Metallocene compounds, precursors, and methods for producing the same

Abstract

The metallocene compound of the present invention is represented by the following chemical formula 1. [Formula 1] TIFF2026514139000044.tif61170 (Z, R1, R2, R3, R4, R5, n, m, p, q, X1, X2, Q1 and Q2 are as defined in the specification)

Description

[Technical Field]

[0001] The present invention relates to a metallocene compound having a novel structure, a precursor, and a method for producing the same. [Background technology]

[0002] Metallocene catalysts are compounds in which ligands such as cyclopentadienyl groups, indenyl groups, or cycloheptadienyl groups are coordinately bonded to a transition metal or a transition metal halogen compound, and are used as catalysts for olefin polymerization.

[0003] The metallocene catalyst is a single-site catalyst composed of the metallocene compound and a co-catalyst such as methylaluminoxane, and the polymer polymerized by the metallocene catalyst has a narrow molecular weight distribution, a uniform comonomer distribution, and higher copolymerization activity compared to the Ziegler-Natta catalyst.

[0004] Related prior art is Korean Patent Publication No. 2021-48677. [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide metallocene compounds having a novel structure, precursors, and methods for producing the same.

[0006] All of the aforementioned and other objectives of the present invention can be achieved by the present invention as described later. [Means for solving the problem]

[0007] 1. One aspect of the present invention relates to a metallocene compound. The metallocene compound is represented by the following chemical formula 1.

[0008] [ka]

[0009] In the above Chemical Formula 1, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), Z is N, R1 and R2 are each independently hydrogen, halogen, substituted or unsubstituted C , 3-20 , 1-20 , 6-20 , , 7-40 , , 3-20 , 2-20 , 6-20 , 6-20 , 1-20 , , 1-20 , , 6-20 , 7-40 , , 3-20 , 1-20 , 2-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamide, or substituted or unsubstituted C 6-20 arylamide, R3 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 2-20 alkoxyalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 7-40 alkylaryl of, substituted or unsubstituted C 7-40 arylalkyl of, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 6-20 aryloxy, substituted or unsubstituted C 3-20 heteroaryl, R4 and R5 are each independently hydrogen, halogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 6-20 aryl, n is an integer from 0 to 4, m is an integer from 0 to 2, p and q are each independently integers from 0 to 4, X1 and X2 are each independently C 1-20 alkyl group, C 6-20It is an aryl group, Q1 and Q2 are independent of halogen and C. 1-20 Alkyl alkyl group, C 6-20 (It is an aryl group.)

[0010] 2. In the specific example in 1 above, M is zirconium (Zr), R1 and R2 are C 1-3 It is alkyl, P is 0, and q is either 0 or 1. R4 and R5 are C 1-3 It is alkyl, n is 0, and m may be 0 or 1.

[0011] 3. In the specific examples of 1-2 above, M is zirconium (Zr), X1 and X2 are independent of each other, C 1-20 It is an alkyl group, Q1 and Q2 may each be halogens, independently of each other.

[0012] 4. In the specific examples of 1-3 above, R3 may have 1 to 10 carbon atoms.

[0013] 5. In the specific examples of 1-4 above, the metallocene compound may be represented by any of the following structures.

[0014] [ka] TIFF2026514139000004.tif215170

[0015] 6. In the specific examples of 1-5 above, the metallocene compound can be a compound represented by the following chemical formula 2 as a precursor.

[0016] [ka]

[0017] In the aforementioned chemical formula 2, Z is N, R1 and R2 are, independently, hydrogen, halogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, or substituted or unsubstituted C 6-20 It is an arylamide, R3 is a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 2-20 Alkoxyalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 7-40 alkylaryl, substituted or unsubstituted C 7-40 arylalkyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryloxy, substituted or unsubstituted C 3-20 It is a heteroaryl, R4 and R5 are, independently, hydrogen, halogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 6-20 It is Ariel, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X1 and X2 are independent of each other, C 1-20 Alkyl alkyl group, C 6-20 (It is an aryl group.)

[0018] 7. In the specific example of 6 above, the metallocene catalyst precursor may be represented by any of the following structures.

