Polypropylene

Abstract

The present invention provides polypropylene that can be utilized as a macromonomer due to its high content of terminal vinyl groups.

Description

Technology Field

[0001] The present invention relates to polypropylene having a high content of terminal vinyl groups and limited molecular weight and stereoregularity. Background Technology

[0003] Polypropylene has been used as a general-purpose resin in various fields due to its low specific gravity, high heat resistance, and excellent processability and chemical resistance. However, polypropylene has a problem with poor melt strength.

[0004] To address this, various methods for introducing long chain branches (LCBs) into polypropylene are being studied, and among them, methods utilizing macromonomers are being considered.

[0005] A macromonomer refers to a polymer in which a functional group containing a double bond is formed at the chain end. The functional group containing the double bond is vinyl or vinylidene, and among these, only the vinyl end group can exhibit activity. Accordingly, the higher the content of vinyl end groups in the polypropylene being produced, the more favorable it may be for LCB formation.

[0006] Accordingly, there is a need to develop macromonomers with properties suitable for providing polypropylene with improved melt strength. The problem to be solved

[0008] The present invention aims to provide polypropylene having a high vinyl end group content and a low vinylidene end group content, and capable of exhibiting excellent melt strength characteristics. means of solving the problem

[0010] To achieve the above objective, according to one embodiment of the present invention,

[0011] The weight-average molecular weight is 20,000 to 70,000 g / mol, and

[0012] The stereoregularity (mmmm) is less than 30%, and

[0013] having a terminal vinyl group content of 0.6 mol% or more,

[0014] Polypropylene is provided.

[0015] The above polypropylene can be prepared by polymerizing propylene in the presence of a catalyst composition comprising a transition metal compound represented by the following chemical formula 1:

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1,

[0019] M is a group 4 transition metal, and

[0020] X1 and X2 are each independently hydrogen; halogen; or C 1-20 It is alkyl, and

[0021] A is carbon or silicon, and

[0022] R 11 and R 12 Each independently, hydrogen; halogen; C 1-20 Alkyl; C 2-20 Alkoxyalkyl; or C 6-20 Arilgo,

[0023] R 21 It is methyl, and

[0024] R 22 is C 3-20 Alkyl; C 3-20 Alkoxyalkyl; or C 3-20 It is alkenil, and

[0025] R 23 Unsubstituted C 6-20 Aryl; or C 7-20 It is an alkylaryl, and

[0026] R 24 and R 25 are each hydrogen or; or R 24 and R 25 are connected to each other C 3-10It forms a cycloalkane ring,

[0027] R 26 C 1-20 It is alkyl, and

[0028] R 27 Unsubstituted C 6-20 Aryl; or C 7-20 It is an alkylaryl. Effects of the invention

[0030] The polypropylene of the present invention has a high terminal vinyl group content and can be utilized as a macromonomer, and can be usefully used in the manufacture of high melt strength polypropylene containing long chain branches (LCBs) within the molecule. Specific details for implementing the invention

[0032] The terms used herein are merely for describing exemplary embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, terms such as “comprising,” “comprising,” or “having” are intended to indicate the presence of the implemented features, steps, components, or combinations thereof, and should be understood as not precluding the existence or addition of one or more other features, steps, components, or combinations thereof.

[0033] The present invention is capable of various modifications and may take various forms, and specific embodiments are illustrated and described in detail below. However, this is not intended to limit the invention to the specific disclosed forms, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0034] The present invention will be described in detail below.

[0036] The polypropylene of the present invention is a homopolypropylene in which propylene monomers are polymerized alone, and includes functional groups containing double bonds, such as vinyl groups or vinylidene groups, at the chain ends, wherein vinyl end groups are included in a high content. Accordingly, the polypropylene of the present invention can be utilized as a macromonomer and can improve the melt strength of the polymer by forming long-chain branches within the polymer during polymerization with propylene.

[0038] The above polypropylene has a weight-average molecular weight (Mw) of 20,000 to 70,000 g / mol, specifically 30,000 g / mol or more, 32,000 g / mol or more, or 35,000 g / mol or more, and may be in the range of 65,000 g / mol or less, 60,000 g / mol or less, or 55,000 g / mol or less. If the weight-average molecular weight exceeds 70,000 g / mol, it is difficult to copolymerize into the main chain as a macromonomer, making it unsuitable for use in the manufacture of high melt strength polypropylene, and if it is less than 20,000 g / mol, it may be difficult to increase the long-chain branch content in the polypropylene.

[0040] The weight-average molecular weight (Mw) of polypropylene can be measured using gel permeation chromatography (GPC), as described in the test examples below. Specifically, it can be measured using a Waters PL-GPC220 instrument with a Polymer Laboratories PLgel MIX-B 300 mm long column in the following manner. The measurement temperature is set to 160 ℃, 1,2,4-trichlorobenzene is used as the solvent, and the flow rate is set to 1 mL / min. The sample is prepared at a concentration of 10 mg / 10 mL and supplied in an amount of 200 μL. The values ​​of Mw and Mn are derived using a calibration curve formed using a polystyrene standard. At this time, nine types of polystyrene standards with weight-average molecular weights (g / mol) of 2,000 g / mol, 10,000 g / mol, 30,000 g / mol, 70,000 g / mol, 200,000 g / mol, 700,000 g / mol, 2,000,000 g / mol, 4,000,000 g / mol, and 10,000,000 g / mol are used.

[0042] Meanwhile, the above polypropylene has a stereoregularity (pentad sequence distribution, mmmm) of less than 30%, preferably 29% or less, or 28.5% or less. If the stereoregularity exceeds 30%, it is difficult to secure a high terminal vinyl group content, so it is not desirable to use it as a macromonomer. Also, if the stereoregularity is excessively low, the content of atactic polypropylene increases when polymerized together with the main chain, which may cause fouling during bulk polymerization; therefore, the stereoregularity is preferably 10% or more, 15% or more, or 20% or more.

[0044] In the present invention, stereoregularity (Pentad sequence distribution, mmmm) can be measured using quantitative nuclear magnetic resonance (NMR) spectroscopy. Specifically, 13After measuring the sequence distribution at the pentad level by C-NMR analysis, it is expressed as the percentage of stereoregular pentad (mmmm) sequences for all pentad sequences. mmmm% is a value based on moles. The specific method for measuring the stereoregularity (pentad sequence distribution, mmmm) is as described in the test examples below.

[0046] The above polypropylene has a terminal vinyl group (-CH=CH2) content of 0.6 mol% or higher relative to 100 mol% of polypropylene, so it can be used as a macromonomer in the manufacture of high melt tension polypropylene. Preferably, the terminal vinyl group content of the above polypropylene may be 0.65 mol% or higher, or 0.7 mol% or higher, and 1 mol% or lower, 0.9 mol% or lower, or 0.85 mol% or lower.

