Supported-metallocene hybrid catalyst and method for producing polyethylene using same

Abstract

The present invention provides a supported-metallocene hybrid catalyst useful in the production of polyethylene of high impact strength as well as good processability, and a method for producing polyethylene using same.

Description

Hybrid supported metallocene catalyst and method for producing polyethylene using the same

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0073746, filed June 5, 2024, and Korean Patent Application No. 10-2025-0073545, filed June 5, 2025, the entire contents of which are incorporated herein by reference.

[0003]

[0004] The present invention relates to a hybrid supported metallocene catalyst useful for producing polyethylene exhibiting high impact strength characteristics along with excellent processability, and a method for producing polyethylene using the same.

[0005]

[0006] Olefin polymerization catalysts can be categorized into Ziegler-Natta and metallocene catalysts, and these two highly active catalysts have been developed according to their respective characteristics. Since their invention in the 1950s, Ziegler-Natta catalysts have been widely applied in existing commercial processes. However, because they are multi-site catalysts with multiple active sites, they are characterized by a broad molecular weight distribution of the polymer, and the uneven distribution of the comonomer composition limits the achievement of desired physical properties.

[0007]

[0008] On the other hand, metallocene catalysts are composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst mainly composed of an organometallic compound composed of aluminum. Such catalysts are homogeneous complex catalysts and are single-site catalysts. Due to the single-site characteristics, a narrow molecular weight distribution is obtained, and a polymer with a uniform comonomer composition distribution is obtained. In addition, the stereoregularity, copolymerization characteristics, molecular weight, and crystallinity of the polymer can be changed by modifying the ligand structure of the catalyst and changing the polymerization conditions.

[0009]

[0010] Meanwhile, linear low-density polyethylene (LLDPE) is manufactured by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst. It is a resin with a narrow molecular weight distribution, short-chain branches of a certain length, and no long-chain branches. Linear low-density polyethylene film has the characteristics of general polyethylene, as well as high breaking strength and elongation, and excellent tear strength and drop impact strength, so it is increasingly being used in stretch films and overlap films, which were difficult to apply to conventional low-density polyethylene or high-density polyethylene.

[0011]

[0012] Recently, with the advent of decarbonization, demand for high-performance linear low-density polyethylene to improve recyclability is increasing, and along with this, demand for linear low-density polyethylene with excellent processability and drop impact strength is also increasing.

[0013]

[0014] Dart drop impact strength is a very important mechanical property that determines the various impact resistance of a resin.

[0015]

[0016] However, linear low-density polyethylene, despite its excellent mechanical properties, suffers from poor processability in blown film and poor transparency. Blown film, also known as inflation film, is manufactured by blowing air into molten plastic to inflate it.

[0017]

[0018] Linear low-density polyethylene generally has the characteristics of better transparency and increased drop impact strength as the density decreases. However, when a large amount of alpha olefin comonomer is used to manufacture low-density polyethylene, there are problems such as an increased frequency of fouling in the slurry polymerization process. Therefore, in the slurry polymerization process, a density of 0.915 g / cm 3 We produce many of the above products.

[0019]

[0020] Therefore, the density is 0.915 g / cm 3 There is a need to develop polyethylene that can achieve excellent mechanical properties such as drop impact strength along with excellent processability.

[0021]

[0022] In order to solve the problems of the above prior art, the present invention aims to provide a hybrid supported metallocene catalyst useful for producing polyethylene exhibiting high impact strength characteristics along with excellent processability.

[0023]

[0024] In addition, the present invention aims to provide a method for producing polyethylene exhibiting excellent drop impact strength characteristics using the hybrid supported metallocene catalyst.

[0025]

[0026] To solve the above problem, the present invention provides a hybrid supported metallocene catalyst comprising: a first transition metal compound represented by the following chemical formula 1; a second transition metal compound represented by the following chemical formula 2; a cocatalyst; and a carrier:

[0027] [Chemical Formula 1]

[0028]

[0029] In the above chemical formula 1,

[0030] M1 is a group 4 transition metal,

[0031] X 11 and X 12 are each independently, C 1-20 Alkyl, or halogen,

[0032] A1 is carbon, silicon, or germanium,

[0033] Q 11 and Q 12 are each independently hydrogen, halogen, C 1-20 Alkyl, or C 2-20 It is an alkoxyalkyl,

[0034] R 11 Inland R 15 are each independently hydrogen, or C 1-20 It is alkyl,

[0035] [Chemical Formula 2]

[0036]

[0037] In the above chemical formula 1,

[0038] M2 is a group 4 transition metal,

[0039] X 21 and X 22 are each independently, C 1-20 Alkyl or halogen,

[0040] R 21 Inland R 25 are each independently, C 1-20 It is alkyl,

[0041] R 26is hydrogen, or C 1-20 It is alkyl,

[0042] R 27 Silver hydrogen, C 1-20 Alkyl, C 2-20 Alkoxy, or C 2-20 It is an alkoxyalkyl.

[0043]

[0044] In addition, the present invention provides a method for producing polyethylene, comprising the step of introducing hydrogen and slurry polymerizing an ethylene monomer and an olefin monomer in the presence of the above-described hybrid supported metallocene catalyst.

[0045]

[0046] In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

[0047] Furthermore, the terminology used herein is merely for the purpose of describing exemplary embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0048] Additionally, in this specification, the "~" indicating a numerical range includes both the upper and lower limits of the numerical range. For example, A~B means greater than or equal to A and less than or equal to B.

[0049] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0050]

[0051] Hereinafter, the hybrid supported metallocene catalyst of the present invention and the method for producing polyethylene using the same will be described in detail.

[0052]

[0053] The hybrid supported metallocene catalyst according to the present invention comprises: a first transition metal compound represented by the following chemical formula 1; a second transition metal compound represented by the following chemical formula 2; a cocatalyst; and a carrier:

[0054] [Chemical Formula 1]

[0055]

[0056] In the above chemical formula 1,

[0057] M1 is a group 4 transition metal,

[0058] X 11 and X 12 are each independently, C 1-20 Alkyl, or halogen,

[0059] A1 is carbon, silicon, or germanium,

[0060] Q 11 and Q 12 are each independently hydrogen, halogen, C 1-20 Alkyl, or C 2-20 It is an alkoxyalkyl,

[0061] R 11 Inland R 15 are each independently hydrogen, or C 1-20 It is alkyl,

[0062] [Chemical Formula 2]

[0063]

[0064] In the above chemical formula 2,

[0065] M2 is a group 4 transition metal,

[0066] X 21 and X 22 are each independently, C 1-20 Alkyl or halogen,

[0067] R 21 Inland R 25 are each independently, C 1-20 It is alkyl,

[0068] R 26 is hydrogen, or C 1-20 It is alkyl,

[0069] R 27 Silver hydrogen, C 1-20 Alkyl, C 2-20 Alkoxy, or C 2-20 It is an alkoxyalkyl.

[0070]

[0071] In the present invention, the substituents of the chemical formula are described more specifically as follows.

[0072]

[0073] The halogen can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0074]

[0075] C above 1-20 The alkyl of may be straight-chain, branched-chain or cyclic alkyl. Specifically, the C 1-20The 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, the alkyl having 1 to 20 carbon atoms may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, or a cyclohexyl group.

[0076]

[0077] C 2-20 The alkenyl of may be a straight-chain, branched-chain or cyclic alkenyl. Specifically, the C 2-20 The alkenyl 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 may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl.

[0078]

[0079] C 1-20 The alkoxy of may be a straight-chain, branched-chain or cyclic alkoxy group. Specifically, the C 1-20The alkoxy 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 cyclohexene group.

[0080]

[0081] C 2-20 Alkoxyalkyl of -R y -OR z Alkyl (-R) with a structure containing y ) is one or more hydrogens of alkoxy (-OR z ) may be a substituent substituted with. Specifically, the alkoxyalkyl having C2 to C20 carbon atoms may be a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhectyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, or a tert-butoxyhexyl group.

[0082]

[0083] Also, group 4 transition metals can include titanium, zirconium, and hafnium.

[0084]

[0085] The hybrid supported metallocene catalyst according to the present invention is a hybrid catalyst comprising a first transition metal compound having a high molecular weight and high polymerizability, and a second transition metal compound having a low molecular weight and low polymerizability.