[0019] [ka] TIFF2026514139000007.tif215170

[0020] 8. In the specific examples described in 1-7 above, the metallocene compound may be produced by adding an organolithium compound to the metallocene catalyst precursor to produce a lithium salt, and then reacting the lithium salt with a group 4 transition metal compound.

[0021] 9. Another aspect of the present invention relates to a metallocene catalyst precursor. The metallocene catalyst precursor is represented by the following chemical formula 2.

[0022] [ka]

[0023] In the aforementioned chemical formula 2, Z is N, R1 and R2 are, independently, hydrogen, halogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, or substituted or unsubstituted C 6-20 It is an arylamide, R3 is a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 2-20 Alkoxyalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20Heterocycloalkyl, substituted or unsubstituted C 7-40 alkylaryl, substituted or unsubstituted C 7-40 arylalkyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryloxy, substituted or unsubstituted C 3-20 It is a heteroaryl, R4 and R5 are, independently, hydrogen, halogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 6-20 It is Ariel, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X1 and X2 are independent of each other, C 1-20 Alkyl alkyl group, C 6-20 (It is an aryl group.)

[0024] 10. In the specific example of item 9 above, the metallocene catalyst precursor may be represented by any of the following structures.

[0025] [ka] TIFF2026514139000010.tif215170

[0026] A further aspect of the present invention relates to a method for producing a metallocene compound represented by chemical formula 1. The method includes the steps of adding an organolithium compound to a metallocene catalyst precursor represented by chemical formula 2 to produce a lithium salt, and reacting the lithium salt with a group 4 transition metal compound.

[0027] 12. In the specific example of 11 above, the group 4 transition metal compound may include TiCl4, ZrCl4, or HfCl4.

[0028] 13. In the specific examples described in 11-12 above, the metallocene catalyst precursor may include the steps of adding an organolithium compound to a tetrahydroindene compound represented by the following chemical formula 3 to produce a tetrahydroindene lithium salt, reacting the tetrahydroindene lithium salt with a silane compound to produce a tetrahydroindenylsilane compound, and reacting the tetrahydroindenylsilane compound with an indenindole lithium salt represented by chemical formula 4.

[0029] 14. Yet another aspect of the present invention relates to a method for producing a metallocene catalyst precursor represented by chemical formula 2. The method includes the steps of adding an organolithium compound to a tetrahydroindene compound represented by chemical formula 3 to produce a lithium tetrahydroindene salt, reacting the lithium tetrahydroindene salt with a silane compound to produce a tetrahydroindenylsilane compound, and reacting the tetrahydroindenylsilane compound with a lithium indenindole salt represented by chemical formula 4.

[0030] 15. Further embodiments of the present invention relate to supported metallocene catalysts. The supported metallocene catalyst comprises a metallocene compound represented by chemical formula 1 and a carrier supporting the metallocene compound.

[0031] 16. In the specific example of 15 above, the carrier may be at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia.

[0032] 17. In the specific examples described in 15-16 above, the supported metallocene catalyst may further include a co-catalyst. [Effects of the Invention]

[0033] The present invention has the effect of providing a metallocene compound having a novel structure, a precursor, and a method for producing the same. [Brief explanation of the drawing]

[0034] [Figure 1]FIG. 1 shows the synthesis reaction formula of Catalyst 1 of Example 1.

Embodiments for Carrying Out the Invention

[0035] Hereinafter, the present invention will be described in more detail. When terms such as "including", "having", "consisting of", etc. mentioned in this specification are used, other parts may be added unless "only" is used. Also, when a component is expressed in the singular form, it includes the case of including a plurality unless otherwise explicitly stated.

[0036] When interpreting a component, even if there is no explicit description, it is interpreted as including an error range.

[0037] In this specification, the term "C A-B " means "having a carbon number of A or more and B or less", the term "A to B" means "having a carbon number of A or more and B or less", and in the term "substituted or unsubstituted", "substituted" means "at least one hydrogen of a hydrocarbon compound or hydrocarbon derivative is substituted with a halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkenyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamide, C 6-20 arylamide or C 1-20 alkylidene", and "unsubstituted" means "at least one hydrogen of a hydrocarbon compound or hydrocarbon derivative is not substituted with a halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkenyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamide, C 6-20Aryl amide or C 1-20 Means "not substituted with alkylidene".