[0048] Meanwhile, as described above, the polypropylene exhibits the characteristic that while the content of terminal vinyl groups capable of participating in polymerization is high, the content of terminal vinylidene groups (:C=CH2, e.g., -C(CH3)=CH2) that cannot participate in polymerization is low. Specifically, the polypropylene of the present invention may have a terminal vinylidene group content of 0.1 mol% or less, 0.08 mol% or less, or 0.06 mol% or less relative to 100 mol% of polypropylene. The lower limit of the terminal vinylidene group content is not particularly limited, and the polypropylene of the present invention may not contain any terminal vinylidene groups, or may contain 0.01 mol% or more relative to 100 mol% of polypropylene.

[0050] The content of terminal vinyl groups and terminal vinylidene groups in polypropylene is as shown in the test examples described below. 1 It can be measured through H-NMR analysis.

[0052] Meanwhile, the polypropylene described above can be prepared by polymerizing propylene monomers in the presence of a catalyst composition comprising a compound represented by the following chemical formula 1. Accordingly, according to one embodiment of the present invention, a method for producing polypropylene having a weight-average molecular weight of 20,000 to 70,000 g / mol, a stereoregularity (tacticity, mmmm) of less than 30%, and a terminal vinyl group content of 0.6 mol% or more is provided, comprising the step of polymerizing propylene monomers in the presence of a catalyst composition comprising a compound represented by the following chemical formula 1:

[0053] [Chemical Formula 1]

[0054]

[0055] In the above chemical formula 1,

[0056] M is a group 4 transition metal, and

[0057] X1 and X2 are each independently hydrogen; halogen; or C 1-20 It is alkyl, and

[0058] A is carbon or silicon, and

[0059] R 11 and R 12 Each independently, hydrogen; halogen; C 1-20 Alkyl; C 2-20 Alkoxyalkyl; or C 6-20 Arilgo,

[0060] R 21 It is methyl, and

[0061] R 22 is C 3-20 Alkyl; C 3-20 Alkoxyalkyl; or C 3-20 It is alkenil, and

[0062] R 23 Unsubstituted C 6-20 Aryl; or C 7-20 It is an alkylaryl, and

[0063] R 24 and R 25 are each hydrogen or; or R24 and R 25 are connected to each other C 3-10 It forms a cycloalkane ring,

[0064] R 26 C 1-20 It is alkyl, and

[0065] R 27 Unsubstituted C 6-20 Aryl; or C 7-20 It is an alkylaryl.

[0067] The substituents of the above chemical formula are explained in more detail as follows.

[0068] Halogens can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0069] C 1-20 The alkyl group of may be a straight-chain, branched-chain, or cyclic alkyl. Specifically, the above C 1-20 The alkyl may be a straight-chain alkyl having 1 to 20 carbon atoms; a straight-chain alkyl having 1 to 10 carbon atoms; a straight-chain alkyl having 1 to 5 carbon atoms; a branched-chain or cyclic alkyl having 3 to 20 carbon atoms; a branched-chain or cyclic alkyl having 3 to 15 carbon atoms; or a branched-chain or cyclic alkyl having 3 to 10 carbon atoms. More specifically, C 1-20 The alkyl group may be a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, or cyclohexyl group, etc.

[0070] C 2-20 The alkenyl of may be a straight-chain, branched-chain, or cyclic alkenyl. Specifically, the above C 2-20The alkenyl of may be a straight-chain alkenyl having 2 to 20 carbon atoms; a straight-chain alkenyl having 2 to 10 carbon atoms; a straight-chain alkenyl having 2 to 5 carbon atoms; a branched-chain alkenyl having 3 to 20 carbon atoms; a branched-chain alkenyl having 3 to 15 carbon atoms; a branched-chain alkenyl having 3 to 10 carbon atoms; a cyclic alkenyl having 5 to 20 carbon atoms; or a cyclic alkenyl having 5 to 10 carbon atoms. More specifically, C 2-20 The alkenyl of may be ethenyl, propenyl, butenyl, fentenyl, or cyclohexanyl, etc.

[0071] C 1-20 The alkoxy group of can be a straight-chain, branched-chain, or cyclic alkoxy group. Specifically, the above C 1-20 The alkoxy group may be a straight-chain alkoxy group having 1 to 20 carbon atoms; a straight-chain alkoxy group having 1 to 10 carbon atoms; a straight-chain alkoxy group having 1 to 5 carbon atoms; a branched-chain or cyclic alkoxy group having 3 to 20 carbon atoms; a branched-chain or cyclic alkoxy group having 3 to 15 carbon atoms; or a branched-chain or cyclic alkoxy group having 3 to 10 carbon atoms. More specifically, the alkoxy group having 1 to 20 carbon atoms may be a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, an n-pentoxy group, an iso-pentoxy group, a neo-pentoxy group, or a cyclohexoxy group, etc.

[0072] C 2-20 The alkoxyalkyl of is -R y -OR z A structure containing alkyl(-R y One or more hydrogens of ) are alkoxy(-OR z It may be a substituent substituted with ). Specifically, the above C 2-20 The alkoxyalkyl group may be a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, or a tert-butoxyhexyl group, etc.

[0073] C6-20 The aryl of may refer to monocyclic, bicyclic, or tricyclic aromatic hydrocarbons. Specifically, the above C 6-20 The aryl group can be a phenyl group, a naphthyl group, or anthracenyl group, etc.

[0074] C 7-20 The alkylaryl of may refer to a substituent in which one or more hydrogens of the aryl are substituted by an alkyl group. Specifically, the above C 7-20 The alkylaryl of may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl, etc.

[0075] Examples of the above Group 4 transition metals include titanium, zirconium, hafnium, etc.

[0077] The transition metal compound represented by the above chemical formula 1 comprises two indene ligands. In particular, one of the two indene rings is characterized by containing a methyl group at position 2, a chain-type substituent with three or more carbon atoms at position 3, and a substituent with high steric hindrance at position 4. Additionally, the other indene ring comprises substituents only at positions 2 and 4, and exhibits a structure containing a substituent with high steric hindrance at position 4.

[0078] When a general beta-hydride elimination reaction proceeds, it results in a vinylidene structure which is an inactive species, but the transition metal compound represented by Chemical Formula 1 can induce a beta-methyl extraction reaction of the polymer chain to form a macromonomer having a double bond at the end. Accordingly, the macromonomer prepared in the presence of the transition metal compound represented by Chemical Formula 1 can be usefully used in the production of polypropylene having a long chain branch (LCB) within the molecule.

[0080] The central metal M of the transition metal compound represented by the above chemical formula 1 is a group 4 transition metal, and preferably can be zirconium (Zr) or hafnium (Hf).