[0086]

[0087] Specifically, the first transition metal compound represented by the above chemical formula 1 contributes to producing a high molecular weight copolymer having a high SCB content, and the second transition metal compound represented by the above chemical formula 2 contributes to producing a low molecular weight copolymer having a low SCB (short chain branch) content.

[0088]

[0089] Accordingly, the hybrid supported metallocene catalyst of the present invention can exhibit high copolymerizability in polyethylene in the high molecular weight range due to the first transition metal compound, while exhibiting low copolymerizability in polyethylene in the low molecular weight range due to the action of the second transition metal compound. As a result, polyethylene produced using the hybrid supported metallocene catalyst according to the present invention can exhibit excellent processability and high impact strength through tie-molecule formation due to strong low crystallinity development in the high molecular weight range.

[0090]

[0091] In the hybrid supported metallocene catalyst according to the present invention, the first transition metal compound contributes to the production of a high molecular weight copolymer and exhibits a relatively high comonomer incorporation rate compared to the second transition metal compound.

[0092] Specifically, in the above chemical formula 1, M1 is zirconium (Zr) or titanium (Ti), and X 11 and X 12 Each independently may be halogen, and preferably, chloro.

[0093] In addition, the compound represented by the above chemical formula 1 is A1(Q) with a bridging group of cyclopentadienyl and amine. 11 )(Q 12 ) group. In the above chemical formula 1, A1 is silicon, and Q, which is a substituent of A1 11 and Q 12 are each independently hydrogen, halogen, C 1-10Alkyl, or C 2-10 It may be an alkoxyalkyl. At this time, Q, which is a substituent of the above A1 11 and Q 12 Either one of C 2-20 It may include an alkoxyalkyl tether group. In this way, when a tether group is present, leaching of the catalyst precursor is prevented during a polymerization reaction, and as a result, fouling due to the reaction of the leached catalyst precursor and the cocatalyst can be prevented.

[0094] In addition, when the bridge group includes a tether group, Q, which is a substituent of A1, 11 and Q 12 One of them is C 2-20 One is alkoxyalkyl, and the other is C 1-20 It can be an alkyl. As a bridging group connecting two ligands, Q 11 and Q 12 Either one of C 2-20 When the tether group of alkoxyalkyl is included, in addition to the leaching prevention effect of the above-mentioned catalyst precursor, the atomic size becomes larger and the available angle increases compared to the carbon bridge in the conventional metallocene compound, so that the monomer can easily approach during the polymerization reaction, thereby exhibiting better catalytic activity. This effect is achieved by Q in the tether. 11 and Q 12 Either of them is -(CH2)nR b (Above R b is C 1-6 Alkoxy group, more specifically C 1-6 Straight chain alkoxy group or C 3-6 It may be a branched alkoxy group, more specifically a C such as a tert-butoxy group. 3-6 branched alkoxy, and n is an integer from 2 to 10, or from 3 to 9), and further, the remaining one is C 1-4 It can be further increased if it is alkyl. Preferably, Q 11 and Q 12One of them may be tert-butoxyhexyl and the other may be methyl.

[0095]

[0096] Also, in the above chemical formula 1, R 11 Inland R 15 are each independently, C 1-6 It can be alkyl. Specifically, in the above chemical formula 1, each hydrogen of cyclopentadienyl is independently C 1-6 It can be substituted with alkyl. When the above cyclopentadienyl is substituted, it can exhibit better catalytic activity due to the inductive effect that can supply sufficient electrons. In this regard, hydrogen in the cyclopentadienyl is more specifically C 1-4 Alkyl, more specifically five hydrogens C 1-4 It can be substituted with alkyl or methyl.

[0097] In addition, in the above chemical formula 1, R, which is a substituent of amine connected through a bridge group with cyclopentadienyl, 15 is C 1-6 It can be alkyl, more specifically C 1-4 Straight chain alkyl, or C 3-6 It may be branched alkyl, more specifically tert-butyl.

[0098]

[0099] Specific examples of the first transition metal compound represented by the above chemical formula 1 include compounds having the following structures, but the present invention is not limited thereto.

[0100]

[0101]

[0102] The first transition metal compound represented by the above chemical formula 1 can be synthesized by applying known reactions, and a more detailed synthesis method can be found in the examples.

[0103]

[0104] Meanwhile, the second transition metal compound represented by Chemical Formula 2 is a non-bridged structure of a hydrogenated indene group, specifically a 4,5,6,7-tetrahydro-1-indene group, and cyclopentadiene, and thus can easily control the electronic / steric environment around the transition metal. As a result, the chemical structure, molecular weight distribution, and mechanical properties of the synthesized polyethylene can be easily controlled.

[0105]

[0106] Specifically, in the above chemical formula 2, M2 is zirconium (Zr), and X 11 and X 12 Each independently may be a halogen, and preferably, may be chloro. When Zr is included as the central metal of the second transition metal compound represented by the above chemical formula 2, compared to when other Group 14 elements such as Hf are included, it has more orbitals capable of accepting electrons, and thus can easily bind to the monomer with higher affinity, and as a result, it can exhibit a superior catalytic activity improvement effect.

[0107]

[0108] In addition, all hydrogens of the cyclopentadienyl group of the second transition metal compound represented by the above chemical formula 2 are C 1-20 It is a structure substituted with alkyl. Specifically, in chemical formula 2, the cyclopentadienyl group is R 21 Inland R 25 By substituting with a substituent of the first transition metal compound represented by the above chemical formula 1, it is possible to exhibit superior catalytic activity through the inductive effect that can supply sufficient electrons, and by appropriately controlling the distribution of the comonomer of polyethylene manufactured in combination with the first transition metal compound represented by the above chemical formula 1, impact strength and processability can be improved simultaneously.

[0109] Substituent R of the above cyclopentadienyl 21 Inland R 25 are each independently, C1-10 Alkyl, more specifically C 1-4 Alkyl, more specifically methyl.

[0110]

[0111] In addition, by including a hydrogenated indene group as a ligand, i.e., a 4,5,6,7-tetrahydro-1-indene group, it exhibits superior hydrogen reactivity compared to the case of including a conventional indene group, thereby reducing the amount of hydrogen input and wax generated during the polymerization reaction, and as a result, improving process stability. In addition, when combined with the first transition metal compound represented by the above chemical formula 1, the distribution of comonomers in the final polyethylene produced can be concentrated toward a high molecular weight due to the synergistic effect, thereby significantly improving impact strength.

[0112]

[0113] In addition, the second transition metal compound represented by the above chemical formula 2 may be unsubstituted or substituted at positions 1 and 3 of the 4,5,6,7-tetrahydro-1-indene group. That is, as described above, R, which is a substituent of the 4,5,6,7-tetrahydro-1-indene group of the second transition metal compound 26 is hydrogen, or C 1-20 Alkyl, R 27 Silver hydrogen, C 1-20 Alkyl, C 2-20 Alkoxy, or C 2-20 It may be an alkoxyalkyl. Specifically, R 26 is hydrogen, or C 1-6 Alkyl, R 27 Silver hydrogen, C 1-6 Alkyl, or -(CH2) n -R b (Above R b is C 1-6 Alkoxy group, more specifically C 1-6 Straight chain alkoxy group or C 3-6 It may be an alkoxyalkyl group having a branched alkoxy group, and n is an integer from 2 to 10. In addition, the above -(CH2) n -Rb In R b is C 3-6 C, such as a branched alkoxy group, more specifically a tert-butoxy group 3-6 Branched alkoxy, and n can be an integer from 3 to 9.

[0114] Preferably, the R 26 is hydrogen, or methyl, and R 27 may be hydrogen, methyl, ethyl, or tert-butoxyhexyl.

[0115]

[0116] Specific examples of the second transition metal compound represented by the above chemical formula 2 include compounds having the following structures, but the present invention is not limited thereto.

[0117] .

[0118]

[0119] The second transition metal compound represented by the above chemical formula 2 can be synthesized by applying known reactions, and a more detailed synthesis method can be found in the examples.

[0120]

[0121] Meanwhile, the hybrid supported metallocene catalyst according to the present invention can increase catalytic activity and further improve the properties of the polymer produced by controlling the molar ratio of the first and second transition metal compounds.