[0038] The metallocene compound of the present invention is represented by the following Chemical Formula 1.

[0039] [Chemical formula]

[0040] In the above Chemical Formula 1, M is titanium (Ti), zirconium (Zr) or hafnium (Hf), Z is N, R1 and R2 are each independently hydrogen, halogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamide, or substituted or unsubstituted C 6-20 arylamide, R3 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 2-20 alkoxyalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 7-40 alkylaryl of, substituted or unsubstituted C 7-40 arylalkyl of, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 6-20 aryloxy, substituted or unsubstituted C 3-20 heteroaryl, R4 and R5 are each independently hydrogen, halogen, substituted or unsubstituted C 1-20Alkyl, substituted or unsubstituted C 6-20 It is Ariel, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X1 and X2 are independent of each other, C 1-20 Alkyl alkyl group, C 6-20 It is an aryl group, Q1 and Q2 are independent of halogen and C. 1~20 Alkyl alkyl group, C 6-20 (It is an aryl group.)

[0041] In specific examples, the metallocene compound may include, but is not limited to, the following structures.

[0042] [ka] TIFF2026514139000013.tif215170

[0043] In one specific example, the metallocene compound may be produced by adding an organolithium compound to a metallocene catalyst precursor represented by the following chemical formula 2 to produce a lithium salt, and then reacting the lithium salt with a group 4 transition metal compound.

[0044] [ka]

[0045] In the aforementioned chemical formula 2, Z is N, R1 and R2 are, independently, hydrogen, halogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, or substituted or unsubstituted C 6-20 It is an arylamide, R3 is a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 2-20 Alkoxyalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 7-40 alkylaryl, substituted or unsubstituted C 7-40 arylalkyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryloxy, substituted or unsubstituted C 3-20 It is a heteroaryl, R4 and R5 are, independently, hydrogen, halogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 6-20 It is Ariel, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X1 and X2 are independent of each other, C 1-20 Alkyl alkyl group, C 6-20 (It is an aryl group.)

[0046] The following chemical formulas may be included, but are not limited to, the above-mentioned chemical formula 2.

[0047] [ka] TIFF2026514139000016.tif215170

[0048] In one specific example, the metallocene catalyst precursor can be dissolved in a nonpolar solvent, and then an organolithium compound can be gradually added dropwise and reacted at room temperature to produce a lithium salt of the following chemical formula 3.

[0049] [ka]

[0050] In the above chemical formula 3, Z, R1, R2, R3, R4, R5, X1, X2, n, m, p, and q are as defined in the above chemical formula 2.

[0051] Alkyllithium may be used as the organolithium compound. Alkyllithium having 1 to 6 carbon atoms may be used.

[0052] The lithium salt of chemical formula 3 is placed in an organic solvent and stirred, then a group 4 transition metal compound is added and the reaction is carried out at a low temperature. The temperature at which the group 4 transition metal compound is added may be -80 to 0°C, for example, -55 to -10°C. After adding the group 4 transition metal compound, the reaction temperature is raised to room temperature and stirring is continued. After that, the solvent and by-products are removed to obtain the metallocene compound.

[0053] The group 4 transition metal compound may include TiCl4, ZrCl4, or HfCl4.

[0054] The metallocene catalyst precursor represented by chemical formula 2 may be produced by the following method.

[0055] In one specific example, a tetrahydroindene lithium salt of chemical formula 5 can be produced by adding an organolithium compound to a tetrahydroindene compound represented by chemical formula 4 below.

[0056] [ka]

[0057] [ka]

[0058] (In the above chemical formulas 4 and 5, R4, R5, n, and m are as defined above.

[0059] The tetrahydroindenite lithium salt of the aforementioned chemical formula 5 is a silane compound SiX1X2(X3)2(X1 and X2 are each independently C 1-20 Alkyl alkyl group, C 6-20 The tetrahydroindenylsilane compound of chemical formula 6 can be produced by reacting it with an aryl group (where X3 is a halogen group).

[0060] [ka]

[0061] (In the above chemical formula 6, R4, R5, n, and m are as defined above. X1 and X2 are independent of each other, C 1-20 Alkyl alkyl group, C 6-20 It is an aryl group, and X3 is a halogen group.