[0081] Preferably, X1 and X2 are each independently halogens, and more preferably, both can be chlorine (Cl).

[0082] Preferably, A is silicon.

[0083] Preferably, R 11 and R 12 C each independently 1-10 Alkyl; C 2-10 Alkoxyalkyl; or C 6-10 It is an aryl. Preferably, R 11 and R 12 Each can independently be methyl; ethyl; n-propyl; n-butyl; n-pentyl; n-hexyl; t-butoxyhexyl; or phenyl.

[0085] More preferably, M is zirconium (Zr) or hafnium (Hf), X1 and X2 are both chlorine, A is silicon, and R 11 and R 12 Each is independently methyl; ethyl; n-propyl; n-butyl; n-pentyl; n-hexyl; t-butoxyhexyl; or phenyl.

[0087] Preferably, R 22 is C 3-10 Alkyl; C 3-10 Alkoxyalkyl; or C 3-10 It is an alkenyl. Preferably, R 22 is C 4-10 Alkyl; C 5-10 Alkoxyalkyl; or C 3-8 It is an alkenyl. More preferably, R 22 is butyl; t-butoxyhexyl; or 2-propene.

[0089] Preferably, R 23 is unsubstituted phenyl; or C 1-10 It is an alkyl-substituted phenyl. More preferably, R 23It is phenyl; or t-butylphenyl.

[0091] Preferably, R 24 and R 25 are each hydrogen or; or R 24 and R 25 They are connected to each other to form a cyclopentane ring or a cyclohexane ring.

[0093] Preferably, R 27 is unsubstituted phenyl; or C 1-10 It is an alkyl-substituted phenyl. More preferably, R 27 It is phenyl; or t-butylphenyl.

[0095] According to one embodiment, R in Chemical Formula 1 11 and R 12 C each independently 1-10 Alkyl; C 2-10 Alkoxyalkyl; or C 6-10 Arilgo,

[0096] R 22 is C 3-10 Alkyl; C 3-10 Alkoxyalkyl; or C 3-10 It is alkenil, and

[0097] R 23 is unsubstituted phenyl; or C 1-10 It is an alkyl-substituted phenyl, and

[0098] R 24 and R 25 are each hydrogen or; or R 24 and R 25 They are connected to each other to form a cyclopentane ring or a cyclohexane ring, and

[0099] R 27 is unsubstituted phenyl; or C 1-10 It is an alkyl-substituted phenyl.

[0101] Preferably, in the above formula 1, M is zirconium or hafnium, and

[0102] X1 and X2 are each independently halogens, and

[0103] A is silicone, and

[0104] R 11 and R 12 C each independently 1-10 Alkyl; C 2-10 Alkoxyalkyl; or C 6-10 Arilgo,

[0105] R 22 is C 3-10 Alkyl; C 3-10 Alkoxyalkyl; or C 3-10 It is alkenil, and

[0106] R 23 is unsubstituted phenyl; or C 1-10 It is an alkyl-substituted phenyl, and

[0107] R 24 and R 25 are each hydrogen or; or R 24 and R 25 They are connected to each other to form a cyclopentane ring or a cyclohexane ring, and

[0108] R 27 is unsubstituted phenyl; or C 1-10 It is an alkyl-substituted phenyl.

[0110] More preferably, in the above formula 1, M is zirconium (Zr) or hafnium (Hf), and

[0111] X1 and X2 are both goats,

[0112] A is silicone, and

[0113] R 11 and R 12 Each is independently methyl; ethyl; n-propyl; n-butyl; n-pentyl; n-hexyl; t-butoxyhexyl; or phenyl, and

[0114] R 22 is butyl; t-butoxyhexyl; or 2-propene, and

[0115] R 23 is phenyl; or t-butylphenyl, and R 24 and R 25 are each hydrogen or; or R 24 and R25 They are connected to each other to form a cyclopentane ring,

[0116] R 27 It is phenyl; or t-butylphenyl.

[0118] The transition metal compound represented by the above chemical formula 1 may be any one selected from the group consisting of the following:

[0120]

[0121]

[0123] Meanwhile, the method of preparing the compound represented by the above chemical formula 1 is not particularly limited, but, for example, it can be prepared by the method shown in the following reaction formula 1.

[0124] Although the compound represented by the above chemical formula 1 is difficult to synthesize due to the steric hindrance of the indene ligand, the compound of the above chemical formula 1 can be prepared with high yield and high purity according to a method such as the following reaction scheme 1.

[0125] Accordingly, according to one embodiment of the present invention, the compound represented by the chemical formula 1 is,

[0126] A step of preparing a compound of Chemical Formula 1-1 by reacting a compound represented by Chemical Formula a with a compound represented by Chemical Formula b;

[0127] A step of preparing a ligand of Formula 1-2 by reacting a compound represented by Formula 1-1 with a compound represented by Formula 1-11; and

[0128] It can be manufactured by a manufacturing method comprising the step of reacting a ligand of Chemical Formula 1-2 with a halogen salt of a transition metal represented by Chemical Formula 1-21:

[0129] [Reaction Equation 1]

[0130]

[0131] In the above reaction scheme 1,

[0132] M, X1, X2, A, R11 , R 12 , R 21 to R 27 is as defined in Chemical Formula 1, and

[0133] X' are each independently halogens.

[0135] The compound of Chemical Formula 1 above has a substituent with high steric hindrance (R) at the 4th position of the indene ligand. 23 and R 27 It includes ). Accordingly, as shown in Reaction Scheme 1 above, first, two indene ligands are formed into a bridge group (-A(R 11 )(R 12 After connecting with )-), R 22 The yield of the ligand can be increased by introducing a substituent.

[0136] At this time, the indene ligand a with a bridge group attached can be prepared by reacting the indene ligand with a bridge group-providing compound such as a silane halogenated, as shown in Reaction Scheme 1-1 below.

[0137] [Reaction Equation 1-1]

[0138]

[0139] In the above reaction scheme 1-1,

[0140] X', A, R 11 , R 12 , R 26 , and R 27 It is as defined in Chemical Formula 1.

[0142] Each step of the above reaction scheme 1 can be carried out in the presence of an organic base such as an alkyl lithium having 1 to 10 carbon atoms, and the step of preparing the compound of formula 1-1 can be carried out in the presence of the organic base and an inorganic copper salt such as CuCN.

[0143] The reactions of each of the above steps can be performed by applying known reactions, and a more detailed synthesis method can be referenced in the examples described below.

[0145] The catalyst composition for producing the polypropylene macromonomer of the present invention may include a transition metal compound of Formula 1 as a single component, and may be in the form of a supported metallocene catalyst comprising the transition metal compound and a carrier. When a supported metallocene catalyst is used, the morphology and physical properties of the polypropylene produced are excellent, and it can be suitablely used in conventional slurry polymerization, bulk polymerization, or gas phase polymerization processes.