[0122]

[0123] For example, the hybrid supported metallocene catalyst may include the first and second transition metal compounds in a molar ratio of 1:1 to 10:1. When the above-mentioned mixing ratio conditions are satisfied, the activity of the catalyst is excellently maintained, while the high and low copolymerizabilities of the polyethylene produced from the hybrid supported catalyst are optimized, thereby further improving the drop impact strength and processability. More specifically, the molar ratio of the first and second transition metal compounds may be 2:1 to 8:1, or 3:1 to 7:1.

[0124]

[0125] Additionally, the hybrid supported metallocene catalyst according to the present invention includes a cocatalyst. When the hybrid supported metallocene catalyst includes a cocatalyst, it can exhibit high catalytic activity while improving process stability.

[0126] Specifically, the cocatalyst may include at least one compound represented by the following chemical formula 3.

[0127] [Chemical Formula 3]

[0128] -[Al(R 41 )-O]a-

[0129] In the above chemical formula 3,

[0130] R 41 is a halogen; or C substituted or unsubstituted with a halogen 1-20 It is hydrocarbyl;

[0131] a is an integer greater than or equal to 2.

[0132]

[0133] Meanwhile, in the present specification, a hydrocarbyl group is a monovalent functional group in the form of removing a hydrogen atom from a hydrocarbon, and may include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, and an alkynylaryl group. In addition, the hydrocarbyl group having 1 to 20 carbon atoms may be a hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 20 carbon atoms is a straight-chain, branched-chain, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or a cyclohexyl group; Or it may be an aryl group such as a phenyl group, a naphthyl group, or anthracenyl group.

[0134]

[0135] Examples of compounds represented by the above chemical formula 3 include alkylaluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and any one of these or a mixture of two or more thereof may be used.

[0136]

[0137] Among the above compounds, the cocatalyst may be, more specifically, an alkylaluminoxane cocatalyst such as methylaluminoxane.

[0138]

[0139] The above alkylaluminoxane cocatalyst can further enhance catalytic activity by including a metal element that stabilizes the first and second transition metal compounds and acts as a Lewis acid to form a bond through a Lewis acid-base interaction with a functional group introduced into a bridge group of the first and second transition metal compounds.

[0140]

[0141] In addition, the amount of the cocatalyst used can be appropriately adjusted depending on the properties or effects of the desired catalyst and polyethylene. For example, when silica is used as the carrier described below, the cocatalyst can be supported in an amount of 100 g or more, 1000 g or more, or 2000 g or more, and 6000 g or less, or 5500 g or less, or 5400 g or less, based on the weight of the carrier, for example, 1,000 g of silica.

[0142]

[0143] In addition, the hybrid supported metallocene catalyst according to the present invention may include a carrier. When the hybrid supported metallocene catalyst includes a carrier, the first and second transition metal compounds are used in the form of a supported catalyst supported on the carrier.

[0144]

[0145] As the carrier, a carrier having a highly reactive hydroxyl group, silanol group, or siloxane group on the surface can be used, and for this purpose, a carrier whose surface has been modified by calcination or whose surface has had moisture removed by drying can be used.

[0146]

[0147] For example, silica manufactured by calcining silica gel, silica such as silica dried at high temperature, silica-alumina, and silica-magnesia can be used, and these can typically contain oxide, carbonate, sulfate, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.

[0148]

[0149] When used in a supported catalyst state, the particle shape and bulk density of the polymer produced are excellent, and it can be suitably used in conventional slurry polymerization, bulk polymerization, and gas phase polymerization processes. In addition, among various supports, the silica support is supported by chemical bonding of the functional group of the transition metal compound, so that almost no catalyst is liberated from the surface of the support during the ethylene polymerization process, and as a result, fouling caused by adhesion of the reactor wall or polymer particles to each other can be minimized when producing polyethylene by slurry or gas phase polymerization.

[0150]

[0151] The above-mentioned carrier may have an average particle diameter (D50) of 20 to 40 μm. When the above-mentioned particle size is present, the transition metal compound can be supported with superior efficiency, and as a result, the catalytic activity can be enhanced. More specifically, the carrier may have an average particle diameter of 20 μm or more, or 25 μm or more, and 40 μm or less, or 30 μm or less.

[0152]

[0153] Meanwhile, in the present invention, the average particle diameter (D50) of the carrier refers to the particle diameter at the 50% point of the cumulative distribution of the number of particles according to particle size (particle diameter). The D50 can be measured using a laser diffraction method. Specifically, the target carrier is dispersed in a dispersion medium such as deionized water, and then introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac S3500), and when the particles pass through the laser beam, the difference in the diffraction pattern according to the particle size is measured to calculate the particle size distribution. The particle size at the point where it becomes 50% of the cumulative distribution of the number of particles according to the particle diameter in the measuring device is calculated, and this is taken as the average particle size.

[0154]

[0155] In addition, when supported on the carrier, the first and second transition metal compounds may be supported in an amount of, for example, 1 mmol or more, 3 mmol or more, 5 mmol or more, 7 mmol or more, or 10 mmol or more, and 100 mmol or less, or 80 mmol or less, or 60 mmol or less, or 50 mmol or less, based on 1,000 g of the silica carrier. When supported in the above amount range, it may exhibit appropriate supported catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

[0156]

[0157] The hybrid supported metallocene catalyst according to the present invention having the above-described configuration can be produced by a manufacturing method comprising the steps of supporting a promoter compound on a support, and supporting the first and second transition metal compounds on the support, wherein the supporting order of the promoter and the first and second transition metal compounds can be changed as needed, and the supporting order of the first and second transition metal compounds can also be changed as needed. The first and second transition metal compounds may be supported simultaneously. Considering the effect of the supported catalyst having a structure determined according to the supporting order, among these, supporting the promoter on the support and then sequentially supporting the first and second transition metal compounds can enable the produced supported catalyst to realize high catalytic activity and better process stability in the process of producing polyethylene.

[0158]

[0159] As described above, the hybrid supported metallocene catalyst according to the present invention can exhibit excellent catalytic activity by including first and second transition metal compounds having specific structures. Accordingly, the hybrid supported metallocene catalyst can be suitably used for the polymerization of ethylene monomers and olefin monomers.

[0160]

[0161] Accordingly, the present invention provides a method for producing polyethylene, comprising a step of polymerizing an ethylene monomer and an alpha-olefin monomer while introducing hydrogen in the presence of the hybrid supported metallocene catalyst.

[0162]

[0163] Specific examples of the above alpha-olefin monomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc., and two or more of these monomers may be mixed and copolymerized. More specifically, the alpha-olefin monomer may be 1-butene, 1-hexene, or 1-octene.

[0164] The amount of the alpha-olefin monomer added may be determined depending on the properties of the polyethylene to be manufactured. For example, considering the properties of the polyethylene to be implemented in the present invention and the effects of high drop impact strength and improved processability, the alpha-olefin monomer may be added in an amount of 5 to 20 wt% based on the total weight of the monomers including the ethylene monomer and the alpha-olefin monomer. More specifically, the alpha-olefin monomer may be added in an amount of 6 wt% or more, or 7 wt% or more, or 9 wt% or more, and 19 wt% or less, or 18 wt% or less, or 17 wt% or less based on the total weight of the monomers including the ethylene monomer and the alpha-olefin monomer.

[0165]

[0166] The above polymerization reaction is carried out under the condition of hydrogen input.

[0167] Specifically, hydrogen may be introduced in an amount of 15 to 45 ppm, more specifically 15 ppm or more, or 20 ppm or more, or 25 ppm or more, and 45 ppm or less, or 40 ppm or less, or 35 ppm or less, based on the total weight of monomers including ethylene monomers and alpha-olefin monomers. When introduced in the above range, it is easier to implement the physical properties of the polyethylene described above. When the polymerization reaction is performed under conditions without introducing hydrogen, the melt index (MI) of the polyethylene produced may be significantly lowered.

[0168]

[0169] The above polymerization reaction can be carried out as a slurry polymerization reaction.

[0170] Accordingly, it can be performed using a single continuous slurry polymerization reactor or a loop slurry reactor.

[0171] In addition, the hybrid supported catalyst can be dissolved or diluted and injected into an aliphatic hydrocarbon solvent having 4 to 12 carbon atoms, such as isobutane, pentane, hexane, heptane, nonane, decane, and their isomers, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene, etc. It is preferable to use the solvent used here after removing a small amount of water or air, etc. that act as catalyst poisons, by treating it with a small amount of alkyl aluminum, and it is also possible to use it by further using a cocatalyst.