[0062] The tetrahydroindenylsilane compound of chemical formula 6 can be reacted with a lithium salt of an indenindole compound represented by chemical formula 7 to produce a metallocene catalyst precursor of chemical formula 2.

[0063] The lithium indenindole salt of chemical formula 7 is obtained by reacting an indenindole compound represented by chemical formula 8 with an organolithium compound.

[0064] [ka]

[0065] [ka]

[0066] (In chemical formulas 7 and 8 above, Z, R1, R2, R3, p, and q are as defined above.

[0067] A further aspect of the present invention relates to a supported metallocene catalyst. The supported metallocene catalyst comprises a metallocene compound represented by chemical formula 1 and a carrier supporting the metallocene compound.

[0068] The carrier may be at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia.

[0069] A further aspect of the present invention relates to a catalyst for olefin polymerization. The catalyst for olefin polymerization may include the supported metallocene catalyst and the co-catalyst. The co-catalyst compound may be a known co-catalyst compound, such as a borate compound, or methylaluminoxane, alkylaluminum, alkylboron, etc., but is not limited to these.

[0070] The olefin polymerization catalyst may be used to polymerize olefin monomers to produce an olefin polymer. The olefin monomers may be, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene. The olefin polymer may be produced by, for example, a gas-phase polymerization method, a solution polymerization method, or a slurry polymerization method. When the olefin polymer is produced by the solution polymerization method or the slurry polymerization method, examples of solvents used include pentane, hexane, heptane, nonane, decane, and their isomers. 5-12Examples include, but are not limited to, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene, and mixtures thereof.

[0071] The present invention will be described more specifically below through examples, but such examples are for illustrative purposes only and should not be construed as limiting the present invention. [Examples]

[0072] Examples Example 1: Synthesis of Catalyst 1 Manufacturing Example 1: Production of (5,8-dimethyl-5,10-dihydroindeno[1,2-b]indolyl)dimethyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)silane

[0073] Manufacturing Example 1-1: Preparation of 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-one(2-1) (Step 1) Cyclohexyl methacrylate (1) (4.4 g, 26.15 mmol) was mixed with polyphosphoric acid (10 mL) and stirred at 130°C for 8-12 hours. The viscous solution was poured into ice water (5 mL) and stirred until the polyphosphoric acid was completely dissolved. 5 g of NH4Cl solid was added to the brown solution and extracted with ether (30 mL). After separating the organic and aqueous layers, the organic layer was washed with saturated NaHCO3 (10 mL) solution, and then washed again with saturated brine (10 mL). After drying with MgSO4, the solvent was carefully removed using a rotary evaporator. By performing a short column chromatography purification with hexane solvent, the following results were obtained: 1 A 1:1 mixture of 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-one(2-1), which has a 1H-NMR spectrum, and its byproduct, 2-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-1-one(2-2), was obtained.

[0074] 1 H NMR(300 MHz,CDCl3):2.70(m,1H),2.37(m,1H),2.29(m,2H),2.11(m,2H),1.69(m,5H),1.17(d,3H)

[0075] Manufacturing Example 1-2: Preparation of 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-ol(3) (Step 2) A mixture (1.6 g, 10.65 mmol) of 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-one(2-1) and 2-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-1-one(2-2) prepared in the above-mentioned Production Example 1-1 was dissolved in ether (30 mL) and stirred at 0°C. LiAlH4 (162 mg, 4.27 mmol) was gradually added in three portions. After raising the temperature to room temperature and stirring for 3 hours, the reaction was confirmed to have proceeded completely by TLC, and the temperature was lowered again to 0°C. Distilled water (30 mL) was gradually added, and after extraction with ether (20 mL), the organic layer and aqueous layer were separated. The obtained organic layer was washed once with saturated brine, dried with MgSO4, and the solvent was removed using a rotary evaporator. By performing column chromatography purification with EA:Hex(1:4) solvent, the following can be obtained: 1 Pure 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-ol(3) with a 1H-NMR spectrum was obtained in two steps with a yield of 28%.