[0147] Specifically, the carrier may be a carrier having highly reactive hydroxyl groups, silanol groups, or siloxane groups on its surface, and for this purpose, a carrier that has been surface-modified by calcination or has had moisture removed from its surface by drying may be used. For example, silica prepared by calcining silica gel, silica dried at high temperatures, silica-alumina, and silica-magnesia may be used, and these may typically contain oxide, carbonate, sulfate, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.

[0149] The temperature for calcination or drying of the above-mentioned carrier may be 200°C to 700°C, or 250°C to 650°C. If the calcination or drying temperature of the above-mentioned carrier is low, there is a risk that the surface moisture will react with the co-catalyst due to an excessive amount of moisture remaining on the carrier, and the co-catalyst loading rate may be relatively high due to an excess amount of hydroxyl groups, but this requires a large amount of co-catalyst. In addition, if the drying or calcination temperature is excessively high, the pores on the surface of the carrier merge, reducing the surface area, and many hydroxyl or silanol groups are removed from the surface, leaving only siloxane groups, which may reduce the number of reaction sites with the co-catalyst.

[0151] For example, the amount of hydroxyl groups on the surface of the carrier may be 0.1 to 10 mmol / g or 0.5 to 5 mmol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the manufacturing method and conditions of the carrier or drying conditions, such as temperature, time, vacuum, or spray drying. If the amount of hydroxyl groups is excessively low, there are few reaction sites with the co-catalyst, and if it is excessively high, it may be due to moisture in addition to the hydroxyl groups present on the surface of the carrier particles.

[0153] Among the aforementioned carriers, in the case of silica, particularly silica prepared by calcining silica gel, the functional group of the compound of Formula 1 is chemically bonded to the silica carrier and supported thereon, so there is almost no catalyst released from the surface of the carrier during the olefin polymerization process, and as a result, fouling of the reactor walls or polymer particles sticking together can be minimized when producing polyolefins by slurry or gas phase polymerization.

[0155] In addition, when supported on a carrier, the compound of Formula 1 may be supported in a content range of 30 μmol or more, or 40 μmol or more, and 120 μmol or less, or 80 μmol or less, based on 1 g of silica, per weight of the carrier. When supported in the above content range, it exhibits appropriate supported catalyst activity, which may be advantageous in terms of maintaining catalyst activity and economic efficiency.

[0157] In addition, the catalyst composition may further include one or more co-catalysts together with the aforementioned transition metal compound and carrier.

[0159] The above co-catalyst may include one or more compounds represented by the following chemical formula 3 or chemical formula 4.

[0160] [Chemical Formula 3]

[0161] -[Al(R 31 )-O] m -

[0162] In the above chemical formula 3,

[0163] R 31 are identical or different from each other, and each independently halogen; C 1-20 alkyl or C 1-20 It is a haloalkyl;

[0164] m is an integer greater than or equal to 2.

[0166] Examples of compounds represented by the above chemical formula 3 include aluminoxan-based compounds such as methylaluminoxan, ethylaluminoxan, isobutylaluminoxan, or butylaluminoxan, and any one or more of these may be used.

[0168] [Chemical Formula 4]

[0169] J(R 32 )3

[0170] In the above chemical formula 4,

[0171] R 32 are identical or different from each other, and each independently halogen, C 1-20 alkyl or C 1-20 It is a haloalkyl;

[0172] J is aluminum or boron.

[0174] Examples of compounds represented by the above chemical formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc., and more specifically, may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

[0176] The above co-catalyst may be supported in an amount of 1 mmol or more, or 3 mmol or more, and 25 mmol or less, or 20 mmol or less, based on the weight of the carrier, for example, based on 1 g of the carrier. When included within the above-mentioned content range, a sufficient effect of reducing fine particle generation can be obtained along with an effect of improving catalyst activity due to the use of the co-catalyst.

[0178] As described above, the catalyst composition includes a transition metal compound of Formula 1 and exhibits excellent catalytic activity for olefin polymerization, and in particular, can be used for the polymerization of propylene to form a macromonomer having a vinyl group at the end.

[0180] Accordingly, the polypropylene macromer according to the present invention can be produced by polymerizing propylene in the presence of the catalyst composition described above.

[0182] The above polymerization reaction can be carried out by homopolymerizing propylene using a single continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

[0184] And, the above polymerization temperature is 25 o C to 500 o C, or 25 o C to 300 o C, or 30 o C to 200 o C, or 50 o C to 150 o C, or 60 o C to 120 o It may be C. In addition, the polymerization pressure may be 1 kgf / ㎠ to 100 kgf / ㎠, or 1 kgf / ㎠ to 50 kgf / ㎠, or 5 kgf / ㎠ to 45 kgf / ㎠, or 10 kgf / ㎠ to 40 kgf / ㎠, or 15 kgf / ㎠ to 35 kgf / ㎠.

[0186] The above-mentioned supported metallocene catalyst can be dissolved or diluted and injected in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and their isomers, an aromatic hydrocarbon solvent such as toluene and benzene, or a hydrocarbon solvent substituted with chlorine atoms such as dichloromethane and chlorobenzene. It is preferable to use a solvent that has been treated with a small amount of alkyl aluminum to remove small amounts of water or air, which act as catalyst poisons, and it is also possible to carry out the process using additional co-catalysts.

[0188] Preferred embodiments are presented below to aid in understanding the present invention; however, the following embodiments are merely illustrative of the invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the invention, and that such changes and modifications fall within the scope of the appended claims.

[0190] [실시예]

[0191] <전이 금속 화합물의 제조>

[0192] 실시예 1

[0193]

[0194] (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0195] 2-iPr-4-tBu-Phenyl Indene (where eq. ≤ 1 eq. refers to molar equivalent (eq / mol)) mixed with toluene:tetrahydrofuran (THF) (where the volume ratio is 10:1, 0.5 M. ≤ 0.5 M; all solvent ratios are volume ratios, and molar concentration refers to the number of moles of solute (mol) per 1 L of solvent mixed at the corresponding volume ratio). After dissolving in water, n-BuLi (1.05 eq) was slowly added dropwise at -25℃ and stirred at room temperature for 3 hours. Then, Dichloro dimethyl Silane (1.05 eq) was added at -10℃ and stirred overnight at room temperature.

[0196] In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Then, CuCN (2 mol%) was added and stirred for 30 minutes, after which the first reaction product, the mono-Si solution, was added. Afterward, the mixture was stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and n-BuLi (2.1 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, stirred overnight at room temperature, worked up with water, and dried to obtain the ligand.