[0172]

[0173] In addition, the polymerization reaction may be carried out at a temperature of 40°C or higher, or 60°C or higher, or 80°C or higher, and 110°C or lower, or 100°C or lower, or 90°C or lower. In addition, when the pressure conditions are further controlled during the polymerization reaction, the polymerization reaction may be carried out under a pressure of 5 bar or higher, or 10 bar or higher, or 20 bar or higher, and 50 bar or lower, or 45 bar or lower, or 40 bar or lower. When polymerization is carried out under such temperatures and pressures, the desired physical properties of polyethylene can be more easily realized.

[0174]

[0175] Polyethylene manufactured using the above-described manufacturing method exhibits excellent processability, as represented by processing pressure, and impact strength, as measured by drop weight. In a preferred embodiment, the polyethylene may be an ethylene / 1-hexene copolymer.

[0176]

[0177] Specifically, the polyethylene produced using the hybrid supported metallocene catalyst satisfies the following conditions (i) to (iii):

[0178] (i) Density measured according to ASTM D1505: 0.91 to 0.93 g / cm 3

[0179] (ii) Drop impact strength of 700 gf or more as measured according to ASTM D1709 [Method A].

[0180]

[0181] Additionally, the polyethylene has a density of 0.91 g / cm as measured according to ASTM D1505. 3 or 0.915 g / cm 3 and 0.93 g / cm 3 or less, or 0.925 g / cm 3 or less, or 0.923 g / cm 3Below. In general, as the density of polyethylene increases, the drop impact strength decreases. According to the research of the present inventors, it is 0.93 g / cm 3 In the case of high-density polyethylene, it exhibits a low drop impact strength of 300 gf or less. Meanwhile, the polyethylene according to the present invention exhibits excellent drop impact strength as it has a density within the above-mentioned range.

[0182]

[0183] In addition, the polyethylene is manufactured using a film forming machine into a polyethylene film (having a blown-up ratio (BUR) of 2 to 3, more specifically 2.5, and a film thickness of 45 to 55 μm, more specifically 50 μm), and the drop impact strength measured according to ASTM D1709 [Method A] is 800 gf or more, more specifically 800 to 2000 gf, or 820 to 1500 gf, or 840 to 1300 gf.

[0184]

[0185] In addition, the polyethylene has a processing pressure (processing load, (bar)) of 250 bar or less, more specifically 150 to 250 bar, or 155 to 230 bar, or 160 to 215 bar, measured at a speed of 40 rpm and cylinder-1 / -2 / -3 / die=180 / 185 / 185 / 190 using a Haake extruder.

[0186]

[0187] Additionally, the polyethylene may have a melt strength of 50 mN or more, more specifically, 50 to 150 mN, or 55 to 130 mN, or 60 to 125 mN, or 65 to 125 mN. A method for measuring the melt strength may be specified in the examples described below.

[0188]

[0189] As described above, the hybrid supported metallocene catalyst according to the present invention exhibits high activity in olefin polymerization and can produce polyethylene having high impact strength characteristics along with excellent processability.

[0190]

[0191] Accordingly, polyethylene manufactured using the hybrid supported metallocene catalyst has excellent processability, mechanical properties, and transparency, and can be usefully used for purposes such as films.

[0192]

[0193] Hereinafter, preferred embodiments are presented to aid understanding of the invention. However, the following examples are intended only to illustrate the invention and are not intended to limit the invention to these embodiments.

[0194]

[0195] <Preparation of Transition Metal Compounds>

[0196] Synthesis Example 1-1

[0197] (Cat 1-1)

[0198] Preparation of ligands

[0199] Tetramethylcyclopentadiene (TMCP, 1 equiv) was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. t-BuOHexSiMeCl2 (1.00 eq) was added to the resulting reaction mixture at -10°C, followed by stirring at room temperature overnight. The solvent was completely vacuum-dried, and tBuNH2 (10 eq) was added and stirred at room temperature overnight. Afterwards, the mixture was worked up with water and dried to obtain the ligand.

[0200]

[0201] Preparation of transition metal compounds

[0202] The above-mentioned ligand was dissolved in toluene (0.3 M), n-BuLi (2.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, TiCl4(THF)2 (titanium tetrachloride tetrahydrofuran adduct, 1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using toluene (1.0 M).

[0203] Upon completion of the reaction, the solvent was vacuum-dried, DCM was re-introduced, LiCl was removed through a filter, and the filtrate was vacuum-dried to obtain a liquid transition metal compound.

[0204] 1 H NMR (500 MHz, CDCl3) δ 3.34 (t, 2H), 2.24 (d, J = 1.7 Hz, 6H), 2.13 (d, J = 3.2 Hz, 6H), 1.57 - 1.45 (m, 6H), 1.42 (s, 9H), 1.32 - 1.22 (m, 4H), 1.18 (s, 9H), 0.67 (s, 3H).

[0205]

[0206] Synthesis Example 1-2

[0207] (Cat 1-2)

[0208] The transition metal compound prepared in Synthesis Example 1-1 was dissolved in toluene (0.3 M), and MeLi (2.05 eq) was added at -25°C, followed by stirring at room temperature for 3 hours.

[0209] Upon completion of the reaction, the solvent was vacuum-dried, DCM was re-introduced, LiCl was removed through a filter, and the filtrate was vacuum-dried to obtain a liquid transition metal compound.

[0210] 1H NMR (500 MHz, CDCl3) δ 3.34 (t, 2H), 2.25 (s,3H), 2.23 (s, 3H), 2.14 (s, 6H), 1.58 - 1.43 (m, 6H), 1.40 (s, 9H), 1.30 - 1.22 (m, 4H), 1.21 (s, 9H), 0.68 (s, 3H), -1.31 (s, 3H), -1.38 (s, 3H).

[0211]

[0212] Synthesis Example 1-3

[0213] (Cat 1-3)

[0214] A transition metal compound having the above structure was prepared in the same manner as in Synthesis Example 1-1, except that ZrCl4(THF)2(Zirconium tetrachloride tetrahydrofuran adduct) was used instead of TiCl4(THF)2(Titanium tetrachloride tetrahydrofuran adduct) when preparing the transition metal compound.

[0215] 1 H NMR (500 MHz, CDCl3) δ 3.42 (t, 2H), 2.29 (s, 3H), 2.28 (s, 3H), 2.22 (s, 6H), 1.64 - 1.36 (m, 6H), 1.49 (s, 9H), 1.32 - 1.24 (m, 4H), 1.27 (s, 9H), 0.69 (s, 3H).

[0216]

[0217] Synthesis Example 2-1

[0218]

[0219] Preparation of transition metal compounds

[0220] Indene was dissolved in Ether (0.3 M), n-BuLi (1.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, PMCpZrCl3 (Pentamethylcyclopentadienylzirconium trichloride) (1 eq) was prepared in another flask, added to the Indene-Li flask using a cannula at -25°C, and washed and added using Ether (1.0 M).

[0221] Upon completion of the reaction, the solvent was vacuum-dried, DCM was reintroduced, LiCl was removed through a filter, the filtrate was vacuum-dried, and slurry was formed using hexane. The resulting solid was then filtered and vacuum-dried to obtain a solid metallocene compound intermediate.

[0222]

[0223] In a glove box, the above metallocene compound intermediate was placed in a mini parr, and 5 mol% of Pd / C (10 wt%) was added. A magnetic bar was inserted here and moved outside the glove box using a closing system. DCM (0.5 M) was added to this parr, and H2 gas (10 barg) was added. After repeating the vent-charge cycle three times, the mixture was placed in a 40°C oil bath and stirred. When the pressure of the parr decreased below 5 barg, the previous charging process was repeated, and the reaction was continued until there was no more consumption of H2 gas. When the reaction was complete, the remaining H2 gas was vented and replaced with Ar gas. After cooling to room temperature, the mixture was filtered using a cannula, and the filtrate was vacuum-dried. The dried filtrate was slurried using hexane, and this was filtered to obtain a solid transition metal compound.