[0076] 1 H NMR(300MHz,C6D6):4.21(br.1H),2.34(m,1H),2.19(m,2H),1.80(m,4H),1.51(m,4H),1.04(d,3H)

[0077] Manufacturing Example 1-3: Preparation of 2-methyl-4,5,6,7-tetrahydro-1H-indene(4-1) (Step 3) The 2-methyl-2,3,4,5,6,7-hexahydro-1H-inden-1-ol(3) (1.1g, 7.32 mmol) prepared in the above-mentioned Production Example 1-2 was dissolved in pentane (20 mL), and after adding MgSO4 (150 mg), the mixture was cooled for 8 hours. After gradually lowering the temperature, the MgSO4 was removed by filtration, and the following was obtained. 1 ¹H-NMR spectroscopy confirmed that 2-methyl-4,5,6,7-tetrahydro-1H-indene(4-1) and 2-methyl-2,4,5,6-tetrahydro-1H-indene(4-2) were generated as a mixture in approximately a 1:1 ratio.

[0078] 1 H NMR(300MHz,CDCl3):5.88(s,1H),2.25(m.2H),2.08(m,2H),2.01(s,3H),1.67(m,4H),1.65(m,2H)

[0079] Manufacturing Example 1-4: Preparation of (2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)lithium(5) (Step 4) The pentane solutions of 2-methyl-4,5,6,7-tetrahydro-1H-indene(4-1) and 2-methyl-2,4,5,6-tetrahydro-1H-indene(4-2) prepared in the above-mentioned Production Examples 1-3 were cooled to -78°C, and then the flask was connected to a Schlenk line and degassed to remove air. 7 mL of n-BuLi (1.6 M in hexane) solution was added, and the temperature was gradually raised to room temperature and stirred overnight. The resulting white solid was obtained by filtration and thoroughly washed with hexane to remove 2-methyl-2,4,5,6-tetrahydro-1H-indene(4-2), yielding pure (2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)lithium(5) in 37% yield.

[0080] Manufacturing Example 1-5: Preparation of Chloro(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)dimethylsilane (6) (Step 5) Dichlorodimethylsilane was gradually added to the (2-methyl-4,5,6,7-Tetrahydro-1H-inden-1-yl)lithium produced in the above production examples 1-4, stirred at room temperature, and then LiCl was removed by filtration to obtain the following product in 56% yield. 1 chloro(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)dimethylsilane (6) with a 1H-NMR spectrum was obtained.

[0081] 1 H NMR (300MHz, CDCl3): 6.07 (s, 1H), 2.10 (s, 3H), 2.40-1.57 (m, 8H), 0.34 (s, 3H), 0.30 (s, 3H).

[0082] Manufacturing Example 1-6: Manufacturing of 5,10-dihydroindeno[1,2-b]indole (8) (Step 6) A solution of 1-Indanone(7) (30.6 g, 232 mmol) in p-tolylhydrazine hydrochloride (37.0 g, 233 mmol) in EtOH (350 mL) was mixed with an aqueous HCl solution (12 N, 18 mL), and the mixture was heated under reflux for 90 minutes. The minimum mixture was cooled and filtered, and the solid was washed with EtOH (600 mL), then with a 20% aqueous EtOH solution (400 mL), and finally with hexane (200 mL). The grayish-white solid was dried under vacuum (36.5 g, 72%).

[0083] Manufacturing Example 1-7: Manufacturing of 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole](9) (Step 7) 5,10-dihydroindeno[1,2-b]indole (36.5g, 166 mmol) prepared in the above production examples 1-6, NaOH aqueous solution (112 mL, 20 M, 2.2 mol), C 16 H 33NMe3Br (0.65 g, 1.78 mmol) and toluene (112 mL) were vigorously stirred at room temperature. After adding a toluene (15 mL) solution of MeI (17.0 mL, 273 mmol) dropwise, the mixture was stirred at room temperature for 4 hours and refluxed for 3 hours. A crystalline solid formed upon cooling and was filtered, washed at -78°C (300 mL), and then washed with hexane (100 mL). The layers were separated, and the aqueous portion was washed twice with toluene (100 mL). Organic matter was mixed in, dried over Na2SO4, and filtered. Volatile substances were removed under vacuum, and the precipitate was dried to obtain 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (total yield 25.7 g, 66%).

