then maintained constant by adding ethylene. After 10 minutes of polymerization, a molar excess of terminator (CO2) relative to the transition metal complex was added to quench the polymerization. Immediately afterwards, the reactor was vented, the temperature was lowered, and the container was opened. The solution was drained into an aluminum dish containing a few milligrams (approximately 500 ppm associated with the resulting copolymer) of Irganox 1076. The dish was then placed in a well-ventilated fume hood until the volatiles evaporated. The collected residues were analyzed by HT-SEC and DSC according to the methods reported in the polymer characterization section.

[0177] Table 1: Results of C2 / C8 copolymerization Invention embodiments IE1-IE5 and comparative example CE1

[0178] For all embodiments except IE3, cocatalyst AB was used, while TB in IE3 was used as a cocatalyst.

[0179] Table 1 shows that although zirconium complexes have high activity: a) Compared with zirconium analogs, the hafnium complexes according to the present invention have much higher comonomer reactivity; b) Hafnium complexes exhibit higher molecular weight properties compared to zirconium analogs, even for copolymers with higher octene content (lower density).

[0180] In other words, hafnium complexes generally have better performance than zirconium analogs and are used to produce low-density, high-molecular-weight C2 / α-olefin (preferably octene) copolymers.

Claims

1. Catalyst system, wherein, The catalyst system includes (i) at least one metallocene complex of formula (I) （I） in, Mt1 is Hf, Each X is independently R 6 Group or OR 6 Group, wherein R 6 C 1-6 -alkyl, phenyl, or benzyl, R 1 R 2 R 3 They may be the same or different, and can be hydrogen or saturated straight-chain or branched C1-C. 10 Alkyl group, wherein the alkyl group may optionally contain up to two heteroatoms belonging to groups 14-16 of the periodic table, or R 1 With R 2 or R 2 With R 3 It can form rings with 4 to 6 carbon atoms and 1 to 3 double bonds. R 4 and R 5 They may be the same or different from each other, and can be saturated straight-chain or branched C1-C. 10 Alkyl, C5-C 10 Aryl, C6-C 20 Alkyl or C6-C 20 Aryl groups, which may optionally contain up to two heteroatoms belonging to groups 14-16 of the periodic table, n can be from 1 to 5. Ar represents unsubstituted or substituted by 1-5 straight or branched C1-C1 chains. 10 Alkyl-substituted C6-C 20 -Aryl or C6-C 20 - heteroaryl, and (ii) Boron-containing cocatalysts.

2. The catalyst system according to claim 1, wherein, Each X is independently C 1-4 -Alkyl or benzyl.

3. The catalyst system according to claim 1, wherein, The catalyst system comprises a mixture of the metallocene complex shown in formula (I) and the metallocene complex shown in formula (I'). （I'） Where Mt2 is Zr, n, X, R 1 To R 5 As defined in Ar as a complex of formula (I), the mixture contains more than 50 mol% of a complex of formula I and wherein Mt 1 is Hf.

4. The catalyst system according to claim 1, wherein, In equation (I) Mt1 is Hf, X is independent of R 6 Group or OR 6 Group, wherein R 6 C 1-6 -alkyl, phenyl, or benzyl, R 1 R 2 R 3 They may be the same or different from each other, and may be hydrogen or saturated straight-chain or branched C1-C6 alkyl groups, wherein the alkyl group does not contain any heteroatoms belonging to groups 14-16 of the periodic table, or R 1 It is hydrogen and R 2 With R 3 It forms a ring with 5 to 6 carbon atoms and 1 to 3 double bonds. R 4 and R 5 They may be the same or different from each other, and can be saturated straight-chain or branched C1-C. 10 Alkyl or C6-C 10 Aryl groups contain no heteroatoms belonging to groups 14-16 of the periodic table. Ar is an unsubstituted C6-C alkyl group or a C6-C alkyl group substituted with a straight-chain or branched alkyl group. 10 -Aryl or C6-C 10 - heteroaryl And n can be 2 to 4.

5. The catalyst system according to claim 4, wherein, In equation (I) Mt1 is Hf, X is independent of R 6 Group or OR 6 Group, wherein R 6 C 1-6 -alkyl, phenyl, or benzyl, R 1 R 2 R 3 They may be the same or different from each other, and can be hydrogen, saturated straight-chain or branched C1-C4 alkyl groups, wherein the alkyl group does not contain any heteroatoms belonging to groups 14-16 of the periodic table, or R 1 It is hydrogen and R 2 With R 3 It forms a ring with 6 carbon atoms and 3 double bonds. R 4 and R 5 They may be the same or different from each other, and can be saturated straight-chain or branched C1-C6 alkyl or phenyl groups, wherein the groups do not contain any heteroatoms belonging to groups 14-16 of the periodic table. Ar represents unsubstituted C6-C. 10 Aryl, and n is 2 to 4.