[0224] 1H NMR (500 MHz, CDCl3) δ 5.91 (t, J = 2.8 Hz, 1H), 5.46 (d, J = 2.8 Hz, 2H), 2.88 (dt, J = 16.2, 6.3 Hz, 2H), 2.51 (dt, J = 16.2, 6.0 Hz, 2H), 2.04 (s, 15H), 1.92 - 1.78 (m, 2H), 1.62 (dd, J = 12.5, 6.2 Hz, 2H).

[0225]

[0226] Synthesis Example 2-2

[0227] (Cat 2-2)

[0228] Preparation of ligands

[0229] Indene (1 eq) was dissolved in THF (0.3 M), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, and the mixture was stirred at room temperature for 3 hours. After that, CH3-I (1.05 eq) was added at -10°C, and the mixture was stirred overnight at room temperature, worked up with water, and dried to obtain 3-methyl-Indene.

[0230]

[0231] Preparation of transition metal compounds

[0232] The above-mentioned ligand was dissolved in Ether (0.3 M), n-BuLi (1.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, PMCpZrCl3 (Pentamethylcyclopentadienylzirconium trichloride) (1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using Ether (1.0 M).

[0233] Upon completion of the reaction, the solvent was vacuum-dried, DCM was reintroduced, LiCl was removed through a filter, the filtrate was vacuum-dried, and slurry was formed using hexane. The resulting solid was then filtered and vacuum-dried to obtain a solid metallocene compound intermediate.

[0234]

[0235] In a glove box, the above metallocene compound intermediate was placed in a mini parr, and 5 mol% of Pd / C (10 wt%) was added. A magnetic bar was inserted here and moved outside the glove box using a closing system. DCM (0.5 M) was added to this parr, and H2 gas (10 barg) was added. After repeating the vent-charge cycle three times, the mixture was placed in a 40°C oil bath and stirred. When the pressure of the parr decreased below 5 barg, the previous charging process was repeated, and the reaction was continued until there was no more consumption of H2 gas. When the reaction was complete, the remaining H2 gas was vented and replaced with Ar gas. After cooling to room temperature, the mixture was filtered using a cannula, and the filtrate was vacuum-dried. The dried filtrate was slurried using hexane, and this was filtered to obtain a solid transition metal compound.

[0236] 1 H NMR (500 MHz, CDCl3) δ 5.62 (s, 1H), 5.14 (d, J = 2.1 Hz, 1H), 2.85 - 2.75 (m, 2H), 2.48 - 2.33 (m, 2H), 2.02 (s, 15H), 1.96 - 1.79 (m, 2H), 1.89 (s, 3H), 1.65 - 1.53 (m, 2H).

[0237]

[0238] Synthesis Example 2-3

[0239] (Cat 2-3)

[0240] Indene (1 eq) was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, and the mixture was stirred at room temperature for 3 hours. Then, CH3-I (1.05 eq) was added at -10°C, and the mixture was stirred overnight at room temperature, worked up with water, and dried to obtain 3-MethylIndene. 3-MethylIndene (1 eq) thus synthesized was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, and the mixture was stirred at room temperature for 3 hours. Then, CH3-I (1.05 eq) was added at -10°C, and the mixture was stirred overnight at room temperature, worked up with water, and dried to obtain 1,3-dimethyl-Indene.

[0241]

[0242] Preparation of transition metal compounds

[0243] The above-mentioned ligand was dissolved in Ether (0.3 M), n-BuLi (1.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, PMCpZrCl3 (Pentamethylcyclopentadienylzirconium trichloride) (1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using Ether (1.0 M).

[0244] Upon completion of the reaction, the solvent was vacuum-dried, DCM was reintroduced, LiCl was removed through a filter, the filtrate was vacuum-dried, and slurry was formed using hexane. The resulting solid was then filtered and vacuum-dried to obtain a solid metallocene compound intermediate.

[0245]

[0246] In a glove box, the above metallocene compound intermediate was placed in a mini parr, and 5 mol% of Pd / C (10 wt%) was added. A magnetic bar was inserted here and moved outside the glove box using a closing system. DCM (0.5 M) was added to this parr, and H2 gas (10 barg) was added. After repeating the vent-charge cycle three times, the mixture was placed in a 40°C oil bath and stirred. When the pressure of the parr decreased below 5 barg, the previous charging process was repeated, and the reaction was continued until there was no more consumption of H2 gas. When the reaction was complete, the remaining H2 gas was vented and replaced with Ar gas. After cooling to room temperature, the mixture was filtered using a cannula, and the filtrate was vacuum-dried. The dried filtrate was slurried using hexane, and this was filtered to obtain a solid transition metal compound.

[0247] 1 H NMR (500 MHz, CDCl3) δ 5.60 (s, 1H), 2.90 (dt, J = 16.4, 6.3 Hz, 2H), 2.32 (dt, J = 16.3, 6.0 Hz, 2H), 2.04 (s, 15H), 1.79 - 1.66 (m, 2H), 1.67 (s, 6H), 1.64 - 1.54 (m, 2H).

[0248]

[0249] Synthesis Example 2-4

[0250] (Cat 2-4)

[0251] A transition metal compound having the above structure was prepared in the same manner as in Synthesis Example 2-2, except that CH3-CH2-I was used instead of CH3-I when preparing the ligand.

[0252] 1H NMR (500 MHz, CDCl3) δ 5.60 (d, J = 2.7 Hz, 2H), 5.20 (d, J = 2.7 Hz, 2H), 2.83 - 2.71 (m, 2H), 2.49 - 2.36 (m, 3H), 2.21 (dd, J = 15.1, 7.6 Hz, 1H), 2.01 (s, 15H), 1.98 - 1.80 (m, 2H), 1.66 - 1.51 (m, 2H), 1.03 (t, J = 7.6 Hz, 3H).

[0253]

[0254] Synthesis Example 2-5

[0255] (Cat 2-5)

[0256] A transition metal compound having the above structure was prepared in the same manner as in Synthesis Example 2-2, except that tert-butoxyhexyl-I was used instead of CH3-I when preparing the ligand.

[0257] 1 H NMR (500 MHz, CDCl3) δ 5.61 (d, J = 2.6 Hz, 1H), 5.21 (d, J = 2.6 Hz, 1H), 3.32 (t, J = 6.8 Hz, 2H), 2.99 - 2.86 (m, 2H), 2.39 - 2.27 (m, 2H), 2.17 - 2.04 (m, 2H), 2.02 (s, 15H), 1.98 - 1.87 (m, 1H), 1.83 - 1.55 (m, 4H), 1.55 - 1.35 (m, 4H), 1.35 - 1.21 (m, 3H), 1.19 (s, 9H).

[0258]

[0259] Synthesis Example 2-6

[0260] (Cat 2-6)

[0261] Indene (1 eq) was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterwards, CH3-I (1.05 eq) was added at -10°C, and stirred overnight at room temperature, worked up with water, and dried to obtain 3-MethylIndene. 3-MethylIndene (1 eq) thus synthesized was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterwards, tert-butoxyhexyl-I (1.05 eq) was added at -10°C, stirred overnight at room temperature, worked up using water, and dried to obtain 1-methyl-3-(tert-butoxyhexyl)-Indene.

[0262]

[0263] Preparation of transition metal compounds

[0264] The above-mentioned ligand was dissolved in Ether (0.3 M), n-BuLi (1.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, PMCpZrCl3 (Pentamethylcyclopentadienylzirconium trichloride) (1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using Ether (1.0 M).

[0265] Upon completion of the reaction, the solvent was vacuum-dried, DCM was reintroduced, LiCl was removed through a filter, the filtrate was vacuum-dried, and slurry was formed using hexane. The resulting solid was then filtered and vacuum-dried to obtain a solid metallocene compound intermediate.

[0266]

[0267] In a glove box, the above metallocene compound intermediate was placed in a mini parr, and 5 mol% of Pd / C (10 wt%) was added. A magnetic bar was inserted here and moved outside the glove box using a closing system. DCM (0.5 M) was added to this parr, and H2 gas (10 barg) was added. After repeating the vent-charge cycle three times, the mixture was placed in a 40°C oil bath and stirred. When the pressure of the parr decreased below 5 barg, the previous charging process was repeated, and the reaction was continued until there was no more consumption of H2 gas. When the reaction was complete, the remaining H2 gas was vented and replaced with Ar gas. After cooling to room temperature, the mixture was filtered using a cannula, and the filtrate was vacuum-dried. The dried filtrate was slurried using hexane, and this was filtered to obtain a solid transition metal compound.