[0084] Manufacturing Example 1-8: Preparation of 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole]lithium salt (10) (Step 8) 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (43.9 g, 188 mmol) prepared in the above-mentioned Production Examples 1-7 was dissolved in toluene (560 mL), and n-butyllithium (n-BuLi) (120 mL, 2.5 M, 1.6 mol) was added dropwise to the solution. After 1 hour, a precipitate formed, and the mixture was left to stand for 48 hours before filtration. The solid was washed with toluene (500 mL), then with hexane (500 mL), and dried under vacuum to obtain the white solid 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole]lithium salt (10) (40.3 g, 90).

[0085] Manufacturing Example 1-9: Synthesis of (5,8-dimethyl-5,10-dihydroindeno[1,2-b]indolyl)dimethyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)silane (11) (Step 9) The solution of chloro(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)dimethylsilane (6) (200 mg, 0.89 mmol) prepared in the above-mentioned Preparation Examples 1-5 was dissolved in ether (10 mL) and cooled to -30°C. The white solid 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole]lithium salt (10) (211 mg, 0.89 mmol), prepared in Preparation Examples 1-8, was gradually added and the mixture was stirred overnight at room temperature. After gradually adding water and saturated NH4Cl solution to terminate the reaction, the mixture was extracted with ether, treated with MgSO4 to remove water, and then dried. The Crude compound was purified by column chromatography (100% hexane), dried, and then the pure compound (rac / meso = 1:1) (243 mg, 65%) was obtained.

[0086] 1 H NMR(300MHz,CDCl3):7.65-7.03(m,7H), 6.10(s,0.5H), 6.09(s,0.5H), 4.08(s,1.5H), 4.07(s,1.5H), 3.48-3.46(m,1H), 3.38(br s,1H), 2.47(s,1.5H), 2.46(s,1.5H), 2.13(s,1.5H), 2.08(s,1.5H), 1.84-1.81(m,2H), 1.70-1 .60(m,4H), 1.30-1.25(m,2H), -0.21(s,1.5H), -0.34(s,1.5H), -0.40(s,1.5H), -0.45(s,1.5H)

[0087] Production Examples 1-10: Synthesis of Dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)(5,8-dimethyl-5,10-dihydroindeno[1,2-b]indoleyl dilithium(12)) (Step 10) (5,8-dimethyl-5,10-dihydroindeno[1,2-b]indolyl)dimethyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)silane(11) (243 mg, 0.57 mmol) prepared in the above-mentioned Preparation Examples 1-9 was dissolved in hexane (10 mL), and 430 μL of n-BuLi((1.6 M in hexane)) was gradually added dropwise to the solution, and the mixture was stirred overnight at room temperature. After confirming that the clear solution had changed to a white suspension, the hexane solvent was removed by filtration, and the resulting white solid was dried to obtain Dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)(5,8-dimethyl-5,10-dihydroindeno[1,2-b]indoleyl dilithium(12) (250 mg, 100%).

[0088] Manufacturing Example 1-11: Synthesis of [Dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)(5,8-dimethyl-5,10-dihydroindeno[1,2-b]indoleyl zirconium Dichloride(12) (Step 11)] Dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)(5,8-dimethyl-5,10-dihydroindeno[1,2-b]indoleyl dilithium(12)) (250 mg, 0.57 mmol) prepared in the above-mentioned Production Examples 1-10 was mixed with ether (15 mL) and then cooled to -30°C. ZrCl4 (133 mg, 0.57 mmol) was added and the mixture was gradually raised to room temperature, after which it was stirred overnight. After removing the ether with a vacuum pump, the catalyst was extracted with toluene, and LiCl was removed by filtration to obtain pure Catalyst 1 (rac / meso = 3:2) in a yield of 78%.

[0089] 1H NMR(300MHz,CDCl3):8.02-7.08(m,7H), 6.57(s,0.4H), 6.39(s,0.6H), 4.15(s,1.8H), 4.10(s,1.2H), 2.82(s,1.2H), 2.48(s,1.8H) ), 2.13(s,1.8H), 1.89(s,1.2H), 2.92-2.81(m,2H), 2.61-2.40(m,6H), 1.38(s,1.2H), 1.34(s,1.8H), 1.31(s,1.8H), 1.28(s,1.2H)

[0090] Manufacturing Example 2-17 Metallocene catalyst precursors were synthesized by changing the substituents of the tetrahydroindene compound of chemical formula 3 and the lithium indenindole salt of chemical formula 4, yielding the following chemical formulas (2-2) to (2-17).