6. The catalyst system according to claim 5, wherein, In equation (I) Mt1 is Hf, X is independently a C1-C4 alkyl or benzyl group. R 1 R 2 R 3 They are the same and all are hydrogen, or R 1 It is hydrogen and R 2 With R 3 It forms a ring with 6 carbon atoms and 3 double bonds. R 4 and R 5 They are the same, being saturated straight-chain or branched C2-C6 alkyl groups. n is 2 to 4, and Ar is phenyl.

7. The catalyst system according to claim 1, wherein, The metallocene complexes of formula (I) are selected from compounds including (phenyl)(but-3-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium (phenyl)(but-3-en-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dibenzylhafnium (phenyl)(4-penten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)dimethylhafnium (phenyl)(4-penten-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)dibenzylhafnium (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dimethylhafnium (phenyl)(5-hexen-1-yl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)dibenzylhafnium (phenyl)(3-phenylpropyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dimethylhafnium (phenyl)(3-phenylpropyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)dibenzylhafnium It can be optionally mixed with the corresponding metallocene complex of formula (I'), wherein Mt 2 is Zr, provided that the mixture contains more than 50 mol% of the formula I complex and Mt 1 is Hf.

8. The catalyst system according to claim 1, wherein, The catalyst system is a homogeneous or unsupported catalyst system. The catalyst system can be prepared by contacting a metallocene complex of formula (I) or a mixture of the metallocene complex of formula (I) and the metallocene complex of formula (I') in solution, provided that the mixture contains more than 50 mol% of the formula I complex and Mt 1 is Hf, as a solid or solution, with a boron-containing co-catalyst placed in a hydrocarbon diluent or pre-dissolved in an aromatic solvent. Alternatively, it can be formed by directly adding the catalyst components in sequence into a polymerization reactor.

9. The catalyst system of claim 1, wherein, The boron-containing cocatalyst includes anions of the following formula: (Z)4B - (II) Wherein, Z is an optionally substituted phenyl derivative, and the substituent is a halogenated -C. 1-6 -Alkyl or halogen groups.

10. The catalyst system of claim 9, wherein, The boron-containing cocatalyst is selected from borates including: Triphenylcarbium tetra(pentafluorophenyl)borate, N,N-Dimethylcyclohexylammonium tetra(pentafluorophenyl)borate, N,N-Dimethylbenzylammonium tetra(pentafluorophenyl)borate or N,N-Dimethylphenylammonium tetra(pentafluorophenyl)borate.

11. The catalyst system of claim 1, wherein, This system exhibits a polymerization reactivity ratio (Creactivity) of at least 0.1 in high-temperature solution methods for preparing ethylene copolymers. AO / C2, where AO is C 4-10 α-olefin comonomer.

12. Use of the catalyst system according to any one of claims 1 to 11 in a high-temperature solution process above 100°C for the polymerization of ethylene and C 4-10 α-olefin comonomer.

13. A method for preparing an ethylene copolymer, the method comprising: In the presence of a catalyst as defined in any one of claims 1 to 11, ethylene is reacted with C by a high-temperature solution method at a temperature above 100°C. 4-10 α-olefin comonomer polymerization.

14. The method of claim 13, wherein, Aggregation occurs a) At a polymerization temperature of at least 110°C, b) Pressure range of 50 to 300 bar, and c) In the selection of C 5-12 - In the hydrocarbon solvent of hydrocarbons, the C 5-12 - Hydrocarbons can be unsubstituted or converted to C 1-4 Alkyl-substituted and liquid under the polymerization conditions defined above.

15. The ethylene copolymer obtained by the polymerization method of claim 13, wherein, The ethylene is ethylene and C. 4-10 Copolymers of α-olefin comonomers, having (i) The comonomer content is as high as 45 wt%. (ii) Density (measured according to ISO 1183-187) is 0.850 g / cm³. 3 To below 0.920 g / cm 3 , (iii) The Mw / Mn value is 2.0 to 4.5, preferably 2.5 to 4.

5. (iv) Melting point (measured by DSC according to ISO 11357-3:1999) is below 110°C.

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