[0268] 1 H NMR (500 MHz, CDCl3) δ 5.57 (s, 1H), 3.31 (t, J = 6.7 Hz, 2H), 2.95 - 2.85 (m, 2H), 2.37 - 2.28 (m, 2H), 2.18 - 2.03 (m, 2H), 2.02 (s, 15H), 1.96 - 1.88 (m, 1H), 1.82 - 1.77 (m, 1H), 1.75 (s, 3H), 1.71 - 1.55 (m, 3H), 1.53 - 1.36 (m, 4H), 1.36 - 1.20 (m, 3H), 1.18 (s, 9H).

[0269]

[0270] Synthesis Example 3-1

[0271] (Cat 3-1)

[0272] A transition metal compound having the above structure was prepared by the following method according to Manufacturing Example 2 of Korean Patent Publication No. 10-2018-0161297.

[0273]

[0274] Synthesis Example 3-2

[0275] (Cat 3-2)

[0276] We purchased and used product 447862 (Cas. No. 73364-10-0) from Sigma Aldrich.

[0277]

[0278] Synthesis Example 3-3

[0279] (Cat 3-3)

[0280] A transition metal compound having the above structure was prepared using the same method as the manufacturing example of Korean Patent Publication No. 10-2020-0064245.

[0281]

[0282] Synthesis Example 3-4

[0283] (Cat 3-4)

[0284] A transition metal compound having the above structure was prepared using the same method as Synthesis Example 1 of Korean Patent Publication No. 10-2020-101750.

[0285]

[0286] Synthesis Example 3-5

[0287] (Cat 3-5)

[0288] A transition metal compound having the above structure was prepared using the same method as Manufacturing Example 1 of Korean Patent Publication No. 10-2021-0032820.

[0289]

[0290] Synthesis Example 3-6

[0291] (Cat 3-6)

[0292] A transition metal compound having the above structure was prepared using the same method as in Manufacturing Example 4 of Korean Patent Publication No. 10-2020-0090041.

[0293]

[0294] Synthesis Example 3-7

[0295] (Cat 3-7)

[0296] A transition metal compound having the above structure was prepared using the same method as Manufacturing Example 2-3 of Korean Patent Publication No. 10-2016-0029718.

[0297]

[0298] Synthesis Example 3-8

[0299] (Cat 3-8)

[0300] A transition metal compound having the above structure was prepared according to the method disclosed in J. AM. CHEM. SOC. VOL. 126, No. 46, 2004 pp. 15231-15244.

[0301]

[0302] Synthesis Example 3-9

[0303] (Cat 3-9)

[0304] A transition metal compound having the above structure was prepared using the same method as Example 1 of Korean Patent Publication No. 2011-130839.

[0305]

[0306] Synthesis Example 3-10

[0307] (Cat 3-10)

[0308] A transition metal compound having the above structure was prepared using the same method as in Manufacturing Example 1 of Korean Patent Publication No. 10-2015-0045368.

[0309]

[0310] Synthesis Example 3-11

[0311] (Cat 3-11)

[0312] A transition metal compound having the above structure was prepared using the same method as Synthesis Example 1 of Korean Patent Publication No. 10-2021-0038379.

[0313]

[0314] Synthesis Example 3-12

[0315] (Cat 3-12)

[0316] A transition metal compound having the above structure was prepared using the same method as Manufacturing Example 1 of Korean Patent Publication No. 10-2021-0032820.

[0317]

[0318] Synthesis Example 3-13

[0319] (Cat 3-13)

[0320] A transition metal compound having the above structure was prepared using the same method as Manufacturing Example 2-4 of Korean Patent Publication No. 10-2016-0029718.

[0321]

[0322] Synthesis Example 3-14

[0323] (Cat 3-14)

[0324] I purchased and used product 532126 (Cas. No. 100163-29-9) from Sigma Aldrich.

[0325]

[0326] Synthesis Example 3-15

[0327] (Cat 3-15)

[0328] A transition metal compound having the above structure was prepared using the same method as Example 1 of Korean Patent Publication No. 10-2011-0130839.

[0329]

[0330] Synthesis Example 3-16

[0331] (Cat 3-16)

[0332] A transition metal compound having the above structure was prepared using the same method as in Manufacturing Example 2 of Korean Patent Publication No. 10-2015-0045368.

[0333]

[0334] Synthesis Example 3-17

[0335] (Cat 3-17)

[0336] A transition metal compound having the above structure was prepared using the same method as Synthesis Example 1 of Korean Patent Publication No. 10-2022-0082511.

[0337]

[0338] Synthesis Example 3-18

[0339] (Cat 3-18)

[0340] A transition metal compound having the above structure was prepared using the same method as Manufacturing Example 2-8 of Korean Patent Publication No. 10-2016-0029718.

[0341]

[0342] Synthesis Example 3-19

[0343] (Cat 3-19)

[0344] Preparation of ligands

[0345] Indene (1 eq) was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. Afterwards, (tert-butoxyhexyl)-I (1.05 eq) was added at -10°C, stirred overnight at room temperature, worked up with water, and dried to obtain 3-(tert-butoxyhexyl)-Indene.

[0346]

[0347] Preparation of transition metal compounds

[0348] The above-mentioned ligand was dissolved in Ether (0.3 M), n-BuLi (1.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, PMCpZrCl3 (Pentamethylcyclopentadienylzirconium trichloride) (1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using Ether (1.0 M).

[0349] Upon completion of the reaction, the solvent was vacuum-dried, DCM was reintroduced, LiCl was removed through a filter, the filtrate was vacuum-dried, and slurry was formed using hexane. The resulting solid was then filtered and vacuum-dried to obtain a transition metal compound having the above structure.

[0350] 1 H NMR (500 MHz, CDCl3) δ 7.63 (d, J = 8.3 Hz, 1H), 7.32 (d, J = 8.4 Hz, 1H), 7.28 - 7.20 (m, 4H), 5.93 (dd, J = 11.0, 2.6 Hz, 2H), 3.30 (t, J = 6.7 Hz, 2H), 3.09 - 2.97 (m, 1H), 2.59 - 2.45 (m, 1H), 1.93 (s, 3H), 1.92 (s, 3H), 1.88 (s, 3H), 1.85 (s, 3H), 1.66 - 1.23 (m, 8H), 1.17 (s, 9H).

[0351]

[0352] Synthesis Example 3-20

[0353] (Cat 3-20)

[0354] 2-Bromofluorene (1 eq) was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 10 minutes. Then, (tert-butoxyhexyl)-I (1.05 eq) was added at -10°C, stirred overnight at room temperature, worked up with water, and dried to obtain 2-(tert-butoxyhexyl)-fluorene.

[0355]

[0356] Preparation of transition metal compounds

[0357] The above-mentioned ligand was dissolved in Ether (0.3 M), n-BuLi (1.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, PMCpZrCl3 (Pentamethylcyclopentadienylzirconium trichloride) (1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using Ether (1.0 M).

[0358] Upon completion of the reaction, the solvent was vacuum-dried, DCM was reintroduced, LiCl was removed through a filter, the filtrate was vacuum-dried, and slurry was formed using hexane. The resulting solid was then filtered and vacuum-dried to obtain a transition metal compound having the above structure.

[0359] 1H NMR (500 MHz, CDCl3) δ 8.16 (d, J = 8.4 Hz, 1H), 8.02 (d, J = 7.4 Hz, 1H), 7.77 (d, J = 7.4 Hz, 1H), 7.69 (d, J = 8.6 Hz, 1H), 7.48 (t, J = 7.5 Hz, 1H), 7.41 (s, 1H), 7.36 (t, J = 7.5 Hz, 1H). 6.30 (s, 1H), 5.62 (s, 1H), 2.13 - 2.02 (m, 2H), 1.93 (s, 3H), 1.92 (s, 3H), 1.88 (s, 3H), 1.85 (s, 3H), 1.55 - 1.12 (m, 8H), 0.81 (t, J = 7.0 Hz, 3H)

[0360]

[0361] Synthesis Example 3-21

[0362] (Cat 3-21)

[0363] A transition metal compound having the above structure was prepared using the synthetic method of Comparative Synthesis Example [Chemical Formula 4] of Korean Patent Publication No. 10-2015-0052803.