[0198] Dimethyl-silanediyl(3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0199] The above ligand was dissolved in Toluene:Ether (volume ratio 2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25℃, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0200] When the reaction is complete, the solvent is vacuum dried and dichloromethane (DCM) is reintroduced to remove LiCl through a filter, the filtrate is vacuum dried and recrystallized using hexane and DCM, and the resulting solid is filtered and vacuum dried to obtain a solid transition metal compound.

[0201] 1 H-NMR (500 MHz, CDCl3): 8.30 (d, 2H), 7.29-7.39 (m, 12H), 6.36 (s, 1H), 3.51 (t, 2H), 2.38 (m, 1H), 2.12 (s, 3H), 1.92 (m, 2H), 1.40-1.50 (m, 8H), 1.31 (s, 18H), 0.91 (d, 6H), 0.86 (s, 6H)

[0203] 실시예 2

[0204]

[0206] (3-(6-(tert-butoxy)hexyl)-2-methyl-4-phenyl-1H-inden-1-yl)(2-isopropyl-4-phenyl-1H-inden-1-yl)dimethylsilane 의 제조

[0207] 2-iPr-4-PhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-PhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and then n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature. The mixture was then worked up with water and dried to obtain the ligand.

[0209] Dimethyl-silanediyl(3-(6-(tert-butoxy)hexyl)-2-methyl-4-phenyl-1H-inden-1-yl)(2-isopropyl-4-phenyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0210] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0211] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0212] 1 H-NMR (500 MHz, CDCl3): 8.26 (d, 2H), 7.38-7.52 (m, 14H), 6.35 (s, 1H), 3.51 (t, 2H), 2.38 (m, 1H), 2.12 (s, 3H), 1.92 (m, 2H), 1.40-1.50 (m, 8H), 0.91 (d, 6H), 0.86 (s, 6H)

[0214] 실시예 3

[0215]

[0216] (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)diethylsilane 의 제조

[0217] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodiethyl Silane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature. The mixture was then worked up with water and dried to obtain the ligand.

[0219] Diethyl-silanediyl(3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0220] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0221] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0222] 1 H-NMR (500 MHz, CDCl3): 8.29 (d, 2H), 7.29-7.40 (m, 12H), 6.36 (s, 1H), 3.50 (t, 2H), 2.38 (m, 1H), 2.11 (s, 3H), 1.92 (m, 2H), 1.40-1.50 (m, 8H), 1.31 (s, 18H), 0.91 (d, 6H), 0.86 (t, 6H), 0.74 (m, 4H)

[0224] 실시예 4

[0225]

[0226] (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)methylpropylsilane 의 제조

[0227] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichloromethylpropyl Silane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and then n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature. The mixture was then worked up with water and dried to obtain the ligand.

[0229] Methylpropyl-silanediyl(3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0230] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0231] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0232] 1 H-NMR (500 MHz, CDCl3): 8.30 (d, 2H), 7.30-7.41 (m, 12H), 6.37 (s, 1H), 3.52 (t, 2H), 2.39 (m, 1H), 2.12 (s, 3H), 1.93 (m, 2H), 1.42-1.52 (m, 8H), 1.31 (m, 20H), 0.98 (t, 3H), 0.86 (d, 6H), 0.72-0.81 (m, 5H)

[0234] 실시예 5

[0235]

[0236] (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)methylhexylsilane 의 제조

[0237] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichloromethylhexyl Silane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and then n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature. The mixture was then worked up with water and dried to obtain the ligand.

[0239] Methylhexyl-silanediyl(3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0240] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0241] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0242] 1 H-NMR (500 MHz, CDCl3): 8.29 (d, 2H), 7.30-7.38 (m, 12H), 6.35 (s, 1H), 3.50 (t, 2H), 2.40 (m, 1H), 2.12 (s, 3H), 1.92 (m, 2H), 1.32-1.52 (m, 16H), 1.30 (s, 18H), 1.09 (t, 3H), 0.85 (d, 6H), 0.68-0.81 (m, 5H)

[0244] 실시예 6

[0245]

[0246] (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)methylphenylsilane 의 제조

[0247] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichloromethylphenyl Silane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and then n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature. The mixture was then worked up with water and dried to obtain the ligand.

[0249] Methylphenyl-silanediyl(3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0250] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0251] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0252] 1 H-NMR (500 MHz, CDCl3): 8.28 (m, 2H), 7.38-7.52 (m, 19H), 6.34 (s, 1H), 3.50 (t, 2H), 2.39 (m, 1H), 2.12, 2.13,2.16 (s, 3H), 1.92 (m, 2H), 1.40-1.50 (m, 8H), 0.91, 0.92, 0.94 (d, 6H), 0.86 (s, 3H)

[0254] 실시예 7

[0255]

[0256] (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)methyl(6-(tert-butoxy)hexyl)silane 의 제조

[0257] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Then, Dichloromethyl(6-(tert-butoxy)hexyl) Silane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. Subsequently, the mixture was stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Afterward, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature, working up with water, and drying to obtain the ligand.

[0259] Methyl(6-(tert-butoxy)hexyl)-silanediyl(3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0260] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0261] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0262] 1 H-NMR (500 MHz, CDCl3): 8.31 (d, 2H), 7.30-7.39 (m, 12H), 6.37 (s, 1H), 3.52 (t, 4H), 2.38 (m, 1H), 2.11 (s, 3H), 1.92 (m, 4H), 1.41-1.52 (m, 16H), 1.31 (s, 18H), 0.92 (d, 6H), 0.81 (s, 3H)

[0264] 실시예 8

[0265]

[0266] (3-buthyl-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0267] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and then n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, butylbromide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature, work-up with water, and drying to obtain the ligand.

[0269] Dimethyl-silanediyl(3-buthyl-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0270] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0271] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0272] 1 H-NMR (500 MHz, CDCl3): 8.29 (d, 2H), 7.28-7.37 (m, 12H), 6.35 (s, 1H), 2.38 (m, 1H), 2.08 (s, 3H), 1.92 (m, 2H), 1.28-1.34 (m, 22H), 0.99 (m, 9H), 0.86 (s, 6H)

[0274] 실시예 9

[0275]

[0276] (3-(1-propene)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0277] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, 3-bromoprop-1-ene (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature. The mixture was then worked up with water and dried to obtain the ligand.

[0279] Dimethyl-silanediyl(3-(1-propene)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0280] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0281] Once the reaction is complete, the solvent is vacuum dried, DCM is reintroduced to remove LiCl through a filter, etc., and the filtrate is vacuum dried, and

[0282] After recrystallization using Hexane / DCM, the resulting solid was filtered and vacuum dried to obtain a solid transition metal compound.