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] Example 2-17: Synthesis of catalysts 2-17 The procedure was carried out in the same manner as in Example 1, except that compounds (2-2) to (2-17) were used as precursors instead of (5,8-dimethyl-5,10-dihydroindeno[1,2-b]indolyl)dimethyl(2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)silane (11).

[0097] The structures of the manufactured catalysts are shown in the following chemical formulas (1-2) to (1-17).

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] Mere modifications or alterations of the present invention can be readily carried out by a person with ordinary skill in the art, and any such modifications or alterations can be considered to fall within the scope of the present invention.

Claims

1. The metallocene compound represented by the following chemical formula 1: 【Chemistry 1】 In the aforementioned chemical formula 1, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). Z is N, R １ and R ２ each independently is hydrogen, halogen, substituted or unsubstituted C １－２０ alkyl, substituted or unsubstituted C ２－２０ alkenyl, substituted or unsubstituted C ６－２０ aryl, substituted or unsubstituted C １－２０ heteroalkyl, substituted or unsubstituted C ３－２０ heteroaryl, substituted or unsubstituted C １－２０ alkylamide, or substituted or unsubstituted C ６－２０ arylamide, and R ３ C is either substituted or non-substituted. １－２０ Alkyl, substituted, or unsubstituted C １－２０ Alkoxy, substituted, or unsubstituted C ２－２０ Alkoxyalkyl, substituted or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ３－２０ Cycloalkyl, substituted or unsubstituted C ３－２０ Heterocycloalkyl, substituted or unsubstituted C ７－４０ alkylaryl, substituted or unsubstituted C ７－４０ arylalkyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryloxy, substituted or unsubstituted C ３－２０ It is a heteroaryl, R ４ and R ５ These are, independently, hydrogen, halogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ６－２０ It is Ariel, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X １ and X ２ Each of them is independent of C １－２０ alkyl group, C ６－２０ It is an aryl group, Q １ and Q ２ These are, independently, halogen and C １－２０ alkyl group, C ６－２０ It is an aryl group.

2. The above M is zirconium (Zr), R １ and R ２ C １－３ It is alkyl, P is 0, and q is either 0 or 1. R ４ and R ５ C １－３ It is alkyl, The metallocene compound according to claim 1, wherein n is 0 and m is 0 or 1.

3. The above M is zirconium (Zr), X １ and X ２ Each of them is independent of C １－２０ It is an alkyl group, Q １ and Q ２ The metallocene compound according to claim 1, wherein each of the elements is independently a halogen.

4. The aforementioned R ３ The metallocene compound according to claim 1, wherein the number of carbon atoms is 1 to 10.

5. The metallocene compound according to claim 1, which is represented by any of the following structures: 【Chemistry 2】 【change】 。

6. The metallocene compound according to claim 1, wherein the compound represented by the following chemical formula 2 is used as a metallocene catalyst precursor: 【Transformation 3】 In the aforementioned chemical formula 2, Z is N, R １ and R ２ These are, independently, hydrogen, halogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, or substituted or unsubstituted C ６－２０ It is an arylamide, R ３ C is either substituted or non-substituted. １－２０ Alkyl, substituted, or unsubstituted C １－２０ Alkoxy, substituted, or unsubstituted C ２－２０ Alkoxyalkyl, substituted or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ３－２０ Cycloalkyl, substituted or unsubstituted C ３－２０ Heterocycloalkyl, substituted or unsubstituted C ７－４０ alkylaryl, substituted or unsubstituted C ７－４０ arylalkyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryloxy, substituted or unsubstituted C ３－２０ It is a heteroaryl, R ４ and R ５ These are, independently, hydrogen, halogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ６－２０ It is Ariel, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X １ and X ２ Each of them is independent of C １－２０ alkyl group, C ６－２０ (It is an aryl group.)

7. The metallocene catalyst precursor is the metallocene compound according to claim 6, which is represented by any of the following structures: 【Chemistry 4】 【change】 。

8. The metallocene compound is The metallocene compound according to claim 6, comprising the steps of adding an organolithium compound to the metallocene catalyst precursor to produce a lithium salt, and reacting the lithium salt with a group 4 transition metal compound.