[0364]

[0365] Synthesis Example 3-22

[0366] (Cat 3-22)

[0367] A transition metal compound of the above structure was prepared by the method described in Organometallics (2006), 25(5), 1217-1229.

[0368]

[0369] <Preparation of Hybrid Supported Metallocene Catalysts>

[0370] Manufacturing Example 1

[0371] 2.0 kg of toluene and 1000 g of silica (SP2410, Grace Davision) were charged into a 20L SUS high-pressure reactor, and the reactor temperature was raised to 40°C while stirring. 5.4 kg of methylaluminoxane (10 wt% in toluene, Albemarle) was charged into the reactor, the temperature was raised to 70°C, and the reactor was stirred at about 200 rpm for about 12 hours. Thereafter, the temperature of the reactor was lowered to 40°C, and stirring was stopped. The reaction product was allowed to stand for about 10 minutes and then decantated. 2.0 kg of toluene was then charged into the reaction product, stirred for about 10 minutes, stopped, and the reactor was allowed to stand for about 30 minutes before decantation.

[0372]

[0373] 2.0 kg of toluene was charged into the reactor, and then the first transition metal compound, compound Cat 1-1 (50.0 mmol) prepared in Preparation Example 1, the second transition metal compound, compound Cat 2-1 (10.0 mmol) prepared in Preparation Example 2, and 1000 mL of toluene were charged. The temperature of the reactor was raised to 85°C, and stirring was performed for about 90 minutes.

[0374]

[0375] Afterwards, the temperature of the reactor was lowered to room temperature, stirring was stopped, the reaction product was allowed to stand for about 30 minutes, and the reaction product was decantated. Next, 3 kg of hexane was added to the reactor, and the hexane slurry solution was transferred to a 20 L filter dryer, the solution was filtered, and dried under reduced pressure at 50 °C for about 4 hours to obtain 1.5 kg of a hybrid supported metallocene catalyst.

[0376]

[0377] Manufacturing Examples 2 to 8 and Comparative Manufacturing Examples 1 to 22

[0378] As described in Table 1 below, a hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the types of the first and second transition metal compounds were changed.

[0379]

[0380] Catalyst 1 Transition metal compound 2 Transition metal compound Preparation example 1 Cat 1-1 Cat 2-1 Preparation example 2 Cat 2-2 Preparation example 3 Cat 2-3 Preparation example 4 Cat 2-4 Preparation example 5 Cat 2-5 Preparation example 6 Cat 2-6 Preparation example 7 Cat 1-2 Cat 2-1 Preparation example 8 Cat 1-3 Cat 2-1 Comparative Preparation example 1 Cat 1-1 Cat 3-1 Comparative Preparation example 2 Cat 3-2 Comparative Preparation example 3 Cat 3-3 Comparative Preparation example 4 Cat 3-4 Comparative Preparation example 5 Cat 3-5 Comparative Preparation example 6 Cat 3-6 Comparative Preparation example 7 Cat 3-7 Comparative Preparation example 8 Cat 3-8 Comparative Preparation example 9 Cat 3-9 Comparative Manufacturing Example 10 Cat 3-10 Comparative Manufacturing Example 11 Cat 3-11 Comparative Manufacturing Example 12 Cat 3-12 Comparative Manufacturing Example 13 Cat 3-13 Comparative Manufacturing Example 14 Cat 3-14 Comparative Manufacturing Example 15 Cat 3-15 Comparative Manufacturing Example 16 Cat 3-16 Comparative Manufacturing Example 17 Cat 3-17 Comparative Manufacturing Example 18 Cat 3-18 Comparative Manufacturing Example 19 Cat 3-19 Comparative Manufacturing Example 20 Cat 3-20 Comparative Manufacturing Example 21 Cat 3-21 Cat 2-1 Comparative Manufacturing Example 22 Cat 3-22 Cat 2-1

[0381] <Manufacturing of polyethylene>

[0382] Examples 1 to 8 and Comparative Examples 1 to 22

[0383] A 140 L continuous polymerizer capable of performing an isobutene slurry loop process with a polymerization reactor and operating at a reaction velocity of approximately 7 m / s was prepared. The reactants required for polyethylene polymerization were continuously fed into the reactor as described in Tables 2 and 3. The catalysts used in each polymerization reaction were those prepared in the Manufacturing Examples or Comparative Manufacturing Examples described in Table 1, and were mixed with the isobutene slurry and fed. The polymerization reaction was performed at a pressure of approximately 40 bar and a temperature of approximately 85°C.

[0384]

[0385] The main conditions of the above polymerization reaction are shown in Table 2.

[0386]

[0387] Catalytic ethylene input (kg / hr)1-Hexene input 1 (wt%) hydrogen input 2(ppm)Activity (kgPE / kgSiO2·hr)Example 1 Manufacturing Example 125.015345.8Example 2 Manufacturing Example 225.113336.0Example 3 Manufacturing Example 323.814326.7Example 4 Manufacturing Example 424.415274.5Example 5 Manufacturing Example 525.516386.3Example 6 Manufacturing Example 626.011285.7Example 7 Manufacturing Example 725.516355.9Example 8 Manufacturing Example 825.413336.1Comparative Example 1 Comparative Manufacturing Example 124.812345.5Comparative Example 2 Comparative Manufacturing Example 226.416335.4Comparative Example 3 Comparative Manufacturing Example 324.013294.9Comparative Example 4Comparative Manufacturing Example 424.114284.5Comparative Example 5Comparative Manufacturing Example 523.89365.6Comparative Example 6Comparative Manufacturing Example 626.211385.2Comparative Example 7Comparative Manufacturing Example 724.815345.3Comparative Example 8Comparative Manufacturing Example 823.715275.1Comparative Example 9Comparative Manufacturing Example 926.816275.4Comparative Example 10Comparative Manufacturing Example 1024.815265.9Comparative Example 11Comparative Manufacturing Example 1126.413326.5Comparative Example 12Comparative Manufacturing Example 1227.312254.9Comparative Example 13Comparative Manufacturing Example 1325.417345.8Comparative Example 14Comparative Manufacturing Example 1425.815385.4Comparative Example 15Comparative Manufacturing Example 1523.118345.6Comparative Example 16Comparative Manufacturing Example 1622.214244.2Comparative Example 17Comparative Manufacturing Example 1723.515264.3Comparative Example 18Comparative Manufacturing Example 1826.413275.8Comparative Example 19Comparative Manufacturing Example 1921.813343.3Comparative Example 20Comparative Manufacturing Example 2024.714234.7Comparative Example 21Comparative Manufacturing Example 2122.810244.2Comparative Example 22Comparative Manufacturing Example 2223.69284.8

[0388] In Table 2 above, the activity (Activity, kgPE / kgSiO2·hr) was calculated as the ratio of the weight of polymer (kg PE) produced per weight of supported catalyst (kg) used per unit time (hr).

[0389] In addition, the 1-Hexene input amount (wt%) is calculated as a percentage of the 1-Hexene input amount based on the total weight of monomers including ethylene and 1-hexene, and the hydrogen input amount (ppm) is calculated as a percentage of the total weight of monomers including ethylene and 1-hexene.

[0390]

[0391] Experimental example

[0392] The physical properties of the polyethylene manufactured in the examples and comparative examples were measured as follows, and the results are shown in Table 3 below.

[0393] (1) Density (g / cm) 3 )

[0394] Measured according to ASTM D1505 standard

[0395]

[0396] (2) Drop impact strength (gf)

[0397] The drop impact strength of a 50 ㎛ thick film manufactured by the following method was measured according to ASTM D1709 [Method A], and the average value was taken from measurements performed more than 20 times per film sample.

[0398]

[0399] Film Manufacturing

[0400] 1500 ppm of antioxidant (Songnox 1076 (Songwon): Songnox 1680 (Songwon) = 1:2 weight ratio) and 300 ppm of 3M Dynamar Polymer Processing Additive FX5929 based on the total weight of polyethylene manufactured in the above examples or comparative examples were added and mixed, and extruded at an extrusion temperature of 190°C and an extrusion amount of 35 kg / hr using a twin screw extruder (TEK 30 MHS, manufactured by SMPLATECH CO., diameter 32 pi, L / D = 40), to manufacture a composition for forming a pellet-shaped film weighing about 18 kg.