[0283] 1 H-NMR (500 MHz, CDCl3): 8.28 (d, 2H), 7.29-7.39 (m, 12H), 6.33 (s, 1H), 5.98 (m, 1H), 5.50-5.52 (m, 2H), 2.62 (d, 2H), 2.38 (m, 1H), 2.10 (s, 3H), 1.91 (m, 2H), 1.28 (s, 18H), 0.99 (d, 6H), 0.85 (s, 6H)

[0285] 실시예 10

[0286]

[0287] (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0288] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Then, Dichloro dimethyl Silane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. Subsequently, the mixture was stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Afterward, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature, working up with water, and drying to obtain the ligand.

[0290] Dimethyl-silanediyl (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0291] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0292] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0293] 1 H-NMR (500 MHz, CDCl3): 8.29 (d, 1H), 7.31-7.39 (m, 11H), 6.36 (s, 1H), 3.52 (t, 2H), 2.38-2.44 (m, 5H), 2.12 (s, 3H), 1.92-1.95 (m, 4H), 1.40-1.50 (m, 8H), 1.31 (s, 18H), 0.91 (d, 6H), 0.86 (s, 6H)

[0295] 실시예 11

[0296]

[0297] (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0298] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and then n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature. The mixture was then worked up with water and dried to obtain the ligand.

[0300] Dimethyl-silanediyl(3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Hafnium dichloride의 제조

[0301] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. HfCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0302] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0303] 1 H-NMR (500 MHz, CDCl3): 8.32 (d, 2H), 7.31-7.40 (m, 12H), 6.25 (s, 1H), 3.52 (t, 2H), 2.41 (m, 1H), 2.21 (s, 3H), 1.92 (m, 2H), 1.40-1.50 (m, 8H), 1.31 (s, 18H), 1.11 (d, 6H), 0.86 (s, 6H)

[0305] 실시예 12

[0306]

[0307] (3-buthyl-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0308] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and then n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, butylbromide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature, work-up with water, and drying to obtain the ligand.

[0310] Dimethyl-silanediyl(3-buthyl-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Hafnium dichloride의 제조

[0311] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. HfCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0312] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0313] 1 H-NMR (500 MHz, CDCl3): 8.33 (d, 2H), 7.30-7.38 (m, 12H), 6.21 (s, 1H), 2.40 (m, 1H), 2.21 (s, 3H), 1.92 (m, 2H), 1.28-1.34 (m, 22H), 0.99-1.10 (m, 9H), 0.86 (s, 6H)

[0315] 비교예 1

[0316]

[0317] bis(2-Methyl-4-(4’-tertbutylphenyl)Inden-1yl) silane의 제조

[0318] 2-Methyl-4-(4'-tertbutylphenyl)Indene (1 eq) was dissolved in Toluene:THF (10:1 0.3 M), and n-BuLi (2.1 eq) was slowly added dropwise at -25 ℃, followed by stirring at room temperature for 3 hours. Subsequently, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of dichlorodimethylsilane (0.53 eq) at -10 ℃, and the mixture was stirred overnight at room temperature. After stirring overnight at room temperature and working up with water, the mixture was dried to obtain the ligand.

[0320] Dimethylsilanediylbis(2-Methyl-4-(4’-tertbutylphenyl)Inden-1yl) zirconium dichloride의 제조

[0321] The ligand prepared above was dissolved in Toluene:Ether (volume ratio 10:1, 0.1 M), and n-BuLi (2.05 eq) was added at -25 °C, followed by stirring at room temperature for 5 hours. A slurry was prepared in a separate flask by mixing ZrCl4 (1 eq) with toluene (0.17 M), added to the ligand solution, and stirred overnight at room temperature. Once the reaction was complete, the solvent was vacuum dried, dichloromethane was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and dichloromethane / hexane was added to recrystallize at room temperature. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0323] 비교예 2

[0324]

[0325] (4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0326] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reactant, the mono-Si solution. Afterward, the ligand was obtained by stirring overnight at room temperature, working up with water, and drying.

[0328] Dimethyl-silanediyl(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0329] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0330] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0332] 비교예 3

[0333]

[0334] (4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)methylphenylsilane 의 제조

[0335] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichloromethylphenyl Silane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. Afterward, the ligand was obtained by stirring overnight at room temperature, working up with water, and drying.

[0337] Methylphenyl-silanediyl(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0338] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0339] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0341] 비교예 4

[0342]

[0343] (4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)(6-(tert-butoxy)hexylmethylsilane 의 제조

[0344] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichloro (6-(tert-butoxy)hexylmethyl Silane (1.05 eq) was added at -10°C, and the mixture was stirred overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, and using water After working up, the ligand was obtained by drying.

[0346] (6-(tert-Butoxy)hexylmethylmethyl-silanediyl(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0347] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0348] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0350] 비교예 5

[0351]

[0352] (2,3,4,5-tetramethylcyclopentadienyl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0353] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reactant, the mono-Si solution. Afterward, the ligand was obtained by stirring overnight at room temperature, working up with water, and drying.

[0355] Dimethyl-silanediyl(2,3,4,5-tetramethylcyclopentadienyl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0356] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0357] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0359] 비교예 6

[0360]

[0361] (3-Butyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0362] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, and the mixture was stirred overnight at room temperature. In another reactor, 3-Bu-Indene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried to obtain the ligand.

[0364] Dimethyl-silanediyl(3-Butyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride의 제조

[0365] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0366] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0368] 비교예 7

[0369]

[0370] (4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)(9H-fluoren-9-yl)dimethylsilane 의 제조

[0371] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, and the mixture was stirred overnight at room temperature. In another reactor, Fluorene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried to obtain the ligand.

[0373] Dimethyl-silanediyl(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)(9H-fluoren-9-yl) Zirconium dichloride의 제조

[0374] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0375] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0377] 비교예 8

[0378]

[0379] (3-Methyl-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane 의 제조

[0380] 2-iPr-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-4-tBuPhIndene (1 eq) was dissolved in Toluene:THF (5:1, 0.7 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterward, CuCN (2 mol%) was added and stirred for 30 minutes, followed by the addition of the first reaction product, the mono-Si solution. The mixture was then stirred overnight at room temperature, worked up with water, and dried. This was dissolved in Toluene:THF (2:1, 0.2 M), and then n-BuLi (2.1 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, Methyliodide (1.05 eq) was dissolved in THF (0.6 M) and added at -25℃, followed by stirring overnight at room temperature, work-up with water, and drying to obtain the ligand.