9. The metallocene catalyst precursor represented by the following chemical formula 2: 【Transformation 5】 In the aforementioned chemical formula 2, Z is N, R １ and R ２ These are, independently, hydrogen, halogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, or substituted or unsubstituted C ６－２０ It is an arylamide, R ３ is a substituted or unsubstituted C １－２０ alkyl, a substituted or unsubstituted C １－２０ alkoxy, a substituted or unsubstituted C ２－２０ alkoxyalkyl, a substituted or unsubstituted C ２－２０ alkenyl, a substituted or unsubstituted C ３－２０ cycloalkyl, a substituted or unsubstituted C ３－２０ heterocycloalkyl, a substituted or unsubstituted C ７－４０ alkylaryl, a substituted or unsubstituted C ７－４０ arylalkyl, a substituted or unsubstituted C ６－２０ aryl, a substituted or unsubstituted C ６－２０ aryloxy, a substituted or unsubstituted C ３－２０ heteroaryl, and R ４ and R ５ each independently represents hydrogen, halogen, substituted or unsubstituted C １－２０ alkyl, or substituted or unsubstituted C ６－２０ aryl, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X １ and X ２ Each of them is independent of C １－２０ alkyl group, C ６－２０ (It is an aryl group.)

10. The metallocene catalyst precursor described above is the metallocene catalyst precursor according to claim 9, which is represented by any of the following structures: 【Transformation 6】 【change】 。

11. A metallocene compound represented by the following chemical formula 1, A carrier supporting the metallocene compound, Supported metallocene catalysts including: 【Transformation 7】 In the aforementioned chemical formula 1, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). Z is N, R １ and R ２ These are, independently, hydrogen, halogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, or substituted or unsubstituted C ６－２０ It is an arylamide, R ３ C is either substituted or non-substituted. １－２０ Alkyl, substituted, or unsubstituted C １－２０ Alkoxy, substituted, or unsubstituted C ２－２０ Alkoxyalkyl, substituted or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ３－２０ Cycloalkyl, substituted or unsubstituted C ３－２０ Heterocycloalkyl, substituted or unsubstituted C ７－４０ alkylaryl, substituted or unsubstituted C ７－４０ arylalkyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryloxy, substituted or unsubstituted C ３－２０ It is a heteroaryl, R ４ and R ５ These are, independently, hydrogen, halogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ６－２０ It is Ariel, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X １ and X ２ Each of them is independent of C １－２０ alkyl group, C ６－２０ It is an aryl group, Q １ and Q ２ These are, independently, halogen and C １－２０ alkyl group, C ６－２０ (It is an aryl group.)

12. The metallocene compound according to claim 11, wherein the compound represented by the following chemical formula 2 is used as a metallocene catalyst precursor: 【Transformation 8】 In the aforementioned chemical formula 2, Z is N, R １ and R ２ These are, independently, hydrogen, halogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, or substituted or unsubstituted C ６－２０ It is an arylamide, R ３ C is either substituted or non-substituted. １－２０ Alkyl, substituted, or unsubstituted C １－２０ Alkoxy, substituted, or unsubstituted C ２－２０ Alkoxyalkyl, substituted or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ３－２０ Cycloalkyl, substituted or unsubstituted C ３－２０ Heterocycloalkyl, substituted or unsubstituted C ７－４０ alkylaryl, substituted or unsubstituted C ７－４０ arylalkyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryloxy, substituted or unsubstituted C ３－２０ It is a heteroaryl, R ４ and R ５ These are, independently, hydrogen, halogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ６－２０ It is Ariel, n is an integer between 0 and 4. m is an integer between 0 and 2. p and q are independent integers between 0 and 4. X １ and X ２ Each of them is independent of C １－２０ alkyl group, C ６－２０ (It is an aryl group.)

13. The aforementioned R ３ The supported metallocene catalyst according to claim 11, wherein the number of carbon atoms is 1 to 10.

14. The supported metallocene catalyst according to claim 11, wherein the support is at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia.

15. The supported metallocene catalyst according to claim 11, wherein the supported metallocene catalyst further comprises a co-catalyst.

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