[0401]

[0402] The film-forming composition manufactured above was extruded under the following film extrusion conditions to manufacture a film.

[0403] <Film extrusion conditions>

[0404] Single Screw Extruder (Eugene Engineering Single Screw Extruder, Blown Film M / C, 50 pi, L / D=32)

[0405] Melting temperature (or extrusion temperature): 170 ℃

[0406] Die Gap: 2.0 mm

[0407] Die diameter: 120 mm

[0408] Blown-Up Ratio: 2.5

[0409] Maintain Frost Line Height at 250~260 mm

[0410] Sample extrusion rate: 300~500 g / min

[0411] Film thickness: 50 ㎛

[0412]

[0413] (3) Machining pressure (machining load, bar)

[0414] The processing pressure (bar) was measured using a Haake extruder at cylinder-1 / -2 / -3 / die=180 / 185 / 185 / 190 and a speed of 40 rpm.

[0415]

[0416] (4) Melting strength (mN)

[0417] The melt strength of olefin polymers was measured using a Goettfert Rheotens 71.97 equipped with a Model 3211 Instron capillary rheometer. The olefin copolymer melt was discharged through a capillary die (flat die, 180° angle) with a length to diameter (L / D) ratio of 15. After equilibrating the sample at 190°C for 10 min, the piston was moved at a speed of 1 in / min (2.54 cm / min). The standard test temperature was 190°C. The sample was moved at 1.2 mm / s 2 The die was pulled uniaxially by a set of accelerating nips located 100 mm below the die with an acceleration of . The tension was recorded as a function of the pulling speed of the nip rolls. The melt strength was defined as the average value of the force (mN) when the pulling force was 100 mm / s and 150 mm / s. The following conditions were used for the melt strength measurements.

[0418] Plunger speed: 0.423 mm / s

[0419] Capillary die L / D: 15

[0420] Shear rate: 72 / s

[0421] Wheel initial speed: 18 mm / s

[0422] Wheel acceleration: 1.2 mm / s2

[0423] Barrel diameter: 9.52 mm

[0424]

[0425] Density (g / cm3) Drop impact strength (gf) Pressure (bar) Melt strength (mN) Example 10.9201054163114 Example 20.92191216898 Example 30.9201218178123 Example 40.92298917187 Example 50.9211159189106 Example 60.91684221468 Example 70.918100416896 Example 80.92098916988 Comparative Example 10.92165819888 Comparative Example 20.91964817679 Comparative Example 30.921542218131 Comparative Example 40.919484206124Comparative Example 50.92364519794Comparative Example 60.920746209102Comparative Example 70.921638198121Comparative Example 80.918687245111Comparative Example 90.916746241108Comparative Example 100.92175123796Comparative Example 110.917754224108Comparative Example 120.91754621499Comparative Example 130.91669019888Comparative Example 140.914678205122Comparative Example 150.920612201119Comparative Example 160.920598199108Comparative Example 170.919587203118Comparative Example 180.919761204108Comparative Example 190.918348200111Comparative Example 200.921744178122Comparative Example 210.92064018876Comparative Example 220.92354023169

[0426] As can be confirmed in Table 3 above, the polyethylene of the example manufactured using a hybrid supported metallocene catalyst including a first transition metal compound represented by Chemical Formula 1 and a second transition metal compound represented by Chemical Formula 2 according to the present invention was confirmed to have a high density and high drop impact strength due to a combination of high molecular weight high polymerization characteristics expressed from the first transition metal compound and low molecular weight high polymerization characteristics expressed from the second transition metal compound, while having low processing pressure and excellent processability and impact strength.

[0427]

[0428] Meanwhile, it was confirmed that the polyethylene of the comparative example manufactured using the hybrid supported metallocene catalyst including the transition metal compound of the comparative manufacturing example had a wide molecular weight distribution and included long branch chains (LCB), and thus the processing pressure and melt strength were at levels similar to those of the polyethylene of the example, but the impact strength was low.

Claims

1. A first transition metal compound represented by the following chemical formula 1; A second transition metal compound represented by the following chemical formula 2; co-catalyst; and containing a carrier, Hybrid supported metallocene catalysts: [Chemical Formula 1] In the above chemical formula 1, M1 is a group 4 transition metal, X 11 and X 12 are each independently, C 1-20 Alkyl, or halogen, A1 is carbon, silicon, or germanium, Q 11 and Q 12 are each independently hydrogen, halogen, C 1-20 Alkyl, or C 2-20 It is an alkoxyalkyl, R 11 Inland R 15 are each independently hydrogen, or C 1-20 It is alkyl, [Chemical Formula 2] In the above chemical formula 2, M2 is a group 4 transition metal, X 21 and X 22 are each independently, C 1-20 Alkyl or halogen, R 21 Inland R 25 are each independently, C 1-20 It is alkyl, R 26 is hydrogen, or C 1-20 It is alkyl, R 27 Silver hydrogen, C 1-20 Alkyl, C 2-20 Alkoxy, or C 2-20 It is an alkoxyalkyl.

2. In paragraph 1, M1 is zirconium (Zr) or titanium (Ti), X 11 and X 12 are each independently a halogen, Hybrid supported metallocene catalyst.

3. In paragraph 1, A1 is silicone, Q 11 and Q 12 Either one of them is -(CH2) n -R b (Above R b is C 3-6 A branched alkoxy group, n is an integer from 2 to 10) is an alkoxyalkyl, and the remaining one is C 1-4 alkyl, Hybrid supported metallocene catalyst.

4. In paragraph 1, R 11 Inland R 15 are each independently, C 1-6 alkyl, Hybrid supported metallocene catalyst.

5. In paragraph 1, R 11 Inland R 14 are each independently methyl, R 15 is tert-butyl, Hybrid supported metallocene catalyst.

6. In paragraph 1, The above first transition metal compound is any one selected from the group consisting of the following compounds: Hybrid supported metallocene catalysts:

7. In paragraph 1, M2 is zirconium (Zr), X 21 and X 22 are each independently a halogen, Hybrid supported metallocene catalyst.

8. In paragraph 1, R 21 Inland R 25 are each independently methyl, Hybrid supported metallocene catalyst.

9. In paragraph 1, R 26 is hydrogen, or C 1-6 It is alkyl, R 27 Silver hydrogen, C 1-6 Alkyl, or -(CH2) n -R b (Above R b is C 3-6 A branched alkoxy group, and n is an integer from 2 to 10) of alkoxyalkyl, Hybrid supported metallocene catalyst.

10. In paragraph 1, The above second transition metal compound is any one selected from the group consisting of the following compounds: Hybrid supported metallocene catalysts: .

11. In paragraph 1, The first transition metal compound and the second transition metal compound are included in a molar ratio of 1:1 to 10:1, Hybrid supported metallocene catalyst.

12. In paragraph 1, The above cocatalyst is at least one selected from the group consisting of compounds represented by the following chemical formula 3. Hybrid supported metallocene catalysts: [Chemical Formula 3] -[Al(R 41 )-O]a- In the above chemical formula 3, R 41 is a halogen; or C substituted or unsubstituted with a halogen 1-20 It is hydrocarbyl; a is an integer greater than or equal to 2.

13. In paragraph 1, The carrier comprises silica, alumina, magnesia or a mixture thereof. Hybrid supported metallocene catalyst.

14. A step of polymerizing an ethylene monomer and an alpha-olefin monomer by introducing hydrogen in the presence of a hybrid supported metallocene catalyst according to paragraph 1. Method for producing polyethylene.

15. In paragraph 14, The above alpha-olefin monomer is added in an amount of 5 to 20 wt% based on the total weight of monomers including ethylene monomer and alpha-olefin monomer, The above hydrogen is added at 15 to 45 ppm based on the total weight of monomers including ethylene monomer and alpha-olefin monomer. Method for producing polyethylene.

16. In paragraph 14, The above alpha-olefin monomer is 1-butene, 1-hexene, or 1-octene, Method for producing polyethylene.

17. In paragraph 14, The above polyethylene satisfies the conditions (i) and (ii) below. Method for manufacturing polyethylene: (i) Density measured according to ASTM D1505: 0.91 to 0.93 g / cm 3 , (ii) Drop impact strength of 800 gf or more as measured according to ASTM D1709 [Method A].

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