[0382] Preparation of Dimethyl-silanediyl(3-methyl-4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl) Zirconium dichloride

[0383] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0384] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0385] 1 H-NMR (500 MHz, CDCl3): 8.33 (d, 2H), 7.30-7.38 (m, 12H), 6.21 (s, 1H), 2.40 (m, 1H), 2.21 (s, 3H), 1.80 (s, 3H), 1.34 (s, 18H), 0.90 (d, 6H), 0.86 (s, 6H)

[0387] Comparative Example 9

[0388]

[0389] Preparation of (3-(6-(tert-butoxy)hexyl)-2-methyl-1H-inden-1-yl)(2-isopropyl-1H-inden-1-yl)dimethylsilane

[0390] 2-iPr-Indene (1 eq) was dissolved in Toluene:THF (10:1, 0.5 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Then, Dichlorodimethylsilane (1.05 eq) was added at -10°C, followed by stirring overnight at room temperature. In another reactor, 2-Me-Indene (1 eq) was dissolved in Toluene:THF (2:1, 0.2 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Subsequently, tert-ButhoxyHexyl-Iodide (1.05 eq) was dissolved in THF (0.6 M), added at -25°C, stirred overnight at room temperature, and then dried after work-up with water. This was dissolved in Toluene:THF (5:1, 0.7M), and n-BuLi (1.05 eq) was slowly added dropwise at -25℃, followed by stirring at room temperature for 3 hours. Subsequently, CuCN (2 mol%) was added and stirred for 30 minutes, after which the first reactant, the mono-Si solution, was added. The mixture was then stirred overnight at room temperature, worked up with water, and dried to obtain the ligand.

[0392] Preparation of Dimethyl-silanediyl(3-(6-(tert-butoxy)hexyl)-2-methyl-1H-inden-1-yl)(2-isopropyl-1H-inden-1-yl) Zirconium dichloride

[0393] The above ligand was dissolved in Toluene:Ether (2:1, 0.53 M), n-BuLi (2.05 eq) was added at -25°C, and the mixture was stirred at room temperature for 5 hours. ZrCl4 (1 eq) was added to a flask to make a slurry in Toluene (0.17 M), and the mixture was stirred overnight at room temperature.

[0394] Once the reaction was complete, the solvent was vacuum dried, DCM was reintroduced to remove LiCl using a filter, the filtrate was vacuum dried, and the mixture was recrystallized using Hexane / DCM. The resulting solid was then filtered and vacuum dried to obtain a solid transition metal compound.

[0395] : 7.37-7.42 (m, 6H), 7.21-7.22 (m, 2H), 6.37 (s, 1H), 3.50 (t, 2H), 2.37 (m, 1H), 2.02 (s, 3H), 1.92 (m, 2H), 1.40-1.50 (m, 8H), 0.98 (d, 6H), 0.85 (s, 6H)

[0397] Comparative Example 10

[0398]

[0399] We attempted to synthesize the (3-(6-(tert-butoxy)hexyl)-4-(4-(tert-butyl)phenyl)-2-ethyl-1H-inden-1-yl)(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)dimethylsilane ligand in a manner similar to Example 1, but a mixture was produced as shown in the above reaction scheme, so the desired ligand could not be obtained.

[0401] Preparation of Supported Catalysts

[0402] 100 g of silica (Grace, SYLOPOL 952X, calcined under 250 ℃) was added to a 2 L reactor (Buch) under an argon atmosphere, and 10 mmol / g Si of methylaluminoxan (MAO) was added. The mixture was slowly injected at room temperature and stirred at 90°C for 15 hours. After the reaction was complete, the reaction mixture was cooled to room temperature and left to stand for 15 minutes, after which the solvent was removed using a cannula. Then, 400 mL of toluene was added and stirred for 1 minute, followed by leaving it to stand for 15 minutes, after which the solvent was removed using a cannula.

[0403] The transition metal compound (70 μmol / g Si) of each example and comparative example was dissolved in toluene (400 mL) and then introduced into a reactor using a cannula. After stirring at 50 °C for 5 hours, the mixture was cooled to room temperature and left for 15 minutes, after which the solvent was removed using a cannula. Subsequently, toluene (400 mL) was added, stirred for 1 minute, left for 15 minutes, and the process of removing the solvent using a cannula was repeated twice. Then, hexane (400 mL) was added in the same manner, stirred for 1 minute, left for 15 minutes, and the solvent was removed using a cannula.

[0404] An antistatic agent (Atmer 163, 3 g) was dissolved in hexane (400 mL) in a separate container and then introduced into a reactor using a cannula. The mixture was stirred at room temperature for 20 minutes, then transferred to a glass filter to remove the solvent. Subsequently, it was dried under vacuum for 5 hours and then dried under vacuum at 45 ℃ for 4 hours to obtain a supported catalyst.

[0406] Manufacture of Polypropylene

[0407] A 2L stainless steel reactor was vacuum dried at 65°C and cooled. At room temperature, 3 mmol of triethylaluminum was added, followed by the addition of 827 ppm of hydrogen (based on propylene content) and 770 g of propylene. After stirring for 5 minutes, 30 mg of the prepared supported catalyst was introduced into the reactor under nitrogen pressure. Subsequently, the reactor temperature was gradually increased to 70°C, and polymerization was carried out for 1 hour. After the reaction was completed, the unreacted propylene was vented.

[0409] <Evaluation of Physical Properties of Polypropylene>

[0410] The physical properties of polypropylene prepared in the presence of a supported catalyst containing a transition metal compound of each of the above examples and comparative examples were evaluated in the following manner. The results are shown in Table 1 below.

[0412] (1) Weight-average molecular weight (Mw, g / mol) and number-average molecular weight (Mn, g / mol)

[0413] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using gel permeation chromatography (GPC).

[0414] Specifically, a Waters PL-GPC220 instrument was used for gel permeation chromatography (GPC), and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. The measurement temperature was 160 °C, 1,2,4-trichlorobenzene was used as the solvent, and the flow rate was set to 1 mL / min. Polymer samples according to the examples and comparative examples were each pretreated by dissolving them in trichlorobenzene containing 0.0125% BHT at 160 °C for 10 hours using a GPC analyzer (PL-GP220), prepared to a concentration of 10 mg / 10 mL, and supplied in a volume of 200 μL. The values ​​of Mw and Mn were derived using a calibration curve formed using a polystyrene standard specimen. Nine types of polystyrene standard specimens with weight-average molecular weights of 2,000 g / mol, 10,000 g / mol, 30,000 g / mol, 70,000 g / mol, 200,000 g / mol, 700,000 g / mol, 2,000,000 g / mol, 4,000,000 g / mol, and 10,000,000 g / mol were used.

[0416] (2) Terminal vinyl group content (mol%) and terminal vinylidene group content (mol%)

[0417] After dissolving polypropylene in 1,1,2,2-tetrachloroethane-d2 (TCE-d2) solvent at a concentration of 10 wt%, 1 H NMR analysis (500 MHz) was performed.

[0418] In the NMR spectrum, sp 3 When the integral value of all peaks (δ 0.5-2.5) derived from hydrogen bonded to carbon was set to 100, the integral value of peaks derived from terminal vinyl groups and terminal vinylidene groups was calculated to derive the mol% of terminal vinyl groups and terminal vinylidene groups relative to 100 mol% of total polypropylene.

[0420] (3) Stereoregularity (Pentad sequence distribution, mmmm, %)

[0421] The stereoregularity of polypropylene was measured using quantitative nuclear magnetic resonance (NMR) spectroscopy, as in the paper by V. Busico and R. Cipullo, Progress in Polymer Science, 2001, 26, 443-533.

[0422] Specifically, the stereoregularity (Pentad sequence distribution) for the polypropylene of the examples and comparative examples is, 13 After measuring the sequence distribution at the pentad level by C-NMR analysis, the results were expressed as the percentage of stereoregular pentad (mmmm) sequences for all pentad sequences. mmmm% is a value based on moles.

[0423] At this time, a Bruker 500 MHz NMR was used as the measuring instrument, and polypropylene was dissolved in 1,1,2,2-tetrachloroethane (TCE-d2) solvent and measured at an absolute temperature of 393 K ( 13 C; pulse sequence=zgig30, ns=4096, d1=10 sec, 1H; pulse sequence=zg30, ns=128, d1=3 sec), the sequence distribution was analyzed by referring to the analysis method AMT-3989-0k, and the stereoregularity (mmmm%) was calculated according to the paper, V. Busico and R. Cipullo, Progress in Polymer Science, 2001, 26, 443-533.

[0425] NMR analysis (mol%) Mw(g / mol) Stereoregularity (mmmm %) terminal vinyl group terminal vinylidene group Example 1 0.81 0.06 43,000 28.5 Example 2 0.82 0.05 38,000 27.5 Example 3 0.81 0.05 42,000 27.4 Example 4 0.79 0.06 51,000 28.4 Example 5 0.80 0.02 37,000 28.6 Example 6 0.77 0.01 55,000 27.8 Example 7 0.77 0.03 35,000 27.8 Example 8 0.76 0.03 42,000 27.4 Example 9 0.81 0.05 45,000 28.3 Example 10 0.71 0.04 52,000 28.5 Example 11 0.82 0.03 50,000 28.1 Example 12 0.76 0.02 51,000 28.3 Comparative Example 1 0 0.05 113,000 98.0 Comparative Example 2 0 0.04 34,000 98.0 Comparative Example 3 0 0.03 41,000 98.1 Comparative Example 4 0 0.05 80,000 97.8 Comparative Example 5 0 0.03 51,000 98.0 Comparative Example 6 0.10 0.03 143,000 35.5 Comparative Example 7 0.01 0.02 120,000 96.8 Comparative Example 8 0.41 0.11 89,000 68.5 Comparative Example 9 0.61 0.18 43,000 38.1

[0426] Referring to Table 1 above, it can be seen that the homopolypropylene prepared using the catalysts of Examples 1 to 12 has a vinyl end group ratio of 0.7 mol% or higher, while the vinylidene end group ratio is significantly lower.

[0427] However, in the case of Comparative Examples 1 to 7, vinyl end groups were not formed, or the proportion was significantly lower compared to the Examples. In addition, the polypropylene produced from the catalysts of the Comparative Examples showed a significant difference from the polypropylene produced from the catalysts of the Examples in terms of molecular weight and stereoregularity.

[0428] In addition, in Comparative Example 8, the effect of the substituent at the 3rd position of indenyl decreased, resulting in a decrease in vinyl terminals and a significant increase in vinylidene terminals. In Comparative Example 9, the steric effect decreased, resulting in a decrease in vinyl terminals and an increase in vinylidene terminals.

[0429] From these results, it can be seen that the transition metal compound represented by the above chemical formula 1 is more effective in the formation of macromonomers during polypropylene polymerization.

Claims

Claim 1 Polypropylene having a weight-average molecular weight of 20,000 to 70,000 g / mol, a stereoregularity (tacticity, mmmm) of 20% or more to less than 30%, and a terminal vinyl group content of 0.6 mol% or more to 1 mol% or less. Claim 2 Polypropylene according to claim 1, having a terminal vinylidene group content of 0.1 mol% or less. Claim 3 In claim 1, polypropylene having a weight-average molecular weight of 30,000 to 60,000 g / mol. Claim 4 delete Claim 5 In claim 1, polypropylene having a terminal vinyl group content of 0.7 mol% or more relative to 100 mol% of polypropylene. Claim 6 In claim 1, the polypropylene is prepared by polymerizing propylene in the presence of a catalyst composition comprising a transition metal compound represented by the following chemical formula 1: [Chemical Formula 1] In the above Chemical Formula 1, M is a Group 4 transition metal, and X1 and X2 are each independently hydrogen; a halogen; or C 1-20 It is alkyl, A is carbon or silicon, and R 11 and R 12 Each independently, hydrogen; halogen; C 1-20 Alkyl; C 2-20 Alkoxyalkyl; or C 6-20 Arilgo, R 21 is methyl, and R 22 is C 3-20 Alkyl; C 3-20 Alkoxyalkyl; or C 3-20 It is alkenyl, and R 23 Unsubstituted C 6-20 Aryl; or C 7-20 It is an alkylaryl, and R 24 and R 25 are each hydrogen or; or R 24 and R 25 are connected to each other C 3-10 It forms a cycloalkane ring of, and R 26 C 1-20 It is alkyl, and R 27 Unsubstituted C 6-20 Aryl; or C 7-20 It is an alkylaryl. Claim 7 In Paragraph 6, R 22 is C 3-10 Alkyl; C 3-10 Alkoxyalkyl; or C 3-10 Alkenyl, polypropylene. Claim 8 In Paragraph 6, R 23 is unsubstituted phenyl; or C 1-10 Polypropylene, which is alkyl-substituted phenyl. Claim 9 In paragraph 6, M is zirconium or hafnium, X1 and X2 are each independently halogens, A is silicon, and R 11 and R 12 C each independently 1-10 Alkyl; C 2-10 Alkoxyalkyl; or C 6-10 Arilgo, R 22 is C 3-10 Alkyl; C 3-10 Alkoxyalkyl; or C 3-10 It is alkenyl, and R 23 is unsubstituted phenyl; or C 1-10 It is an alkyl-substituted phenyl, and R 24 and R 25 are each hydrogen or; or R 24 and R 25 They are connected to each other to form a cyclopentane ring or a cyclohexane ring, and R 27 is unsubstituted phenyl; or C 1-10 Polypropylene, which is alkyl-substituted phenyl. Claim 10 In claim 6, the transition metal compound represented by the above chemical formula 1 is any one selected from the group consisting of the following, polypropylene:

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